INTERFACIAL

ELECTROCHEMISTRY
Theory, Experiment, and Applications

edited by

ANDRZEJ WIECKOWSKI
University of Illinois at Urbana-Champaign
Urbana, Illinois

MARCEL

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Foreword

The discovery ofthe interrelation ofelectricity and chemical change goes back to the beginning ofthe nineteenth century,
and that century saw great phenomenological advances such as the preparation of new elements by Davy, the invention
ofpower sources by Plana~ and Grove, and great industrial processes such as the electrochemical smelting of aluminum
by Hall and Heroult. Faraday made a key advance in the understanding ofelectrochemical processes through his quan-
titative laws ofelectrolysis, and Gibbs showed how thermodynamics could be applied to equilibrium cells and to obtain
the composition of interfaces. However, the study of the kinetics ofelectrode reactions did not begin until Tafel's obser-
vations at the beginning of the twentieth century. Progress in understanding the rate of electrode reactions was slow
despite the workofButler,Volmer, Frumkin, and Heyrovsk)'. Even in 1947 the overpotential was being interpreted by some
at the Liverpool Faraday Discussion in thermodynamic terms or as a result of blockage by a surface film. Nevertheless,
the work ofFrumkin and his colleagues, followed by that ofRandles, led to the integration ofelectrochemical kinetics into
the general scheme of the kinetics of interfacial reactions, but with the special feature of rate constants dependent on
potential. The investigation of the composition and structure of the metal-electrolyte interphase was more developed,
largely because of the properties of mercury, in the pioneering work of Gouy. These developments led to the use of the
dropping mercury electrode by Heyrovsk)' and almost the only work on a clean electrode surface in the first half of the
century. The precision measurement of the interfacial capacity by Grahame followed. Despite the great advances in
techniques, until 1970 measurements were macroscopic and the interpretations inevitably made contact with experimen-
tation at this level, even though optical interrogation of the interface was already being discussed in the Faraday
Symposium ofl970 in London.
The great advance ofthe last three decades ofthe twentieth century has been the introduction ofmolecular level tech-
niques that enabled the interpretation ofelectrochemical phenomena at this level. The landmark here was the meeting
in Snowmass, Colorado in 1979 on non-conventional approaches to the study of the solid-electrolyte interface (T. E.
Furtak, K. L. Kliewer, and D. W Lynch, eds., Surface Science 101 (1980)). Although earlier attempts to use vibrational
spectroscopy were made, the breakthrough came in the work of Fleischmann, Hendra, and McQuillan, followed by
Van Duyne, on surface-enhanced Raman spectroscopy and that of Bewick and Robinson, who showed how infrared
spectroscopy could be used to study the metal-electrolyte interface. Almost at the same time, Hubbard and his colleagues
showed how an electrode could be transferred cleanly into an ultrahigh vacuum where the structure and composition
ofits surface could be examined using the panoply ofelectron spectroscopies and scattering techniques developed by vac-
uum surface scientists. By the following decade Clavilier had advanced the knowledge ofsingle-crystal electrode surface
by a simple and elegant method, and the discovery of scanning tunneling microscopy by Binnig and Rohrer had led to
the study of surface structure in situ. These experimental advances were paralleled by greater theoretical insight made
possible by the enormously increased power ofdigital computers, which enabled models at the molecular level to be com-
pared with direct observations. It must be said that the sophisticated theory of electrode kinetics awaits a comparable
verification at the molecular level, although the stochastic approach discussed by Fleischmann et al. at the Snowmass
meeting seems to point the way.
iii
iv Foreword

This volume presents accounts ofmany ofthe outstanding developments ofthe past two decades, by the scientists from
various disciplines who have been attracted to the study ofelectrochemical interfaces by the possibility ofmaking signifi-
cant progress in understanding this important type of system. Their names guarantee the great interest of the articles,
which reflect the current state ofknowledge ofelectrochemisty at the molecular level. These chapters provide a firm basis
for those who wish to continue innovation in this field in the coming century. They will no doubt acknowledge their debt
to Andrzej Wieckowski for his foresight and skill in assembling this overview of the many aspects of interfacial
electrochemistry.

Roger Parsons
Department ofChemistry
The University
Southampton, England

I
I,
I
~

L-
l

Preface

We offer the reader an authoritative treatise that provides comprehensive coverage ofrecent advances in interfacial elec-
trochemistry by prominent scholars in the field and depicts its prospects for growth. The volume will be of interest to
electrochemists, surface scientists, and theorists, as well as to materials scientists and engineers who value the electrified
solid-liquid interface as a reactive zone for materials protection, modifications, and transformations. This is a modern
reference for instruction in electrochemistry, electroanalysis, and surface science on the graduate level that offers a
perspective on the size, content, and growth dynamics of interfacial electrochemistry, at the turn of the century.
The recognition given to electrochemistry by the international scientific community in the second halfofthe twentieth
century has been high due to both its fundamental and applied contributions, with two Nobel Prize highlights: in 1959
to HeyrovskY for polarography and in 1992 to Marcus for theory of electron transfer, including heterogeneous
(electrochemical) electron transfer reactions. The recent period of development has focused predominantly on
characterization properties of the solid-liquid interface and has given rise to interfacial electrochemistry as a rapidly
expanding discipline. Research in this field is identified by progress in theory and modeling in support ofexperiments,
continuing progress in the understanding of charge transfer reactions, investigations of the effect of electrode surface
structure on interfacial reactivity (structure-function relationships) and remarkable expansion of the array of
electrochemical, thermodynamic, and physical methods used to further the understanding of the interface on the
molecular level.
Although interfacial electrochemistry is mainly an experimental area, theory and modeling are a crucial adjunct, and
applications are derived from the fundamental experimental findings. Therefore, in order to demonstrate the overlap
among theory, experiment, and applications, the theoretical chapters are presented first, followed by the key results for
basic experimental strategies from which application prospects emanate. The applications discussions are not meant to
be reviews ofcurrent electrochemical technologies, but to describe experimental strategies that have clearly identifiable
applied goals or contexts. Although the division is more intuitive than formal, the reader should be able to navigate
through the volume easily, and see the prevailing logic in the theory ---+ experiment ---+ application sequence.
A new approach, comprehensively reviewed in this volume, has basically aligned electrochemists' interests in inter-
faces with the mainstream of modern topics in surface science and physical chemistry [1, 2]. The primary development
has been the demonstration ofthe intimate connection between electrochemical experiment and practice of interfacial
spectroscopies, both ex situ [3] and in situ [4-6], such as: (i) electron spectroscopies ofultrahigh vacuum (UHV) surface
science [3, 7-9], including double-layer modeling in UHV [10], (ii) optical techniques in the visible range:
electro-reflectance [7], second harmonic generation [11, 12] and Raman spectroscopy (mainly, surface enhanced Raman
spectroscopy) [13], (iii) infrared spectroscopy and related area [5, 6], (iv) synchrotron x-ray techniques [4, 14], (v) scanning
probe microscopies: scanning tunneling microscopy (STM) and atomic force microscopy [15], including joint STM
and UHV efforts [16], and, even more recently, (vi) solid-state nuclear magnetic resonance (NMR) [17]. The
electrochemistry-spectroscopy connection is amply highlighted in the volume (see, for instance, chapters by Soriaga,

v
vi Preface

Weaver, Tadjeddine, Pettinger, and their collaborators). There has been a parallel refinement in conventional electro-
chemical and thermodynamic [18] methods (chapters by Lipkowski et al. and by Silva and Martins), as well as
progress in electrochemical instrumentation, including the availability offully computerized potentiostats and facilitated
data storage, processing, and display, and a strong drive to use other physical techniques in the field: radioactive labeling
[19], quartz microbalance [20], and mass spectrometry [21]. Recent success in these strategies is well documented in
the book. The attractiveness and future prospects of the field have encouraged a healthy influx of numerous young
researchers, and the field continues to expand rapidly. Because of the complex nature of solid-liquid electrified
interfaces, theoretical investigations have long used simplified models, such as continuum dielectric and charged wall
models, to describe the solution and metal components of the interface [22]. More recently, however, Monte Carlo and
molecular dynamics simulations, and density functional theory direct dynamics (ultimately, quantum mechanical ab
initio) treatments have progressed to the level where it is now possible to model the molecular structure of the electrolyte
near discrete and charged metal surfaces, as well as to predict electrostatic parameters such as work function changes
and spectroscopic findings [23, 24]. Thorough discussions of these topics are provided in Part I, Theory and Modeling
by Haley, Blum, Berkowitz, Rikvold, Sellers, Anderson, Newton, Ulstrup, and by their collaborators.
The book aspires to cover recent progress of interfacial electrochemistry on the molecular level, requiring
crystallographically well-defined electrodes ofknown elemental surface composition as templates for adsorption, and/or
electrode rearrangement processes. The chapters on surface reconstruction (see the chapter by Kolb) and modeling of
electrical double-layer in ultrahigh vacuum (Ito et al. and Pirug et al.) manifest this trend most accurately. Such
well-defined electrodes are prepared not only via ultrahigh vacuum procedures derived from surface science, but by a
simple and ingenious so-called flame-annealing method [25]. In the chapter by Clavilier, the originator of the
flame-annealing method, a strong case is made about the virtues of his technique and for prospects for its continued
utilization. Although the contribution by ex situ techniques to electrochemistry and electrocatalysis remains strong (see
chapters by Hubbard,Wandelt, Soriaga,Tanaka, and their collaborators), the simplicity ofthe flame-annealing approach
has opened the field to many investigators who, most probably, would not consider using preparative methods requiring
extensive use ofvacuum instrumentation. It has also paved the way for new approaches to access the structure of electrical
double-layer, for instance, reliable measurements of potentials of zero charge using forced desorption-replacement
reactions (see the chapter by Feliu et al.). Besides, the flame-annealing methods are simple to couple with in situ tech-
niques ofelectrode surface characterization. The umbrella subfield ofelectrochemistry covering electrochemical research
with such well-characterized system can be termed electrochemical surface science. The progress in electrochemical sur-
face science, including the utilization of increasingly refined electrochemical, physical and theoretical (see, for instance,
Blum and Huckaby et al. in Ref. 23) methods, has immensely improved our understanding of molecular and ionic
adsorption, ultrathin metallic film formation, and electrocrystallization processes and has allowed investigators to dem-
onstrate structure- function relationships in electrochemistry for the first time since rate processes became the subject
ofelectrochemical scrutiny. This subfield ofinterfacial electrochemistry is comprehensively documented in Part II, Elec-
trochemical Surface Science.
The purpose of this book is to document that interfacial electrochemistry is a dynamic discipline with a rapidly
expanding scientific profile. Along this line, Conway and Savadogo, depict current trends in electrochemical hydrogen
science [26]. Chapters by Bernasek, Marcus, Jerkiewicz, and collaborators demonstrate the advanced efforts in promot-
ing corrosion research (also surface oxidation, dissolution, and passivation processes [27]) to become a vibrant part of-
contemporary physical and materials science activity. In Part III, Nonmetallic and Semiconductor Electrodes, Kulesza
et al. review the most recent progress and opportunities in solid-state electrochemistry, and McCreery et al. report on
the current status ofelectrochemistry ofcarbon electrodes [28]. Further, the status oforganic and inorganic surfactants
(thin films) on solid electrode surfaces is highlighted in chapters by Lipkowski, Buess-Herman, and their collaborators,
and the cutting-edge highlights related to semiconductor/solar energy [29] and to conducting polymer research [30],
are provided in chapters by Schultze, Augustynski, Uosaki, Rajeshwar, Stickney et al., and by Mark and Rubinson,
respectively. The reader will find very useful the updated demonstration of such powerful techniques as infrared
spectroelectrochemistry (chapters by Weaver, Korzeniewski, and Iwasita and collaborators), synchrotron x-ray methods
(chapter by Ocko/Adzic et al.), scanning tunneling microscopy (chapters by Kolb, Itaya, and collaborators), sum fre-
quency generation (Tadjeddine et al.), SERS (Weaver et al.), differential electrochemical mass spectrometry (Baltruschat),
radiotracers (Honlnyi), electroactive integrated optical waveguide spectroelectrochemistry (Armstrong), quartz
microbalance (Hepel), and UHV (e.g., Wieckowski et al.). Likewise, the topics covered in Part IV, Electrocatalysis
(beginning with the chapter by Trasatti that deals with catalysis on conductive oxides), conclusively demonstrate that
Preface vii

interfacial electrochemistry is an important part of the global effort to develop clean and renewable energy resources,
including fuel cells (see, for instance, chapters by Stuve, Ross/Markovic, Hamnett, Lamy, McBreen, and their
collaborators).
Thus, this collection of51 chapters serves as a focal point for the presentation ofthe diverse range oftopics in interfacial
electrochemistry, both experimental and conceptual, with regard to their future impact in physical surface sciences,
analytical chemistry, and energy-based technologies.We hope that this compilation ofchapters reflecting viewpoints by
many leading experts on solid -liquid interfacial issues has produced the material oflasting value to electrochemistry.
From a more personal perspective, this volume was developed as a forum to offer the authors an opportunity to sum-
marize recent contributions that they believe are most germane to their specific research areas and future work.We hope
that they have enjoyed preparing their contributions and we are confident that readers will recognize this sentiment. Most
of the chapters are not formal reviews, since presenting such reviews would amount to replicating the mission of
prominent monographs in electrochemical science. Therefore, the reader should not expect that all authors have covered
a comprehensive range of topics relevant to their interests. As a supplement, a snapshot of recently published books,
chapters, and proceedings volumes in the interfacial electrochemistry area is added, to provide supplementary and,
perhaps, unifYing material for the scope ofwork covered in this volume, see References.

THE FUTURE

Electrochemists have championed the use of modern surface spectroscopic and theoretical methods in fundamental,
atomic-level studies, but the period of their scrutiny has been too brief to capitalize on their accomplishments. There
are many challenges ahead. For instance:
(i) The significance of the electrode surface as a dynamic entity in controlling the structure/reactivity of electrified
interfaces needs to be vigorously demonstrated via both experimental and theoretical work.
(ii) Rates ofcatalytic reactions involving organic fuels are still too low to satisfY the demands ofthe fuel cell community,
and no more potent catalytic materials are in hand.
(iii) The degradation ofconstruction and electronic materials is far from being under satisfactory control.
(iv) Nanoscale procedures [31] emerging from electrochemistry are still in their infancy.
(v) Theoretical formalisms that fulfill a criterion of predictability as to the structure, binding energies, lateral
interactions, and interfacial reactivity have not yet been fully developed.
(vi) The nature ofthe surface chemical bond remains inadequately understood despite progress in the identification of
surface structure and adsorbate binding sites for a variety of systems.
(vii) Understanding of the dissociative electron transfer is poor as compared with that already developed for
outer-sphere electron transfer reactions [32].
(viii) Knowledge ofelementary steps involved in metal deposition has not yet meaningfully affected the pratice of indus-
trial deposition methods, and the contribution of interfacial electrochemistry to studies of electrified
. li~id -liquid and biological interfaces needs to be rapidly expanded.
Above all, confronted with the avalanche ofexperimental data ofhigh precision and depth, electrochemists increasingly
need expertise from theorists interested in the modeling ofsolid -liquid interfaces using powerful quantum mechanical,
molecular dynamics, and Monte Carlo techniques. Electrochemists also need to push for further expansion in research
methodology that will allow them to produce more experimental data on the quantum mechanical level, which, has so
far been rare.

ACKNOWLEDGMENTS
I gratefully acknowledge editorial assistance by my colleagues Professors G. Tremiliosi-Filho and W Chrzanowski.
Ms. Arvilla Humes' invaluable help with the management of the volume throughout the editing process is highly
appreciated.

Andrzej Wieckowski
viii Preface

REFERENCES
1. S Trasatti, K Wandelt. Surface Science and Electrochemistry, Proceedings of the IUVSTA Workshop on Surface Science and
Electrochemistry, San Benedetto del Tronto, Italy, 12-16 September, 1994, edited by S Trasatti and K Wandelt, Elsevier (1995).
Reprinted from Surface Sci 335: 1995.
2. M Weaver. Electrochemical interfaces: some structural perspectives. J Phys Chern 100:13079, 1996.
3. AT Hubbard. In: RG Compton, ed. Chemical Kinetics. Reactions at the Liquid-Solid Interface,Vol. 28, Chap. 1. Oxford: Elsevier,
1989.
4. H Abrufia, ed. Electrochemical Interfaces: ModernTechniques for In-Situ Surface Characterization. NewYork: VCH Publishers,
1991.
5. MJ Weaver, X Gao. In situ electrochemical surface science. Ann Rev Phys Chern 44:459, 1993.
6. C Korzeniewski. Infrared spectroscopy in electrochemistry: new methods and the connection to UHV surface science. Crit Rev
Anal Chern 27:81,1997.
7. DM Kolb. UHV techniques in the study ofelectrode surfaces. Phys Chern Neue Folge, Bd 154 S:179, 1987.
8. MP Soriaga. Ultra-high vacuum techniques in the study of single-crystal electrode surfaces. Prog Surface Sci 39:325, 1992.
9. EM Stuve and N Kizhakevariam. Chemistry and physics of the liquid/solid interface: a surface science perspective. J Vac Sci
Technol A 11:2217, 1993.
10. FT Wagner. In: J Lipkowski, PN Ross, Jr., eds. Structure of Electrified Interfaces. New York: VCH Publishers, Inc., 1993, p. 309.
11. GL Richmond. In: H Gerischer, CW Tobias, eds. Advances in Electrochemical Science and Engineering. New York: VCH
Publishers, 1992,Vol. 2 p. 141.
12. RM Corn, DA Higgins. Optical second harmonic generation as a probe of surface chemistry. Chern Rev 94:1071994.
13. ES Brandt, TM Cotton, eds. Surface-Enhanced Raman Scattering, 2nd ed. New York: John Wiley & Sons, 1993.
14. BM Ocko, J Wang. In: CA Melendres, A Tadjeddine, eds. Synchrotron Techniques in Interfacial Electrochemistry. Kluwer
Academic Pub., 1993.
15. AA Gewirth, BK Niece. Electrochemical applications of in situ scanning probe microscopy. Chern Rev 97:1129, 1997.
16. K Itaya. In situ scanning tunneling microscopy in electrolytic solutions. Progr. Surf. Sci., 58:121, 1998.
17. YY Tong, E Oldfield, A Wieckowski. Exploring metal/solution electrochemical interfaces by solid-state nuclear magnetic
resonance. Anal Chern A 70:518A, 1998.
18. J Lipkowski, L Stolberg. In: J Lipkowski, PN Ross eds. Adsorption of Molecules at Metal Electrodes. NewYork: VCH Publishers,
1992.
19. G Honlnyi. In: Reviews in Analytical Chemistry. London: Freund, 1995, p. 1.
20. D Buttry. The Quartz Crystal Microbalance as an In SituTool in Electrochemistry. In: H Abrufia, ed. Electrochemical Interfaces:
Modern Techniques for In-Situ Surface Characterization. New York: VCH Publishers, 1991, p. 531.
21. B Bittins-Cattaneo, E Cattaneo, P Kinigshoven,W Vielstich. In: AJ Bard, ed. Electroanalytical Chemistry: A Series ofAdvances,
Vol. 17. NewYork: Marcel Dekker, 1991, p. 181.
22. AWieckowski, KA Friedrich, U Stimming, eds. ACS symposium on Electrochemical Surface Science in the International Scene,
Orlando, FL, 1996. Colloids and Surfaces A-Physicochemical and Engineering Aspects, A 134 (1),1998. Special issue.
23. L Blum. Structure ofthe electric double layer. Adv Chern Phys 78:171, 1991; DA Huckaby, MD Legault, L Blum. Cluster variation
study ofthe underpotential deposition ofCu on Au (Ill) in the presence of bisulfate. J Chern Phys 109:3600, 1998.
24. JW Halley. Studies ofthe interdependence ofelectronic and atomic dynamics and structure at the electrode-electrolyte interface.
Electrochim Acta 41:2229,1996.
25. J Clavilier, A Rhodes, K EI Achi, MA Zamakhchari. Electrochemistry of Platinum Single Crystal Surfaces in Acidic Media:
Hydrogen and Oxygen Adsorption. In special issue of J Chim Phys (France), 88:1291, 1991, Electrode Surface Structure,
Adsorption, Desorption and Recombination of Non-Metallic Species, J Oudar, P Marcus, J Clavilier, eds.
26. BE Conway, G Jerkiewicz, eds. Electrochemistry and Materials Science of Hydrogen Absorption and Adsorption, The ECS
Proceedings,Vol 94-2LThe Electrochemical Society, Pennington, NJ 1994.
27. P Marcus, J Oudar, eds. Corrosion Mechanisms in Theory and Practice. New York: Marcel Dekker, 1995.
28. RL McCreery. In: AJ Bard, ed. Electroanalytical ChemistrY,VoI.17. New York: Marcel Dekker, 1991, p. 221.
29. PV Kamat, D Meisel, eds. Semiconductor Nanoclusters: Physical, Chemical, and Catalytic Aspects. Amsterdam: Elsevier, 1997.
30. K Doblhofer, K Rajeshwar. In: TA Skotheim, RL Elsenbaumer, JR Reynolds, eds. Handbook of Conducting Polymers, 2nd ed.
New York: Marcel Dekker, 1998.
31. WJ Lorenz, W Plieth, eds. Electrochemical Nanotechnology: In-situ Local Probe Techniques at Electrochemical Interfaces.
Weinheim: Wiley-VCH, 1998.
32. AA Kornyshev, M Tosi, J U1strup, eds. Proceedings of the Conference on Electron and Ion Transfer in Condensed Media,
Theoretical Physics for Reaction Kinetics, ICTp, Trieste, Italy, July, 1996, Singapore: World Scientific, 1997.

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Contents

Foreword Roger Parsons iii

Preface v
Contributors xiii

I. Theory and Modeling

1. Theoretical Modeling of the Solid - Liquid Interface: Chemically Specific Simulation Methods
J W Halley, Sean Walbran, and David Lee Price
2. Theory of the Metal- Electrolyte Interface 19
L. Blum, Marc D. Legault, and Dale A. Huckaby

3. Structure of Water at the Water- Metal Interface: Molecular Dynamics Computer Simulations 33
M. L. Berkowitz, In-Chul Yeh, and Eckhard Spohr
4. Monte Carlo Methods for Equilibrium and Nonequilibrium Problems in Interfacial Electrochemistry 47
G. Brown, P A. Rikvold, S. J Mitchell, and M. A. Novotny
5. Electronic Structure Calculations of Polyatomic Oxyanions Adsorbed on Metal Surfaces 63
Patricia Paredes Olivera, Martin Patrito, and Harrell Sellers
6. Quantum Chemical Modeling of Electrocatalytic Reactions, Including Potential Dependence: Beginning
Stages 83
Alfred B. Anderson
7. Theory and Computational Modeling: Medium Reorganization and Donor-Acceptor Coupling in Electron
Transfer Processes 97
Marshall D. Newton, S. W Feldberg, and J F Smalley
8. Interfacial Electron Transfer in Electrochemistry and In Situ Scanning Tunneling Microscopy 115
Esben P Friis, Marianne Hallberg Thuesen, lingdong Zhang, and lens Ulstrup

II. Electrochemical Surface Science

9. Electrochemical Processes Involving H Adsorbed at Metal Electrode Surfaces 131
Brian E. Conway

ix
x Contents

10. Reconstruction of Gold Surfaces 151

A. S. Dakkouri and D. M. Kolb
11. In Situ Surface X-Ray Scattering Studies of Electrosorption 175
Jia X Wang, Radoslav R. A diic , and Benjamin M. Ocko
12. Atomic-Scale Aspects of Anodic Dissolution of Metals: Studies by In Situ Scanning Tunneling Microscopy 187
Kingo Itaya
13. Auger Spectroscopy of Electrode Surfaces 211
ArthurT Hubbard
14. Flame-Annealing and Cleaning Technique 231
Jean Clavilier
IS. Interfacial Chemistry of Palladium Electrodes 249
Manuel P Soriaga, Youn-Geun Kim, and Jose E. Soto
16. Electrochemical Double-Layer Modeling Under Ultrahigh Vacuum Conditions 269
G. Pirug and H P Bonzel
17. Modeling of the Electrochemical Double-Layer in Ultrahigh Vacuum: Adsorption of Sulfuric Acid Species on
Pt(lll) 287
Yoshitaka Shingaya and Masatoki Ito
18. Adsorbate Bonding and Reactivity in Electrochemistry: Some Vibrational Spectroscopic Links to Surface Science
and Interfacial Chemistry 301
Michael J T#averand Shouzhong Zou
19. Sum and Difference Frequency Generation at Electrode Surfaces 317
Abderrahmane Trldjeddine and Alain Le Rille
20. Vibrational Coupling Effects on Infrared Spectra of Adsorbates on Electrodes 345
Carol Korzeniewski
21. A FourierTransform Infrared Spectroscopy Approach to Double-Layer and Electrocatalysis Problems 353
Teresa Iwasita and Elena Pastor
22. Second Harmonic Generation Anisotropy from Single Crystalline Electrode Surfaces 373
Bruno Pettinger, Christoph Bilger, Jacek Lipkowski, and Wolfgang Schmickler
23. Amphiphilic and Ionic Surfactants at Electrified Interfaces 405
Dan Bizzotto, Vlad Zamlynny, Ian Burgess, Craig A. Jeffrey, Hong-Qiang Li, John Rubinstein, Rod A. Merril, Jacek
Lipkowski, Zbigniew Galus, Andrew Nelson, and Bruno Pettinger
24. Ordered Organic Adlayers at Electrode Surfaces 427
Claudine Buess-Herman, Sandra Bare, Mireille Poelman, and Michel Tim krieken
25. Capacitive and Voltammetric Responses from Stepped Faces of Gold 449
A. Fernando Silva and Ana Martins
26. Electrochemistry, Spectroscopy, and Scanning Tunneling Microscopy Images of Small Single-Crystal
Electrodes 463
V Climent, R. Gomez, J M. Orts, A. Rodes, Antonio Aldaz, and Juan M. Feliu
27. Radiotracer Studies of Adsorption/Sorption Phenomena at Electrode Surfaces 477
Gyorgy HrJr(inyi
28. Structure and Reactivity of Rhodium and Rhodium-Based Alloys 493
Ken-ichi Tanaka and Akira Sasahara

...........
Contents xi

29. Spectroelectrochemistry of Monolayer and Submonolayer Films Using an Electroactive Integrated Optical
Waveguide 513
Darren Dunphy, Sergio Mendes, S. Scott Saavedra, and Neal R. Armstrong
30. Surface Science Studies of Organic Monolayer Corrosion Inhibitors 527
Steven L. Bernasek
31. Structure of Thin Anodic Oxide Films Formed on Single-Crystal Metal Surfaces 541
Philippe Marcus and Vincent Maurice
32. Surface Oxidation of Noble Metal Electrodes 559
Gregory Jerkiewicz
33. Differential Electrochemical Mass Spectrometry as a Tool for Interfacial Studies 577
Helmut Baltruschat
34. Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 599
Maria Hepel

III. Nonmetallic and Semiconductor Electrodes

35. Electrochemical Properties of Carbon Surfaces 631
Richard L. McCreery
36. Bulk and Surface States of Reactive Oxide Films: An Extended Semiconductor Model with Ti, Ni, and Fe as
Examples 649
Uwe Konig and Joachim Walter Schultze
37. Solid-State Voltammetry 673
Pawel J Kulesza and Marcin A. Malik
38. Conducting Polymer Films as Electrodes 689
Judith F. Rubinson and Harry B. Mark, Jr.
39. Photoelectrochemistry of Nanostructured Semiconductors: The Case of Anatase Ti0 2 707
Jan Augustynski
40. Semiconductor Nanocomposite Films for Photoelectrochemical Applications 721
Krishnan Rajeshwar and Norma R. de Thcconi
41. Electronic and Morphological Structures of Semiconductor Electrodes 737
Kohei Uosaki, Michio Koinuma, and Shen Ye
42. Epitaxial Compound Electrodeposition 757
Travis L. Wade, Thomas A. Sorenson, and John L. Stickney

IV, Electrocatalysis
43. Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis 769
Sergio Trasatti
44. Kinetic Modeling of Electrocatalytic Reactions: Methanol Oxidation on Platinum Electrodes 793
S. Sriramulu, T D. Jarvi, and E. M. Stuve
45. Properties of Bimetallic Electrodes: Spectroscopic Characterization and Electrocatalysis 805
Christopher Stuhlmann, Henning Hoffschulz, and Klaus rfandelt
46. Electrocatalysis at Well-Defined Surfaces: Kinetics of Oxygen Reduction and Hydrogen Oxidation/Evolution on
Pt(hkl) Electrodes 821
Nenad M Markovic and Philip N Ross, Jr.
xii Contents

47. Mechanism of Methanol Electro-Oxidation 843

Andrew Hamnett
48. Advanced Electrode Materials for the Direct Methanol Fuel Cell 885
Claude Lamy and Jean-Michel Leger
49. In Situ X-Ray Absorption Studies of Carbon-Supported Pt and Pt Alloy Nanoparticles 895
James McBreen and Sanjeev Mukerjee
50. Synergetic Effects of Surface Active Sites on the Hydrogen Evolution Reaction 915
0. Savadogo
51. Methanol Oxidation Catalysis on Well-Defined Platinum/Ruthenium Electrodes: Ultrahigh Vacuum Surface
Science and Electrochemistry Approach 937
Wojciech Chrzanowski and Andrzej Wieckowski

Index 955

I
L
Contributors

Radoslav R. Adzic Chemical Sciences Division, Department of Applied Science, Brookhaven National Laboratory,
Upton, New York

Antonio Aldaz Department of Physical Chemistry, University of Alicante, Alicante, Spain

Alfred B. Anderson Department of Chemistry, Case Western Reserve University, Cleveland, Ohio

Neal R. Armstrong Department of Chemistry, University of Arizona, Tucson, Arizona

Jan Augustynski University of Geneva, Geneva, Switzerland

Helmut Baltruschat Institute of Physical and Theoretical Chemistry, University of Bonn, Bonn, Germany

Sandra Bare Service de Chimie Analytique, Universite Libre de Bruxelles, Brussels, Belgium

M. L. Berkowitz Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina

Steven L. Bernasek Department of Chemistry, Princeton University, Princeton, New Jersey

Christoph Bilger Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin. Germany

Dan Bizzotto Department of Chemistry, University of British Columbia,Vancouver, British Columbia, Canada

L. Blum Department of Physics, University of Puerto Rico, Rio Piedras, Puerto Rico

H. P. Bonzel Institut fUr GrenzfHichenforschung und Vakuumphysik, Forschungszentrum Jiilich GmbH, Jiilich,
Germany

G. Brown Center for Materials Research and Technology, Supercomputer Computations Research Institute, and
Department of Physics, Florida State University, Tallahassee, Florida

Claudine Buess-Herman Service de Chimie Analytique, Universite Libre de Bruxelles, Brussels, Belgium

xiii
xiv Contributors

Ian Burgess Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

Wojciech Chrzanowski* Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois

Jean Clavilier CNRS, Meudon, France

V. Climent Department of Physical Chemistry, University of Alicante, Alicante, Spain

Brian E. Conway Department of Chemistry, University of Ottawa, Ottawa, Ontario, Canada

A. S. Dakkouri t Department of Electrochemistry, University of Ulm, Ulm, Germany

Norma R. deTacconi Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, Texas

Darren Dunphy Department of Chemistry, University of Arizona, Tucson, Arizona

S. W. Feldberg Chemical Sciences Division, Department of Applied Science, Brookhaven National Laboratory,
Upton, New York

Juan M. Feliu Department of Physical Chemistry, University of Alicante, Alicante, Spain

Esben P. Friis Department of Chemistry, Technical University of Denmark, Lyngby, Denmark

Zbigniew Galus Department of Chemistry, University of Warsaw, Warsaw, Poland

R. Gomez Department of Physical Chemistry, University of Alicante, Alicante, Spain

J. W. Halley Department of Physics, University of Minnesota, Minneapolis, Minnesota

Andrew Hamnett University of Newcastle, Newcastle upon Tyne, England

Maria Hepel Department of Chemistry, State University of New York at Potsdam, Potsdam, New York

Henning Hoffschulz t Institut fUr Physikalische und Theoretische Chemie, University of Bonn, Bonn, Germany

Gyorgy Horanyi Institute of Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Budapest,
Hungary

Arthur T. Hubbard Santa Barbara Science Project, Santa Barbara, California

Dale A. Huckaby Department of Chemistry, Texas Christian University, Fort Worth, Texas

Kingo Itaya Department of Applied Chemistry, Faculty of Engineering, Tohoku University, Sendai, Japan

Masatoki Ito Department of Chemistry, Keio University,Yokohama, Japan

Current affiliations:
* Physical Chemistry Department, Technical University of Gdansk, Gdansk, Poland.
tDepartment of Materials Science, Institute for Corrosion Science and Surface Technology, University of Erlangen - Nuremberg,
frlangen, Germany.
+ SAP AG, Walldorf, Germany.
Contributors xv

Teresa Iwasita Department of Physical Chemistry, Institute of Chemistry of Sao Carlos, University of Sao Paulo, Sao
Carlos, Brazil

T. D. Jarvi Department of Chemical Engineering, University of Washington, Seattle,Washington

Craig A. Jeffrey Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

Gregory Jerkiewicz Department of Chemistry, University of Sherbrooke, Sherbrooke, Quebec, Canada

Yonn-Geun Kim Department of Chemistry, Texas A&M University, College Station, Texas

Uwe Konig [nstitut fUr Physikalische Chemie und Elektrochemie II, Heinrich-Heine-Universitat, Dusseldorf,
Germany

Michio Koinuma Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, Japan

D. M. Kolb Department of Electrochemistry, University ofUlm, Ulm, Germany

Carol Korzeniewski Department of Chemistry and Biochemistry,Texas Tech University, Lubbock, Texas

Pawel J. Kulesza Department of Chemistry, University of Warsaw, Warsaw, Poland

Claude Lamy Department of Chemistry, University of Poitiers, Poitiers, France

Alain Le Rille LURE, CNRS, Orsay, France

Marc D. Legault Department of Physics, University of Puerto Rico at Bayamon, Bayamon, Puerto Rico

Jean-Michel Leger Department of Chemistry, University of Poitiers, Poitiers, France

Hong-Qiang Li Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

Jacek Lipkowski Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

Marcin A. Malik Department of Chemistry, University of Warsaw, Warsaw, Poland

Philippe Marcus Laboratoire de Physico-Chimie des Surfaces, Ecole Nationale Superieure de Chimie de Paris,
CNRS- Universite Paris VI, Paris, France

Harry B. Mark, Jr. Department of Chemistry, University of Cincinnati, Cincinnati, Ohio

Nenad M. Markovic Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California

Ana Martins Department of Chemistry, Faculdade de Ciencias do Porto, Centro de Investigac;ao em Quimica, Porto,
Portugal

Vincent Maurice Laboratoire de Physico-Chimie des Surfaces, Ecole Nationale Superieure de Chimie de Paris,
CNRS- Universite Paris VI, Paris, France

James McBreen Material Science Division, Department of Applied Science, Brookhaven National Laboratory,
Upton, New York
xvi Contributors

Richard L. McCreery Department of Chemistry, Ohio State University, Columbus, Ohio

Sergio Mendes Optical Sciences Center, University of Arizona, Tucson, Arizona

Rod A. Merril Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

S. J. Mitchell Center for Materials Research and Technology, Supercomputer Computations Research Institute, and
Department of Physics, Florida State University, Tallahassee, Florida

Sanjeev Mukerjee* Material Science Division, Department of Applied Science, Brookhaven National Laboratory,
Upton, New York

Andrew Nelson Plymouth Marine Laboratory, Plymouth, England

Marshall D. Newton Department of Chemistry, Brookhaven National Laboratory, Upton, New York

M. A. Novotny Center for Materials Research and Technology, Supercomputer Computations Research Institute, and
Department of Physics, Florida State University, Tallahassee, Florida

Benjamin M. Ocko Department of Physics, Brookhaven National Laboratory, Upton, New York

J. M. Orts Department of Physical Chemistry, University of Alicante, Alicante, Spain

Patricia Paredes Olivera Unidad de Matematica y Fisica, Instituto de Investigaciones en Fisicoquimica de Cordoba,
Facultad de Ciencias Quimicas, Universidad Nacional de Cordoba, Cordoba, Argentina

Elena Pastor Department of Physical Chemistry, University of La Laguna, La Laguna, Tenerife, Spain

Martin Patrito Unidad de Matematica y Fisica, Instituto de Investigaciones en Fisicoquimica de Cordoba, Facultad
de Ciencias Quimicas, Universidad Nacional de Cordoba, Cordoba, Argentina

Bruno Pettinger Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany

G. Pi rug Institut fUr GrenzfHichenforschung und Vakuumphysik, Forschungszentrum Jiilich GmbH, Jiilich, Germany

Mireille Poelman Service de Chimie Analytique, Universite Libre de Bruxelles, Brussels, Belgium

David Lee Price Department of Physics, University of Memphis, Memphis, Tennessee

Krishnan Rajeshwar Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, Texas

P. A. Rikvold Center for Materials Research and Technology, Supercomputer Computations Research Institute, and
Department of Physics, Florida State University, Tallahassee, Florida

A. Rodes Department of Physical Chemistry, University of Alicante, Alicante, Spain

Philip N. Ross, Jr. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California

Judith F. Rubinson Department of Chemistry, University of Cincinnati, Cincinnati, Ohio

* Current affiliation: Northeastern University, Boston, Massachusetts.

io.........-
Contributors xvii

John Rubinstein Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

S. Scott Saavedra Department of Chemistry, University of Arizona, Tucson, Arizona

Akira Sasahara The Kanagawa Academy of Science and Technology Foundation, Kawasaki, Japan

O. Savadogo Department of Physics and Material Engineering, Ecole Polytechnique de Montreal, Montreal, Quebec,
Canada

Wolfgang Schmickler Department of Electrochemistry, University ofUlm, Ulm, Germany

Joachim Walter Schultze Institut fUr Physikalische Chemie und Elektrochemie II, Heinrich-Heine-Universitat,
Dusseldorf, Germany

Harrell Sellers Department ofChemistry and Biochemistry, South Dakota State University, Brookings, South Dakota

Yoshitaka Shingaya Department of Chemistry, Keio University,Yokohama, Japan

A. Fernando Silva Department of Chemistry, Faculdade de Ciencias do Porto, Centro de Investiga~ao em Quimica,
Porto, Portugal

J. F. Smalley Chemical Sciences Division, Department of Applied Science, Brookhaven National Laboratory, Upton,
New York

Thomas A. Sorenson Department of Chemistry, University of Georgia, Athens, Georgia

Manuel P. Soriaga Department of Chemistry, Texas A&M University, College Station, Texas

Jose E. Soto Department of Chemistry, Texas A&M University, College Station,Texas

Eckhard Spohr Department of Theoretical Chemistry, University ofUlm, Ulm, Germany

S. Sriramulu Department of Chemical Engineering, University of Washington, Seattle,Washington

John L. Stickney Department of Chemistry, University of Georgia, Athens, Georgia

Christopher Stuhlmann* Institut fUr Physikalische und Theoretische Chemie, University of Bonn, Bonn, Germany

E. M. Stuve Department of Chemical Engineering, University of Washington, Seattle,Washington

AbderrahmaneTadjeddine LURE, CNRS, Orsay, France

Ken-ichi Tanaka Saitama Institute of Technology, Saitama, Japan

Marianne Hallberg Thuesen Department of Chemistry, Technical University of Denmark, Lyngby, Denmark

Sergio Trasatti Department of Physical Chemistry and Electrochemistry, University of Milan, Milan, Italy

Jens Ulstrup Department of Chemistry, Technical University of Denmark, Lyngby, Denmark

* Current affiliation: Innosoft GmbH, Cologne, Germany.

xviii Contributors

Kohei Uosaki Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, Japan

Michel Van krieken Service de Chimie Analytique, Universite Libre de Bruxelles, Brussels, Belgium

Travis L. Wade Department of Chemistry, University of Georgia, Athens, Georgia

Sean Walbran School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota

Klaus Wandelt Department of Physical Chemistry, Rheinische Friedrich-Wilhelms-University, Bonn, Germany

Jia X.Wang Chemical Sciences Division, Department of Applied Science, Brookhaven National Laboratory, Upton,
New York

Michael J. Weaver Department of Chemistry, Purdue University,West Lafayette, Indiana

Andrzej Wieckowski Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois

Shen Ye Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, Japan

In-Chul Yeh Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina

Vlad Zamlynny Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada

Jingdong Zhang Department of Chemistry, Technical University of Denmark, Lyngby, Denmark

Shouzhong Zou Department of Chemistry, Purdue University,West Lafayette, Indiana

1
Theoretical Modeling of the Solid-Liquid Interface:
Chemically Specific Simulation Methods
J. W. Halley and Sean Walbran
University ofMinnesota, Minneapolis, Minnesota
David Lee Price
University ofMemphis, Memphis, Tennessee
ABSTRACT
We review recent progress in microscopic modeling
of structure and kinetics at electrochemical interfaces.
With respect to structure, a good account of the struc-
ture of sp metal-water interfaces can be achieved,
but verification is lacking because of the dearth of
experimental information. For noble metal-water
interfaces, direct dynamics models that are simplified to
meet computational constraints give reasonable results
for copper surfaces, although experimental confirmation
of details is incomplete. It is now possible to
computationally model some outer sphere electron
transfer processes quantitatively and to use computations
of barrier heights to select between candidate transition
states. We report details of recent work on the
cuprous-cupric electron transfer reaction. Inner sphere
processes, including adsorption and dissolution, can be
attacked by the same direct dynamics methods used to
describe structure and capacitance, but computational
requirements are very large.We describe some results for
chloride adsorption on a model of copper. Finally, we
briefly discuss the problem of modeling semiconductor
(or oxide)-solvent interfaces.
I. INTRODUCTION
The modern theory ofthe electrode-electrolyte interface
can be said to have reached an important early milestone
with the publication of D. Grahame's review [1] of his
1
experiments on the differential capacitance of the
mercury-aqueous electrolyte interface 50 years ago.
Fifteen years ago, there was no consensus on the meaning
of the results, though the reliability of the data had
withstood (and continues to withstand) the test of time.
People were just beginning in the early 1980s [2-4] to
model effects of the electronic structure at the interface
on capacitance (though anticipated by many years by
Rice [5]). In the first part of this chapter we review pro-
gress since that time on understanding of the structure
of the interface through computational modeling, which
includes electronic structure and atomic relaxation at
electrolyte metal interfaces.
With regard to kinetics at the electrochemical
solid-liquid interface, the early landmarkwork is charac-
terized by the papers of Marcus [6-11] (with independent
work of a similar nature by various Soviet workers [12]).
Recently, it has become possible [13-15] to make explicit
computational models of the electron transfer processes
described in this earlier work. The second part of this
chapter reviews progress on the modeling ofthese kinetic
processes, mainly electron transfer at metal- electrolyte
interfaces.
Finally, it is of great practical importance to under-
stand both the structure and dynamics of interfaces
between electrolytes and semiconducting materials,
including both the semiconductors of interest to the elec-
tronics industry and the metallic oxides that playa key
2 Halley et al.
role in the passivation of metals to corrosion. We briefly
review the rather more fragmentary progress made in
modeling such interfaces.
II. STRUCTURE OF THE
METAL-ELECTROLYTE INTERFACE
The aspect ofthe Grahame data that resisted explanation
was the inner layer part of the capacitance, obtained by
subtracting offa term associated with the ionic screening
of the electric field by the electrolyte and modeled with
the Gouy-Chapman theory [16,17]. It was strikingly
asymmetric about the point ofzero charge. Until the early
1980s, all attempts to account for this asymmetry were
based on elaborations of the Stern model [18], which
attributed the inner layer capacitance to a layer oftightly
packed water at the surface of the metal electrode. Such
a layer surely exists, but attempts to model its effects by
use of relatively simple statistical mechanical models of
a layer of dipoles did not easily yield the observed asym-
metry [see, e.g., Refs.19-22].What these models were able
to explain convincingly was the maximum in the inner
layer capacitance at the point ofzero charge, arising from
the saturation of the dielectric response of the water layer
at potentials far from the point ofzero charge. This maxi-
mum appeared clearly at lower temperatures than
Grahame's data, although the main feature is the asym-
metry already noted. Later, when reliable data on solid
noble metal electrodes appeared, however [23-25], the
predicted peakwas even more in evidence but still accom-
panied by an asymmetry that was not easily understood
within the models.
Exhaustive work by specialists in the integral equation
approach to liquid-state theory have shown quite con-
vincingly [26] that the problems in accounting for data
like that of Grahame and others do not arise primarily
from the effects offinite ion size that would lead to correc-
tions to the Gouy-Chapman theory, at least at the low
ionic concentrations relevant to most aqueous solvent
electrochemistry. (Molten salt electrochemistry is
another matter.) One can convince oneself that this is
reasonable on the basis of quite simple length scale
arguments. The smallest relevant length scales in the fluid
are the screening length and the distance of closest
approach of an ion to the electrode, and each of these is
5 A or more. A continuum theory should treat such a sys-
tem quite well, as it is found to do. This is fortunate
because a realistic simulation of the double-layer region
remains beyond current simulation capacity at present if
we wish to include a microscopic description of the sol-
vent in the simulation. The order of magnitude reason
for this is that one needs to include on the order of 10 2
water molecules for each ion and on the order of 10 2 ions
so that the needed simulations are on the order of more
than 10 2 times (because cost scales at least as the square
of the number of molecules) more expensive than the
simulations of the Stern layer. Although classic
simulations of such a size are feasible (particularly in
massively parallel implementations), including the
calculation of the electronic structure of the electrode
makes such a study prohibitively expensive (and difficult
to parallelize, due in part to the need for global
orthogonalization of wavefunctions described by a large
number of coefficients). On the other hand, because the
length scale variations of the potentials in this region are
also larger, at low ionic strengths, by about an order of
magnitude, the mean field representation given by the
classical Gouy-Chapman theory [16] is rather good in
this region. To determine the capacitance of the entire
;.
system, however, one must couple this theory in a correct
way to the model for the region near the electrode as dis-
cussed below.
In models that include the effects of rearrangement of
the electronic structure of the metal in response to the
applied potential, on the other hand, it is possible to
understand the asymmetry in the capacitance qualitat-
ively without too much difficulty [2,27-30]. When the
electrode is negatively charged, the electrons of the metal r
push the water molecules away, effectively increasing the
charge separation and reducing the capacitance, whereas
when the electrode is positively charged, the water mol-
ecules follow the electrons back toward the metal,
effectively reducing the charge separation and increasing
the capacitance. This gives an asymmetry ofthe right sign
and order of magnitude to account for the asymmetry in
the Grahame and other data on inner layer capacitance.
Early jellium-like models always found such an effect
[27-30], as long as they allowed the separation between
the model ofthe solvent and the metal to vary in order to
minimize the total energy at fixed electrode charge.
Results for the inner layer capacitance for a number of
those earlier jellium-like models are summarized in Fig.
1, where they are compared with experimental results
for the inner layer capacitance of cadmium. The sign
and order of magnitude of the effect are consistently
correct, but these theories are clearly not quantitative.
The jellium-based models did not easily account for a
peak in the inner layer capacitance near the point of zero
charge. These circumstances suggested that both the
inner water layer and the electronic structure might be
playing a role. A simple order of magnitude argument
suggests a similar conclusion: The capacitance ofa layer
is inversely proportional to the distance by which it
separates the charges and proportional to the effective
i..
 Theoretical Modeling
~"""-:::rl;::=C~~--------'
-1 0 I
-3 -2
0-( n- 3 a. U. )
Figure 1 Comparison ofresults ofthe models ofRef. 2 CD), 27
(A), 28 (B), and experiment (C) for Cd as described in Ref. 28.
dielectric constant so that lie ex d/ f. For the electronic
structure contribution d~ATF, the Thomas Fermi
screening length, which is characteristically ~ 10- 1A
and I; ~ I. For the inner water layer, d ~ I A and E ~ 10.
Thus, adding the capacitances in series, one sees that they
both should contribute roughly equally. Some efforts to
combine jellium with polarizable dipole layer models
were reported, based on this insight [31]. However, a
quantitative understanding has remained elusive. For
example, a simple series model in which a "metallic"
capacitance is simply added to a Stern layer capacitance
t could be suggested, in which the high-temperature
Grahame data are attributed to the metallic capacitance
entirely. However, it is hard to reconcile such a model with
the data without introducing negative capacitances for
some of the layers, and although these are not excluded
in principle [32], this is not a satisfactory state of affairs
when there are not good physical grounds for such a sep-
aration into two capacitors added in series.
Recent simulation models include both the effects of
the inner Stern-like layer of water and of the response of
the electronic structure of the applied potential and are
beginning to produce a more satisfactory account of the
structure of the interface. Most of this work uses some
form ofa standard central potential molecular dynamics
model [33] for water to describe the solvent of the
electrolyte. Such models contain oxygen centers and
hydrogen centers each carrying a partial charge, with full
account of the Coulomb interactions. The molecules are
3
flexible in the model and have the correct internal
dynamics, treated, however, classically. The structure of
bulk water resulting from a simulation using such a mol-
ecular dynamics model agrees very well with
experimental neutron data on real water. The calculated
dielectric constant (e.g., 34) is close to the experimental
value. This is a much more realistic representation of
water than the various lattice models often used to model
the inner layer and mentioned above.
The key to using this molecular dynamics model suc-
cessfully to understand the inner layer is to couple a simu-
lation ofa small sample of such a model of water to both
the metal and the electrolyte sides. Because one only uses
the molecular dynamics model to model the inner layer,
then as long as one compares with experiments in which
no ion adsorption is believed to be occurring on the
electrode, no problem concerning the absence of ions in
the simulation arises, as far as short-range forces go. With
regard to the electric fields produced by the ions and act-
ing on this inner layer of water, these are treated as
uniform. This is certainly an approximation, because
there will be inhomogeneities in these fields arising from
the ions. However, the approximation is much less drastic
than those present in most other models. In such
simulations one is usually practically constrained to
about 104 atomic centers ifone wishes to repeat the calcu-
lations many times as is required in electrochemical
applications, though this upper limit is rapidly
increasing. This corresponds to "samples," a few tens of
angstroms on a side. However, this is just the right scale
for an understanding of the electrostatic behavior of the
Stern-like properties of this inner layer of water. Though
we refer to this molecular dynamics model for the inner
layer water as a model for the Stern layer, and this is
an historically appropriate reference to Stern's original
idea, this model has many features that Stern's did not.
All nonlinear nonlocal electrodynamic responses of
real water are present quite accurately up to infrared
frequencies.
In the electrochemical application we use such a water
model together with an account of the wave functions of
all electrons in a model of the electrode. We describe
results from recent work on copper [35] and cadmium
electrodes, in which the rigid TIPS water model [36] is
used, and further studies of copper electrodes in the
presence of a flexible water model [33]. (The results pre-
sented here use a highly imperfect model of copper, in
which only the s electrons are treated explicitly. This
approximation is currently necessary to make these
simulations computationally tractable and provides a
reasonable picture of electronic structure relaxation,
because the d states are more tightly bound. However, it
4 Halley et a1.

results in copper-copper interactions that are more

repulsive than if the d states were included, precluding at
this time a study in which the copper surfaces are allowed
to relax.) In practice, wave functions for about 10 2 elec-
trons are recalculated each time the water molecules are f a)

moved (approximately every 1/2 fs). The electrons inter-

act with the water molecules through a pseudopotential
·~
o
V=1.9 -
v=o
~
that is constructed to describe electrons in the ~
neighborhood of water molecules by solving the ~
all-electron, density functional problem for a single water ·~
o

molecule and fitting a combination of central pseudo-

potentials to the resulting self-consistent effective poten-
tial. The electrons also interact with ion cores in the l).</':

fcc structure of the model of the copper electrode. This 10 12 14 16 18 20

olstance from slab center (au)
is described in detail in Refs. 35 and 37. We note that this
approach treats the electrons of the metal explicitly but
differs from preceding jellium-like treatments in two
ways: The full lattice structure of the electrode is present
and, unlike earlier work, the time scales are treated cor-
rectly, and the electrons, which relax much faster than ;<-

the atoms, follow the motions of the water molecules l

o
b)

.,~
instantaneously, as they should be in the Born V=·1,9 -
V=o

i\I~'\~
Oppenheimer approximation because they have much ~
i/, I

n:I'~ \
~
lower mass than the atoms. •

'~\j\ j1J1 !il

~
In much earlier simulation work on the interface
[38-46], the electronic structure of the electrode is taken
·~
o

\,: I

into account only through the short-range potential that

describes the interaction of the water with the electrode \, ~. \ ! /:'
,11
I
in an entirely classic simulation. (Sometimes electrostatic VUL'" V

images of the partial charges on the model solvent mol- 10 12 14

distance from slab center (au)
16 18 20

ecules are also included.) These calculations are done as

follows. One uses a quantum mechanical calculation
(e.g.. one of the readily available Hartree Fock quantum
chemical packages) to calculate the energy of one water
molecule plus a small cluster of atoms representing the
electrode as a function of distance andlor orientation of
the water with respect to the metal atoms representing
the electrode. The resulting energy surface is then fitted
to a classic potential function that is used to calculate
forces on the water molecules in a classic simulation. In
this approach, one is assuming that the forces are
pairwise additive, as is not necessary in the direct
dynamics approach [35]. One of the most interesting
results from early simulations using the new methods pro-
vides striking evidence that the forces are not additive in
this way
In Fig. 2, we show the density ofoxygen centers found
in a direct dynamics model of a copper electrode [35].
(The figure is essentially the same as one in Ref. 35.) The
point of interest is that when the interface is charge
neutral, a small number of water molecules are bound to
on-top sites with the oxygen pointing down in a position
Figure 2 Density ofoxygen as a function ofdistance z from the
electrode in the model: (a) zero potential drop and potential
drop of 1.9 V and (b) zero potential drop and potential drop of
-1.9 V.
predicted by a calculation with one water molecule and
the model of the electrode to be the ground state. (This
is the peak between 9 and 10 au in Fig. 2a, and 2b.)
However, when we added many water molecules to the
simulation, only a few of the water molecules attached
themselves in this way This means that the additivity often
assumed as discussed above in classic molecular
dynamics simulations is not operative here. Once one
molecule binds in the on-top site, others are prevented
from doing so as a result ofthe rearrangement ofthe elec-
tronic structure around the bound water molecule. (We
find that classic interactions fit to the single water
molecule-electrode energy require an additional
three-body potential to reproduce this behavior, even
when the electrostatic image interaction is included [47].)

....
.,,
Theoretical Modeling
This is further confirmed by the results for the cases of
positively and negatively charged surfaces. When the sur-
face is negatively charged, the peak associated with
bound on-top site water molecules disappears com-
pletely, whereas when the surface is positively
charged, practically all on-top sites are filled. This
interesting many-body effect provides a detailed
mechanism for the movement of the solvent toward and
away from the electrode when it is positively and
negatively charged, respectively, in this model. It is quali-
tatively consistent with the movement found in the jellium
models as discussed above, but the details are both
interesting and relevant to a complete quantitative
description.
It is instructive to review recent results and methods in
the use of this simulation to compute the capacitance of
a model of two low-index faces of copper in a
copper-electrolyte interface [48]. Equilibration of the
water in response to a change in the field took such a long
time (of order 50 ps) that it was found expedient to run a
classic simulation [49] at each new field before initiating
the direct dynamics equilibration at each field. Explicitly,
the simulation sample consisted, for the 100 surface, of
245 flexible water molecules [33] and 180 copper atoms
periodically continued, in a cell of dimensions
80 x 29 x 29 au as in Ref. 35. As in Ref. 35, for the 100
surface, the electronic wave functions were calculated in
a "small cell" of dimensions 40 x 29 x 29 au. For the III
surface, the water sample contained 216 water molecules,
the unit cell had the dimensions 61.4 x 33.6 x 33.6 au
(32.5 x 17.8 x 17.8 A), and the small cell had dimensions
32.75 x 33.6 x 33.6 au. The time step used for integrating
the motion was 0.5 fs. The sample was allowed to relax
for approximately 80,000 time steps in the classic
simulation, until the bulk polarization of the sample
was stable in time. This was followed by 2000 time steps
of equilibration in the quantum mechanical simulation
with the electrons frozen in place, allowing the waters at
the electrode surface to adapt to the local potential
without disturbing the electronic structure. Subsequently,
the system was allowed to run with full coupling between
the electrons and all atomic centers for a further 3000
time steps. Statistical measurements were made during
the final 1000 time steps. The calculations were carried
out on a Thinking Machines CM-5, on a CrayT3E, and
on a Cray C90 machine. The classic equilibration runs
on theT3E required about 5 h using eight processors on
the T3E for each field value; the quantum mechanical
runs required approximately 30 h on the C90 for each
field value. The sample was periodically repeated an infi-
nite number oftimes in all three dimensions as described
in Ref. 35.
5
20 ,.-...,----,---,.-...,----,---,-------,----,---,----~
15 Cu(lll) * -
Cu(100) +-
10
a(J1.C/em') 0 -------------j~-----___j
-10
-15
.20 L......:.:....L_...L..----'L......:.:....L_...l....-_L......:.:....L_...l....-_L......:--.J
-1.2 -1 -08 -06 -0.4 -02 0 02 0.4 0.6 08
¢( V) versus ,cro charge
Figure 3 Charge (J on the electrode versus potential drop rjJ
across the copper-water interface for the III and the 100
surfaces ofcopper as calculated in the model.
Figure 3 shows the calculated potential drop ¢ across
the interface as a function of the charge a on the III and
100 surfaces of copper. ¢ is the drop from the center of
the copper slab to a point 11 A from cores of the surface
layer relative to this drop at zero charge. From the data
in Fig. 3 one can determine the differential capacitance
of this part of the model alone by differentiation, but the
results are subject to the large errors associated with
differentiation of numerical data and it turns out to be
more useful to compare results with the integrated
experimental capacitance (charge) as a function of
potential. One can understand that the capacitance
arising from this part of the model has a peak near the
point ofzero charge. The peak is not precisely at the point
ofzero charge because ofasymmetry in the response with
respect to inversion of the sign of the charge on the
electrode. Much of this asymmetry comes from the
response ofthe electrons ofthe metal in this model, as dis-
cussed qualitatively above and in the references to pre-
vious work there.
To describe the total capacitance, one must include the
contributions of the ions of the electrolyte to this model.
Although the Gouy-Chapman theory describes the
behavior of the ions quite well, the boundary condition
for this theory is different from that implicitly assumed
by simply adding the capacitances of the surface layer
with an expression from the Gouy-Chapman theory. If
one simply adds the Gouy-Chapman capacitance in
series with the capacitance of the Stern layer, then one
implicitly and unrealistically postulates a sharp interface
between the Stern layer and the region in which the elec-
trolyte can be treated by the Gouy-Chapman model.
If such a sharp interface existed, then the boundary
6 Halley et at.
condition on the macroscopic electric field in the
Gouy-Chapman theory would be simply 4n times the
charge rJ applied to the electrode, leading to the usual
series expression for the lumped capacitances. However,
when the interface is not sharp, the boundary condition
for the Gouy-Chapman model can be estimated from
the molecular dynamics simulation by calculating the
macroscopic electric field at the plane z = Zc at which
the model begins to represent the system by the
Gouy-Chapman model. (This can be shown to be equiv-
alent in the linear response regime to taking account of
the nonlocal and/or inhomogeneous character of the
dielectric response of the solvent.) The appropriate value
of Zc is not known a priori.
Given the macroscopic electric field E(z) for a given
charge rJ on the electrode and assuming that in the con-
tinuum theory the solvent responds linearly to the field,
we have, on the electrolyte side of zc, that
d from inside the electrode to the bulk of the solution as
dz E(z)E(z) = 4np(z)
where p is the ionic charge density in the electrolyte and
we have allowed for the possibility that the local dielectric
constant of the solvent is different from the bulk one but
have assumed a local response function. We assume that
all ionic charge is on the electrolyte side of Zc (which we
take to be in the direction of positive z) and integrate the
last equation from Zc to positive infinity. The total ionic
charge must exactly balance the charge rJ on the electrode,
giving
= 4n J~ p(z)
£(oo)E(oo) - E(zc)E(zc)
The field at + 00 is completely screened, so this gives
-E(zc)E(zc) = -4nrJ
Our procedure is to determine E(zc) from the molecular
dynamics simulation. The preceding shows that if, as will
usually be the case, the E(zc) so determined is not equal
to 4nrJ/ £bulk, where £bulk is the bulk dielectric constant
of the solvent, then we cannot simultaneously use E(zc)
as a boundary condition, retain charge neutrality of the
interface, and use the Gouy-Chapman theory in its usual
form with a constant value of ( for the solvent. A simple
and physically reasonable path out of this situation is to
adopt a simple extension of the Gouy-Chapman model
in which E varies smoothly with z from the simulation
determined value £(z,,) = 4nrJ/ E(zc) to the bulk value far
from the electrode:
-(:-::,,\
feZ) = £(z,,) + (£bulk - £(zc))(1 - (----C;;-)
We found that the net capacitance which we calculated
from the resulting model depended only weakly on the
decay length, which was taken to be Zo = 5 A. (Taking
Zo = 5 ± 2 A results in potential variances of < 0.02 V in
capacitance plots such as Figs. 6-8.) With this form for
E(Z), we numerically solved the Poisson-Boltzmann
equation for z > Zc
= 4np(z)
- -d £( z) -----cr;-
dcPGC (I)
dz _
where cPGC is the total electrostatic potential in the con-
tinuum model on the electrolyte side of Zc with the charge
density
p(z) = 2n oqo sinh(,BqocPGdz))
corresponding to a 1 : 1electrolyte with charge q 0 at bulk
number density no. This yielded the net potential drop
cP =(cPMD(z --+ -00) - cPMD(z = zc))
(2)
+ (cPGd z = zc) - cPGdz --+ 00))
where cPMD is the electrostatic potential obtained from the
simulation shown in Fig. 3. In practice, z --+ - 00 is
replaced by a point inside the model metal slab where
the macroscopic field is essentially zero.
We calculated smoothed values of the macroscopic
electric field E as found from the simulations at various
planes z as a function of the electrode charge rJ. The
smoothing was accomplished by averaging the calculated
fields over the xy plane and around each z value with
a Gaussian weight of width 5 A for the III surface
and 7 A for the 100 surface; this removes irrelevant
fluctuations due to detailed molecular structure and cor-
responds to the standard definition of the macroscopic
electric field [50]. (The appropriate width ofthe Gaussian
is obviously not defined a priori and was chosen to be as
small as possible to retain information about the change
in field with distance from the electrode while minimizing
noise; we were able to use a smaller width for the III sur-
face in part because the simulation's cross-sectional area
gave more water molecules per unit distance and hence
less noise in the raw simulation data.) In Eq. (2) we use
Slab center
cPMD(Z --+ -00) - cPMD(z = zc) = .
Jz,
E dz
where E is this macroscopic field. The same macroscopic
field E at Zc is used as the boundary condition when
integrating Eq. (1).
~

i Theoretical Modeling 7

Cu(100) lace-l00: low field

0,8 -~~/J
06 11A + + / I
8A x x
0.4

0,2

E/41r(rC/ em'p
5A /:,

~
+?
n ······J,I
0,2 '" macroscopiC freld

I
/:,
/:,x potentlal/l0. (volts)

x + - electronic dem.lty

-0.4
l\+ -O-2~I.OO 40.00
-0,6
+ (a)

-08 ! ! I
-15 -10 -5 0 10 15
(a) "(r C/ em ')

Cu(111)
08
x
0,6 11A +
8A x
0.4 5A l\ +
02 + !
o *
l\ 'L
00
E/41r(rC/ em')
~
dlSlance (A)
l\ (b)
0.2
+ ¥ 'I-
-0.1 lace-l11 :Iow field
x
-06
-08
l\
-1
-20 -15 -10 10 15 20
(b)

Figure 4 Calculated macroscopic electric fields in the simu-

lation cell at various planes Zc are shown as a function of the
charge IJ on the electrode for (a) the 100 surface and (b) the 111
surface. The electric field is plotted as E/4n in /lCjcm 2 to facili- distance (A)
tate reading the dielectric constant E = 4nIJ / E.

We show values of the calculated field in Fig. 4. An

interesting feature ofthese results is that the macroscopic
field can be lower near the interface than it is deep in the
solvent. This is qualitatively different from results
obtained from classic models, in which the fields near
the interface are almost always higher than they are in
bulk. The lower fields near the surface are due to the
screening ofthe fields by the electrons ofthe metal, giving
a smooth rise of the field from the bulk metal to the bulk
solvent. We illustrate this effect explicitly for some cases Figure 5 Electrostatic potential and calculated macroscopic
in Fig. 5. electric fields are shown as a function of z for a fixed values of
Using the calculated macroscopic fields as boundary the charge IJ on the electrodes. For reference purposes, the elec-
conditions, we used Eq. (2) to determine the charge on tron density is plotted along with solid circles indicating the pos-
ition of copper centers. Units of the quantities shown are
the interface with results shown for the two faces in Figs.
chosen for presentation purposes as E in VIA, ¢ in Vdivided by
6-8. The only undetermined parameter in this model for
10, and the electron density in ej a~ multiplied by 10.The 100 face
the capacitance is zc, the point at which the continuum is shown at charge IJ = 10.3 and 12.0/lCjcm 2 in a and b,
and simulation models are matched. In Fig. 6 we show respectively, whereas the III face is shown at charge IJ = 10.0
the comparison with experimental data from Ref. 51 for and 18.8 /lCjcm 2 in c and d, respectively.
8 Halley et al.

C"(100),005 M G-C Electrolyte Cu(111), ,01 M G-C Electrolyte

20~-
I
~xp, pzc: V/S(~E
I
-Z4 I J-------'--------'---- 20
Exp, pzc- -.40 V/SCE
Exp, pzc= -.45 V/SCE -
\C:;
6 x +
x +
20 hp, pZC_ - 19 V /SCE 15
Exp, pzc= -,84 V/SCE ",I. Exp, pzc= -,,50 V/SCE . , ..
15 zc=l1A + 10 Zc = 11A + LY+
z, = SA x
7,c=8A x I I'fj,' ~ ++ &
10 zc=5A .6. i\r'~ + z, = 0.4 6 +
./.,

(J(!Je/cm') 5 rr(!JC/cm Z ) 0

-5
-5

-10
~
+x6

-10 + -15
+ x + +8: ')\; + x 6
-15 ''----'----'---'----'----'-----'----'--~ -20
+ x ,6 I

-I -0,8 -0,6 -OA -02 0 0,2 04 0,6 -L1 -1 -0,5 0 0,5

¢(V) VS, zero charge ¢(V) vs, zero charge

Figure 6 Calculated charge versus total potential drop for a Figure 8 Same as Fig. 7 but compared with the data of Ref. 52,
0,005 molar 1-1 electrolyte and various values of the matching both theory and experiment with electrolyte concentration
distance Zc for the 100 surface, Integrated experimental results 0.01 M.
are shown from Ref. 51 with the zero of potential for the
experimental results indicated, The reported potential of zero
charge of Ref. 51 is -0,79 V/SCE for this surface, statement about the best value for Zc and the potentials
of zero charge does not seem possible given the
Cu(111) ,005:W G-C Electrolyte uncertainties in the model and the inconsistencies
'JO
. 1
IC~_=:r=--.-;;-;-~T-----,-.:.::..:..:~-~--~
Exp, pzL -AO V /seE '6 x +1
between the data reported from the experiments, though
]" Exp, pzc= -Ao V/SCE _ 6 x + our results are not in disagreement with the conclusions
Exp, pzc= -,50 V/SCE ' , ,-
of Ref. 51.

II
10 Z, = 11A + LY+
Z,' = 8"4 x i
z, = 5,1 6 + ~

_"C!,m') "f
-5
III. ELECTRON TRANSFER PROCESSES AT
THE ELECTRODE-ELECTROLYTE
-10 - +x INTERFACE

-15
-20 + x
+
6
x 6 J We first describe equilibrium considerations that fix the
equilibrium potential for electron transfer reactions at
-15 -105 0 0:) interfaces and then discuss the calculation of barrier
<1>( II) vs zero charge
heights and determination of mechanism. Consider a
redox reaction in which the oxidized species is 0 and
Figure 7 Same as Fig, 6 but for the III surface of copper. The
reported potential of zero charge of Ref 51 is -0,45 V/SCE for the reduced one is R. The standard equilibrium is
this surface. achieved when the ratio of concentrations of Rand 0,
given by

the 100 surface, and in Figs. 7 and 8 we compare
experimental data from Ref. 52 and 51 for the III surface.
In each case we have shown the experimental results
integrated to give eT( ¢) and have chosen the zero ofpoten-
tial as the reported potential of zero charge of ref. 51,
namely 0.45 VlSCE and -0.79 V/SCE for the III and
100 surfaces, respectively. In addition, we show the
experimental curves assuming a potential ofzero charge
displaced by ± 0.05 V from the above values. For each
surface the magnitude of the calculated capacitance is
roughly consistent with the reported numbers of Ref. 51.
For the 111 face, our capacitance values are larger than
the results of Ref. 52 for all values of zc. A definitive
[0] = e-/JJ'..F
[R]
are equal, so that AF = O. The components of the free
energy difference AFare
AF =I - AFsol v - A¢~20 - I1l
where I is the ionization potential, AFsolv is the difference
ofsolvation energies, A¢~{,O is the potential drop between
the electrode and the ion, and I1l is the electrode work
function. Supposing that the quantities I, AFsol v , and I1l
that are available in principle from experiments on free
ions, bulk solutions, and the vacuum metal interface,
respectively, we can deduce the required value of A¢~20
Theoretical Modeling 9

Table I Factors Determining the Equilibrium Potential for Selected Redox Reactions

Reaction

I !'.F <1> !'.rP~,o PZC Veq Veq(expt) bVeq

(eV) (eV) (eV) (eV) (ViSCE) (ViSCE) (ViSCE) (V)

atCu (100)
CuOjCu+ 1 7.73 2.46 4.45 0.82 -0.79 0.03 0.52 -0.49
Cu+ 1 jCu+ 2 20.29 15.36 4.45 0.48 -0.79 -0.31 0.16 -0.47
Fe+ 2 jFe+ 3 30.65 25.14 4.45 1.06 -0.79 0.27 0.77 -0.50
Co+2jCo+ 3 33.50 26.78 4.45 2.27 -0.79 1.48 1.84 -0.36
AgOjAg+! 7.58 2.01 4.45 1.12 -0.79 0.33 0.80 -0.47
at Cu (Ill)
CuOjCu+ 1 7.73 2.46 4.63 0.64 -0.45 0.19 0.52 -0.33
Cuo jCu+ 2 20.29 15.36 4.63 0.30 -0.45 -0.15 0.16 -0.31
F e J-2 jFe+ 3 30.65 25.14 4.63 0.88 -0.45 0.43 0.77 -0.34
C O J-2 jCo+ 3 33.50 26.78 4.63 2.09 -0.45 1.64 1.84 -0.20
AgO jAg+! 7.58 2.01 4.63 0.94 -0.45 0.49 0.80 -0.31
at Ag(100)
CuOjCu+ 1 7.73 2.46 4.22 1.05 -0.41 0.64 0.52 0.12
CU+!jCu+ 2 20.29 15.36 4.22 0.71 -0.41 0.30 0.16 0.14
Fe+ 2 jFe+ 3 30.65 25.14 4.22 1.29 -0.41 0.88 0.77 0.11
Co+ 2jCO+ 3 33.50 26.78 4.22 2.50 -0.41 2.09 1.84 0.25
AgO jAg+ 1 7.58 2.01 4.22 1.35 -0.41 0.94 0.80 0.14
at Ag(llO)
Cuo jCu+ 1 7.73 2.46 4.14 1.13 -0.22 0.91 0.52 0.39
Cu+ 1 jCU+ 2 20.29 15.36 4.14 0.79 -0.22 0.57 0.16 0.41
Fe+ 2 jFe+ 3 30.65 25.14 4.14 1.37 -0.22 1.15 0.77 0.38
Co+ 2jCO+ 3 33.50 26.78 4.14 2.58 -0.22 2.36 1.84 0.52
AgOjAg+ 1 7.58 2.01 4.14 1.43 -0.22 1.21 0.80 0.41
at Ag(lll)
Cuo jCu+ 1 7.73 2.46 4.46 0.81 -0.53 0.28 0.52 -0.24
Cu+! jCu+ 2 20.29 15.36 4.46 0.47 -0.53 -0.06 0.16 -0.22
Fe+ 2jFe+ 3 30.65 25.14 4.46 1.05 -0.53 0.52 0.77 -0.25
Co+ 2 jCo+ 3 33.50 26.78 4.46 2.26 -0.53 1.73 1.84 -0.11
AgOjAgJ-l 7.58 2.01 4.46 1.11 -0.53 0.58 0.80 -0.22

Sources: I, Ref. 57; !'J.F, Refs. 58 and 59; <D, Ref. 60; PZC, Refs. 51 and 61; Veq , Ref. 53, Appendix C (pp. 699-701).

at equilibrium to such determinations ofequilibrium potentials in Table

From this, if one knows the point of zero charge of the
electrode versus some standard, such as SeE, one can
deduce a prediction for the equilibrium potential
versus that standard. (The dependence on the electrode
that appears on the right- and lefthand sides of the
last equation should disappear when one takes account
of the point of zero charge of the electrode, leading to
the expected result [e.g., 53] that the equilibrium
potential is independent of characteristics of the
electrode surface.) We show some values [57-61] leading
1. A remarkable feature of these data is that the discrep-
ancies between the predicted and observed equilibrium
potentials depend systematically on the electrode
material and crystal face. This suggests that the errors
are in the quantities that depend on crystal face and
electrode material, namely the work function and
the point of zero charge. In fact, experimentally
reported values of the work functions in the literature
disagree in several cases by tenths of volts, and as we
saw for the case of copper in the last section,
experimental values of the point of zero charge depend
on a model for the capacitance and are often at least as
uncertain.
10 Halley et at.

As illustrated by these data, the determination of the Table 2 Solvation Energies of the Cuprous and Cupric Ions
equilibrium potential for a given electron transfer
Eso!valion (MD) Experiment
reaction by simulation methods is equivalent to determi-
nation of the solvation energies of the redox species and Cu+ 1 580±70 576
the point of zero charge of the electrode in question. The Cu+ 2 2085±70 2105
point of zero charge can in principle be determined by /l,.E 1505 ±70 1529
studies of the charge as a function of potential as /l,.F 1485 ±70 1481
described in the last section, though in practice, one saw
that the uncertainties sometimes remain quite large. For Values are expressed in klima!.
Source: Experimental values from Ref. 58.
the determination ofsolvation energies, quite satisfactory
results can be obtained by simulation methods. We illus-
trate for the case of the cupric-cuprous electron transfer
reaction. whereas the free energy is obtained using the relation [55]
Potentials for the copper ion simulations were
r dA( ~on-waterh
1
obtained from ab initio Hartree- Fock calculations on Fso1 =
clusters by Larry Curtiss. The ion oxygen potentials are .0
of form
where the average is performed in an ensemble in which
the ion - water forces are described by the potential
VCu - o = Ae- Br - Clr4 - Dlr6 - Flr l2 Ie Vion-water . We compare results for the cuprous and
cupric ions in water with the experimental values in
Table 2.
The potentials are shown in Fig. 9. It should be empha-
To calculate kinetic parameters for such electron
sized that although in the simulation the interactions of
transfer reactions requires an explicit simulation of the
the copper ions with the oxygen of the water model is
ion at the electrode-electrolyte interface. We first
treated as a sum of two body forces, the actual values of
describe a formal treatment [48] for the case of a
the parameters in the effective two-body force were
nonadiabatic (diabatic) reaction.We start with the Fermi
adjusted to take account of the many body effects arising
Golden rule expression for the transfer rate, in a classic
from interactions between the solvated water molecules
approximation for the solvent:
as revealed by Hartree--Fock cluster calculations [54].
With these potentials we obtained satisfactory solvation
energies and free energies for the cuprous and cupric ions rate = ~n (IA({R})1 26(V;({R}) - V;((R}))i
by a molecular dynamics simulation of a few hundred
(precisely 216) water molecules and one ion. The energy A( {R}) is the electronic matrix element for the electron
is obtained by simply averaging the difference in energy transfer rate. The dependence of this matrix element on
between thewateralone and thewatercontainingone ion, nuclear positions {R} is an important feature of the pre-
sent problem. V; is the potential energy of the system
when the ion is in its initial state and V;
is the potential
Short .ange Cu..-' and CU+2 poler>liale
energy of the system at the same' set of nuclear
~11:1 = coordinates {R} but when the ion is in its final state.
(V;({R}) - V/({R})) contains a term E e containing terms
in the energy difference between reactant and product
that are not included explicitly in the molecular dynamics
~ model. We separate this part of the energy difference out,
"¥ writing (Vf({R}) - V;({R})) = (Vi({R}) - Vr({R}) -Ee .
The average (... )i is an equilibrium average in which the
system is described by V;({R}). We separate the
coordinate;: describing the distance of the ion from the
4
electrode out of the integrals, giving rate = fdZll;(z)C(z)
,[AJ
in which
Figure 9 Two body potentials describing the interaction of
cupric and cuprous ions with the oxygen ofthe central potential K(Z) = ~n IA(z)[2(<5(V;({R}) - V;C{R})))i.z
model ofwater.
Theoretical Modeling
where (...)i,z is an equilibrium average taken with the
constraint that z is fixed. C(z)dz is the probability of
finding the ion in the range of distances z to z + dz from
the electrode. In the canonical ensemble, C(z) takes the
form
J do.e-{3v,
C(z) = ";;--~
J dRe-{3V;
where the integral J dO.. .. is over all coordinates {R}
except z. Noting that C(z) will vanish as 1/L, where L is
the sample depth in the z-direction, we can produce a
finite quantity in the limit L --+ 00 and make contact with
the experimentally measured electrochemical rate con-
stant K ec (which has units ofvelocity) by rewriting the pre-
vious expressions as Kec = dZK(Z)C(Z), in which J accomplishing the confinement in Ref. 56.
C(z) = limL--> 00 LC(z) can be interpreted as the ratio of
the reactant ion density at z to the reactant ion density in
the bulk of the electrolyte.
We rewrite these expressions in terms of a sum over
slices ofthe sample volume taken parallel to the electrode
surface. We denote the center of each such slice by Z~ and
its width by Ll Then the expression for the rate becomes
K ec = L~ K~ C~ in which
K~ -
_~ J:,'~:g dz Jdo.IA(z)12b(V;({R}) -
"--------'-------'-----,..--;~--~-----"------
V/({R}))
Iz,-d/2 dZ JdO.e-(3V'
z ,+d/2
and C~ is the number of ions in slice c< divided by the bulk
number of ions per unit distance normal to the electrolyte
surface.We write K~ in terms ofa free energy at fixed value
I1E of the difference Vi - VI' We define
Fi,~(LlE) = I1E -
_ In
f,+d/2 dz IA(z)1
z,-d/2 kBT
2
Jdo.e-{3v; b(I1E - E e - v: + V)]
I I
[
Iz,-d/2 J
z ,+d/2 d
d"~~e
Z
-(3V
'
An arbitrary factor of k B T is inserted inside the In in the
definition to make the units of Fi (l1, z) those of energy.
(The result in the next equation is independent of this
factor.) Then the rate constant can be written as
in which I1F: = -kB T In C~ is a free energy associated
with the approach of the reactant ion to the electrode.
We take the matrix element A(z) out ofthe integral in the
above definition and replace it by its average, A~, over a
11
slice, giving
K ec -
"IA~12 2n e-{3(F'
_ L..-J--- l,::t:
(dE=E
e.2
)+dF")
ex
~ kBT Ii
in which
(3)
Here the average is taken over the ensemble in which the
forces are defined by the potential Vi and the ion is con-
fined to slice c<. The confinement is accomplished by the
imposition of reflecting "walls" that reflect the ion but
not the solvent in an energy-conserving way. There is a
description of some aspects of the algorithm for
If the reaction is adiabatic, then the calculation of the
free energy barrier proceeds somewhat differently. One
constructs an adiabatic free energy surface by use of mol-
ecular dynamics simulations in which the forces on the
atoms are determined from the potential energy function
given by mixing the potential energy functions associated
with the product and reactant states through the mixing
matrix element A(z)
Specifically, the simulation force fields on the ions
included those arising from the lowest eigenvalue of this
matrix VI = (V; + V/)/~ - (l/2)j((V; - V/)2 + 4A .
2
The free energy surface IS then gIven by Eq. (3) with
the argument of the delta function replaced by
J( V; - v;i + 4A(z)2 + 2A(z).
In the case ofthe cuprous-cupric electron transfer at a
copper electrode, a description ofthe forces between the
water and a copper electrode that was entirely classic
but consistent with the many body effects arising from a
full direct dynamics description as described in the last
section was obtained. We use a combination of
single-particle potentials (referenced to the position of
the electrode) and two-body potentials in which prox-
imity to the electrode modifies the water-water interac-
tion in a way that classically reproduces some aspects of
our direct dynamics model of the copper-water
interface. The water wall potential is of the form
V(z) = A/z9 - Be- z / a for the single-particle parts and
vctl , (2) = Ce- ri /(r o /2l (~
z9
+~)
z9
1 2
for the many-body part. (Here, r1- is the magnitude of the
. . 0 fh
prOjectIOn t e vector --+--+
r I - r 2 between oxygens onto
12 Halley et al.

Table 3 Results for the Kinetic Barrier for the Cuprous-

150 - Cupric Electron Transfer Reaction
100
Quantity Value (kllmol)
50

Diabatic barrier 100 ± 20

Adiabatic barrier, 1st A 70±20
-50
Adiabatic barrier, 2nd A 30± 10
500

The plunge of the surfaces toward negative values in

Figure 10 Diabatic free energy surface for the
cuprous-cupric reaction as described in the text. the adiabatic surfaces near the electrode is a consequence
of the fact that the copper actually plates out on the sur-
face after the cupric to cuprous electron transfer (though
F (kJ/mol) this last stage of the process is not described correctly in
150 -
the present model). The free energies of activation result-
100
ing from the adiabatic model are much closer to the
experimental result than the one obtained assuming the
reaction is diabatic. Results are summarized in Table 3.
What is remarkable about these results is that if one
interprets them to mean that the reaction is adiabatic (as
50~
500 we do, despite the large uncertainties in the values of the
o
Delta E (kJ/mol) calculated barriers arising from uncertainties in the
matrix element A), then the barrier for this
F (kJ/mol)
cuprous-cupric electron transfer reaction arises from
150 -
the requirement that the copper ion get close enough to
the electrode (the z direction in Figs. 10-12) and not, as
100
often assumed and as we concluded in our analysis [13]
50 of the corresponding ferrous-ferric reaction, from the
requirement that the solvent is rearranged around the
ion to permit electron transfer (the !J.E direction in Figs.
500r~
I
-50 10-12). Thus, these examples suggest the possibility of
using such simulations together with experiments to
draw qualitative conclusions about kinetic mechanism
that are otherwise not always anticipated.
Figure 11 and 12 Adiabatic free energy surfaces for two To make more definitive conclusions concerning the
choices of the matrix element A(z). cuprous-cupric reaction requires more definitive values
of the matrix element A(z), and this in turn requires a
a plane parallel to the metal walls and ZI andz 2 are the dis- simulation that includes more of the electronic structure
tances of oxygens 1 and 2 from the wall.) We compare of the copper electrode than we have attempted in our
some results on the structure of the water in this classic studies so far. In particular, we require that at least some
simulation with the direct dynamics one in Ref. 47. We of the copper ions of the electrode be described in a way
used a form for A(z) that decayed exponentially with that takes account ofthe d electrons and thus goes beyond
distance from the electrode in a way consistent with the model described in the preceding section describing
Hartree- Fock calculations on small clusters by our capacitance calculations. (The cluster calculations used
Argonne collaborator L. Curtiss. With the model thus for our estimates of A(z) do take account of all electrons
described, we obtained diabatic and adiabatic free energy but at the price of drastically limiting both the number
surfaces for the cuprous-cupric electron transfer of atoms in the cluster and the number of configurations
reaction as shown in Figs. 10-12. There are two results studied.) Unfortunately, as discussed briefly below, the
for the adiabatic case, because the surfaces are sensitive challenge associated with a full description of transition
to the poorly known form ofthe matrix element A(z) near and noble metals by direct dynamics in this way is quite
the electrode. computationally formidable.
 Theoretical Modeling
Clearly, it would be desirable to extend the simulation
methods discussed here to study reactions in which the
reactants are closer to the electrode surface and which
have greater chemical effects on the surfaces than do the
outer shell electron transfer processes discussed so far.
Such "inner shell" kinetic problems pose a much greater
computational challenge. Here we describe some recent
work on adsorption of chloride on a copper surface that
illustrates the difficulties and the promise ofsuch studies.
We chose to study the chloride ion at a copper surface
because it is well known [62] that adsorbed chloride
greatly enhances the rates of electron transfer reactions
at electrochemical interfaces. It is widely believed [63]
that the role ofadsorbed chloride is to provide a "bridge"
by which the electron can pass to or from the metal elec-
trode to the ion in solution through some sort of resonant
state, though such a picture is not supported by any quan-
tum mechanical calculations ofwhich we are aware [64].
We undertook [66] a study using direct dynamics
methods in which a molecular dynamics simulation of
the water molecule trajectories is carried out for a few
hundred water molecules in the presence of the electrons
ofthe metal and chloride ion.We adopted the same model
and supercell used in Ref. 35 for the 100 surface of copper,
with the addition of a chlorine atom in the solvent. The
dimension ofthe smaller supercell in which the electronic
wave functions are followed is somewhat larger:
29 x 29 x 60 au; 54,000 plane waves were used in the
basis. To calculate wave functions, an improved steepest
descent algorithm was used. We use the following local
pseudopotential VPS(r) for the seven valence electrons
from CI 3s and 3p VPS(r) = 0.25Vf:(r) + 0.75Vf;(r),
where Vf;'(r) and Vf; are the pseudopotentials for Cl 3s
and 3p orbitals derived from the Troullier and Martins
scheme [65]. The resulting Cl pseudopotential was tested
extensively on molecules, including NaCl, HCl, and
CuCl, yielding reasonable agreement with exact values
for interatomic distances and vibrational frequencies.
In the absence of solvent, two positions for Cl were
found to be stable: a site above the center of a square
formed by four neigboring Cu (four-fold site) or a site
directly above a surface Cu atom (on-top site). The lowest
energy was found [66] for the four-fold site, in agreement
with previous studies [67-69]. For the four-fold con-
figuration, our calculation yielded a Cl to Cu distance in
better agreement with experimental measurements than
that from a small cluster calculation [70]. The electron
density distribution in a plane containing Cl and perpen-
dicular to the Cu surface is shown in Fig. 13.
To evaluate the ionic charge on the chloride atom, we
integrated the calculated charge density around the chlor-
ide ion for various distances of the ion from the copper
t
13
l
I 0.293743
0.130437
0,0579207
I ~:~~~:~~:
i! 0.00786297
,;,,~, 0.00507147
I 0.00225199
0.001
Figure 13 Contour plot ofthe electron density in a plane con-
taining Cl and perpendicular to the Cu surface.
surface. This is a well-defined procedure when the ion is
far from the surface and rather arbitrary at the equilib-
rium position. The estimate of the valence charge is
- 7.9 I e I (for a total ionic charge of -0.9 I e I) when the
atom is at the equilibrium position, compared with nearly
-8 (total charge -1) found in Ref. 70, whereas at the
largest distance from the metal surface (8 A from the first
row of copper atoms) the valence charge is -7.07 I e I so
that the atom is essentially neutral (total charge
-0.Q71 e I).
To study chloride at the Cu-water interface, we
improved the pseudopotential by which the interaction
of the electrons with the hydrogen centers of the water
model is described. We show comparisons of the results
for the interaction of water with the chloride ion with
our previous pseudopotential (DP), the new
pseudopotential (New), and a full Hartree-Fock
calculation [LDA(HF)] in Fig. 14.
With this new pseudopotential we get satisfactory
behavior of the solvation of the Cl- ion in bulk water:
We find a solvation of energy of 3.36 eV compared with
an experimental value of about 3.6 eY. The calculated
hydrogen coordination number is 7.5. Experimental
numbers range from 5 to 11. The CI-H nearest neighbor
distance is calculated to be 2.1 A compared with
experimental values around 2.2 A. We also checked that
the new hydrogen pseudopotential did not significantly
alter the structure ofthe water at the copper-water inter-
face in the model. We studied the binding of the chlorine
to the copper interface in the presence of water with
results shown in Fig. 15.
14 Halley et al.

0.020 the need to reparametrize the pseudopotential

I
characterizing the electron interaction with the centers
I
\
of the water model illustrates that, at the level at which
I
we are currently working, the pseudopotentials are not
always transferable from one chemical system to another.

I
I
I A second characteristic problem encountered in the
0000 'I
:i II chloride problem is that it was necessary to very
~ \1 substantially increase the number ofplane waves retained
'"
2' in the calculation relative to the model for the
"c II I
copper-water interface to adequately describe the
"
~
I
localized electronic structure around the chloride. This
-0.020 r , _ LDA(HF) resulted in an increase of more than a factor of 4 in the
DP
[_.- New
computational cost of the direct dynamics.
These problems will recur in such inner shell
processes. For example, we are currently developing a
more realistic model for copper, taking account of the d
-0.040 ~._~~-~---'---~---'----~-- electron structure with the corresponding nonlocal
0.0 5.0 10.0 15.0 20.0
CI-O distance (a.u.)
pseudopotentials. This is essential for study of the chlor-
ide enhancement of the electron transfer process
Figure 14 The chloride water energy as calculated using mentioned earlier and for studies of copper dissolution
our previous (DP) and revised (new) hydrogen-electron that are of interest to us. The nonlocal pseudopotential
pseudopotentials compared with the Hartree- Fock code for a copper electrode containing a cluster of five
[LDA(HF)] result. copper fully described copper atoms (with a full
component of 4s and 3d electrons) in a larger electrode
Toral energy of Cion Cu (100) surfllce
containing the "pseudocopper" of Ref. 35 (only s-like
-11.400 electrons) is currently costing 200 s per direct dynamics
step on a Cray C90 computer and cannot be run to repro-
-11.600 duce our earlier study with presently available resources.
Thus, these studies are pushing the limits of currently
i -11.800 J available technology and will ultimately require both
~
~
5;
-12.000 // improved software and hardware to realize their full
promise.
-12.200

-12.400
I
\'-//
0.0 2.0 4.0
distance of CI to top layer Cu (A.)
Figure 15 Energy as a function of distance of Cl from the
copper surface with and without water.
By contrast to the metal vacuum case, the charge on the
chlorine atom at large distances is found in this case to
be essentially -1, as expected, so that the water stabilizes
the chloride ion in the model, as it should. By repeating
these calculations for charged electrodes, it will be poss-
ible to estimate the charge at which chloride is removed
from the surface, to compare this result directly with elec-
trochemical experiments.
In this preliminary work on ion adsorption, one sees
that studies of such inner shell processes are possible but
also that many new difficulties arise. In particular,
l no solvent
with solvent
I
I
I
~---.J
A similar set ofdifficulties is associated with modeling
of electrodes that are semiconducting, including oxides.
Such electrodes are well known to be extremely import-
6.0 B.O
ant in a variety of technical applications associated with
catalysis, corrosion, and photoelectrochemistry. The
electronic wave functions are much more localized than
they are in simple metals, and very large numbers ofplane
waves are required for direct dynamics approaches. One
possible way out of this difficulty is to attempt to
parametrize the electronic structure of the material as
determined from a first principles method with a simpler
model, such as a tight binding model, and then to use
the resulting tight binding model in a direct dynamics
calculation. We briefly describe some recent progress in
this direction in work on a self-consistent tight binding
description of rutile titanium dioxide surfaces [71]. We
first fit a tight binding model to a bulk first principles
calculation [72] of the bulk band structure and energy
for various values of the bulk lattice parameters and the
use it to calculate the electronic structure of other atomic
Theoretical Modeling
Table 4 Calculated Work Functions <I> for Low Index Rutile
Surfaces Compared with Experiment
<I> <I> Experiment
Surface (Unrelaxed, eV) (Relaxed, eV) (eV)
001 1.42 2.64 Not known
100 5.48 5.99 5.8
110 4.81 5.54 5.3
configurations using a Coulomb self-consistent tight
binding calculation parametrized by the fit to the bulk
electronic structure. We compare calculated work
functions with experimental ones and calculated surface
energies for the relaxed and unrelaxed low index surfaces
and displacements of surface atoms with those obtained
in recent first principles calculations [73-76] and also
experiment [77]. In the Table 4 we show calculated work
functions compared with experiment [78-82]. Calculated
surface relaxations and energies are also in quite good
agreement with first principles results [71]. We plan to
begin study of models of water- titania interfaces using
this code in the near future. A further difficulty in
modeling the water-oxide interface, however, is the
strong tendency for water to dissociate at such surfaces.
Thus, in principle, dissociable models of water are
desirable. Only a few of these are available [e.g., 83], and
the most accurate of them are very expensive to run.
IV. CONCLUSIONS AND DISCUSSION
Detailed microscopic models of electrochemical inter-
faces and of the reactions that take place near them are
slowly becoming a reality. So far, the best results are for
metal- water interfaces. The case of sp metals poses the
fewest complications from the computational point of
view, but the experimental data on the electrochemistry
of such metals as electrodes are very sparse and they are
oflimited technological interest. It would be useful never-
theless to the development of a sound scientific base for
these developments if the experimental community were
to produce reliable capacitance, x-ray structure, and
other structure-related data for low index faces of sp
metals like cadmium, zinc, and so on with which direct
dynamics calculations at the present state ofdevelopment
could be compared. Lacking such information, we are
reduced to using less than complete models of noble
metals (copper in the case discussed here) for compari-
son with experiment. For structural features, reflected in
the capacitance, the results are reasonable and better than
15
those obtained with more primitive models, but the com-
parison with experiment is not definitive, not only
because of uncertainties in the theory but also because
of disagreements between different sets of experimental
data.
With regard to kinetic problems, we are able to make
quite complete models of outer shell electron transfer
reactions and to make nearly quantitative calculations of
barrier heights in some cases.We cited examples in which
we believe it has been possible to determine the nature
ofthe transition state by comparison ofsuch calculations
with experiment, not always with the expected results.
Even these outer shell calculations, however, can still be
improved, particularly with better models for the
coupling matrix elements that will come with improve-
ments ofthe electronic structure calculations on the elec-
trode side. For inner shell processes, we have only a few
results.We cited work on chloride adsorption. Simple dis-
solution and metal adsorption should be possible to study
realistically for sp metals in the near future. Believable
calculations describing noble and transition metal dissol-
ution are a little farther in the future.
Many additional difficulties attend the study of oxide
and semiconductor electrodes. Here we have not dis-
cussed the fact that the screening lengths are much longer
in the semiconducting systems. This changes the scale of
the simulation problem entirely. For many purposes, the
dynamics of the carriers in the electrode, which can be
treated semiclassically, dominates the dynamics in kinetic
experiments. For a full microscopic model, we then
require a Boltzmann model ofcarrier transport [e. g., 84],
supplemented by cross-sections for processes taking
place at the electrode-electrode electrolyte interface that
may be modeled by methods like those discussed here.
ACKNOWLEDGMENTS
Work of A. Mazzolo, P. Schelling, B. Smith, N. Yu, and
Y Zhou, some still unpublished, has been cited here.
We are grateful to L. Curtiss and collaborators at
Argonne for collaborations and discussion over many
years. Earlier collaborators in this program include N.Tit,
M. Michalewicz, H. Shore, and W Smyrl and
collaborators. We are grateful to A. Nozik and collabor-
ators for discussions of electron transfer problems at
semiconducting electrodes and to 1. Rustad and
coworkers for collaborations and discussions on prob-
lems of geophysical relevance. This work was supported
in part by the U.S. Department of Energy grant
OF-FG02-91-ER45455 the National Science Foundation
grant DMR-9522286, and by the Minnesota
Supercomputing Institute.
16 Halley et at.

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2

Theory of the Metal- Electrolyte Interface

L. Blum
University ofPuerto Rico, Rio Piedras, Puerto Rico
Marc D. Legault
University ofPuerto Rico at Bayamon, Bayamon, Puerto Rico
Dale A. Huckaby
Texas Christian University, Fort Worth, Texas

ABSTRACT face has 10-8 particles relative to the bulk phases,

Some recent progress toward an understanding of the
electrolyte-electrode interface is presented. Both
screening and dynamic sum rules that must be satisfied
by an ionic solution at the interface are discussed. A
simple model for interfacial adsorption is presented in
which the three-dimensional system reduces to an equiv-
alent two-dimensional lattice gas. This model is used to
study the underpotential deposition of copper on the III
surface of a crystalline gold electrode in the presence of
bisulfate. A cluster variation approximation to the model
system yields realistic adsorption isotherms, and the
resulting model voltammogram agrees well with
experiment.
I. INTRODUCTION
The study of the charged metal-electrolyte interface is of
theoretical and technological importance. The techno-
logical applications are numerous and are widely used
throughout various industries. A theory of the interface
is truly multidisciplinary and can be quite complex
because it must connect the solid-state theoryofthe metal
bulk and surface with the statistical mechanics of the
electrolyte. The complexity of the charged interface not
only excludes any simple theoretical interpretation but
also presents experimental difficulties. Because the inter-
19
surface-specific experimental methods that can dis-
criminate between a signal from the surfaces and bulk
are required. These methods have provided a wealth of in-
formation about the interface.
In this chapter we present a theory of the
metal- electrolyte interface that is applied specifically to
the process ofunderpotentia1deposition. Sum rules that
the charge density must satisfY near the interface are dis-
cussed in Sec. Il.A. A model for the adsorption at the
interface is presented in Sec. II. B., and how quantum
effects can be included in the formalism are indicated.
In Sec. III the model is used to study the underpotential
deposition ofcopper on the III surface ofa gold electrode
in the presence of bisulfate. Here a cluster variation
method is used to investigate the structure of phases and
phase transitions that occur at the metal-electrolyte
interface during the deposition. The theory provides a
framework in which the electrovalence of adatoms can
change during the electrodeposition process.
II. THEORY
A simplest theory of the metal-electrolyte interface
should include at least a discussion oftwo kinds offorces:
the short-ranged forces and the long-ranged Coulomb
forces. The short-ranged forces are essentially responsible
for the chemical bonds and for the repulsion between
atomic cores. The long-ranged Coulomb forces give rise
to the screening ofcharges in conducting media. Because
ofthe quantum nature ofthe electrons in a metal, import-
ant quantum effects, for example the fractional charge of
adsorbates, are manifested [I]. Most theoretical treat-
ments of these quantum effects focus on a description of
the metal side of the interface and do not provide a
detailed picture of the liquid side.
In earlier work [2-4] we used the sticky site model
(SSM) [5,6] to separate the difficult three-dimensional
problem of the adsorption on a single crystal interface
into a one-dimensional problem normal to the electrode
surface and a two-dimensional problem of the substrate
lattice. The SSM can be considered as a mean field model
in which the details of the adsorption forces are replaced
by an adsorption chemical potential at a point site on
the electrode interface.
In our model, the quantum aspects can be included in
the following way:
All atoms and molecules are treated as classical objects.
Valence electrons of metal ions at the electrode interface
are treated using quantum mechanics.
Inner electrons of these atoms are included in the
pseudopotentials for the atom - atom interactions.
The interface is modeled as a smooth charged hard
wall near an ionic solution represented by a collection
of charged hard spheres in a continuum of dielectric
constant c. The continuum solvent is then replaced by
the simple hard sphere with a point dipole [7] molecular
model. In some simple cases this particular molecular
model can be treated analytically. More elaborate
models of the solvent can be used, but they usually intro-
duce complications in the numerical computations. A
recently proposed model of ionic solutions [8] uses a
solvent model with tetrahedrally coordinated sites. This
model is analytically solvable in the presence of ionic
solutes. Recent studies [9] of water clusters strongly
suggest a tetrahedral and rather flexible potential for
water that is consistent with the tetrahedral model of
the solvent.
A. Exact Sum Rules for the Interface
The density profiles near electrodes have to satisfY a
number of exact sum rules. These sum rules are divided
into two sets: the screening sum rules and the dynamic
sum rules. The first set is due to the long-range nature of
the Coulomb forces and the second originates from force
balance requirements.
1. Screening Sum Rules
The screening sum rules are specific to Coulomb forces.
Because of the long-range nature of the electrostatic for-
ces, the stability of the system is maintained only if all
charges are surrounded by a neutralizing cloud. The sur-
face charge must satisfY electroneutrality
oo m
qs =-
Jo L eiPi(z) = €Eo/4n
dz
i= I
(1)
where Eo is the external field.
In homogeneous systems of molecules, the screening
of charges and multipoles is intuitive because of the
isotropy of the system. In a homogeneous solution, every
charge is surrounded by an ionic cloud of exactly the
opposite charge and every dipole is surrounded by a
charged cloud that has a dipole moment (charge dis-
tribution) exactly opposite to that of the original dipole.
In general, one can show [10,11] that this applies to any
arbitrary neutral charge distribution in a homogeneous
system. The proof of these theorems is based on the
Born-Green- Yvon hierarchy and on the assumption of
clustering of the correlation functions.
In a neutral system, any configuration offixed charges
is screened by the mobile charges. In the homogeneous
bulk phase this fact is obvious because ifthe long-ranged
Coulomb forces were not screened, then the partition
function would diverge [12]. The charge distribution
around a given charge ei is therefore of equal value but of
opposite sign and is given by
-ei = Jd2 L ejPjhij( 1. 2) (2)
J
In bulk fluids rotational invariance requires that
charges and also multipoles of any order are screened by
the mobile charges [10,11]. Although this is much less
intuitive in the neighborhood of a charged electrode, the
theorems do hold, and perfect screening of all classical
multipoles occurs in both homogeneous and
inhomogeneous systems. However, in quantum systems
or nonequilibrium systems, perfect screening of all
multipoles does not occur [13].
There are additional sum rules for hard planar
electrode surfaces. A sum rule for calculating density
profiles in the electric double layer is the dipole rule
[14]:
kT aln Pi(1)/aEo = Jd2 L eiPi(2)hij(1. 2)(ZI -
.I
Z2)
(3)
Theory of the Metal-Electrolyte Interface 21

where Eo is the bare field at the surface. The differential where the pressure p normal to the electrode wall is given
capacity, as

(4)
p= -kT L -I Jdxdy J dz-'7-
m

i= I S S
aw(r) p;(r)
a_
(6)
where qs is the surface charge and 11¢ is the potential drop,
satisfies the sum rule where Wier) represents the interaction between the mol-
ecules of the fluid and the electrode. In the most general
case,

Wier) = w~S(r) + w~o\'(r) (7)

where the interaction Wier) consists ofthe sum oftwo con-

2. Dynamic Sum Rules
Momentum conservation and force balance must be
satisfied for conservative systems. These considera-
tions form the basis of the dynamic sum rules [15].
Unfortunately, momentum conservation and force bal-
ance are not satisfied by some ofthe approximate theories
used in the description of the electrode interface.
In our model we consider a system bounded by a sur-
face that can be smooth or rough but that on the average
is planar. We can also include in our system a single
crystal metal surface that is considered macroscopically
smooth but has a microscopically rough interface.
Consider a prism of height L with a large
cross-sectional area S, where S = MSa , M -+ 00 is the
number of adsorption sites IX, and Sa is a unit prism as
shown in Fig. I. The forces parallel to the electrode surface
through the prism walls are of order O(Sl-O), where
t5 -+ 0, as S -+ 00. Let r == (x, y, z), where x and yare the
coordinates in the electrode plane and z is normal to the
electrode plane.
The force balance equation is integrated over the vol-
ume V = SL 1 of the prism of height L] :'S L, summing
over all ionic and neutral species i. The pair interactions
for central forces are cancelled out exactly over the sur-
face S. At the plane L 1 , these forces will contribute to
the bulk pressure P. The dynamic balance gives P = p,
• a dipole (or higher multipoles) is zero because the dipoles
electrod.
surface
• •dsorption
sit.
•
Figure 1 A prism on an electrode surface.
tributions: a Coulomb or electrostatic (es) term and a
nonelectrostatic covalent (cov) term such as, for example,
van der Waals or hard core (hc).
We give a briefdiscussion ofthe dynamic sum rules for
five different cases.
(a) A Flat Electrode in Contact with a Primitive Model
(Continuum Dielectric) Electrolyte. In this case the
interaction is given as
Wier) = w7 C (r) + w~S(r) (8)
The hard core potential H!;c yields the force
(9)
whereas the electrostatic contribution yields
aw7S(z)
- - - = -eiEoz (10)
az
where ei is the charge of i and Eo is the bare electric field.
Using the electroneutrality relation we obtain
m
P L....,p;(ai/ 2) - 8£ [Eo] 2
= kT '"'" (11)
i=1 n
This expression shows that the total pressure consists ofa
kinetic term due to the collisions of the molecules at the
wall minus an attractive electrostatic contribution as in
a planar capacitor with charge density qs = (£Eo/4n).
(b) A Flat Electrode in Contact with a Nonprimitive
Model Electrolyte. The net electrostatic force on a sol-
vent consisting of hard spherical neutral molecules with
interact with the gradient of the applied field VE o, which
is equal to zero. However, the force due to the hard
repulsive interactions between molecules is
(12)
and we obtain The sum ofthe electrostatic and nonelectrostatic interac-
tions yields a general contact theorem for a planar, but
not necessarily smooth, hard surface
1
kT ~ Pi((Ji/2)
m
P = [
+ Ps((Js!2) ] - 8n [EO]2 (13)
m

P = kT L Pi((Ji/2) - f/8n([EzCl)]2 ls
i=1
The absence of the dielectric constant in the above (19)
equation means that the electrostatic contribution to the _ t(PJI) aWfOV(l))
pressure in a solvent of high dielectric constant, for i=! aZ I s
example water, is small compared with that of the primi-
tive model. Also, the hard-core term contributes more This theorem, a generalization ofpreviously derived con-
significantly to the form of the concentration profile near tact theorems, applies to the realistic case of rough elec-
the electrode. trode surfaces.
(c) A Structured Electrode in Contact with a Primitive For a soft surface the contact theorem is
Electrolyte. This case is complicated because the charge
distribution at the electrode surface is nonuniform. a cov(1»)
=- ~ w~ZI
m (
P pJI) s-f/8n([EzCl)]2ls (20)
Therefore, the contact density for soft or hard surfaces
will be a function of z and the position (x, y) on the
surface. Simple relations exist only for average quantities. For a surface of area S with an array of M sticky
For example, the average contact density near a hard adsorption sites as in the case ofthe SSM [3,4,16], the con-
plane is given by tact theorem becomes

m
pJO) = 1/S.I dxldYIPJXI,YI,Zs) (14) P = kT L pMi/2) - f/8n([EAl)]2 ls
i=1
(21 )
Starting from Poisson's equation
+
M)."
S
,",(a
L..J a-
Y ;(1»)).
I,
i=! -I

4 m
2
V t/t(1) =- nI'>iPi(1) = VI' E(1) (15) where Ao is the activity of an adsorbed atom of species a.
f i= I
(d) A Rough Hard Electrode in Contact with a
Nonprimitive Electrolyte. As opposed to the case b of a
and considering that the electrostatic forces along the sur- plane surface in contact with a solvent of dipolar hard
face are vanishingly small for a random rough surface or spheres, here we must include the effect of nonzero elec-
zero for a periodic crystal surface, we obtain tric field gradients near the electrode.
The total electrostatic force is [17]
m
liS dl Le;p/l)E:(1) = -f/8n([Ez (l)fls (16) aw~S(r) ~ 1. ~ ~
.I i=1 --- = eaE o +P~' ('lEo) +-6q~· ('l'lEo)
ar
(22)
where S is the surface ofa unit cell and the average square
field in the Z direction is given by
where p, and qa are the dipole moment and quadrupole

([Ez(l)fls = liS L dxldyjE;(xl,YI,zs) (17)

The short-range nonelectrostatic covalent interaction
between the molecules, ions, and the surface is given by
tensor ofthe solvent particle IX. The single particle density
Ps(l) is a function ofrl and of the orientation of the mol-
ecules with respect to the electrode. In the case of linear
dipoles, the density Ps(1) is given in terms of the two
angles (}I and ¢1'
The dipole contribution to the pressure is

( Ps(
ihVC()V(I») J' dx,dYI JLI awCOI(l) l)aw~S(l») = _ 4n . .Ioo ~.Id d (l)aEo(1)
( Pi(l)-'--
aZ I s
= liS
S C,(XI.}'I)
dz1P;(I)-'--
aZ I
a--'I s
3 Ps 0 S XI YIPs az!
(18) (23)
Theory of the Metal-Electrolyte Interface 23

where B. Adsorption at Structured Interfaces

A tractable model for interfacial adsorption is one in

E o(1) = L E~(rde~
m
(24)
which a "binding affinity" is associated with the adsorp-
tion of a chemical species on a lattice site. Although the
and e~ are the polar components of the unit vector. This details of the couplings are lost in this approximation, it
leads to is sufficient to model the cooperative effects and to give
a complete description of the phases and transitions that
take place at the interface.
p = kT[~P;(0';/2) + Ps(0';/2)] - (1/8n)([Ez (l)]2)s Consider a planar surface at z = O. For an adsorbate j
with diameter O'i' the contact plane for its adsorption is
at z = O'i12. There is a lattice Ai on this contact plane that

. I a_I
v
_ t(p;(l) aw r: (1)) _ 4n,us
s 3
(L:>1. m
aE~:(rd)
a~1
has sites directly above the adsorption sites. Let
r = (x, y, z) be a vector from an adsorption site rJ. to the
1= m S
center of an adsorbate j and let R a be a vector from the
(25) adsorption site to the corresponding site on the contact
plane. If uSer) is the interaction potential between the
where adsorbate and the sticky adsorption site, we define the
binding affinity, A, by
(26)
(29)

The last term of Eq. (25) corresponds to a new
electrostriction effect that vanishes for uniform external
field Eo.
(e) A Rough Soft Electrode Near a Nonprimitive
Electrolyte. The sum rules presented here are relevant
to computer simulations of realistic solvents near a met-
allic surface. In most of those computer simulations,
water is modeled as a neutral molecule with local point
charges. Equation (19) gives
where we use a "smeared" Dirac delta function
(30)
which is normalized over the region above and below the
contact plane.
If the adsorbate is within a sphere centered on a site of
Ai' with radius rsph » L\, then

= kT[~P;(0';/2) + PAO';/2)] - (l/8n)([EA1)]2)s

(31 )
p

where Vsph is the volume of the spherical region as

- t(P;(l) awrv(1)) +/ Ps(1) L qv aEz(~~ +b v
))
pictured in Fig. 2. For simplicity, we shall let L\ ---+ 0 and
;= I ZI S \ v ~I S
approximate <Sil(r) by the Dirac delta function, <S(r). Then
we have a collection of sticky adsorption sites, such that
(27) if the adsorbate center is on a site of Ai' it is stuck to an
adsorption site on the Z = 0 surface with a binding affinity
where the sum over the charges in each molecule is equal to)_
indicated by the index v, and p.J0';/2) is defined for the
orientation-dependent density function of the solvent
contact plane with
with embedded charges. lattice AJ
For soft surfaces we get

(28) electrode surface

Figure 2 A lattice Aj at the contact plane above a planar

surface with sticky sites.
 In the present work we are concerned with a system where Zo is the quantum partition function for the system
containing two types of adsorbates with diameters 0"1 with a smooth wall and
and 0"2 .We consider a fluid containing N 1 particles of type
I and N2 particles of type 2 in a volume Vin contact with o 1
a planar surface at z = 0 with a lattice ofsticky adsorption
Pnl,n, (rl.l, .... r2,n,) = Z o (N 1 _ nl·
)'(N _
2
)'
n2,
sites. The Hamiltonian for the system is
x Jdrl. nl +1 . , , drl,N I dr2,n,+1 ... dr2,N, Tr[e- fJHo ]

fl = flo + Hs (32) (37)

Here pJ = pJ,o[rj.! = (x, y, O"j /2)] is the contact density of

where k, is the Hamiltonian operator in the absence of
a particle oftypej,Ifwe define the potential ofmean force,
the sticky sites. flo is an operator in which only the valence
U(rl,l, ... , r2.n,), as
electrons are treated as quantum particles, the atoms
together with their core of inner electrons being treated
exp[ -/3 U(rl.l' , r2.n,)]
as classical particles. H s represents the interaction (38)
between the sticky sites and the adsorbates. = P~I.n, (rl,l, , r2.n, )(p~) -nl (P2) -n,
Following the above discussion, the sticky potentials
and if we change from a sum over labeled adsorbates in
are defined as [18]
Eq. (36) to a sum over lattice sites of Al and A 2 , we obtain

e-/JU/(r,,) = I + Aj L e5(rj,i - R~) (33) :=: = Z/Zo = L(J'1pf) L' U(A2P2)L"'e-/JU(!'i,)) (39)
R,EII.,
I'i.iI

where j = I or 2 and rj,i is the position of the particle
numbered i of type j, Here the origin of the coordinate
system is fixed at one of the adsorption sites. The
Hamiltonian due to the sticky potentials is then given
by
where 'j,; equals I ifsite i of Aj is occupied by an adsorbate
oftypej and equals 0 otherwise.
Equation (39) implies that the system is equivalent to a
two-component lattice gas with chemical potentials /11
and {l2 given by

NI N,
e/Jl'i = }'jpJ (40)
Hs = L Uf(ri,i) +L Uf(r2,i) (34)
and with a many-body interaction energy equal to the
i=1 i=1
potential of mean force U({'j.;}). Using a pairwise
The canonical partition function for the system IS
superposition approximation for the distribution func-
given by tion of Eq. (38) yields an equivalent lattice gas that has
pairwise interactions,

Z
N j !N2!
J
I - drNldrN'e-/JH'Tr[e-/JHo ]
= --
I 2
. (35) U({'j.;}) = L 1,2 L=nn fj.}"j, i';'.i' (41)
j.}' = (i. i')

where the trace is taken over the states ofthe valence elec- where fj,j' is the interaction energy between a pair ofj and
trons and everything else is treated classically. The for- j' type of particles on sites of Aj and A;, that correspond
malism is equivalent to a classical Hamiltonian for the to neighboring adsorption sites i and t. The fraction of
atoms with an effective potential that depends on the local sites occupied by particles of type j is then given by
electron density.
Inserting Eqs. (33) and (34) into Eq. (35) and Aj ~ In :=: (42)
then expanding the resulting product and integrating Bj = IAI aAj
yields
where IAI is the number of adsorption sites.
NI N, Ani An, If we turn off the interactions (fj.j' = 0) and if an
Z/Zo= '"' '"'~, 2, '"' p~ n,(rl.l, ... ,r2,n,) adsorption site can be occupied by at most one particle,
~~nl.n2'~ I"
then Eq. (39) becomes
nl =0112 =0 ~J"EAJ

(36) ~
.=. = (1 + AIPI
1 0 • 0)111.1
+ A2P2 (43)
Theory of the Metal-Electrolyte Interface
which yields the Langmuir adsorption isotherms
(44)
where} = 1or 2.
The presence of nonzero lateral interactions leads to
the possibility of phase transitions occurring in the sys-
tem for some values of the chemical potential or, more
specifically, of the activity Zj = Ajp). Generally speaking,
an attractive lateral interaction can give rise to a
first-order phase transition characterized by a finite jump
in coverage in the adsorption isotherm, and a repulsive
lateral interaction will often lead to an order-disorder
transition with a continuous change in coverage but a
jump in adsorption rate.
In our model for underpotential deposition described
in Sec. III, we include lateral pairwise interaction ener-
gies and we assume the activities Zj are functions of the
applied potentialljJ as both the binding affinity Aj and con-
tact density pJ are functions of the applied potential.
Specifically, the binding affinity is a function of the bind-
ing free energy fj between the adsorbate} and sticky site,
as in
(45)
As the potential bias of the electrode surface is changed,
the electron density at the surface will vary and so will
the binding free energy [19].We suggest that
(46)
where e is the elementary charge, ljJ is the potential bias,
and ljJj.ref is the electrosorption reference potential of a
given adatom} and substrate. (j is the partial charge of
the adsorbate) that is equal to its electrovalence in sol-
ution minus an integral over the local electron density.
The contact density for low ionic concentration is
given by the Poisson- Boltzmann formula
(47)
where pJ(O, 0) is the contact density ofadsorbate} at zero
potential and Vj is the electrovalence ofthe ion}. The con-
tact density also varies with potential bias ljJ.
These activities combined with potential-dependent
lateral interaction energies will be used to obtain adsorp-
tion isotherms and a voltammogram for an electrochemi-
cal system that undergoes voltage-dependent phase
transitions at the fluid-electrode interface during the
underpotential deposition process.
25
III, Cu UNDERPOTEN'rlAL DEPOSITION ON
Au(111) WITH HS0 4
The adsorption or deposition ofa given metal ion onto an
electrode surface consisting of atoms of its own kind
occurs at an electrode potentialljJ. At this ljJ, the electrode
electrons have sufficient potential energy to fill the vacant
molecular orbitals of the ions in solution. However, the
deposition of a metal on a foreign metal substrate may
occur at a more positive electrode potential. This depo-
sition is called underpotential deposition (UPD) and is
caused by the attractive interactions between the adsorb-
ate and the foreign metal substrate. Lateral interactions
between the adsorbed atoms influence the form of the
adsorption isotherm and the electrode potential at which
adsorption occurs.
One of the most studied systems, both experimentally
[20-35] and theoretically [16,18,36-44], is the UPD of
copper on the III surface of a crystalline gold electrode
in the presence of bisulfate. We introduced a
one-component model for this UPD focusing first
on copper adsorption [16] and then on bisulfate
adsorption [36-38]. We then generalized the model to
treat two-component coadsorption [18,39], treating the
bisulfate hard-core exclusion exactly [3], the effect of the
finite interactions being approximated using a
"mean-neighbor" approximation [39]. In Sec. lILA. we
use a cluster variation approximation to study this system
[40]. The cluster method will not only generate adsorp-
tion isotherms and a model voltammogram of the UPD,
but it will also give the local structure of the
voltage-dependent phases present during the deposition
process [40].
A, Cluster Approximation for Cu and HS0 4
Adsorption Isotherms
The adsorption sites on the III surface ofa crystalline gold
electrode form a triangular lattice A with IAI sites.We con-
struct a cluster approximation using six-site clusters of
the type illustrated in Fig. 3. If we neglect edge effects
and assume periodic boundaries, there are IAI translates
of this cluster on the 111 surface of the electrode.
Suppose N c of the adsorption sites are occupied by
copper (C), N s are occupied by bisulfate (S), and the
others are vacant (or occupied by solvent). We consider
all allowed configurations of Cs, Ss, and vacancies on
these clusters and then restrict the overall configurations
on the IAI clusters on the lattice by requiring that a total
of N c Cs and N s Ss are present on the electrode surface.
Two Ss experience a strong steric repulsion and cannot
occupy a pair of first-neighbor sites. This hard-core
repulsion restricts 8s = NsflAI to values no larger than
 and

gc -_L..JniWiPi
", - Be = 0 (50)
i

Because each Sand C species is shared by 6 clusters, we let

n; and nf equal 1/6 the respective number of Ss and Cs in
the cluster. The equilibrium value of the probability, Pi,
that a cluster has a configuration of type i is determined
by minimizing the Helmholtz free energy. A = E - TS,
under the restrictions of Eqs. (50). Thus, for every con-
figuration i at constant B" Be, T, and IA I,
Figure 3 A shaded six-site cluster on the lattice of adsorption
sites. aAlkT s
- - - I n f--In f,,--In fe-=O
ag ag age
(51)
api api . api api
1/3. To ensure B,:::: 113 within our six-site cluster
approximation. we allow no more than two Ss per cluster where we have introduced the Lagrange multipliers In f,
and then only if they are second neighbors. We also In f s • and In f e .
include finite interaction energies (s,2 between pairs of Eq. (51) gives
second-neighbors Ss, (eel and f ee 2 between pairs of first-
· _ e-(;/ kT r ";'r : II'
ll

and second-neighbor Cs, and (e,1 between first-neighbor P1 - S c ":::I (52)

CSpairs.
where
The Guggenheim-McGlashan cluster approxi-
mation method [45-49] proceeds by approximating the Q= LWie-(,/kTr~;r~~; (53)
entropy per adsorption site by I

S 1 is a "cluster-generating function." Each six-site cluster has

k = IAl ln no - LWiPi In Pi (48)
three "edge sites" and three "vertex sites." In Table 1 we
I

group the cluster configurations according to the seven

where Pi is the probability a cluster has a configuration of
type i and Wi is the number of ways a cluster on the lattice
can have a configuration oftype i. The "cons tant" no is cal-
culated in the high-temperature limit where the system
is equivalent to a lattice gas of N, hard hexagons and N c
noninteracting species.
The internal energy per adsorption site is given by
different ways the three edge sites can be occupied by Ss
and Cs regardless of the configuration at the three vertex
Table 1 9= L;=
19; Is the Cluster-Generating Function of
Eq. (53), where 9i Is the Contribution from all Clusters with a
Fixed Configuration at the Edge Sites. Here We Let
tijl = exp( -fiji /3kT) and tij2 = exp( -fij2/kT)

E= LfiWiPi (49)
Qi

where ( i is the interaction energy within a cluster oftype i. "fi L s [(1 + Xc + x s)3]
Each first-neighbor interaction is shared by three
clusters. but each second-neighbor interaction occurs in ~ 3XcL, [(1 + tcclx e + t cs1 x s)2(1 + t cc2 x c + x,)]
only one cluster. Thus, a cluster is assigned 1/3 of the
first-neighbor and all second-neighbor interaction ener-
gies within that cluster.
~ 3tcc1 x c2L, [(1 + t~c1xC + t~lx,)(l + tCc1tcc2Xc + tC'lX,)2]
c

The cluster configurations are normalized and, as ~ tCel3Xc3Ls [(1 + t~Cltcc2Xc + t~SlXs)3]
mentioned above, they are restricted to yield the correct
values ofB s = Ns/lAI and Be = NelIAI. That is, ~ 3x,(1 + tcs1 Xc?(1 + Xc + t"2X,)
g = L Wi Pi - I =0 ~ 6tcs1 x cx,(1 + tceltcslxc)(l + tcc2tc'lXC) (1 + tcelxc + tc"t"2X,)
c

gs = Ln~wiPi - Bs =0 ~ 3tCCltc,j2Xc2X,(1 + tCeltcC2tc,jXc)2(1 + t~elXC + t~'lt"2X,)

Theory of the Metal-Electrolyte Interface 27

sites.We then calculate gi, the contributions to g that arise function, then
from each ofthese seven groups ofclusters. To incorporate
I I
the restriction that only one ofthe vertex sites can be occu- (Pa/kT) =-In S = - I n ""(zDC)N'(1 +zDC)IAI-N,
DC IAI DC IAI LN, s c
pied by an S, it is useful to define
= In(1 + z~) = I~I In SH(ZJ)
(54)
(59)

where ao and al are polynomials in Xc. where the partition function 3 H (zJ) is for a lattice gas of
hard hexagons with activity
Inserting the expression for Pi given by Eq. (52) into the
formulas for E and S, the Helmholtz free energy is given
by (60)

I Then
A/kT = - TAT In 0 0 + Bs In r s + Be In r e -In g

B,
,
= zO: _a_
az;o
(_I
IAI
In 3 00 ) I
T _XO
= BH(ZJ) (61)
(55) '-c

where BH(ZJ) is the density ofhard hexagons at activity ZJ.

The bisulfate activity Zs is then given by Likewise,

Be = I z'{" [I - BH(zJ)] (62)

In - /l / kT -_ aIAIA/kT I
Zs - -_ aA/kT I + z;:o
.1 aNs T,IAI,N,
aB,. T.O,
which can be rearranged to give

=- a: C~I In (
s
0 ) I
0,.
+ In rs Be
z': = -----,,-____=_ (63)
I - Be - Bs
(56)
Equations (60) and (63) then give
A similar expression results for the copper activity Ze: 1- B
zO: = I _ Be ~ B FJ(B s ) (64)
s

(57) where F J = F J(B s ) has been calculated exactly by Baxter

[50] and Joyce [51,52] and is given in the appendix of Ref.
40.
We next calculate r'{" and r': by constructing the
We infer from Eqs. (56) and (57) thatzs/r s andzc/r e can
cluster generating function at high temperature,
be expressed as temperature-independent functions of
Bs and Be. We can calculate these ratios in the goo = (l + x coo )6 + 6xsoo (l + x,:",)5
( + 3x (l + x oo )4 002
S C
high-temperature limit, noting that
= (l + x,:)6(l + 6u + 3u2 ) = (l + x,:)6p(u)
Zs ZOO (65)
_.1_

rs rOO
.1 where
ZOO
(58)
Ze _e_
re rOO
xc;o
e U=--'- (66)
I + x;:o
We first calculate z': and z'{" using the grand canonical and P(u) depends on the particular choice of the clusters
ensemble. In the high-temperature limit, the adsorption used. Equations (50), (52), and (53) then yield for Bs and Be
model is equivalent to a lattice gas of hard hexagon Ss
and noninteracting Cs. If P is the spreading pressure, a Bs = rO: aoo In
ar, goo I
r"
00 = u dd [~6 In P(U)] (67)
is the area per adsorption site, and 3 is the grand partition U
and 2.5 I r~~~~I~~~~~'~~~~I~~~~T~~~~:]
2.0 I ______

Be = r ~
CXJ
In goo I = ~(1 - B,) (68)
, ar;:c ri" I + x;:c . 1.5

1.0
Equations (66) and (68) then give
IB~'.ulfa!" el,:ctr.?_sofJ2~i.?n vale~~y y,
~ 0.5 f-- -
Copper electrosorption valency y," J
B, 00
x~ = I - 0, - Be
-0.5
(69)
(1 - B,)u
x,:xl -- I - Bs - Be
-1.0 f-------- ------ ------------------------------------------------------
-1.5 [ I ! j
0.00 0.10 0.20 0.30 0.40 0.5C
The expressions for zC:. zC::, xC:' xC::' and Eq. (58) then E (V) Vs. Ag/AgCl
yield the temperature-independent functions
Figure 4 The potential dependence of the effective electro-
~=
r.1
(I - I-B,
e, - e.,) 5 :fAes )
u6
sorption valencies ofcopper, ['co and ofbisulfate, YS'

(70)
~ = (I - e, - e.,) 5 It has been suggested that one quantum mechanical
r, e, effect manifested at the interface is that of fractional
adsorbate charge. As the electrode potential is changed
For our particular choice of clusters, Eqs. (65) and (67) one can easily picture the metallic surface electron
yield orbitals actually changing or moving into the interface
and effectively changing the surface charge density
I - 6B s - ~---:;~ [1,53-55]. The effective charge of the ions adsorbed will
(71 )
u= 2(3B, - 1) be affected by these potential-dependent electron
orbitals. It has been found from near-edge x-ray absorp-
In Sec. III.B., the relationships tion fine structure experiments [14] that adsorbed copper
in a low-density phase and in a high-density phase has a
Bs = r\~
aI's
gl 1n
I,. T
different charge. In our model we keep the effective
electrovalence of HS0 4 constant at -1 and that of Cu is
(72)
re -/!- In gl
0, = varied between 1.6 and 2, as shown in Fig. 4. We presume
aI', r,. T that because the HS0 4 adlayer is farther away from the
metal surface than is the Cu adlayer, it is less affected by
and Eqs, (70) are solved by iteration to yield adsorption
the changing electron orbitals. The electrosorption refer-
isotherms.
ence potential ofcopper is also changed during the poten-
tial scan as shown in Fig. 5, whereas that of bisulfate is
kept constant.
B. Adsorption Isotherms and a
Voltammogram 04 ~'~~~~,~~~~I~-~~~r~~-~..,~~~--
In Eqs. (70) and (72), the relevant variables for an adsorp-
tion isotherm are the interaction energies and the activity, OJ

Zi, of each species i. In UPD, however, instead of the

activity ofspecies i, the variables ofinterest are the applied

potential, !/J, and the effective electrovalcnce, Ii' and the ~ 0.2

reference potential, !/Ji' of species i. Combining Eqs. (45),

(46), and (47) we find that these variables are related to 0.1 Copper reference potential \If,"
the activity of species i by the equation ~~..ulfa~e_~,:~er".,!~e !2?!~~t~~ '1'..

kT In ::i = J1i = -"rie(!/J -!/Ji) (73) 0.0

0.00 0.10 0.20 0.30 0040 0.50
E (V) vs. Ag/AgCl
where e is the elementary charge, and the effective
electrovalence Ii is related to the partial charge (i and figure 5 The potential dependence of the electrosorption
electrovalence Vi of ion iby Ii = Vi - C. reference potentials ofcopper, J/J" and ofbisulfate, J/Js'
Theory of the Metal-Electrolyte Interface 29

1.0
"
0.9
----------- ~"!"'.~":P'~~EH!13~t2
4.0 f-f--_ _ ~-_---"'\\ !",!.,=_':":!'i~~,,!.~t)
0.8
0.7
\.
Copper coverage
to<: exp(-E~/3kt) Bisulfate coverage
..... ------~
3.0 f-- \ !": ~xpS-E,.lkt~ 0.6 ............... I ~P.;;~~~~~~p~~~~~~~J.":.I!Lo.).1
\'" 0.5 .....\
~
' ....... _------ ------------------------------ --- 0.5
2.0 1- .
0.4
--------------------
0.3
1.0 . _ . _ _ _. 0.2
0.1 J ............... __ .
0.0 L....c~~--'--~~~.L-.LI~~--'-~~~L.......-~~-" 0.0
/

0.00 0.10 0.20 0.30 0.40 0.50 0.00 0.10 0.20 0.30 0.40 0.50
E (V) Vs. Ag/AgCI E (V) vs. Ag/AgCI

Figure 6 The potential dependence of the exponentials of the Figure 7 The adsorption isotherms for copper and bisulfate
interaction energies. An interaction is attractive if tij is greater using potential-dependent effective electrosorption valencies
than one and repulsive if tij is less than one. and interaction energies.

As was assumed for the effective electrovalencies, we nonphysical aspect of the adsorption isotherms of the
propose that the interaction energies between the cluster approximation have been removed from the
adsorbates also change as the electrode potential is adsorption isotherms shown in Fig. 7.
changed. Because the copper is partially charged in its To obtain a formula for calculating the spreading
low-density phase, we suggest that nearest neighbors pressure P of a phase, note that the Gibbs free energy is
experience a mild repulsion there. Because the copper given by
adatoms are increasingly reduced as the electrode poten-
tial is lowered, the nearest-neighbor interaction becomes G= Nsll s + Nelle = jAIA + PlAia (74)
more attractive and the second nearest-neighbor and
Equations (55) and (58), combined with Eq. (74), yield the
copper-bisulfate interactions become increasingly more
computationally useful relation
attractive. These potential-dependent interaction ener-
gies are shown in Fig. 6.
To calculate a point (8 e , t/J) on the copper adsorption Pa/kT = ln(l + z:"') + I~I In SHe;:;]) + In(~ )
isotherm and a point (8." t/J) on the bisulfate adsorption
(75)
isotherm at temperature T, we choose t/J, Yi, t/Ji' and cij.
Equation (73) then yields values for the activities Zi. We The reduced spreading pressure Pa/kTas a function of
then solve Eqs. (70) and (72) using the following iteration electrode potential is shown in Fig. 7. Exact formulas for
procedure. Initial values of 8e and 8s are chosen and are SH(;:;])rtT in the thermodynamic limit IAI-+ 00 were
substituted into Eq. (70), which yields initial values of r e obtained by Joyce [52] and are given in the appendix of
and r s . These values of r e and r s are then used in Eq. (72) Ref. 40.
to give new values of 8e and 8s . The iteration converges In our previous work [38-40] we have been unable to
quite well and was used to calculate adsorption isotherms model all the features of the adsorption isotherms, as
for our model as shown in Fig. 7. shown in Fig. 7, using constant (potential-independent)
Because ofthe nature ofthe cluster approximation, the interaction energies and constant effective electro-
calculated adsorption isotherms are S-shaped at sorption valencies and reference potentials. This is con-
first-order phase transitions and do not show a finite jump sistent with the results of Tarasenko and Jastrabi [44] of
in coverage. To remove this nonphysical aspect of the their calculation of the adsorption isotherms of a similar
cluster approximation and locate a first-order phase system using the method of the real space re-
transition, we use the fact that two phases, I and II, are normalization group. For one set of parameters, we suc-
in equilibrium at fixed Tand P if Il~ = Il~I and Il~ = Il~I. cessfully obtained a copper adsorption isotherm
Because the chemical potential and the applied potential showing a Langmuir adsorption, followed bya first-order
are essentially linearly related, a plot of P versus t/J will transition to an ordered low-density phase, followed by
then produce a line that crosses at a phase transition adsorption to a monolayer high-density phase, but with
and that contains a nonphysical loop. The S-shaped no first-order phase transition to the high density phase.
 50 ,I~~~-"'-,"~~~~--r~~~~-,-~~~~,-'-'-'-",--,
With a second set of parameters we obtained a copper
adsorption isotherm that showed first-order transitions Experimental voltammogram
to both the low- and high-density phases but no Langmuir 40
CVJ~!_':.~~t~!U!U.?J;~~
adsorption leading to the first phase transition [40]. This ,-...
motivated us to model the UPO process using variable M 8 30

interaction energies, charge, and reference potentials.

A voltammogram ofthe UPO process can be obtained
~:::1. 20
~
from the adsorption isotherms of copper and bisulfate
by noting that for faradaic discharge of the copper 10

adlayer, the current density due to this charge transfer is

o b....?-/ '-t--~----- ._~ --0 J
given by 0.00 0.10 0.20 0.30 040 0.50
E(V) vs. Ag/AgCI
.iF = (M j A)e[-e cu dku
dt/!
+"ICu dOdt/!cu ] dt
dt/!. (76) Figure 8 A model voltammogram obtained using the cluster
variation method as compared with an experimental volt-
ammogram ofOmar et al. [56]. The sweep rate is 5 mYls.
wherejF is the current density with units ofcurrentlareaof
the faradaic discharge of copper and M /A is the number
ACKNOWLEDGMENTS
of adsorption sites per unit area. All other parameters
have been defined previously. Experimentally, the ratio Supported by the Office of Naval Research, by the
dt/! /dt is the scan (or sweep) rate. The second term in the OOE-EPSCoR grant OE-FC02-9lER75674, by The
square bracket ofthe above equation is simply the deriva- Robert A.Welch Foundation grant P-0446, and by a grant
tive ofthe adsorption isotherm multiplied by the effective from the Comite de Investigaci6n Academica of the
electrosorption valency. The first term is calculated using Colegio Universitario de Bayam6n.
the fol1owing exponential form for the partial charge of
copper:

CCu(t/!) = eW:(Ij;-~/cu)
The broadening of the baseline in the voltammogram is
fitted by adjusting we and t/!cu'
We suggest that the bisulfate contribution to the total
current density of the voltammogram is primarily
capacitive, that is, it discharges very little and, second,
its contribution to the current is small. The capacitive cur-
rent density due to the bisulfate adlayer is given by
dC] dt/!
Jc = OjA) [ C + t/! dt/! dt oc(MjA)eys dt/! dt
where C is the integral capacitance ofthe adlayer. Here we
assume a similar functional form for the current density
of bisulfate to that for faradaic discharge but where ys is
to be interpreted as a fitting parameter.
The sum of the two current contributions due to
copper and bisulfate as calculated from the adsorption
isotherms of the cluster variation method gives a
voltammogram as shown in Fig. 8. This voltammogram
is compared with an experimental voltammogram
obtained by Omar et al. [56].
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3
Structure of Water at the Water-Metal Interface: Molecular
Dynamics Computer Simulations
M. L. Berkowitz and In-Chul Yeh
University ofNorth Carolina, Chapel Hill, North Carolina
Eckhard Spohr
University of Ulm, Ulm, Germany
ABSTRACT
In this chapter we discuss the structure of water next to
two typical metal surfaces: platinum and mercury. The in-
formation on this structure is obtained from molecular
dynamics computer simulations. It is emphasized that
such simulations, although able to mimic the reality in
more details, compared with simple models used in ana-
lytical theories, are still limited to the description of
models. From our simulations we observe that water next
to an uncharged metallic surface is perturbed to a dis-
tance of ~l nm. Next to the charged surface. water is
reorienting and, when the external field is strong, under-
goes a layering transition.
I. INTRODUCTION
A detailed molecular level description of the structure
and dynamics ofwater and aqueous solutions next to met-
allic surfaces is of fundamental importance for studies
in electrochemistry, catalysis, and corrosion [I]. The
structure of a water monolayer adsorbed on a metal sur-
face can be investigated using a variety of experimental
techniques [2]. However, very little is known from exper-
iment about the structural details of a metal-aqueous
solution interface [3-6]. This is why computer
simulations can playa significant role in the promotion
ofour understanding of this interface.
33
In classic molecular dynamics computer simulations,
one solves Newton's equations of motion for the
particles. To minic the large number of particles present
in a bulk sample (~ 10 23 ) by a simulation that contains
only ~1000 particles, one uses a periodic boundary
conditions. The data from the simulation are
accumulated and analyzed to extract information about
the structural and dynamical properties of the system
[7]. Given that molecular dynamics algorithms and
analysis are set up correctly and work properly, the
results of the simulations depend mostly on the proper-
ties and character of the forces that govern the motion
of the particles. These forces are obtained from the
derivatives of the potential functions that describe the
energy of interaction between the particles in the
system. Consider for example an aqueous salt solution
next to the Pt surface. To describe this system in terms
of an often-used approximation where only pairwise
interactions between atoms are considered, one needs
to know water-water, water-ion, water-Pt, ion-Pt,
ion-ion, and Pt-Pt interaction potentials. Moreover, it
is not clear if it is a good idea at all to use pairwise
potentials to describe the water-metal and especially
ion-metal interactions. Considering the large amount
of work done on the determination of potential
functions, we know surprisingly little about these
functions when we want to describe water-metal or
ion-metal interactions. Therefore, the potential
34
functions that we use today should be considered as
semiquantitative model functions and the results from
the simulations should be viewed appropriately. How
well the model potentials do the job can be judged by
the comparison between the simulation data and the
experiment. At the same time, one should not forget that
the experimental data also need an interpretation and
therefore may be also model dependent. That makes
the issue of comparison not trivial.
II. MODELS
Considering the complexity of the problem, one may
want to start the simulations on a system where only the
pure water-metal interface is considered. Thus, one
needs to know the potentials for the water-water,
water-metal. and metal-metal interactions for such a
system. The water-water interaction potential is prob-
ably studied in more detail than any other potential. In
the pairwise model, the water-water interaction is rep-
resented as an interaction between two Lennard-Jones
spheres that contain embedded charges. These charges
interact through Coulomb's Law. The Lennard-Jones
parameters, the number ofcharges, their values, and their
location are determined to reproduce the properties of
bulk water. As an example of a good pairwise model of
water, consider the extended simple point charge
(SPC/E) model [8], where three charges that represent
one oxygen atom and two hydrogens are imbedded in a
Lennard-Jones sphere. It is quite remarkable how many
water properties are reproducible by such a simple model.
The model is simple because the charges in this model
are permanent and not fluctuating in response to the
environment, as the electron density in real water does.
To include the charge dependence of water on the
environment, one may add the polarizability effects [9]
or consider some scheme that allows charge
fluctuations [10]. Do we need to go beyond the pairwise
water potentials to study the water-metal interface? It
is always suspected that in the inhomogeneous environ-
ment one needs to go beyond the pairwise model. For
example, it was recently demonstrated that often-used
pairwise models and models that include polarizability
produce different results for the case of a simple anion
solvation in water clusters [see e.g., Ref. 11 and
references therein]. Comparison with experiment
indicated that the use of polarizable model in this case
was needed [see e.g., Refs. 11 and references therein].
We do not know yet how important it is to include
the water polarizability or charge fluctuations into the
molecular dynamics scheme when we consider
water-metal interface. At this stage, because we know
Berkowitz et at.
so little about water-metal interaction, we prefer to
restrict our consideration of water-water interaction
to the pairwise case [12]. In addition to the SPC/E
model, other pairwise additive models like the rigid
4 point transferable intermolecular potential (TIP4P)
[13] and the flexible Bopp-Jansco- Heinzinger (BJH)
[14] water model have also been used in studies of the
water-mercury interface discussed below.
The next interaction that one has to consider is the
water-metal interaction. If the motion of metal atoms
has no influence on the structural properties ofwater next
to the interface, then one can average the water-metal
interaction and represent it as an effective potential.
Moreover, the metal atom-metal atom interaction is
not needed in this case. Parsonage and Nicholson [15,16]
were the first to perform a simulation of the water-metal
interface using this idea. In their simulation the
water-metal interaction contained two parts: a part that
represents a soft wall potential and a part that made the
wall to look like a metal-the electrostatic image part that
represented the effect due to the collective motion of elec-
trons in the metal.
A similar model was considered by Gardner and
Valleau [17], who performed a Monte-Carlo simulation
with TIP4P water next to the hard wall instead of
considering a soft wall. The results from simulations
of Gardner and Valleau were compared with the results
from simulations of Lee et al. [18] performed on
water-hydrophobic wall interface. Lee et al. concluded
that water molecules next to a hydrophobic nonmetallic
wall have a tendency to point out one of its hydrogens
toward the wall. Gardner and Valleau noticed that the
presence of the image forces greatly enhanced this
tendency. Such behavior contradicts experimental
observations related to the Pt-water monolayer inter-
face, which show that water tends to situate with its oxy-
gen atom next to the transition metal surface, whereas
the water hydrogens are pointing away. Theoretical cal-
culations on the bonding of water to the transition
metal clusters supported the same conclusion [19].
Based on one of such calculations of water on a Pt
cluster [20], Spohr and Heinzinger [21] developed a
potential describing the interaction between water mol-
ecule and Pt surface. This potential correctly predicted
the adsorption of water molecules through the oxygen
on the a-top sites of the lattice with the binding energy
on this site of approximately -40 kJlmol, which is in
the range ofweak chemisorption energies. Quantum cal-
culations showed that this energy is due to the overlap of
the protruding orbitals of the transition metal and lone
pair orbitals of water. Such an overlap has a local
character. The potential also predicted the correct
Structure of Water at the Water-Metal Interface
adsorption distance for the water molecule. Using this
potential, Spohr [22,23] performed a molecular
dynamics simulation of a slab of water between two
Pt(lOO) surfaces. In Spohr's simulation, the Pt surfaces
were explicitly represented by 550 Pt atoms, and the
dynamics ofthese atoms were included in the calculation.
To avoid the calculation of metal atom dynamics,
Berkowitz and collaborators [24-26] developed a
water-platinum surface potential, which takes into
account the symmetry of the Pt surface and its cor-
rugation. This potential allowed them to concentrate on
the motion ofwater molecules only, replacing all Pt atoms
by an effective external field. Comparison of structural
data from the simulation of Foster et al. [24] with Spohr's
[22] simulation ofwater at the pte100) interface displayed
a very good agreement between these two simulations.
That shows that the potential model used in simulations
of Berkowitz and collaborators and the potential model
of Spohr and Heinzinger produce very similar results.
For a more detailed discussion of the water-metal inter-
action potential used in the work of Spohr and collabor-
ators and Berkowitz and collaborators, the reader is
referred to the original Refs. [22-26].
In a similar manner, the results of ab initio calcu-
lations of mercury-water clusters at the SCF level [27]
were parametrized by Boecker et al. [28]. They used a
similar functional form for the mercury-water interac-
tions as for the platinum- water interactions. Together
with a pseudopotential ansatz for the mercury-mercury
interactions of liquid mercury, this potential model was
used by the same group of authors to describe the liquid
mercury-liquid water interface [29,30] (see also below)
and the hydration structure of ions near it [31,32]. Both
the water-platinum and the water-mercury potential
functions contain terms that depend on the atom-atom
distances and its projection on the water-metal surface.
This parametrization is sufficiently flexible to describe
the specific bonding characteristics of water adsorption
both on a rigid metal surface (like that ofPt) and a flexible
one (like that of liquid mercury). Thus, the
water-mercury potential function can be used in
simulations ofsolid and ofliquid mercury in contact with
an aqueous phase.
What is not included in potential models for
water- metal interaction developed in the groups of
Spohr and Heinzinger and by Berkowitz and collabor-
ators is the contribution due to the polarization of the
metal by the point charges on water. For a point charge
q located at some distance r from the metal surface V-
is of the order of few molecular diameters), the field
due to polarization is equivalent to the field produced
by a fictitious charge -q situated at the distance -r
35
from the surface. When the charge approaches the sur-
face closely enough (i.e., it starts overlapping with the
tail of the metal charge distribution), this simple pic-
ture breaks down. To resolve the problem, Siepmann
and Sprik [33] used an approach where the induced
charges in the metal were represented by overlapping
Gaussian distributions centered on the atoms of the
metal. These charges were calculated dynamically
using the Poisson equation during the simulations.
According to Siepmann and Sprik, the energy of inter-
action between the water molecule and the metal was
due to two contributions: those from chemisorption
and those from induction. In all cases studied by
Siepmann and Sprik the induction energy was between
3 and 4 kllmol or less than 10% of the total energy.
Therefore, it is possible to neglect the induction contri-
bution altogether. (Note that in the work of Siepmann
and Sprik, the total energy for Pt-water interaction
was also close to approximately -40 kllmol for the
a-top adsorption of water.) Another argument can also
be put forward that justifies the neglect of the
induction. As was pointed out recently by Shelley et
al. [34], the total image potential due to the net interac-
tion of all water molecules and all their images is quite
small due to the cancellation effect, and therefore it
can be neglected.
Shelley et al. [34] also constructed ajellium model for
the mercury-water interface from the ab initio data by
Nazmutdinov et al. [27]. On the basis of the experience
that in simulations of liquid water the sum of all image
terms (both the self-image interaction between a mol-
ecule and its own image and the distinct image interac-
tions between molecules and the images of other
molecules) is usually very small, they argued that the
self-image term should be first subtracted from the calcul-
ated interaction energies of water-metal clusters before
parametrizing ab initio quantum chemical calculations,
because the interaction ofthe adsorbate with the electron
gas contributes to the cluster energy. The remaining part
of the mercury - water cluster energies from the work of
Nazmutdinov et al. was then parametrized and image
interactions were neglected altogether in the simulations.
Instead, the electronic structure of liquid mercury was
accounted for by the jellium model. The jellium model
describes the metal as a uniform background of positive
charge density representing the nuclei and core electrons
and the associated valence electron density. At the metal
surface, the uniform background charge drops abruptly
to zero. The valence electron density decreases more
smoothly to zero at the interface and extends a short dis-
tance into the other phase. The valence electron density
is obtained using the Hohenberg- Kohn - Sham
implementation ofdensity functional theory and consists
of the solution of an effective one-electron Schroedinger
equation with an effective potential energy containing
exchange-correlation terms, interaction of the electron
gas with the jellium background charge, and the interac-
tion of the electron gas with the liquid phase. Through
the latter term, both phases are coupled.Water molecules
will react to the fields and potential produced by the
jellium; the jellium electrons will react to the presence
ofthe atoms and ions in the liquid phase. Instead of using
the instantaneous coupling between jellium and water,
Shelley et al. [34] simplified the procedure by iterating
over several simulations. During each simulation the
jellium charge distribution is static, starting with the vac-
uum distribution ofthe electrons in the metal.Water mol-
ecules move in the field produced by the jellium and the
other potential energy terms. After the simulation, the
jellium charge density is recalculated using the average
electrostatic potential of the solvent in the Kohn-Sham
procedure that is then used in the next simulation. This
procedure is repeated until convergence is reached, which
requires typically two or three iteration according to the
authors.
III. WATER/PLATINUM-INTERFACE
A. Methodology
A set of molecular dynamics simulations performed on
the water - Pt interface is described here. Two
simulations were done in the absence of an external
electric field, and the other was performed with the
external field turned on. All the simulations were
performed on a lamina of water enclosed by the Pt
walls parallel to x and y directions. The first simulation
was performed on the water next to Pt(lOO) surface.
In the second simulation, we looked at water next to
the Pt(lll) surface. In the simulations with the electric
field turned on, we considered Pt(lll) surfaces to be
homogeneously charged (positively on the left surface
and negatively on the right surface) to the value of
8.85 ,uCjcm 2 in the third simulation, 17.7 ,uCjcm 2 in
the fourth simulation, 26.55 ,uCjcm 2 in the fifth
simulation, and finally to a value of 35.4 ,uCjcm 2 in
the sixth simulation. These correspond to the values of
the external field of I, 2, 3, and 4 VI A, respectively.
All simulations were performed with the unit cell
representing a rectangular prism. The base of the prism
was chosen to be a rectangle with the dimensions
satisfYing the periodicity requirements of the Pt lattice.
Thus, for the Pt(lOO) surface, the side was a square with
the length Lx = L y = 5a = 1.96 nm (a = 0.392 nm is
the lattice constant for Pt). The same base was used in
the simulation with a smooth wall. For the Pt(lll)
surface, the rectangle in the base had the dimensions
of Lx = (ajv'2). 8 = 2.217 nm and L y = (.J3jv'2)a. 4
= 1.920 nm. The width of the water lamina was
adjusted, so that the density of water was I glcc in the
middle of the lamina. The number of water molecules
in all simulations was 512. The molecular dynamics
Verlet algorithm was used to propagate the trajectories
with the time step of 2.5 fs and Shake subroutine was
used to preserve the rigidity of the water molecules.
The temperature of the run was kept at 300 K, and this
was accomplished by coupling the system to the heat
bath using the algorithm of Berendsen and
collaborators. The relaxation time of the heat bath was
taken to be 0.1 ps. (For a discussion of molecular
dynamics algorithms used here see, for example, Ref.
7.) The coordinates were saved every 10 time steps for
the further analysis. The length of the simulations over
which the data were recorded was 100 ps after
equilibration. In the simulations with noncharged
surfaces, the equilibration time was ~100 ps. To per-
form the simulation with the external field of I, 2, and
3 VI A, we turned on the field gradually during 50 ps
and then performed the equilibration for another
100 ps. The field of 4 VI A was turned on gradually over
the period of 100 ps and then equilibrated over
~350 ps.
It was recently established that the implementation of
the minimum image technique produces an artificial
orientational ordering in the middle of water lamina,
whereas a spherical cutoff method does not do this [35].
In addition, it was established that one needs to include
the contribution of the long-ranged force beyond the
spherical cutoff; otherwise, the resulting field is grossly
overestimated [36,37]. Therefore the Ewald sum tech-
nique was recommended in the simulations of aqueous
systems enclosed between walls. One can also use other
methods to take care oflong-ranged force contributions
correctly [38]. In all simulations described in this chapter,
the two-dimensional Ewald summation technique was
used for the Coulomb interactions [37]. To apply this tech-
nique in an economic way, potential, forces, and the
Hessian matrix were tabulated on a three-dimensional
grid. During the simulation, most interaction energies
and forces were calculated from the table entries byTaylor
expansion. Because a three-dimensional grid cannot be
made very fine due to constraints in computer memory,
interactions between charges closer than4 A were calcul-
ated exactly without use ofthe table. The Lennard-Jones
contribution was calculated using the minimum image
method.
Structure of Water at the Water-Metal Interface
B. Results
1. Water Next to Uncharged Pt Surfaces
To understand the structure ofwater at the interface with
the Pt metal, we need to consider the translational and
orientational ordering of water. The translational order-
ing of water along the direction perpendicular to the
plane of the metal surface can be understood from Fig. 1,
where the local oxygen density obtained from the
simulations without external electric field is depicted.
For an easier comparison, the simulation results were
brought to a common origin for oxygen density, and the
point oforigin was taken as 0.0 nm. The results as shown
next to one wall only, because the distribution was sym-
metrical with respect to the middle of the water lamina.
As Fig. 1 shows, in both cases we can clearly distinguish
two peaks in the oxygen density next to the wall. Some
indication of the existence of the third peak located
~0.35 nm away from the second peak is also discernable
from the plot. We also observe that the first peak of water
density next to Pt(WO) is somewhat wider, compared with
the one from the Pt(lll)-water interface. This was noted
by us previously and was attributed to a larger degree of
puckering of square water rings at the Pt(WO). Next to
the Pt(lll) surface, one can observe flat hexagonal rings.
More discussion related to the water rings is given below.
In Fig. 2 we show the oxygen and hydrogen density pro-
files obtained from each of the two simulations. These
density profiles indicate that mostly water molecules are
lying flat on the corrugated surface. This is due to the
hydrogen bonding between the adsorbed waters, because
5 conclusion is confirmed by the density plots in Fig. 2.
4 - Pt(100)
.. -.- Pt(111)
..x:
:::l
3
..0
Q..
---
Q.. 2
1
a from the surface, whereas second hydrogen is creating a
0.0 0.2 0.4 0.6 0.8
Z (nm)
Figure 1 Oxygen density profiles from the simulations of
Pt(lOO)-water (solid line) and Pt(lll)-water (dotted line)
interfaces.
37
a single water molecule will try to orient itself with its
hydrogens looking away from the surface. To get a clear
idea of what goes on with the orientational ordering of
water next to our walls, we consider the distributions for
the angles between the water dipoles and the unit vector
along the normal in z direction that points toward the
wall. We also consider the distributions for the angles
between the OH bond and the normal to the surface.
The dipolar and OH distributions are shown in Figs. 3
and 4. The orientational distributions strongly depend
on the location of the water molecule along the direction
normal to the surface; therefore, we plot these
distributions for the bins of small width. In choosing the
width of the bin, we are guided by the observation that a
water monolayer adsorbed on the surface of the metal
actually may be a bilayer [2]. Because the density profile
from our simulations displays only one peak for the
adsorbed layer (although a hint to the presence of the
adsorbed bilayer is indicated by the oxygen density profile
next to Pt(lOO) surface), we conclude that the adsorbed
layer in our simulations can be a bilayer only if considered
from the orientational distribution point of view.
Therefore, we divide the first layer into two bins. This gives
us bins of width 0.1 nm for our simulations. We call the
bin closest to the surface and that corresponds to the first
half of the adsorbed layer bin Lla, and the second bin
(corresponding to the second half of the adsorbed layer)
is called Lib. Correspondingly, next bins are called L2a,
L2b, L2c, L3a, L3b, L3c, and so on, therefore making
the notation for the bins self-evident. From the
orientational distributions and from the peaks location
in these distributions, we conclude that most of the water
molecules in the bin Lla have their dipole and OH bonds
(and the plane ofthe molecule) parallel to the surface.This
The distribution ofdipolar orientations for the molecules
in the bin Lib (second sublayer of the first layer) is
bimodal. This indicates that this sublayer is made up of
"flip-up" and "flop-down" molecules ("flip-up" are mol-
ecules that have their dipoles pointing away from the
surface, whereas"flip-down" molecules have their dipoles
pointing in the direction toward the surface). The
locations of the peaks of the OH orientational
distributions for the second sublayer show that for the
flip-up molecules, one oftheir hydrogens is pointing away
tetrahedral angle with the first hydrogen. This configur-
ation corresponds to the maximum of the dipole
orientation distribution observed at cos e ~ -0.525.
The second maximum of the dipole orientation distri-
bution is due to the flop-down molecules, which have
both their hydrogens pointing toward the waters of the
.:10 DCIl\.un ILL Cl it..

5
1':[2S]1a
.
~
4
Pt (100)
1 .../ .
1b ~2a
~
:::J
.0
3
0.5
a
/'"
i '
'\ /"""""""'"
~
,
.
.
.. ...!

~1':~2b 2C (d3a
~
--2-
Q..
2
~ 1
1 u
ii:' 0.5 .. \
~~
, ,
0 a
5
4
Pt (111 )
1:~3b. FlFl
~
:::J
3
0.5 .
a-1 -0.5 a 0.5
.
ot:=:]
1 -1 -0.5 a 0.5 1 -1 -0.5 a 0.5 1
.0
Q.. cos6~
...........
Q.. 2
Figure 3 Distributions ofdipole orientations as a function of
cos 8 (8 is the angle between the dipole and the inward normal
1 to the surface). Solid line, Pt(IOO)- water interface; dotted line,
Pt(lll)-water interface.
0
0.0 0.2 0.4 0.6 0.8

Z (nm)
Figure 2 Oxygen (solid line) and hydrogen (dotted line) den-
sity profiles from the simulations of Pt(IOO)- water interface
(top) and Pt(lll)-water interface (bottom). ': 0 ] . L1a . L L1b. L ; J ' b]2a.
0.5 / i . .
adsorbed sublayer. The distributions in the third bin a

r: ld
(L2a) are for the water molecules that are between the

~c
adsorbed layer and the second layer. Because there are 3a
only a few such molecules, the distributions have large
statistical uncertainties. The orientational distributions b]L2b
. . ". ./
in bins L2b and L2c for all the interfaces are very similar :l- 0.5 .' './ .. .
to each other. The positions of the peaks for these a
distributions and the fact that the distributions in bins

:~bJ~bd
L2b and L2c are mirror images ofeach other with respect
to cos e = 0 suggest that water displays an orientational
ordering biased toward the ordering observed in ice-Ih,
similar to the one observed by Lee et al. [18]. We also
observe that the distance between the second and the
third layers is ~O.35 nm, which is the distance between
-1 -0.5 a 0.5 1 -1 -0.5 a 0.5 1 -1 -0.5 a 0.5 1
cos6 0H
layers in ice-Ih structure that has its c axis perpendicular
to the surface. The distributions in bins L3a, L3b, and Figure 4 Distributions of OH orientations as a function of
L3c describe the orientations of water molecules in the cos () (8 is the angle between the OH vector and the inward nor-
third layer. These distributions are again very similar for mal to the surface). Solid line, Pt(IOO)-water interface; dotted
the two interfaces. Although the distributions for the line, Pt(lll)-water interface.
Structure of Water at the Water-Metal Interface 39

Figure 6 Snapshot of a configuration of the adsorbed water

layer at the pte Ill) surface.

Figure 5 Snapshot of a configuration of the adsorbed water

layer at the Pt(lOO) surface. (a)
(b)

third layer are broader and with less-pronounced features

than the distributions for the second layer, the positions
ofthe peaks in layers L2b and L3b are roughly at the same
angles. This means that the orientational bias toward the
ice-Ih structure is still somewhat observed in the third
layer. Definitely, this bias is very weak for the third layer
and disappears in the bin L3d, which is a OJ-nm bin
beyond layer 3.
(e)
To get a better perspective about the structure ofwater
at the adsorbed layer, let us consider Figs. 5 and 6, where
we present snapshots of the adsorbed water layer on top
of the Pt(lOO) and Pt(lll) surfaces, respectively. As we
can see in the case of Pt(WO) surface, every a-top site of
Pt is occupied by a water molecule. Water molecules on
top of Pt(lOO) surface repeat the lateral arrangement of
the square lattice that is characteristic of this surface.
From the snapshot of the water layer adsorbed on Pt(lll),
we see that not every a-top site is occupied, and some sites Figure 7 Projection ofposition of oxygens from the adsorbed
are free. Around empty Pt sites it is possible to form hex- water layer on the xy plane (the plane parallel to the surface of
agonal rings of water, and there are three of such the metal) (a) for the Pt(lOO) surface during 50 ps. (b) Pt(lll)
neighboring rings seen close to the center of the picture. surface during 50 ps, and (c) Pt(lll) surface during 5 ps.
The fact that the distance between Pt near neighboring
sites is very close to the distance observed in ice-I helps
to promote hydrogen bonded structures in the adsorbed of the structure of water in this direction and also of the
layer ofwater. water dynamics in our simulations can be obtained from
To study the average structure of water in the lateral the stroboscopic plots that are shown in Fig. 7a-c. In this
direction, one can look at the radial distribution figure a dot has been drawn every n ps at the (x,y) position
functions, but perhaps the most illustrative exposition of each oxygen atom from the adsorbed layer. Thus, Fig.
40 Berkowitz et al.

7a depicts the positions of water oxygens in the xy plane 5

for the adsorbed layer of water at the water-Pt(lOO) 4 Eo=1.0V/A
interface. This stroboscopic picture is taken over an
~ 3
interval of 50 ps with time interval between snapshots .Q

of 1 ps. As we can see from this figure, the water molecules -2-2
a.
are adsorbed on the a-top positions of Pt atoms, and all 1
......
-',,: \;:.., r - - -...............- - - - " " -
of them are oscillating around these positions during this
a
time interval. Such motions is characteristic of the solid
phase. Fig. 7b depicts the stroboscopic picture of the 4 Eo=2.0V/A
water layer on top of the Pt(lll) surface during the same ~
.Q
3
50 ps. From this figure we observe that although during -2-2
a.
this time interval some of the molecules oscillate around
their equilibrium positions, other water molecules
1 ,. \/\ "'\ n
diffuse and therefore most of the hexagonal rings that a
were present in the instantaneous picture are washed out 4 Eo=3.0V/A
over 50 ps. Fig. 7c again represents a stroboscopic picture
~ 3
of water adsorbed on top of the pte Ill) surface, only this .Q

time the picture was taken over the total time interval of -2-2
a. i\\ r,.
5 ps with O.l-ps time interval between the snapshots. 1 ilJS~ .~
From this figure we conclude that the patch of hexagonal a
rings observed in the instantaneous snapshot is quite well Eo=4.0V/A
4
preserved during the 5-ps interval. For the second water
~ 3

i~WMi\\i i;~l'~~\ a tt
layer next to corrugated surfaces, we observed that the .Q

density of points in the stroboscopic pictures is much -2-2

more homogeneous (not shown), thus indicating that the
layer has a liquid-like character.
2. Water Next to Charged Pt Surfaces
To see how the homogeneous electric field influences the
structure of water at the Pt - water interface, we
performed a set of four simulations of water next to a
charged Pt(lll) surface. In the first of these simulations,
the external field had the value of Eo = 1 VI A (the same
external field was applied in the simulation of Nagy and
Heinzinger [39]); in the second the value of the field was
2 VI A, in the third 3 VI A, and finally in the fourth
4 VI A. The density distributions for oxygen and
hydrogen in the presence of these external fields are
shown in Fig. 8. It is clear from the figure that the density
is no longer having a symmetrical character with respect
to the center of the lamina and that reorientation ofwater
in the lamina started to occur. Thus, we see that even when
the field is 1 VI A, the oxygen density next to the left sur-
face (which was positively charged in the simulation) is
slightly shifted toward the surface, whereas the hydrogen
density is shifted toward the right surface, which is
negatively charged. Still, only two distinct layers are seen
next to the surface.When the external field is 3 VI A, more
pronounced layering is observed in the water next to
surfaces, but still no layering is observed in the middle
of the lamina. When the external field is 4 VI A, the situ-
ation is very different.We observed layering ofwater mol-
a. '\~\.
1 '\\ :\ "\1'1
j '.I J f
a
-2 -1 2
Z (nm)
Figure 8 Oxygen (solid line) and hydrogen (dotted line) den-
sity profiles from the simulations ofPt(III)- water interface with
the external field of I, 2, 3, and 4 VI A.
ecules in the whole lamina that indicates that a solidlike
structure is now present in the system, as one can see from
the Fig. 8. (The value of the external field at which the
layering transition is observed depends on the way one
treats the long-range electrostatic forces in the
simulation.) Thus, when no long-range electrostatic con-
tribution is considered, the layering transition occurs
when the external field has a value somewhere between 1
and 2 VI A, whereas the inclusion ofthelong-range forces
increases the value of the field to be somewhere between
3 and 4 VI A [40]. Figure 9 shows a snapshot of all water
molecules between plates when the field is 4 VIA. The fig-
ure indicates that all water, excluding the first two layers
next to each plate, is crystallized into an imperfect proton
ordered cubic ice-I. Such a transition to cubic ice was
observed by us before when we studied water next to
charged Pt(lOO) [40] and Ag(lll) [41] surfaces. Figure 10
shows an instantaneous snapshot of water on top of the
Structure of Water at the Water-Metal Interface
Figure 9 Snapshot of all water molecules that are
encompassed between two Pt(l1l) surfaces. An external field
of 4 VI A is applied.
Figure 10 Snapshot of a configuration of the adsorbed water
layer at the pte 111) surface. An external field of4 VI A is applied.
41
positively charged Pt(lll) surface (Eo = 4 VI A). Hexag-
onal rings that were present in the simulation with the
uncharged Pt(lll) surface are not observed in this case.
Moreover, the density of water in the first layer is dimin-
ished as the field is increased, due to the reorientation of
water. To support a total orientation of water along the
external field, water molecules under the influence of a
strong field split the first layer, which without the field con-
tained flip-up and flop-down water molecules, into two
layers that contain now all flip-up molecules. This reduces
the density ofthe first layer.
Previous simulations [42,43], theoretical calculations
[44], and experiments [45] provided some indications
that in the presence ofthe electric field water can undergo
a phase transition. A transition to a proton-ordered cubic
ice was also observed when an external electric field was
applied to supercooled water [46]. We do not know if the
structure we observed in our simulation with a large field
is solidlike and stable over long periods of time or if it is
glasslike.Yery long simulations are needed to differentiate
between these two situations.
C. Conclusions
From the results of our simulations we conclude that
water next to the Pt surface is profoundly influenced by
this surface. We conclude that the adsorbed layer ofwater
on top of the corrugated surface is ordered according to
the structural arrangement of the Pt surface that is pre-
sent underneath the water layer. In case of the Pt(WO)
surface, the adsorbed water layer is arranged in a square
pattern and is displaying solidlike behavior with respect
to its mobility during the time of the simulation. We also
observe that for the Pt(lOO) surface all available a-top
adsorption sites are covered by water molecules, whereas
for the Pt(lll) surface some of the a-top sites are free,
because water creates icelike hexagonal rings with a free
Pt site in the center of the ring. This observed difference
between the coverage of Pt(WO) and Pt(lll) surfaces by
water molecules can have important consequences for
the adsorption of the impurities and salt molecules in
aqueous solutions. The presence of the defects in water
structure on top of Pt(lll) is responsible for higher
mobility of water in this layer, compared with the case of
water on top of Pt(lOO). The structure of water next to
Pt(lll) surface in our simulations is somewhat similar to
the ideal structure that was proposed to exist for the
high-density water monolayer adsorbed on a hexagonal
surface [47]. Both our observed structure and the ideal
structure have ~80% ofoccupancy of the a-top sites and
both indicate a high density adsorption. Note also that
the high-density ideal structure [47] see Ref. 25, Fig. 4) is
different from the usually displayed.J3 x .J3R30o struc-
ture of the monolayer. (For a pictorial representation of
the.J3 x .J3R30o structure; see Ref. I; p. 335.) Although
the former one predicts the coverage of ~0.8, the latter
one results in a coverage of 2 /3.
The adsorbed layer of water next to the corrugated Pt
surface is somewhat solidlike (more so for the water next
to Pt(lOO) surface) on the time scale of our simulations.
The second and third layers of water next to the
uncharged Pt surface are liquidlike. The orientational
distributions of these layers show preference toward the
orientations that are characteristic of hexagonal ice. The
same preference was seen in the simulations ofwater next
to hydrophobic walls. In general, one has to be careful
when comparing the properties of water next to
hydrophobic and metallic walls. From our simulations
and from the comparison with the simulation of Lee et
al. [18], we conclude that the structure of the first layer of
water next to the surface is determined by the surface.
The orientational structure ofthe next two layers ofwater
is similar for water next to the Pt wall and water next to
the hydrophobic wall.
In a recent experiment, an attempt was made to deter-
mine the density profile ofwater next to a charged AgOll)
surface using x-ray scattering [5]. The conclusions from
the experiment were that water is layered next to the
charged surfaces, water is reorienting next to the charged
surface, and water undergoes a restructuring in the
presence of the strong field. Our present and previous
simulations are in agreement with these conclusions.
Where we disagree with the experiment is in the estimate
of the areal density ofthe adsorbed layer. AlthoughToney
etal. [5] propose that in the presence ofthe strong external
electric field the density ofthe adsorbed water layer is very
high, our simulations do not confirm this proposal. It is
appropriate at this point to emphasize again that one
should exercise caution in the comparison between
theory and experiment, because both have their short-
comings and challenges.
IV. WATER-MERCURY INTERFACE
A. Methodology
We report results of two simulations of the water - Hg
interface. As for the case of Pt, the water lamina is con-
fined by two mercury phases with the interfaces parallel
to the x and y directions. The first simulation contains a
lamina of 700 TIP4P water molecules between two rigid
slabs of mercury atoms. It thus models the liquid
water-solid mercury interface. The mercury slabs are
modeled as rhombohedral lattices with III surface
structure, which is compatible with the interpretation of
liquid-vapor x-ray diffraction experiments [48]. The
nearest neighbor distance between surface mercury
atoms is 0.3 nm and the distance between mercury layers
is 0.316 nm. The dimensions of the liquid water lamina
in the x and y direction are 3.0 and 2.60 nm, respectively.
The surface layers of the two mercury crystals are
2.88 nm apart. The simulation lasted about 150 ps at a
temperature of 298 K with temperature control through
a Berendsen thermostat with time constant 0.4 ps. The
simulation of an interface between liquid water and a
rigid mercury phase is advantageous because, first, no
knowledge of the interaction potential between mercury
atoms is needed and, second, the interface is more stable
than a liquid-liquid interface. Because the mass differ-
ence between water molecules and Hg atoms is rather
large, one can furthermore assume that the characteristic
motions of the two species are on substantially different
time scales. The second simulation consists of a box of
dimensions L t x L y x L z = 2.40 x 2.598 x 6.98 nm,
which contains 750 flexible water molecules and 880
mercury atoms in two liquid phases, the phase boundary
being again parallel to the x and y directions. The flexible
BJH water model was used in this simulation. This simu-
lation lasted 33 ps at a temperature of 302 K; no tem-
perature corrections were performed during this time
interval.
B. Results
By and large, the quantum chemical models for the
water--platinum and for the water-mercury interface
are rather similar. Consequently, several structural fea-
tures like density profiles, orientational distributions,
and hydrogen bonding are not dramatically different from
the results for the water - Pt interface discussed in the pre-
vious section. Also, the response to an external electric
field is similar and does not yield any new insight. Of
course, some minor differences exist, but they are not dis-
cussed here in any detail. Instead, we attempt to point
out some of the characteristic differences between
liquid-liquid and liquid- solid interfaces.
Of course, if one is to use the liquid-water-solid Hg
model to study the behavior of interfaces, it has to be
established that the behavior of water near solid Hg is
similar to that ofwater near liquid Hg. Simulation results
show that the density profiles of oxygen and hydrogen
atoms near rigid and flexible mercury phases are quite
different. Figure 11 compares the oxygen and hydrogen
density profiles for the interface between pure water and
rigid mercury (solid lines) and water and liquid mercury
(dotted line). The features of the water density profiles at
Structure of Water at the Water-Metal Interface
6 Po(Z) / Pb
4
2 coverage. The number of molecules in the full line and in
o coverage ofroughly one water molecule per surface atom.
------_ ... ":'
,/
6 than the one on Pt(lll). Neither the simulations near Pt
4 nor the ones near Hg give any indication ofa dramatically
2 in the experimental work by Toney et al. [5].
o -------
/.
, .
.'
o 2 4 6 8 10 12 z / A
Figure 11 Oxygen (top) and hydrogen (bottom) density profiles
ofwater near a rigid mercury crystal (solid line) and near-liquid
mercury (dotted line). The dashed curves are the convolution
of the density profiles near the rigid crystal and the first maxi-
mum of the liquid mercury density profile. The dashed curves
are shifted downward by one or two units for better legibility.
the liquid-liquid interface are washed out considerably
relative to those of the liquid-solid interface. However,
in the first layer this effect is almost entirely due to the
roughness of the mercury surface; not all mercury atoms
at the interface are in the same plane (at z = 0) but cover
a range of 0.13 nm. The width of the first layer of mercury
atoms in the liquid is larger than that of the oxygen and
hydrogen peaks near the solid surface. Consequently, to
compare the liquid -liquid with the liquid-solid inter-
face, the density distribution must be convoluted with a
width function describing the mercury motion. If one
chooses a Gaussian distribution with width (f = 0.13 nm,
the same as the width of the first mercury layer in the
liquid phase, one obtains the convoluted density profiles
in Fig. 11 as dashed curves. Clearly, the convolution
accounts for mostofthe structural differences in the range
z < 0.5 nm. The heights of the first peaks of the oxygen
and hydrogen density profiles after convolution are ident-
ical to those of the respective functions at the
liquid-liquid interface. The intermediate maxima in the
hydrogen density profiles around 0.43 and 0.51 nm, which
are due to interlayer hydrogen bonding, vanish. Only in
the second layer are there slight structural differences;
the distance between first and second peak is larger in
the simulation of the liquid-liquid interface than in the
corrected function.
43
This discussion also shows that a high maximum in the
density profile does not imply an increase in density near
the interface. It is the area under the peak that determines
the local density or, as a more appropriate measure, the
the long-dashed line is exactly the same. It amounts to a
This coverage is higher than on the Pt(lll) surface.
However, the nearest-neighbor mercury distance is larger
increased water density near an uncharged electrode, as
Both the rigid and the flexible mercury surfaces are
smoother than the Pt surfaces due to a smaller energetic
corrugation (i.e., the difference in energy between differ-
ent adsorption sites). Consequently, it can be expected
that the lateral mobility of water is larger on the mercury
surface. Boecker et al. [30] analyzed surface trajectories
of adsorbed water near liquid mercury. Over a period of
3 ps, the trajectories look similar to the ones in Fig. 7;
the amplitude ofthe lateral oscillations is, however, larger
than on the Pt(lll) surface. During this time interval,
the water molecules are correlated with the mercury
atoms, a consequence ofthe fact that the on-top adsorp-
tion site is the most stable one. The authors do not observe
exchanges between neighboring water molecules, prob-
ably because all adsorption sites are filled and also
because the simulated time interval of 33 ps is rather
small. At longer times. water molecules were found to
exchange between the first and second layer.
Figure 12 compares the spectral density of lateral
translational motion of water molecules on the Pt(lOO)
(dashed line) and the (rigid) mercury surface (solid line).
In addition, the corresponding spectral density of water
molecules in the bulk are shown as two dotted lines. The
f(v) / ern
0.04
0.03
0.02
001
o 10.0 200 300 400 v /cm- 1
Figure 12 Spectral densities of translational motion of water
parallel to the interfacial plane. Data are displayed for the layer
ofadsorbed water near the mercury surface (solid line) and near
the Pt(lOO) surface (dashed line). The dotted lines are for water
in the bulk regions of both systems.
spectral density of lateral translational motion is defined
as the Fourier transformation of the center-of-mass vel-
ocity autocorrelation function. It contains information
about the frequencies at which characteristic
translational motions occur. In the bulk, the translational
motion shows the characteristic maximum around
50 cm- 1 and the shoulder at 200 cm- 1, which have also
been found in pure bulk water. The small differences
between these dotted lines are due to the different water
models [BJH water near Pt(lOO) and TIP4P water near
Hg(l1l)] and differences in simulation temperature. In
the adsorbed layer, a wide peak at about 150-300 cm- 1
is observed for motion parallel to the Pt(lOO) surface,
which is reminiscent of the corresponding power
spectrum of water at a pressure of 22 kbar [49]. The
high-frequency part of this power spectrum has been
shown to be due to water-water interactions and is a
consequence of the lateral confinement on the surface
that has already been noted above to result in drastically
reduced mobility The spectral density of water motion
parallel to the mercury surface also exhibits a blue shift,
which is smaller in magnitude than on Pt(lOO). The shape
of the distribution is also more similar to that in the bulk
region. Thus, water motion is more bulklike parallel to
the mercury surface. This is a consequence of the
less-severe constraints that the 111 surface of Hg with
low corrugation and larger distances between
neighboring adsorption sites puts on the water molecules.
Note the depletion at low frequencies near both surfaces.
The value at v = 0 cm- 1 is proportional to the
self-diffusion coefficient. The reduction ofwater mobility
near the interface relative to the bulk is as evident as the
higher self-diffusion coefficient of water adsorbed on
mercury in comparison with water adsorbed on Pt(lOO).
C. Conclusions
We compared the structure of the liquid-water-liquid
mercury interface with a hypothetical liquid - water-
solid mercury interface. The liquid -liquid interface
shows, quite expectedly, less pronounced layering of
water. However, it was demonstrated that this trend is
mainly due to the increased roughness of the liquid
mercury surface. In addition, we observe that on the basis
of the pairwise additive potential energy functions used
here, many structural properties of the water-platinum
and the rigid water-mercury interface are similar.
The surface ofliquid mercury is smooth. The potential
functions reflect this in such a way that the energetic sur-
face corrugation (i.e., the difference in adsorption energy
between various sites) is smaller for the mercury-water
interactions than for the platinum-water interactions.
Consequently, the character of the motion of interfacial
water molecules on the mercury surface is changed less
relative to its motion in the bulk liquid than on the Pt
surface. Water mobility is higher on mercury than on
platinum.
v. SUMMARY
In this chapter we concentrated on our simulation studies
of the structural and dynamic properties of water next
to Pt and Hg surfaces, charged and uncharged. Com-
puter simulations of charged metal electrode-aqueous
electrolyte interfaces were performed by Philpott and
Glosli [50] and Spohr [51]. A variety of simulations by
various groups were done to study ion adsorption,
ion hydration, charge transfer at the aqueous solution-
metal, and aqueous solution-liquid interfaces. These
were recently reviewed by Benjamin [52].
In the beginning of this chapter we stated that the
results of the molecular dynamics simulations reflect
the potential functions used to describe the interac-
tions between the molecules. Before we can embark on a
serious quantitative analysis of the aqueous
solution-metal interface we need to obtain reliable
potential energy surfaces describing the forces acting
between molecules [53]. This, however, is currently the
central limitation to simulation studies. In principle, it is
possible to avoid the calculation of the forces altogether
by using the Car-Parrinello [54] methodology, which
combines molecular dynamics and electronic structure
calculations. This promising but computationally
extremely demanding methodology was already applied
to the study of the metal-water interface [55].
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2. PA Thiel, TF Madey. Surf Sci Rep 7:211-385, 1987.
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46:10321, 1992.
4. BM Ocko, J Wang. In: CA Melendres, A Tadjeddine, eds.
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127-155.
5. MF Toney, IN Howard, J Richter, GL Borges, JG Gordon,
OR Melroy, DG Wiesler, D Yee, LB Sorensen. Nature
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6. MFToney, IN Howard, J Richter, GL Borges, JG Gordon,
OR Melroy, DG Wiesler, D Yee, LB Sorensen. Surf Sci
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7. MPAllen, DJ Tildesley. Computer Simulations of Liquids.
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8. HJC Berendsen, JR Grigera, TP Straatsma. J Phys Chern 29. J Boecker, E Spohr, K Heinzinger. Z Naturforsch 50a:611,
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9. LX Dang, JE Rice, JW Caldwell, PA Kollman. JAm Chern 30. J Boecker, Z Gurskii, K Heinzinger. J Phys Chern
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1997. 33. 11 Siepmann, M Sprik. J Chern Phys 102:511, 1995.
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92:1358,1988. 47. DL Doering, TE Madey. Surf Sci 123:3051982.
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Electroanal Chern 369:227,1994. Phenomena. New York: Plenum, 1994, pp.101-118.
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Sci 335:372, 1995. 55. DL Price, JW Halley. J Chern Phys 102:6603, 1995.
4
Monte Carlo Methods for Equilibrium and Nonequilibrium
Problems in Interfacial Electrochemistry
G. Brown, P. A. Rikvold, S. J. Mitchell, and M. A. Novotny
Florida State University, Tallahassee, Florida
ABSTRACT
We present a tutorial discussion of Monte Carlo methods
for equilibrium and nonequilibrium problems in
interfacial electrochemistry. The discussion is illustrated
with results from simulations of three specific systems:
bromine adsorption on silver (100), underpotential
deposition ofcopper on gold (lll), and electrodeposition
ofurea on platinum (100).
I. INTRODUCTION
In the context of interfacial electrochemistry, the bulk
electrolyte can conveniently be thought of as a large
homogeneous reservoir of charge, adsorbate particles,
and energy. Then one can focus on the metal-electrolyte
interface, which can be viewed as an essentially
two-dimensional system of ions and molecules at or near
a solid surface. Consequently, interfacial electrochemis-
try can profitably be thought of as a branch of surface
science. It is therefore natural that a number of
experimental and theoretical methods originally
associated with more traditional branches of surface
science now are routinely applied in interfacial electro-
chemistry, including several that are discussed in this vol-
ume.
On the theoretical side, one such method is com-
putationallattice-gas modeling. This method is particu-
larly well suited to the study of fluctuations and phase
tmnsitions in systems characterized by specific chemi-
sorption at well-defined sites on the surface. Different
aspects ofthis approach have been reviewed several times
47
by others [1-4] and by one of the present authors [5-7].
Here, it is only described briefly. Monte Carlo simulation
of lattice-gas models as a tool for understanding
interfacial electrochemistry is the main topic of this
chapter.
Why bother with Monte Carlo simulation when there
are so many mean-field techniques, ranging from the
simple Frumkin and Temkin isotherms to sophisticated
cluster-variation methods? This is a natural question,
and there are three compelling answers:
1. Mean-field methods are really not very accurate for
most two-dimensional systems [8]. This is not to say
that very useful results cannot be obtained by
mean-field methods, for they certainly can, but
simple mean-field methods ignore the spatial struc-
ture of the system. A nontrivial amount of work and
attention goes into manually incorporating enough
of this structure to give accurate results, especially
in the vicinity ofphase transitions. In contrast, Monte
Carlo codes naturally take spatial fluctuations into
account. Most ofthese codes are quite simple to write
and easily adapted to model different systems.
2. Monte Carlo methods are not limited to the study of
equilibrium properties. Dynamic Monte Carlo
simulations provide a tool to study time-dependent
phenomena in systems where spatial fluctuations
may strongly modifY the time evolution. Applied in
this way, Monte Carlo simulation provides a more
detailed supplement to standard rate-equation
methods.
3. Computer technology has now evolved to a point
where extensive simulations can be performed on
work stations or personal computers that are well
within the budget for most groups. Actually, several
computers that are perfectly able to handle large
Monte Carlo simulations may already be sitting in
your laboratory! The competitive edge of methods
that are analytically solvable or rely on numerical sol-
ution of relatively small sets of equations is much
smaller than it was only a few years ago.
The purpose of this chapter is to discuss some basic
aspects of Monte Carlo simulation directly in the context
of interfacial electrochemistry. It is not intended to be a
full textbook on Monte Carlo simulation. There is no
sense in duplicating the excellent textbooks [9,10] and
large tutorial articles [IU2] that already exist. Rather,
we hope to illustrate some details and pitfalls associated
with constructing and running Monte Carlo simulations
ofspecific systems of interest in surface electrochemistry.
The outline of the rest ofthis chapter is as follows. The
lattice-gas approach to modeling electochemical adsorp-
tion is briefly introduced in Sec. II.A. The process of
comparing numerical and experimental results to adjust
the lattice-gas parameters is the subject of Sec. II.B.
The basics of equilibrium and dynamic Monte Carlo
simulations as nonperturbative methods for analyzing
lattice-gas models at finite temperature are discussed in
Sec. III. These simulations can be used to obtain numeri-
cal results for such experimentally measurable quantities
as adsorption isotherms, voltammetric currents and
charge densities, and images obtained by either
diffraction techniques or atomic-resolution micro-
scopies. In Sec. IV, we discuss three illustrative examples
drawn from our own research experience: the adsorption
of bromine onto Ag(100) [13-15], the underpotential
deposition (UPD) of copper on Au(111) from a
sulfate-containing electrolyte [4,16-21], and the electro-
sorption ofurea on Pt(IOO) from an acid electrolyte [6,22].
Particular emphasis is given to the simulational aspects
of these projects. Because this is not a review article,
references to the original literature have been limited to
those we thought most illustrative for our purposes.
II. LATTICE-GAS MODELS OF
CHEMISORPTION
A. Structure of the Models
In lattice-gas models, adsorption is only allowed on a dis-
crete lattice of adsorption sites. The concentration of
adsorbate at site i, Ci, is I if the site is occupied by the
adsorbate and 0 otherwise. The energy of a particular
configuration of occupied sites, c, is given by the
grand-canonical lattice-gas Hamiltonian
= -p. L L L Ci C)
(11) )
H(c) Ci - <D(I1) - H3(C) (1)
(
i n (ij)
The electrochemical potential ofthe adsorbate in solution
is p., and the first term on the right-hand side is the free
energy ofadsorption when adsorbate-adsorbate interac-
tions are ignored. The next term represents all two-body
adsorbate-adsorbate interactions. The index n indicates
the separation between sites, e.g., n = I indicates nearest
neighbors, whereas "L\':J
indicates the sum over all pairs
of neighbors of rank n. The interaction energy for two
adsorbate particles occupying nth nearest neighbor sites
is _<D(I1). Interactions between three or more adsorbed
particles are possible [2,3]-here they are symbolically
represented as the term H3. The sign convention is such
that p. > 0 denotes a tendency for adsorption in the
absence of lateral interactions, and <D(I1) > 0 denotes an
effective attraction. Models ofparticular electrochemical
systems differ in their binding-site geometries and the
values and ranges of the lateral interactions.
The connection of the theoretical lattice-gas model to
the chemical and electrochemical variables that charac-
terize the experimental system is made through the elec-
trochemical potential. The electrochemical potential of
X is related to its bulk activity [X] and the electrode poten-
tial E as
_ 0 [X]
J1 = J1 + RT In -
[X]o
- zFE (2)
where R is the molar gas constant, T is the absolute
temperature, F is Faraday's constant, and z is the effective
electrovalence of X. The quantities superscripted with a
o are reference values that contain the local binding
energies. Here we treat them as adjustable model
parameters.
The thermodynamic density conjugate to the electro-
chemical potential is the surface coverage
1
0=N- LCi (3)
where N is the total number of adsorption sites. With the
sign convention that oxidation currents are positive, the
adsorbed charge per adsorption site is
q = -ez0 (4)
where e is the elementary charge unit.
Monte Carlo Methods in Interfacial Electrochemistry
Many interesting systems involve the cooperative
chemisorption oftwo different species, say A and B, onto
the surface. In this case there is a concentration for each
species at site i, c~ and c~, with simultaneous adsorption
of both species at one site forbidden [23,24]. The
lattice-gas Hamiltonian for such a two-component sys-
tem can be written as [25]
(5)
The total configuration of the system, which depends on
both the configurations of A and B particles, cA and cB,
is still represented as c. The interactions <D~~ (where X
and Y can be A or B) now depend on the adsorbed species
and the distance between sites. The higher order
interactions, 'H3, may also involve combinations of A
andB.
Each component has its own electrochemical poten-
tial Px, surface coverage ex, and effective electrovalence
zx. When the temperature is fixed, a phase diagram can
be constructed in the (PA' PB) plane. For a specific chemi-
cal system with fixed bulk activities [A] and [B], Eq. (2)
for PA and PB form the parametric representation ofa line
in the phase diagram. The line has slope ZA/ZB, and the
electrode potential E is the parameter that determines
the location along this isotherm.
Because the entropy vanishes at zero temperature, the
T = 0 phase diagram, or ground-state diagram, can be
calculated analytically using Eq. (5). In principle this
can be done directly, but in practice another approach is
often used. For a given point in the phase diagram, the
ground state corresponds to the phase with the
lowest energy. A list of the conceivable ground states
compatible with the lattice symmetry [26] and their
energies is generated. Then a ground-state diagram can
be constructed automatically by finding the lowest
energy phase directly while scanning in the PA and PB
directions.
In contrast, the finite-temperature phase diagram for
most systems can only be mapped out using numerical
methods, such as the Monte Carlo simulations, which
are the main subject of this chapter. Because the number
of possible ground states for systems with longer range
interactions can be very large, it is in practice advisable
49
to check the ground-state calculations and Monte Carlo
simulations at low temperature against each other for
consistency.
When two types of ions adsorb onto the surface, the
adsorbed charge density is
(6)
In the absence of diffusion and in the limit of vanishing
potential sweep rate [27], the voltammetric current can
be estimated in terms of the equilibrium lattice-gas
response functions aex/apy. Specifically, using the
chain rule, this quasi-equilibrium current is obtained as
. dq dq dE
1=-=-- (7)
dt dE dt
The total differential of the charge density is
(8)
which can be simplified with the Maxwell relation
aeA/apB = aeB/apA' For any particular electrochemi-
cal experiment, dpx = -.:xF dE. Substituting this into
Eq. (8) and that result into Eq. (7), the quasi-equilibrium
current becomes
(9)
The response function can, in turn, be estimated from
the equilibrium partition function using standard
statistical-mechanics arguments, as described in the next
section.
Coverages, charges, and currents are given here per
adsorption site. They can be converted to the experimen-
tally measured units of inverse surface area through div-
ision by the area per adsorption site.
B. Model Development and Refinement
Accurate theoretical description of lateral interactions
in an adsorbed layer must consider the complete
substrate-adlayer-solution system. For instance, the
geometry of adlayers observed in situ for CO on Pt( III)
are different for ultrahigh vacuum, high-pressure gas,
and electrochemical environments [28]. In addition,
adsorption or solvation at one point on the surface can
affect adsorption at another point through deformation
of the substrate or distortion of the substrate electron
-'" UI Un-II Cl AI.

structure. Because of the complicated nature of these 30

systems, deriving accurate ab initio estimates of interac- t ......
......
.... ..
tion energies in electrochemical adsorption problems is
presently not feasible. A practical alternative is to treat 20 ~ ......
......
...... • & •• &.
& •• & ••
the interactions as adjustable parameters. Because of \
\
(Ixl)! •• & •• &
• & •• &.
the large number ofparameters and the time-consuming 10 ~
\
\
& •• & ••
•• & •• &
simulations, parameter estimation by a formal \ (0/3 x0/3}:;~
optimization procedure must often be abandoned in favor
of adjusting the parameters manually to incorporate
experimental results and other chemical information
efficiently. This method also has its difficulties. In par-
(5

~
1£
o l . ,~, --'-\
oo/A.ooo
0&0000
&0000&
0000&0
000&00
00&000

~
~
\
(0/3 xv7):I'
ticular, all potential consequences of adjusting a par- -10 \
ameter may not be easily foreseen, and often several 000000

parameters must be adjusted in concert to change a single

000000
000000
000000
, 0&00&0
-20 f 000000 &00&00
aspect ofthe model. In addition, there is no guarantee that 000000 00&00&
(lxl)8 0&00&0
the observations from two radically different sets of inter- &00&00
00&00&
actions are measurably different in the region explored (0/3 x0/3):1'
by the simulations. Nevertheless, the encouraging results
ofprevious lattice-gas studies ofelectrochemical systems
[1,4-6,16-22,25,29,30] indicate that when proper atten- Figure 1 Ground-state diagram for the lattice-gas model of
tion is paid to including all available experimental infor- copper UPD on Au(ll1), shown in the (jis, jid plane. The
mation consistently, this approach has considerable subscripts Sand C denote sulfate and Cu, respectively. The effec-
predictive power. Furthermore, as effective interactions tive interactions are given in Ref. 19. The solid lines represent
obtained by first-principles calculations become avail- zero-temperature phase boundaries, and the dotted line is a
able in the future, results from lattice-gas models will pro- zero-temperature phase boundary that is not observed in
vide crucial information for testing the consistency of room-temperature simulations. The voltammetric scan path
such first-principles interactions with experimentally for the simulations discussed here is represented as the dashed
line. Its end points correspond to E = 110 mY (upper left) and
observed thermodynamic and structural information.
300 mY (lower right) vs. Ag/AgCl, respectively. The phases are
The modeling strategy starts by using theoretical and
denoted as (X x Y)~~. The ground-state configurations corre-
experimental knowledge about the substrate structure sponding to the main phases are also shown. The adsorption
and the shapes and sizes of the adsorbate particles to for- sites are shown as 0, and Cu and sulfate are denoted by •
mulate a specific lattice-gas model. The coverages and and 6, respectively. (Adapted from Ref. 19.)
adlayer structure of different adsorbate phases can be
determined from microscopy, scattering, radiochemical
experiments, or standard electrochemical methods.
Group-theoretical ground-state calculations [26] are
then performed to determine a minimal set of effective
interactions consistent with the observed adsorbate
phases [5,25,29,30]. A ground-state diagram is obtained III. MONTE CARLO SIMULATION
by pairwise equating the ground-state energies ofthe dif-
ferent phases, as obtained from the lattice-gas Ham- A. Monte Carlo Sampling of Equilibrium
iltonian [e.g., Eq. (1) or Eq. (5)]. A typical example, Configurations
corresponding to the model discussed in Sec. IV. B., is In statistical mechanics the properties of a system in
shown in Fig. 1. equilibrium, such as the coverages and response
The finite-temperature properties of the lattice gas, functions mentioned in the previous section, are calcul-
calculated by Monte Carlo or other methods ated from the partition function
[4-6,19,22,25,29,30], can be compared with available
experiments and used to refine the effective interactions. Z = Lexp[-H(c)/RT] (10)
The process should be iterated until satisfactory agree- (e)
ment between model and experiment is achieved. New
experiments may be required to clarifY the properties of where L(e\ is over all possible configurations of the
the chemical system and refine the theoretical model. adsorbates. The expectation value ofa quantity Yat equi-
Monte Carlo Methods in lnterfacial Electrochemistry
librium is the weighted sum
I R(c' ~ c) = ex p (- H(c) - H(C'))
(Y) = - L Y(c) exp[-H(c)/RT] (II)
Z [e)
where the weight is a Boltzmann factor. For most realistic
models it is hard to calculate, or even estimate, Eq. (10)
or (II) analytically. On the other hand, Monte Carlo simu-
lation methods can be used to estimate the properties of
even quite complicated models numerically [9].
The reason for our advocacy of the nonperturbative
numerical Monte Carlo approach is that such calcu-
lations are much more accurate for two-dimensional
systems than even quite sophisticated mean-field
approximations [8]. From Monte Carlo simulations, one
can obtain thermodynamic and structural information
[9,12] using modest computational resources and pro-
gramming effort. In combination with finite-size scaling
analysis [12], Monte Carlo methods have contributed sig-
nificantly to the theoretical understandingoffluctuations
and ordering in adsorbate systems. Monte Carlo codes
also have the advantage that they are relatively easy to
modifY to accommodate changes in lattice structure
and/or interaction geometries and ranges. This is useful
when one wants to modifY the model to improve the
agreement with experiments or refurbish an existing code
to model a different system.
One Monte Carlo method for estimating Eq. (II) is to
evaluate the sum directly from randomly generated
adsorbate configurations. For most problems where tem-
perature is important, this method is inefficient because
only the most energetically favorable configurations
make significant contributions to the sum. A much more
efficient method, called importance sampling, samples
more frequently from the energetically favorable con-
figurations. Usually, this is done by using the Boltzmann
weight, the probability of an equilibrium system being in
a particular state, to determine the sampling probability
of that state. In addition, one can use the idea of detailed
balance, that the rate of going from state c to state c' in
equilibrium is the same as the rate ofgoing in the opposite
direction. If N(c) is the density ofstates for configuration
c and the probability ofgoing from configuration c to con-
figuration c' during a certain period of time is R(c ~ c'),
the transition rate is N(c)R(c ~ c'). Detailed balance
implies that
N(c) R(c' ~ c)
(12)
N(c') R(c ~ c')
To sample configurations according to the Boltzmann
51
weights, the transition probabilities need to obey
R(c ~ c') RT
(13)
An efficient Monte Carlo simulation method for
sampling the equilibrium ensemble of a lattice gas is
obtained by considering a long series of small random
changes in the configuration that obey detailed balance.
Before considering particular algorithms, it is neces-
sary to factor the transition probability into the
probability of attempting a move, A(c ~ c'), and the
probability of accepting the move P(c ~ c'), i.e.,
R(c ~ c') = A(c ~ c')P(c ~ c').
A commonly used and intuitively appealing Monte
Carlo algorithm is the Metropolis algorithm. Given a par-
ticularconfiguration, all possible changes to the configur-
ation are given the same attempt probability A. The
attempted move is then accepted with probability
. ( exp [H(C') - H(C)] . I )
P(c ~ c') = min - RT (14)
which can be verified to obey the detailed-balance con-
dition, Eq. (13), for all cases. A similar algorithm, known
by the name Glauber [31], also obeys detailed balance. It
accepts the move with probability
, I
P(c ~ c) = I + exp[(H(c') _ H(c))/ RT] (15)
The two algorithms become identical as T ~ 0, except for
H(c') - H(c) = O.
Another importance-sampling algorithm is useful
when more than two configurations are possible for the
portion ofthe surface being updated. For one move in this
heat-bath algorithm, the Boltzmann factor for every
possible configuration is calculated, and these weights
are used to randomly choose the final configuration. The
new configuration is accepted automatically, with the
initial configuration as one of the possible choices. In
the case only two configurations are possible, the
heat-bath algorithm reduces to the Glauber algorithm
[31]. That this algorithm satisfies detailed balance can be
easily verified.
Commonly, Monte Carlo updates change only one
adsorption site. However, in many applications
equilibration can be slow, either because of the large
fluctuations that occur near second-order phase
transitions (critical slowing-down [9,12]) or because of
large local energy barriers. In such cases, cluster-update
algorithms [32] that involve several related sites in one
Monte Carlo update can be useful. A specific example of
a heat-bath cluster algorithm designed to overcome
slowing down due to high local barriers against
single-particle moves is discussed in Sec. IVe.
When importance sampling is used to incorporate the
weighting, many thermodynamic averages can be esti-
mated from the moments of the sample quantities. For
example, the qth moment of the number of adsorbed
particles ofspecies X is
M; = S-I t(tc;)q
J=l 1= 1 J
(16)
where s is the number of samples taken during the
simulation. The coverage is then just
I a In
Z M1X
(17)
ex = N acfJ.x/ RT) N figurations and requires the sampling to be performed
with N the number of adsorption sites. The response
functions, ae x / aii x , which are related to the quasi- equi-
librium CV current (see Sec. II), are [33]
ae x I a2 In Z
ajix = RT a(jix/ RT)2
(18)
s M~ - (M~)2
S - I NRT
The response function is proportional to the variance of
the number of adsorbed X particles, which corresponds
to the fluctuations in the coverage. Equation (18) is an
example of the class of important results in statistical
mechanics, called fluctuation-dissipation theorems [34].
In our practical context it provides a convenient way to
calculate the response functions without numerical
differentiation. The cross-response function, aex/ajiy,
is calculated entirely analogously, using the covariance
ofXand Y
In thermodynamic regions far from any phase
transitions, the fluctuations in the numbers of adsorbate
particles have a small correlation length. The surface
can therefore be divided into independent pieces, and
the fluctuations in adparticle numbers are proportional
to the surface area. As a consequence, the relative
fluctuations, which are proportional to Jae x / ajix/ex,
vanish with system size as N- 1/ 2 • Near a second-order
phase transition, on the other hand, the correlation
length becomes comparable with the system size, and
the fluctuations and response functions depend on N as
power laws. The power-law exponents depend on the
nature of the phase transition and can be studied by
finite-size scaling techniques [12,19,35].
The actual execution of a Monte Carlo simulation
involves several steps. An initial configuration is con-
structed, followed by a sufficient number of Monte Carlo
updates to allow it to reach equilibrium. A good habit is
to construct the initial configuration using different
phases for the right and left halves of the simulated
system. This reduces the probability of relaxing to a
long-lived metastable phase rather than true equilibrium.
Also, several quantities should be sampled periodically
during the equilibration process to ensure that the system
has indeed reached thermodynamic equilibrium before
equilibrium sampling begins. Equilibrium samples
should be spaced far enough apart to be statistically
independent. This is normally not a problem in par-
ameter regions far from any phase transitions. Near
phase transitions, however, critical slowing down leads
to very strong correlations between subsequent con-
at longer intervals. Although sampling with intervals that
are too short leads one to underestimate fluctuations
and thereby response functions, sampling too
infrequently is a waste of computer time. Optimal sam-
pling can be achieved by calculating time correlation
functions [9] of the quantities being sampled and
adjusting the interval accordingly. To improve accuracy,
averages should also be performed over several trials,
each consisting ofequilibration followed by sampling.
Finally, it must be noted that there is a difference
between a single attempted move, often called a Monte
Carlo step (mcs) and the more frequently encountered
Monte Carlo step per site (MCSS). The latter is useful
because it is independent of the number of lattice sites
and represents the smallest unit of updates over which
the lattice as a whole can relax. These units should be dis-
tinguished clearly when reporting the results of Monte
Carlo simulations.
B. Dynamic Monte Carlo Simulations
In the previous subsection we discussed the basic
interpretation of Monte Carlo simulation as a method
to measure the equilibrium partition function and
moments of quantities of interest. When it is used in this
way, the simulation says nothing about the time depen-
dence ofthe system. Consequently, one can use any algo-
rithm that speeds up equilibration and reduces the
correlations between subsequent configurations. The
only requirement is that it must obey detailed balance
to ensure that thermodynamic equilibrium is indeed
reached and importance sampling can be used.
Monte Carlo Methods in Interfacial Electrochemistry 53

A very different application of Monte Carlo simu- Free energy

lation results when the numberofMCSS is viewed as time.
Then the simulation can be viewed as a "movie" of the
dynamic process. Several examples of such movies can
be found at the authors' Web site [36]. H'(3e .2e )
H'(3e ,4e )
It is clear that a particular Monte Carlo algorithm does
~
not necessarily say anything about the time evolution of H'( Ie ,4e )
the corresponding chemical or physical system unless it
is specifically constructed to do so. It is possible to con-
struct a Monte Carlo simulation that evolves like the
o
physical system, at least for dynamics that can be reason-
ably modeled as a stochastic process. This is the case when
the dynamics are dominated by thermally activated pro-
cesses such as adsorption, desorption, and diffusion.
Here we describe the recipe for transforming a lattice-gas
Hamiltonian, hopefully determined to reasonable accu- Position of ion
racy by equilibrium studies, into such a dynamical model. Figure 2 Schematic free-energy surfaces for thermally acti-
Essentially, every mcs should correspond to a vated transitions in the dynamic Monte Carlo model. The text
thermally activated transition between states separated describes how these free-energy surfaces, based on the
by energy barriers, with the transition rates described by Butler- Volmer model, are used to calculate energy barriers
Arrhenius rates involving the barrier heights. These bar- for Monte Carlo processes. In our simulations, processes corre-
rier heights can be constructed by a method essentially sponding to adsorption, desorption, and surface diffusion are
equivalent to the Butler-Volmer approximation [27]. included.
This is done in the framework of activated-complex
theory, or transition-state theory, with the initial and final
state, the free energy of the activated complex is
states described by the lattice gas. The activated complex
cannot be represented by the lattice gas, but a free energy (20)
can be assigned to it using the model we now describe.
A schematic free-energy surface is presented in When rJ. 1-1/2, Fig. 2 is not symmetric about the activated
Fig. 2 for several possible lattice-gas configurations, k e. complex. So if He c) I-
activated-complex free energy is
°
while He c) = 0, the
First consider the two states with free energy
°
He c) = Hee) = (depicted as solid line segments). The
horizontal line segments correspond to the lattice-gas (21)
states, which are locally stable. The free energy is taken where the symmetry when rJ. = 1/2 is obvious. For the
to increase linearly as the system moves toward the acti- most general case with He c) and H(4 c), the free energy
vated complex, which occurs where the two free-energy of the activated complex is
surfaces intersect. This linear assumption for the
free-energy increase leads directly to the Butler-Volmer
equation [27]. Theheightofthe free-energy barrier associ-
ated with this case, ~, is a parameter that can be adjusted This free energy is unaltered by reflection around the
to describe particular processes. transition state. In addition, the energy barriers
In general, the slope of the free energy can also be H* -Hee) and H* -H(4 e) are not altered by shifting
adjusted to describe specific chemical systems. If the the zero of the free-energy scale.
two slopes are described by the angles eand ¢, as shown The symmetric case, rJ. = 112, gives the convenient
in Fig. 2, then changes in the activated-complex free relation
energy associated with H(e) I- 0, can be found in terms
1
of the symmetryfactor H*(e, e') = ~ + 2: [H(e) + H(e')] (23)

tan e In this case the activated-complex free energy is found by

rJ. = ----:,.------,- (19)
tan e + tan ¢ adding a constant barrier to the arithmetic mean of the
free energies of the lattice-gas states [37]. Once a consist-
For a transition from the He c) °
= state to the H(4 c) I- ° ent barrier scheme has been identified, a number of
reasonable transition rates can be constructed, subject
only to the requirement ofdetailed balance. The simplest
rate is probably the one given by
( d)
(H(e/) -H(e))
R(e -+ e/) = Va exp - RT exp - 2RT
(24)
where Va is the attempt frequency, typically on the order
of a phonon frequency (10 9_10 13 Hz). Another useful
choice is the transition dynamics algorithm [38],
Va
R(e ---+ c') = [1 + eCW(c,c')-H(c))/RT][l + e(H(c')-H'(c,c'))/RT]
(25)
which is simply the product of the Glauber transition rates
from c to the activated complex and from the activated
complex to c'.
The single-ion processes included in the dynamical
model discussed here are diffusion to nearest-neighbor
sites and adsorption/desorption at single sites.We assume
a single value for the angle in Fig. 2 for all configurations
with the moving ion near the surface, which implies
a = 1/2 for diffusion. In general, the angle associated with
an ion far from the surface has a different value, but we
make the reasonable [27] choice a = 1/2 so Eq. (23) can
be used for all microscopic processes. On the other hand,
we use a different barrier, d~, for each combination of
ion and process P (P = a for adsorption/desorption and
P = d for diffusion). The values of the d~ determine the
relative weights among the different microscopic
processes. Reasonable agreement with experimental
time scales would indicate that the combination of
attempt frequencies and barrier heights chosen is
realistic.
C. The n-fold Way
In many situations of experimental interest, a direct
implementation of an importance-sampling Monte
Carlo algorithm with Butler-Volmer transition rates
would require impossibly long simulation times. The
basic reason for this is that only a very small fraction of
attempted Monte Carlo updates may actually result in a
change of the current configuration. Because we are now
interested in the dynamical details, we cannot solve this
problem by constructing a cluster algorithm, because this
would generally change the dynamics completely. What
is needed is an algorithm that can simply reduce the com-
puter time needed to perform the large number of
unsuccessful attempts that would be made between each
successful update while remaining faithful to the original
dynamics. A class of algorithms that perform this feat
are known as rejeetion-freealgorithms [39,40]. Many such
algorithms have been invented and reinvented over the
years (see [40]), but they are all essentially equivalent. [n
these algorithms the acceptance probability is unity, but
the probability of attempting a move is based on its
Boltzmann weight. They can also be thought of as a
Metropolis or heat-bath simulation with the number of
rejected moves before the next successful move calculated
analytically. The n-fold way [39]. introduced by Bortz, et
al. is one of the best known and earliest of these methods.
Rejection-free algorithms are implemented by keep-
ing a list of all the possible moves. Each move is weighted
by its rate n, so that making a random choice from the list
is biased toward faster processes. The stochastic nature
of real processes is captured by updating the simulation
clock after each move by a random number that rep-
resents the time elapsed since the last move. For the cur-
rent configuration, the overall rate for the system to have
any move accepted is the sum of all the individual move
rates,nco Because the probability of escaping from the
current configuration has a constant rate, the elapsed
time until the accepted change has an exponential distri-
bution and can be found using
M = -n;! In(r) (26)
where r is a random number uniformly distributed on
(0,1). Here dt is a continuous time in units ofmcs.
The weighted list can be visualized as a line segment
whose length equals the sum of all the weights. Then,
choosing from the weighted list is accomplished by
picking a random point along the line segment, i.e.,
picking a number on the interval [0,1) and multiplying
by the segment length. Determining which choice this
corresponds to involves searching the list ofprocess rates.
This searching can become an important bottleneck in
the implementation of n-fold way algorithms, but the
effect can be reduced by using a binary tree to search for
the choice from the weighted list. Building a binary tree
of partial sums (of the rates) to speed up the search is not
difficult, and a great deal of help is available from many
introductory texts on data structures [41]. The rates make
up the leaves at the bottom of the tree, and the value of
each node is the sum ofall the leaves below it. As the simu-
lation proceeds, the values of the leaves change and the
nodes must be updated. Two approaches can be taken.
The simplest is to move up the tree from the changed leaf,
explicitly adding the values of the children to find the
value of the node. A faster approach is to calculate the
change in the leafvalue and add this to all the nodes above
the leaf. Unfortunately, with this faster approach,
Monte Carlo Methods in Interfacial Electrochemistry 55

truncation errors will eventually cause the nodes to not

accurately reflect the values of the leaves. Practically this
method can be used, but the entire tree should be
recalculated every hundred thousand MCSS or so.

IV. SPECIFIC EXAMPLES

A. Br on Ag(100)

Experimental CVs of bromine adsorption onto silver

(100) single-crystal surfaces display a broad peak
followed by a stronger, sharper peak at more positive
potentials [13,42]. In situ surface x-ray scattering shows
that the sharp peak corresponds to a second-order (i.e.,
continuous) phase transition from a disordered low-
coverage phase at negative potentials to an ordered
e(2 x 2) phase at more positive potentials [13]. Because
the adsorption sites for the bromine are the fourfold
hollow sites of the square Ag(IOO) surface [14,15], it is
natural to model this system with a lattice-gas Ham-
iltonian of the form given by Eq. (I) using a square lattice
of adsorption sites.
The ordered phase corresponds to a maximum bro-
mine coverage of 8 = 0.5. This is related to the adsorbed
bromine being bigger than the Ag(100) lattice spacing,
such that adsorption in nearest-neighbor hollow sites is
very unfavorable energetically. This packing feature can
be modeled as an infinitely strong repulsion between
nearest-neighbor bromine, <J>(l) = -00. Relaxing the
nearest-neighbor repulsion to finite, but large, values
does not significantly improve the agreement with exper-
iment [14]. For separations larger than this, pair interac-
tion energies are modeled by unscreened dipole-dipole
interactions:

(27)

where r(n) is the distance between sites, measured in units

ofthe lattice constant. This interaction falls offreasonably
rapidly with distance, and only interactions for n :s 13
were considered in the simulations discussed here.
This corresponds to approximately 87% of the total
dipole-interaction energy. Other lattice-gas simulations
[14] used screened dipole-dipole interactions, but the
effect ofscreening is relatively small for Be at lengths less
than the truncation used here.
If <J>(2) = 0, the only interaction is the infinite
nearest-neighbor repulsion, and the lattice-gas model is
just a hard-square model [43,44]. The hard-square model
has a critical point at j1 ~ 1.334RT, which corresponds
to the onset of percolation [44] at a critical coverage
(b)
Figure 3 Snapshots of configurations from simulation ofbro-
mine adsorption on Ag( 100) for (a) the low-coverage disordered
phase and (b) the ordered e(2 x 2) phase. The light gray circles
represent surface Ag atoms and the black circles the adsorbed
Br atoms. The Br adsorb to the fourfold hollow sites, which form
a square lattice.
8 c ~0.37 [45,46]. Below this concentration a disordered
gas ofadsorbate particles forms, but above 8 c an ordered
e(2 x 2) phase with coverage near 1/2 forms. Typical con-
figurations of the two phases are illustrated in Fig. 3.
Numerical studies of the hard-square model with
repulsive next-nearest neighbor interactions [46,47] indi-
cate that a E> = 1/4 phase (which is not seen experimen-
tally in the system studied here) also becomes important
for strongly repulsive <D(2). This constrains the repulsive
interactions in the lattice-gas model. If the interactions
are too strong, a plateau in the isotherm occurs around
E> = 1/4, in disagreement with experiments.
To generate a numerical adsorption isotherm, the bro-
mine coverage at equilibrium was measured from Monte
Carlo simulations at a discrete set of electrochemical
potentials using a simple Metropolis algorithm. Because
no finite-size scaling analysis was planned, only one
lattice size was used: a 32 x 32 system with periodic
boundary conditions. The size and boundary conditions
used illustrate general rules for simulation of lattice-gas
models:
The system size must be chosen as a multiple of the
periodicities of all important ordered phases. In the
present case this is easy, because the c(2 x 2) phase
has period two in both directions.
Unless there is a specific reason to do otherwise, one elim-
inates edge and corner effects by using periodic
boundary conditions. Geometrically, this can be
visualized as wrapping the system onto a torus. The
system size should be larger than the longest ranged
interaction to avoid wrapping all the way around.
Near critical points, fluctuations are correlated over
lengths comparable with the system size (see Sec. III).
Accurate simulation near critical points therefore
requires large systems.
Some sophistication is needed in the implementation
to make the simulation reasonably efficient. The
long-range repulsion is truncated at the 13th neighbor, a
separation of 5 lattice constants. Because of the long
interaction range, a significant amount ofcomputer time
is spent evaluating the energy change due to an attempted
move. To this end, a data structure tracking the number
of nth neighbor bromines for each site is maintained and
updated only after each successful move. For this
simulation, the Metropolis acceptance rate is around
10%, so this leads to a considerable speed-up. A more
efficient simulation using a heat-bath algorithm with
cluster updates is currently being investigated.
The experimental isotherm, determined by chrono-
coulometry [13,15] for 0.1 mM Br, is shown in Fig. 4
(circles), along with two theoretical results. The effective
electrovalence, z, can be determined from the experi-
mental isotherms by assuming the coverage depends only
on the electrochemical potential and then fitting Z to
isotherms for different electrolyte concentrations using
0.5 ~w
Frumkin I
0.4 - - Monte Carlo i
o Experiment 0.1 m~
- -- ._._~
0.3
::l~
O.O'--o~ I
·1.25 -1.00 -0.75 -0.50 -0.25
E (V vs.seE)
Figure 4 Experimental and theoretical isotherms for bromine
adsorption on Ag(lOO). The circles are chronocoulometry
results from Ref. 13. The solid curve is the numerical Monte
Carlo result, whereas the dashed curve is the best-fit
single-sublattice Frumkin isotherm. The Monte Carlo isotherm
displays the singularity associated with the phase transition,
whereas the Frumkin isotherm does not.
Eq. (2). Using the experimental results from Ref. 15, we
find Z~ -0.736, which is in good agreement with other
estimates [14,15]. With z fixed at this value and <D(2) taken
as a fitting parameter, the best fits for both the
single-sublattice Frumkin isotherm [15] (dotted line)
and the full lattice-gas model evaluated by Monte Carlo
simulations give <D(2) ~ - 24 meV ~ -2.3 kllmol.
Both theoretical isotherms agree qualitatively with the
experimental data, but there is a noticeable difference
near E> ~ 0.35 where the lattice-gas model shows the
singularity in the slope of the isotherm associated with
the phase transition. The Frumkin isotherm does not con-
tain this singularity but only a gradual crossover from
low to high coverage. In this region, there is considerably
better agreement between the experimental and Monte
Carlo results. Reproducing this behavior is important,
because the singularity gives rise to a peak in the
quasi-equilibrium CV (not shown here) that corresponds
to the peak seen in experiments. Thus, the Monte Carlo
simulations provide a theoretical description ofthe essen-
tial part of this electrochemical adsorption process that
the mean-field Frumkin isotherm cannot.
B. Cu on AU(111) in the Presence of Sulfate
In UPD, a monolayer or less of one metal is
electrochemically adsorbed onto another in a range of
electrode potentials more positive than those where bulk
deposition occurs [27]. The UPD of copper on Au(lll)
Monte Carlo Methods in lnterfacial Electrochemistry
(~~v/~
j.~'~V~
100 150 200 250 300
E (mV vs. Ag/AgCI)
Figure 5 Simulated CV profiles for copper UPD on Au(lll),
corresponding to the scan path in Fig. 1. Solid curves are
dynamic simulations with scan rate 10 mVls, whereas dotted
curves are quasi-equilibrium estimates. The model parameters
are the same as in Ref. 19.
electrodes in sulfate-containing electrolytes has been
intensively studied, both experimentally and theo-
retically. A discussion of the literature until 1995 is
included in Ref. 19. The most striking feature in CV exper-
iments on this system is the appearance of two peaks,
separated by ~50-150 mY, upon addition of Cu 2+ ions
to the sulfuric-acid electrolyte [48-51]. Typical simulation
CV profiles, estimated by both quasi-equilibrium and
dynamic methods, are shown in Fig. 5. In the potential
range between the peaks, the adsorbate layer is believed
to have a (.J3 x.J3) structure consisting of 2/3
monolayer (ML) copper and 1/3 ML sulfate [18]. This
structure, which is illustrated in Fig. 1, is strongly
supported by in situ x-ray diffraction data [52].
The two-component lattice-gas model used in Ref. 19
and 53 is a refinement of the original Huckaby and Blum
model for this system. It was extended with interactions
of intermediate range, similar to the extensions to the
original model discussed in Ref. 4. These models
are based on the assumption that the sulfate
coordinates the triangular Au(lll) surface through three
of its oxygen atoms, with the fourth S-O bond pointing
away from the surface. This gives the sulfate a triangular
footprint with a 0-0 distance that reasonably matches
the lattice constant of the triangular Au(lll) unit cell.
The copper is assumed to compete for the same adsorp-
tion sites as the sulfate. The configuration energies are
given by Eq. (5) with A = C for copper and B = S for
sulfate.
57
Just as for the Br/Ag(100) system discussed in Sec.
TV.A, the sulfate ion is sufficiently large that steric interac-
tions prevent two sulfates from binding simultaneously
to nearest-neighbor sites. This is modeled as an infinite
repulsion between nearest-neighbor sulfates, <1>~1~ =
-00. Neglecting other interactions, this corresponds
to the hard-hexagon model [17,18, 20,21], which can be
solved analytically [43,54]. In the limit of strong sulfate
adsorption, ps ---* +00, the infinite nearest-neighbor
repulsion yields a 113 ML sulfate phase. Denoting a phase
with a X x Yunit cell as (X x Y)ps, the highest density
sulfate-only phase is (.J3 x .J3)6/ .c
The (rather complicated) complete ground-state dia-
gram for a lattice-gas model of copper UPD is shown in
Fig. 1. Experimentally, the two CV peaks separate a
copper monolayer, an ordered (.J3 x .J3)ij3 phase,
and a disordered low-coverage (1 x l)~ phase. In
experiments involving sulfate but no copper, the
(l x l)~ and (.J3 x .j7)6/
5
phases are observed
[55,56]. The desire to reproduce this sulfate-only phase
largely dictated the values of the effective sulfate-sulfate
interactions used in the model [19]. In the model, more
positive electrode potentials cause the sulfate to form its
saturated (.J3 x .J3)6f3 hard-hexagon phase. However,
in reality, other chemical processes, such as surface
oxidation, probably occur before this phase is fully
achieved.
The effective electrovalences, zs and zc, must be deter-
mined from experiments [57-59]. Zhang et aI., [19]
obtained the values Zc::::; + 1.7 and zs::::; - 1.1 using data
for the dependence ofthe CV-peak separation on electro-
lyte concentration from Omar et al. [57]. These values
are consistent with independent estimates [58,59]. As
explained in Sec. II, constant-concentration isotherms
are lines of slope zs/zc in the phase diagram. The
isotherm used for this discussion is given by the dashed
line in Fig. 1for 100 ::: E::: 300 mV vs. Ag/AgCl.
Starting from the negative end, we scan in the direction
of positive electrode potential (upper left to lower right
in the figure). Near the CV peak. at approximately 185 mV
vs. Ag/AgCl, the sulfate begins to compete with copper
for the gold surface sites, resulting in a third ofthe copper
desorbing into the bulk and being replaced by sulfate.
Because of the strong effective attraction between the
copper and sulfate adparticles, a mixed (.J3 x .J3)ij~
phase is formed (Fig. I), which extends through the entire
potential region between the two CV peaks. As the CV
peak at approximately 250 mV is reached, most of the
copper is desorbed within a narrow potential range. As
it is thus deprived of the stabilizing influence of the
coadsorbed copper, the sulfate is partly desorbed,
reducing 0 s from 1/3 to approximately 0.05.
 Both equilibrium and time-dependent Monte Carlo 0.005 ~~----~------_------
\ ',',
simulations have been performed for this system, using 1,\

the same model parameters as in Ref. 19. The equilibrium

\
""\" (a)
0.004
\ \
simulations, which produced the quasi-equilibrium CV \ ' - - 24mV
,I, .

\
--,2BmV
currents shown in Fig. 5, were performed with a heat- \ "./ ...... 31 mV

~'\
.~ 0.003 - 33mV
bath algorithm. To circumvent energy barriers that " // \

"~.".~
'"
reduce the acceptance rate for single-site updates, a ~

~
E \/
cluster-update algorithm treating two nearest-neighbor ~ I
\
~/ 1,1 \
' \
""
\ "
<3 0,002 '. \
sites simultaneously was used. The simulations were " '. \ \
\
performed on a rhombus-shaped triangular-lattice sys- \

\ \ \\
,

tem of size 30 x 30 with periodic boundary conditions. 0.001

.\ \
. \
At each value of the electrode potential, the system was \ \,

\
equilibrated for between 50 and 500 MCSS, after which oI ...... /C \" - >.,..- - ...-1

sampling was preformed every 5 MCSS for up to 5000 o 200 400 600

MCSS. Averaging over 20 trials was performed, except

near the sharp peak, where 215 trials were conducted.
Dynamic simulations were also performed on a 0.1 ~~----------~--'---------~
30 x 30 system, using an n-fold way algorithm that
includes adsorption, desorption, and nearest-neighbor (b)
diffusion moves for both Cu and sulfate. We chose
va = 10 10 S-l in Eq. (24) and used the energy barriers - - -15mV

~~ = ~~ = 35 kllmol, ~~ = 55 kllmol, and

~~ = 50 kllmo!' The result for a dynamic simulation of
a CV with scan rate dEldt = 10 mV/s are also included
in Fig. 5. After initial equilibration at a constant electrode
potential and room temperature for 1 s, the dynamic
simulation proceeds by changing E in steps of 1 mY,
simulating for a time determined by the scan rate, and
then sampling once. This process is continued until the
end ofthe scan is reached. The results from each potential
scan are averaged over 75 independent simulation runs,
and separate simulations are used for the positive-going
and negative-going scans. The dynamic CV has broader
peaks than the quasi-equilibrium CVobtained from the
equilibrium simulation. The peaks are also displaced in
the scan direction, relative to the quasi-equilibrium peak
positions. Clearly, dynamic simulations provide infor-
mation about possible dynamic effects in CV exper-
iments with finite potential-scan rates.
Dynamic Monte Carlo simulations can also be used to
study the current transients that occur after the electrode
potential is rapidly stepped across a transition [60]. In this
case, the system is equilibrated on one side of the phase
transition (located by the peak positions in the
quasi-equilibrium CV), then the potential is changed
instantaneously across the transition to its final value.
The results for potential steps simulations across the
(,J3 x ,J3)1;~ ++ (I x I)~ transition are shown in Fig. 6.
Figure 6a records current transients for potential steps
that start in the ordered phase and end between 24 and
33 mV past the transition on the low-coverage side. The
first current transient corresponds to the relatively fast
.~
iii
E 0.05
~
u"
o
o 50 100
t
Figure 6 Simulated current transients after potential steps
across the (l x l)~ +-> (.j3 x .j3)~;~ transition. (a) Positive
steps; (b) negative step. The observed asymmetry is the same
in the simulations as in experiments. (Reproduced with per-
mission from Ref. 6. Copyright 1998 Elsevier Science.)
relaxation to a metastable state with slightly less adsorbed
Cu. This is followed by a second current maximum as
domains of empty surface nucleate and grow. The trend
ofthe second maximum to early times and larger currents
as the step size is increased agrees with recent exper-
iments [60].
The current transient for negative steps in the cell
potential is shown in Fig. 6b. The transient simply
decreases with time, corresponding to adsorption onto
the empty surface that does not require nucleation (i.e.,
the surface is unstable with respect to adsorption after
the potential step). This difference between the observed
Monte Carlo Methods in Interfacial Electrochemistry
transients after positive- and negative-going potential
steps across this particular transition is precisely the dif-
ference seen in experiments of Cu with S04 adsorbing
onto Au(lU) [60].
c. Urea on Pt(100)
The adsorption of urea onto Pt(lOO) surfaces requires an
even more complicated lattice-gas model, than the two
systems discussed above. Experimental and simulated
quasi-equilibrium CV currents for this system are shown
together in Fig. 7. The urea coverage 8 u, measured in situ
[6,22], changes over a narrow potential range from near
zero on the negative side of the CV peak to approximately
1/4 ML on the positive side. Ex situ LEED [6] at potentials
on the positive side of the peak show an ordered e(2 x 4)
structure, consistent with a urea coverage of 1/4 ML. On
the negative side of the peak, only an unreconstructed
(l x I) surface with 8 H = I is seen (H denotes hydrogen).
The model developed to account for these obser-
vations is based on the assumption that urea, CO(NH2h,
coordinates the platinum through its nitrogen atoms, with
the C=O group pointing away from the surface. Because
dE/dt = 0.5 rnV/s
0.08
o MC 32x32
106 MCSS
~0.06
:J(
fLI - - Cv
'0
:;::;:0.04
0.02
-120 -100 -80 -60
Potential E (mV vs. Ag/AgCI)
Figure 7 Room-temperature CY profiles for urea on Pt(lOO)
in 0.1 m HCI0 4 . Experimental (dashed curves) and simulated
(<> and solid curve) quasi-equilibrium normalized CY
currents, i/ (dE/dt), in elementary charges per mY per Pt(lOO)
unit cell, at 1.0 mM bulk urea. The dashed curves are representa-
tive negative-going voltammograms; two are shown to demon-
strate variations between individual measurements. The
effective interactions and electrovalences are given in the
caption of Fig. 4 of Ref. 22. The simulation results shown here
are for a system of 32 x 32 Pt(WO) unit cells. (Reproduced with
permission from Ref. 6. Copyright 1995 Elsevier Science.)
59
Figure 8 Left: the microscopic model for urea on Pt(lOO)
showing urea molecules with their NH 2 groups (dark gray) on
the square Pt(lOO) lattice sites and their C=O groups (C black
and 0 lighter gray) pointing away from the surface. The
hydrogen atoms are shown as single light gray spheres. Right:
a typical equilibrium configuration generated by Monte Carlo
in the ordered e(2 x 4) phase at -60 mY using the model par-
ameters given in Ref. 6. Urea molecules are shown as • on
the lattice bonds and hydrogen as • at the nodes. (Reproduced
with permission from Ref. 6. Copyright 1995 Elsevier Science.)
the unstrained N~ N distance in urea matches the lattice
constant of the square Pt(lOO) surface quite well, urea is
assumed to occupy two nearest- neighbor adsorption sites
on the square Pt(lOO) lattice. Coulometry data indicate
that the hydrogen coverage changes from near unity on
the negative-potential side of the CV peak to near zero
over the same potential range where urea becomes
adsorbed. Therefore, hydrogen is assumed to adsorb in
the same on-top positions as the urea nitrogen atoms. In
the resulting modeL hydrogen is adsorbed at the nodes
and urea on the bonds of a square lattice. Simultaneous
occupation by two or more urea molecules of bonds that
share a node is excluded, as is occupation by hydrogen
of a node adjacent to a bond occupied by urea. An
illustrative Monte Carlo snapshot of a typical e(2 x 4)
configuration with thermal fluctuations is shown in Fig. 8.
The configuration energies of this lattice-gas model
are given by Eq. (5) with A=U (urea) and B=H
(hydrogen). The effective lattice-gas interactions were
determined from ground-state calculations followed by
numerical Monte Carlo simulations of quasi-
equilibrium CV currents [6,22]. To stabilize the observed
e(2 x 4) phase, effective interactions were included
through n = 8 [6,22].
The numerical Monte Carlo simulations, which used
systems with up to 32 x 32 square-lattice unit cells, were
performed with a heat-bath cluster algorithm. The
clusters are cross-shaped regions, consisting of five
nearest-neighbor nodes plus their four connecting bonds.
After symmetry reductions, these clusters have 64 differ-
ent configurations. As a result, the code is relatively slow,
measured in CPU time per attempted update. However,
the algorithm effectively removes energy barriers due to
"jamming"configurations, especially deep in the e(2 x 2)
phase. In that phase region the cross-cluster algorithm
outperforms an algorithm based on a minimal cluster
consisting of one bond plus its two adjacent nodes by at
least a factor of several million in terms of CPU time to
achieve equilibration. The good agreement of the
quasi-equilibrium CV for the lattice-gas model with the
experimental results, which is shown in Fig. 7, again
demonstrates the utility of Monte Carlo simulations in
the study ofelectrochemical adsorption.
v. SUMMARY
Our goal has been to convince practitioners of interfacial
electrochemistry that Monte Carlo simulation is a viable
and useful research tool, well within the computational
means of most laboratories. We have described how
numerical Monte Carlo simulations oflattice-gas models
for specific electrochemical adsorption can provide
realistic estimates for a number of experimentally
observable quantities. These include strictly equilibrium
ones such as coverages and surface charges,
quasi-equilibrium quantities like CV currents for
extremely slow potential-scan rates, and genuine
nonequilibrium quantities such as current transients
and CV currents at high scan rates. Information about
model parameters, including effective lateral interaction
energies and diffusion barriers for adsorption!
desorption and lateral diffusion, can also be obtained.
In this chapter we presented detailed discussions of
three specific systems. In doing so, we attempted to give
enough detail about the simulations and references to
general texts on simulation that it should enable the
reader to write and use her or his own Monte Carlo
simulations.
Most models with realistic geometric structure and
interactions are not exactly solvable, and the solution of
even highly simplified models must be accomplished by
approximate means. Monte Carlo simulation represents
a superior alternative to most mean-field based
approaches because it provides a much more accurate
connection between the model parameters and the values
of the calculated observables. If comparison of
experimental and theoretical results is going to yield
reliable information about the values of microscopic
model parameters, Monte Carlo simulation should
usually be the method ofchoice.
ACKNOWLEDGMENTS
We thank 1. X.Wang, T.Wandlowski, and B. M. Ocko for
the permission to use their data for bromine on Ag(lOO)
in Fig. 4 and 1. X. Wang for helpful comments. We
acknowledge useful discussions on Monte Carlo simu-
lation with M. Kolesik. PA.R. is particularly happy to
acknowledge his long and fruitful collaboration with A.
Wieckowski.
Supported by Florida State University through the
Center for Materials Research and Technology and the
Supercomputer Computations Research Institute (DOE
Contract No. DE-FC05-85ER-25000) and by NSF Grant
No. DMR-963483.
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5
Electronic Structure Calculations of Polyatomic Oxyanions
Adsorbed on Metal Surfaces
Patricia Paredes Olivera and Martin Patrito
Universidad Nacional de Cordoba, Cordoba, Argentina
Harrell Sellers
South Dakota State University, Brookings, South Dakota
ABSTRACT
The adsorption of polyatomic oxyanions (SO~-, HSO",
CIO;, N0 3, PO~-, HC0 3, and CO~-) is investigated
on low index single crystal silver surfaces using ab initio
quantum mechanical calculations. The surfaces are
modeled using metal clusters having from 50 to 100
atoms. The energetics and structural aspects associated
with anion adsorption are discussed. Monovalent anions
have binding energies in the range of 50-70 kcallmol,
divalent anions in the range of 160-230 kcallmol, and
trivalent phosphate has a binding energy of343 kcallmol.
The highest binding energies are obtained on the more
open 110 surface, whereas comparable binding energies
are obtained on the 111 and 100 crystal faces. Both chemi-
cal and electrostatic processes contribute to the binding
energy of the ions. For divalent and trivalent anions, the
metal polarization is the most important contribution.
Chemical contributions involve both charge donation to
the surface and backdonation to empty levels in the
adsorbate, the first one being the most important. The
influence of external electric fields comparable with
those present in electrochemical interfaces on several
adsorbate properties such as binding energy, charge
transfer, geometry, and vibrational frequencies is also
considered. Positive electric fields increase the binding
energy of the anions that leads to shorter anion - metal
bond distances and a higher charge transfer to the
surface. Although the anion geometry distorts in the
presence of electric fields, it is always very close to that
oftypical salts.
63
I. INTRODUCTION
The structure and properties ofthe electrochemical inter-
face result from the interactions of the components ofan
electrolytic solution (anions, cations, and water) with
the metal electrode and among each other. The energetics
of these interactions covers a wide range ofenergies. Cat-
ions strongly interact with water molecules, which form
a tight hydration shell around them. This shell generally
prevents them from interacting directly with the metal
surface and restrains them to the outer Helmholtz plane
of the double layer [1]. The hydration energies of ions
roughly scale with the square of the ion charge. Typical
hydration energies for monovalent, divalent, and
trivalent cations lie in the range of 70-130,400-600, and
1000-1200 kcallmol, respectively [2]. On the other hand,
hydration energies for anions [2] are lower than for
cations, and the anion-metal interaction is strong
enough to compensate for the removal of part of the
hydration shell of the ion and adsorbed water molecules
on the electrode surface, thus giving rise to the so-called
phenomenon of specific anion adsorption. Finally, water
molecules have a weak interaction with metal surfaces.
In the case ofPt, for example, the binding energy ofwater
is around 10 kcallmol [3] and the values on other noble
metal surfaces are similar [4], because the binding ener-
gies of neutral adsorbates do not vary much among
metals [5,6].
 The specific adsorption of anions on electrode
surfaces has been investigated intensively in recent
years thanks to the development of both in situ and
ex situ techniques [7-9] that have allowed a better
understanding of adsorbate structure and bonding at
electrochemical interfaces. Specifically adsorbed ani-
ons have a profound effect on electrochemical structure
and reactivity. They alter the charge distribution and
the structure of the electrochemical interface and
therefore influence the different electrochemical pro-
cesses taking place. Many anion adsorption studies
were stimulated by the appearance of the so-called
unusual adsorption states in the voltammetric profiles
of clean ordered platinum single crystals after the
introduction of the flame treatment method of Clavilier
[10]. The reversible peaks appearing at potentials
anodic of the hydrogen adsorption - desorption region
on Pt(ll1) single crystal electrodes in acidic aqueous
media were observed with several working solutions
containing different anions [II]. The potential range in
which these states appeared was found to depend on
the nature and concentration of the electrolyte in a sig-
nificant way [II]. Today it is a well-established fact that
the anomalous peaks seen in the cyclic voltammetry
of Pt(lll) in sulfuric acid are associated with (bi)sulfate
anion adsorption [12-17].
The influence of adsorbed anions on the reactivity
of electrochemical reactions has been reported by sev-
eral authors. The electro-oxidation of methanol, for
example, is strongly inhibited by specifically adsorbed
anions [18,19]. For this reaction, anion-platinum inter-
action effects have been shown to be as important as
is the surface geometry of the catalyst [19]. The
reduction of N 20 provides another example of
anion-surface interactions influencing the kinetics of
electrode reactions [20,21]. Nitrous oxide reduction
was found to be an efficient probe of anion adsorption
on transition metal surfaces: At potentials more posi-
tive than the potential of total zero charge, the rate of
N 20 reduction decreases, indicating a competition
for surface sites between N 20 and anions. The maxi-
mum rate of N20 reduction occurs at the potential of
total zero charge at which no anion adsorption is
expected.
The influence of adsorbed anions on the under-
potential deposition (UPD) process has also been in-
vestigated by several authors [22-38]. The structures of
UPD monolayers on gold [22,23] and platinum [24,25],
for example, depend on the type of anion used during
the electrodeposition process. Anions not only affect the
structure ofthe UPD layers but also influence the kinetics
and energetics of the deposition process [26-29]. In the
case of the well-studied copper UPD reaction on gold, it
is known that coadsorption of copper and sulfate are
mutually enhancing [26-29].
Among the polyatomic anions, the adsorption of
(bi)sulfate has been widely investigated [11-17,39-83] on
several metals and there are also reports of perchlorate
[52,76,77,84,85], phosphate [86-97], carbonate [98,99],
acetate [100], and nitrate [101] adsorption. A wide
variety of techniques have been used in the study of
adsorbed anions, such as infrared (IR) spectroscopy
[16,17,40-43,63-78,83,90-93,98-101], chronocoulometry
[12,54], radiochemistry [39,45-48,50,54], second har-
monic generation [55], and scanning probe microscopy
[56-62]. Other nonelectrochemical techniques such as
AES, LEEO, and CEEL [15,49,52] have also been used
in recent studies to characterize the nature of the
sulfate-surface bonding.
Therefore, understanding the chemistry of
anion-electrode interactions is offundamental import-
ance in connection to relevant electrochemical pro-
cesses such as corrosion [102], UPD [22-38],
electrocatalysis [18-21], metal phosphating [103,104],
and so on. In this chapter we investigate the nature of
anion-metal interactions from a theoretical point of
view using ab initio quantum mechanical calculations.
We mainly focus on the interactions between
polyatomic oxyanions (SO~-, HSO;, CIO;, NO],
PO~-, HCO], and CO~-) and metal surfaces in the
low coverage limit. Anion-anion and anion-solvent
interactions are not taken into account. Ab initio
studies of ionic adsorption have been mainly restricted
to monoatomic ions such as the halogen and alkali ions
[105-113] and small polyatomic anions such as SCN-
[111,114]. However, the adsorption of polyatomic
oxyanions has not been systematically investigated yet
from a quantum mechanical point of view. In this
chapter we investigate the bonding, energetics, and
structural aspects associated with anion adsorption.
Anion binding energies are calculated on different
crystal surfaces, surface sites, and for different adsorb-
ate coordinations to determine the most stable adsorp-
tion geometries on each crystal surface. The
interaction of an adsorbate with a surface induces
changes in the adsorbate geometry as a consequence
of the formation of surface bonds. In the case of ions,
this interaction is usually accompanied by charge
transfer processes. Therefore, we also discuss the relax-
ation of the anions and the nature of charge transfer
processes. Finally, to simulate the environment of the
electrochemical interface, we considered the effect of
externally applied electric fields on several adsorbate
properties such as binding energy, charge transfer, geo-
Electronic Structure Calculations
metry, and vibrational frequencies. As model surfaces
we have chosen the 111, 100, and 110 crystal surfaces
of silver.
In Sec. II we describe the theoretical methods used in
the calculations and the cluster models of the different
metal surfaces. In Sec. III we deal with several aspects of
the sulfate- metal bonding such as the molecular orbital
structure of the species involved, charge transfer pro-
cesses, and anion relaxation. In Sec. IV we focus on the
calculation of ionic binding energies from both
thermodynamic and quantum mechanical points ofview.
Finally, in Sec. IV we discuss the adsorption of anions
under externally applied electric fields comparable with
those present in the electrochemical double layer.
II. THEORETICAL METHODS
The quality of ab initio quantum mechanical investi-
gations of adsorption processes depends on two
aspects: the representation of the surface and the level
of theory used in the calculation. In the approach
followed by Pisani et al. [115], the surface is represented
by an infinite periodic lattice. This method is well
suited for the study of high adsorbate coverages. But
for low coverages, big unit cells are required, which is
computationally very costly. The disadvantage of the
method is that the energy is usually calculated at the
Hartree- Fock level, and it is difficult to go beyond that
level of theory with traditional electron correlation
methods. The alternative approach is to use cluster
models of the metal surface. In this approach, the
metal cluster-adsorbate complex is treated as a
supermolecule to which the desired level of theory can
be applied. The work of Siegbahn and coworkers
[116-118] showed that metal clusters of even modest
size are adequate to study chemisorption processes,
provided that the metal cluster electronic structure is
adequately chosen. Basically, the adsorbate electrons
must fit into the electronic structure of the cluster. For
example, in the case of a radical adsorbate that has a
singly occupied orbital, the electronic state of the
cluster must also have a singly occupied orbital with
the right symmetry for the adsorbate-metal bond to
be formed. Another key finding of Siegbahn's work
was the lack of correlation between the Fermi level of
the cluster and the chemisorption energy [118]. Clusters
of up to a hundred metal atoms are not yet big enough
to reproduce bulk metal work functions. This is in con-
flict with the conventional solid-state-oriented
understanding, where electron transfer between elec-
tronic levels on the adsorbate and the Fermi level of
the metal is normally emphasized. The explanation is
65
that the outer valence electrons of the adsorbate move
in essentially the same potential as do the outer cluster
electrons. Taking electrons from the cluster to the
adsorbate does not mean that a potential energy differ-
ence will be experienced in the process. Thus, adsorb-
ate binding energies rapidly converge with cluster size
irrespective of the cluster's work function.
The advantage of using metal clusters in chemisorp-
tion studies is that the cluster-adsorbate supermolecule
can be treated at higher levels of theory beyond
Hartree- Fock such as perturbation theory or configur-
ation interaction-based methods [119]. In this way, by
improving the level oftheory one can evaluate the quality
of the calculation. Density functional methods [120]
can also be used for the study of the cluster-adsorbate
supermolecule, but in this case it is more difficult to evalu-
ate the quality of the calculations. The theoretical
methods used to describe chemisorption and adsorbate
reactions on metal surfaces have been reviewed recently
[121].
The calculations presented in this chapter were
performed at the restricted Hartree - Fock+second-
order perturbation (MP2) level of theory. The electronic
structure program TANGO-95 [122] was used for the
calculations. The MP2 correlation energy was calculated
according to a direct scheme as described in Ref. 123.This
level of theory is appropriate for the study of closed-shell
adsorbates that do not bind to the surface through strong
covalent bonds as is the case for radicals.
In cluster studies of metals, one of the fundamental
questions is the convergence of the adsorption energy
and other properties with respect to cluster size. As out-
lined above, small clusters are adequate for the study of
neutral adsorbates [116-118]. Ionic systems, however, are
more problematic. In general, many calculations
reported in the literature involving ions have been
performed on small metal clusters ranging in size from
5 [lll] to 18 [109] atoms. But because one important con-
tribution to the binding energy of ions arises from the
metal polarization [113,114], quantitative values of bind-
ing energies cannot be obtained with small metal clusters
[109,113]. To obtain reliable binding energies of ions, the
cluster model of the surface must be large enough to
accommodate the charge transferred from/to the cluster
[124,125] and to adequately describe image charge inter-
actions [126]. For divalent anions such as sulfate and car-
bonate, for example, convergence of binding energy
with cluster size is attained for clusters with more than
50 atoms [125,127]. For the calculations reported in this
chapter, we used metal clusters with 50-100 atoms
depending on the crystal face, adsorption site, and type
of anion studied. All clusters had between three and four
uu
A.,
V coefficients were obtained by fitting to the atomic orbitals
• atoms: carbon, sulfur, and chlorine: (lIs 7p Id/6s 4p Id);
(b)
Figure 1 (a) Side view oftricoordinated sulfate anion on a 52
metal atom cluster representing the hollow site of Ag(lll). (b)
Top view showing only the first layer of atoms. Sulfate is in a
noneclipsed coordination. In the eclipsed coordination the
anion is rotated 60 degrees and the coordinated oxygen atoms
are nearly on-top of metal atoms. The six silver atoms forming
a triangle are represented by II electron silver atoms.
layers of metal atoms. In the case of the trivalent
phosphate anion, we used a 100 atom cluster (with
36/28/36 atoms in each layer) to obtain a converged bind-
ing energy.
Relativistic effects were introduced in the calculations
by means of the Huzinaga model potentials [128-130]
used to describe the core electrons of the metal atoms.
We used two types of silver atoms. The primary chemi-
sorption site was described by silver atoms with 11 elec-
trons, whereas the remainder of the atomic electron
ran.:ut::" VIIl't:l"a t::l at.
density was replaced by relativistic effect core potentials
(RECP). The atoms in the primary chemisorption site
were embedded in silver atoms with one electron. Figure
1shows side and top views ofa 52 metal atom cluster with
a sulfate ion. This three-layer metal cluster was used to
study the adsorption ofsulfate, bisulfate, and perchlorate
on the hollow site of the III surface. The triangle ofsix sil-
ver atoms in the top layer (Fig. Ib) constitutes the primary
chemisorption site and was represented by 11 electron sil-
ver atoms, whereas the rest of the atoms are one-electron
atoms. Depending on the crystal surface, the primary
chemisorption site was described with five to seven silver
atoms with 11 electrons. For the more open 100 and 110
surfaces, we also considered one atom in the second layer
as part of the primary chemisorption site. The clusters
were built using the bulk metal distance of 2.884 A for
silver [131].
The basis set used for the 11 electron silver atoms is a
(7s Ip 2d/3s Ip 2d) RECP basis set. The contraction
and orbital energies as obtained from relativistic
Hartree- Fock calculations in which the Darwin and
mass-velocity corrections are taken into account. The
basis sets for the 1 and 11 silver atoms were given in Ref.
124. The following basis sets were used for the adsorbate
nitrogen and oxygen: (9s 5p Id/4s 2p Id), and (11s 7p/4s
2p), respectively; hydrogen: (4s Ip/2s Ip). All these basis
sets are of double zeta quality and include polarization
functions in the central atom ofeach adsorbate.
III. ANION METAL BONDING:THE SULFATE
ION
As outlined in the Introduction, the adsorption ofsulfate
has been the most studied on several metals. Therefore,
in this section we investigate the nature of the
sulfate-metal bonding from different points of view. We
first consider the orbital structure of the bare sulfate ion
and then that of the sulfate-cluster system. The two
highest occupied molecular orbitals of sulfate are shown
in Figs. 2 and 3. These orbitals are mainly centered around
the oxygen atoms, and in the case of the HOMO (Fig. 3)
there are no contributions from the orbitals of the sulfur
atom. The orbital in Fig. 2 is a (J bonding orbital, whereas
the HOMO shown in Fig. 3 has a nonbonding character.
On the other hand, the lowest unoccupied molecular
orbitals (LUMOs) of sulfate have a strong contribution
from the sulfur orbitals, mainly centered around the
sulfur atom. Figure 4 shows the LUMO of sulfate, which
Electronic Structure Calculations
Figure 2 0.05 Isocontour ofsulfate high lying orbital. Note the
contribution from the oxygen pz orbitals. The positive lobe is
light gray with contour lines and the negative one is dark gray
with a wireframe. The spheres indicate the atoms.
Figure 3 Top view of 0.05 isocontour of sulfate HOMO. The
sulfur orbitals do not contribute to the HOMO.
67
Figure 4 0.05 Isocontour of sulfate LUMo. The orbital is
mainly centered around the sui fur atom.
is a (J* Mo. The next antibonding orbital is very close in
energy to the LUMO and is a n* MO in the O-S-O
fragment and a (J* MO for the other two S-O fragments.
Figure 5 shows a detail of the HOMO of the
sulfate-cluster system around the primary chemisorp-
tion site for noneclipsed sulfate adsorbed on a 52
atom cluster (Fig. 1). The main contribution to the MO
from sulfate comes from the pz orbitals of the
oxygen atoms. The orbital has stronger contributions
from the oxygen atoms coordinated to the surface than
from the noncoordinated ones, suggesting that the
noncoordinated oxygens lose more charge than the
coordinated ones. On the other hand, the sulfate-metal
cluster HOMO has no contributions from the sulfur
atom. Figure 5 indicates that the HOMO of the
sulfate-metal cluster system originates from the interac-
tion between the high lying orbitals of free sulfate with
the orbitals of the bare cluster. The main contribution
from sulfate to the HOMO in Fig. 5 certainly comes from
the sulfate MO shown in Fig. 2.
The contributions from the metal to the high lying
MOs of the sulfate-cluster system come mainly from the
sand p orbitals ofsilver. Only a minor contribution from
the d orbitals was observed. The minor participation of
the silver d orbitals in the bonding is also evidenced in
the changes of the gross charge populations for s, p, and
d orbitals of the silver atoms in the primary chemisorp-
tion site as shown in Table 1. After the adsorption of
uo ran:ut=:-s Ullvt:£a t:l al.

responsible for the bonding has also been reported by

other authors [121]. Several ab initio calculations have
shown that the interaction between the metal s, p electro-
ns, and nonmetal adsorbates is the principal contributor
to the energetics of metal-adsorbate bonding. Wahlgren
et al. [133] have shown that in the chemisorption ofoxygen
on copper, for example, the participation of the Cu 3d
orbitals in the covalent bond is small and that it only
accounts for a small fraction of the total binding energy.
Torras et al. [134] and Ricart et al. [135] also investigated
the degree of participation of the silver d electrons in the
oxygen chemisorption bond and found that at the SCF
level of theory, the d orbitals only account for 20% of the
total binding energy ofoxygen.
The involvement of the virtual p orbitals of silver
together with the high lying occupied orbitals of sulfate
in the sulfate- metal cluster HOMO indicates the interac-
tion between the occupied orbitals of the adsorbate and
the empty levels of the metal. From this interaction, a
Figure 5 Detail of the HOMO (0.003 isocontour) for
noneclipsed sulfate on a 52 metal atom cluster around the pri-
charge transfer from the adsorbate toward the metal is
mary chemisorption site. Only two silver atoms can be seen. expected. This charge transfer is observed in the Mulliken
The main contribution to the HOMO from sulfate comes from populations of sulfate as indicated in Table 2. The sulfate
the pz orbitals of the oxygen atoms. The coordinated oxygens ion loses ca. 0.4 electrons toward the metal and most of
have a stronger contribution to the MO than the that charge comes from the noncoordinated oxygen
noncoordinated oxygen atom. atoms as expected from molecular orbital considerations.
The charge transferred toward the metal is clearly
Table 1 Changes in the Gross s. P. and d Mulliken Populations
appreciated in electron density difference profiles per-
of the Metal Atoms in the Primary Chemisorption Site upon pendicular to the metal surface. For sulfate, the metal
Sulfate Adsorption for theTwo Sets of Equivalent Atoms cluster and the sulfate-cluster system, the electron density
p(x,y,z;) was integrated along the x and y coordinates to
Atom set s p d obtain p(z), the electron density perpendicular to the
surface. With p(z) we calculated the electron density dif-
Eclipsed I -0.35 0.04 -0.01
2 -0.03 -0.05 0.003
Noneclipsed 1 -0.09 -0.46 -0.100
2 -0.02 -0.41 -0.08 Table 2 Changes in Charges of the Sulfate
Monocoordinated 1 -0.28 -0.03 -0.01 Atoms After Adsorption for Different
2 -0.04 -0.04 0.002 Coordinations

Set 2 corresponds to the atoms in the vertices of the triangle shown in Eclipsed S 0.004
Fig. Ib while set I corresponds to the other three equivalent atoms. O(coord) -0.10
O(uncoord) -0.14
Total -0.42
Noneclipsed S 0.03
sulfate, the gross charge population of the d orbitals O(coord) -0.08
remains virtually unchanged, whereas the sand p gross O(uncoord) -0.15
populations show that the silver atoms in the primary Total -0.35
Monocoordinated S -0.02
chemisorption site lose some charge as a consequence
O(coord) 0.06
of the adsorption of the negatively charged adsorbate
O(uncoord) -0.11
[125]. The same trend concerning the involvement of d Total -0.28
orbitals in the bonding has been observed for SH and
SCH 3 specie adsorbed on silver and gold surfaces [132]. Negative numbers indicate that charge is lost with respect
The fact that the sand p bands of the metal are mainly to free sulfate.
Electronic Structure Calculations 69

third second first

layer layer layer 0 S 0
0.2

::J
CO 0.1
--~
c: 0.0
OJ
....
OJ
:::
'0

->- - 0.1
"fj)
c:
OJ
\.

'0 - 0.2
c:

-0
....
( .J
OJ
W
- 0.3

- 0.4
-7 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6

Z / A
Figure 6 Electron density difference along the coordinate perpendicular to the cluster surface for sulfate adsorbed on the hollow site
ofAg(lll) via one (- ...) and three (--) oxygen atoms. The vertical solid lines indicate the metal atom layers. The vertical dashed lines
indicate the position of the oxygen and sulfur atoms oftricoordinated sulfate (eclipsed mode). Note the accumulation of charge in
the cluster and the depletion of charge around sulfate.

ference P(z)sulfate-c1uster - P(Z)c1uster - P(Z)sulfate, which is

plotted in Fig. 6 for mono- and tricoordinated sulfate on
the hollow site of Ag(lll). The figure shows an accumu-
lation of charge in the cluster together with a depletion
I 0.05 a.u.

of charge around the sulfate ion. Charge is accumulated

between the first two layers and around the third
layer. The accumulation of charge in the cluster for
tricoordinated sulfate is higher than for mono-
coordinated sulfate, a fact which is also revealed in the
Mulliken populations (Table 3).
Table 2 also shows an increase in the sulfur charge for coordinated - - _
adsorbed sulfate with respect to free sulfate. Because all
the lowest unoccupied MOs of sulfate are centered
around the sulfur atom (Fig. 4), this charge increase is
Figure 7 Electron density difference map in the O-S-O
indicating a backbonding as a consequence ofthe interac-
plane of an eclipsed coordinated sulfate. The plot shows a
tion between the occupied orbitals of silver and the net accumulation of electron density around the sulfur atom.
unoccupied ones of free sulfate. The increased electron The coordinated and noncoordinated oxygen atoms are
density around the sulfur atom is shown in Fig. 7, which indicated.
IU ran:ut::s Vllvt:ca t:l al.

Table 3 Anion Binding Energies on Different Crystal Surfaces, Adsorption Sites, and Orientation of the Adsorbate

Anion Crystal Ads. site Orientation Symmetry Charge transfer BE (kcal/mol)

SO~- Ag(100) Hollow O-bridge C2v 0.40 147

O-top C2v 0.33 154
Bridge O-hollow C2v 0.38 156
O-top C2v 0.38 147
Top O-hollow C2v 0.35 109
O-bridge C2v 0.39 III
Ag(llO) Hollow O-hollow C2v 0.38 187
O-bridge C2v 0.40 179
Bridge O-hollow C 2v 0.32 145
O-top C 2v 0.36 142
Top O-bridge C2v 0.31 129
O-top C 2v 0.32 117
Ag(lll) Hollow Eclipsed C 3v 0.42 154
Noneclipsed C 3v 0.35 159
Monocord. C 3v 0.28 129
Bridge O-hollow Cs 0.36 135
Top Tricoord. C 3v 0.41 119
C0 23- Ag(100) Hollow Monocord C 2v 0.49 184
Bicord. C 2v 0.52 196
Ag(llO) Hollow Monocord. C 2v 0.42 200
Bicord. C 2v 0.50 227
Ag(lll) Hollow Tricord. C 3v 0.53 183
POl- Ag(Ill) Hollow Noneclipsed C 3v 0.90 343
CI0 4 Ag(lll) Hollow Noneclipsed C 3v 0.18 48
N0:J Ag(100) Hollow Bicord. C 2v 0.20 53
HS0 4 Ag(lll) Hollow Noneclipsed Cs 0.20 58
HC0:J Ag(lOO) Hollow Bicord. Cs 0.25 74

The symmetry of the anion-cluster system and the charge transferred to the metal are also indicated.

is an electron density difference plot between adsorbed
sulfate and free sulfate. The electron density difference
corresponds to the plane that contains the O-S-O
fragment. Around the oxygen atoms there are regions of
charge accumulation and charge depletion that on aver-
age produce a decrease of the electron density around
these atoms, whereas there is a net charge accumulation
around sulfur. The increased electron density around the
sulfur atoms has been observed experimentally by
Wieckowski and coworkers using core electron energy
loss spectroscopy for (bi)sulfate adsorption on both
Pt(111) [15] and Au(111) [49] surfaces.
The sulfate-silver bond is similar in many respects
to the bonding of S02 to this metal. As with sulfate,
the LUMO of free S02 is predominantly centered on
the sulfur atom. The bonding of sulfur dioxide to silver
is dominated by the interaction between the LUMO
of the adsorbate and the 5s and 5p orbitals of the
substrate [136]. Thus, S02 acts as a strong electron
acceptor that leads to an increase in the electron den-
sity around sulfur upon chemisorption. Rodriguez [136]
found an increase in the sulfur charge of about 0.4 elec-
trons for S02 adsorbed with its plane perpendicular
to the Ag(llO) surface. Similarly, Sellers and
Shustorovich [137] found charge transfers of up to 0.83
electrons for different coordinations on different silver
surfaces. This charge transfer is consistent with the
large electron affinity of S02 in the gas phase (Ll eV
[131]). Other similarities between the S02 and sulfate
bondings have been outlined in Ref. 125 based on the
analysis of the laplacian of the electron density [138]
of the adsorbates. But because sulfate is a charged
adsorbate, electrostatic interactions with the metal are
also expected to have an important contribution to
the bonding. These interactions are considered in detail
in Sec. IV.B.
Electronic Structure Calculations
IV. ION BINDING ENERGIES
The binding energy ofsimple ions can be calculated from
thermodynamic data and from quantum mechanical
calculations. This fact allows us to check the quality of
quantum mechanical calculations based on cluster
models of metal surfaces vs. the thermodynamic
prediction. However, in the case of polyatomic anions,
thermodynamic data are not always available and the
binding energy can only be obtained from quantum
mechanics. In this section we first evaluate the quality of
ab initio binding energies for simple ions and then in Sec.
IYB. we calculate the binding energies ofpolyatomic ani-
ons and discuss the factors contributing to their
magnitude.
A. Thermodynamic Aspects
The binding energies of ions on metal surfaces in the low
coverage limit can be calculated with the Schottky
equations [139] that take the following form for a
monovalent cation and anion:
Qcalion = Qneutral + IP neutral - <D (I)
Qanion = Qneutral + EAneutral + <D (2)
Qneutral is the binding energy ofthe neutral species, IP the
ionization potential of the neutral species, and EA is its
electron affinity. <D is the work function of the metal. In
the case of proton and hydride ions, for example, the
neutral species is the hydrogen atom. Equations (I) and
(2) can be derived using appropriate thermodynamic
cycles [124,140]. Equation (I) shows that the heat of
adsorption of the cation differs from that of the neutral
by the difference between the ionization potential of the
neutral adsorbate and the work function of the clean
metal. For the anion [Eq. (2)], the heat of adsorption dif-
fers from that of the neutral by the electron affinity of the
neutral and the work function of the clean metal. In the
case of polyatomic ions (such as sulfate), these equations
may not be useful because the binding energy of the
neutral species is not generally known and the neutral is
usually unstable on the surface. However, for those
monoatomic ions whose Qneutral is known, Eqs. (I) and
(2) can be used to test the quality ofab initio calculations.
As test cases, we will calculate the binding energies for
the proton and hydride ions on silver. For this case we
have Qneutral = Qhydrogen = 51 kcal/mol [5], IPhydrogen
= 313kcal/mol, EAhydrogen = -18kcal/mol [131], and
<D Ag = 109 kcal/mol [131]. With these values we obtain
Qcation = 255 kcal/mol and Qanion = 142 kcal/mol. In
Ref. 124 we investigated the convergence of the proton
71
and hydride binding energies on metal cluster of different
size modeling the hollow site of Ag(lll). For the biggest
metal clusters, we obtained proton and hydride binding
energies in the ranges 245-249 and 124-130 kcal/mol
(at the Hartree- Fock level) that agree well with the
thermodynamic values of 255 and 142 kcallmol. In the
case of the OH- anion, the binding energy calculated
with Eq. (2) is 102 kcallmol and the value obtained from
ab initio calculations is 108 kcallmol [140]. Thus, we see
that ab initio calculations can yield quite accurate binding
energies for ions provided that metal clusters of adequate
size are chosen [124].
B. Ab Initio Binding Energies of Polyatomic
Anions
Table 3 lists anion binding energies and charge trans-
ferred to the metal calculated for different crystal surfaces
and adsorption sites and for different adsorbates
orientations on the adsorption site. The symmetry of the
adsorbate-metal cluster system is also included. All the
binding energies reported in Table 3 were calculated with
optimized adsorbate geometries. The influence of the
adsorption process on the adsorbate geometry is investi-
gated in the next section.
Before discussing the data in Table 3, a few comments
about the adsorbate coordinations studied are necessary.
The noneclipsed coordination of sulfate on the hollow
site of Ag(lll) is that shown in Fig. 1. The same
coordination was used to calculate the binding energies
of the bisulfate, perchlorate, and phosphate ions on the
hollow site ofAg(ll1). On Ag(lOO) and Ag(llO) we studied
bicoordinated sulfate on different surface sites as shown
in Fig. 8. The nomenclature refers to the position of
the sulfur atom as a reference and the position of
the coordinated oxygen atoms that may be pointing to
hollow, bridge, or top sites. For carbonate. nitrate, and
bicarbonate. the binding energies were calculated on the
hollow sites of Ag(lOO) and Ag(llO) with the plane of the
adsorbate perpendicular to the surface as shown in Fig.
9 for carbonate.
Table 3 shows that for the most stable coordinations,
the binding energy of monovalent anions is in the range
of50-70 kcallmol, whereas divalent anions have binding
energies in the range of 160-230 kcallmol. For trivalent
phosphate, the binding energy is 343 kcallmol.
Regarding the crystal face (and for the most stable
coordinations), the highest binding energies are obtained
on the more open 110 surface, whereas comparable bind-
ing energies are obtained on the III and 100 crystal faces.
For example, sulfate has a binding energy of 159 kcallmol
on Ag(lll) and 187 kcallmol on Ag(1lO), whereas
(a)
:l.
O-bridge O-hollow
>l.
(b)
... O-tap O·hallow
a,( :I-
(c)
~
O-bridge O-top
Figure 8 Side views of the sulfate coordinations investigated
on the (a) top, (b) bridge, and (c) hollow sites of the Ag(100)
surface.
carbonate has 183 kcal/mol on Ag(ll1) and 227 on
Ag(llO). This is to be expected based on arguments of
conservation of bond order [5,6]: On the more open 110
surface, the bond order between the surface metal atoms
and the other metal atoms is lower than in the case of
closer surfaces, and therefore these less coordinated sur-
face atoms bind more strongly to adsorbates.
The energetics of bisulfate adsorption of platinum
electrode were investigated from the modeling of adsorp-
tion isotherms by Bockris et al. [44]. For the process of
putting a bisulfate ion on the electrode surface from
vacuum, they obtained an enthalpy change of
94 ± 4 kcallmoi. This value consists ofat least two contri-
butions [44]: the bond between the metal and the ion
and the interaction of the ion with adsorbed water mol-
ecules and with the water molecules in solution surround-
ing it. After substracting the ion-water interactions,
they obtained a value of 51 ± 14 kcal/mol for the
bisulfate-platinum interaction when the ion is adsorbed
by three ofits oxygen atoms. Our bisulfate binding energy
calculated on hollow site of Ag(ll1) for tricoordinated
.l.
Figure 9 Carbonate ion on the hollow site ofa 66 metal atom
cluster model ofthe 100 surface ofsilver.
bisulfate (Table 3) is 58 kcallmol. This value is in good
agreement with thatof Bockris et aI., taking into account
that they correspond to different metals. However,
adsorbate binding energies do not differ too much among
the noble metals [4,5]. For example, sulfate binding ener-
gies on silver and gold only differ by 10% [125], and the
same trend is observed for halide binding energies on
the most stable sites of Ag and Pt [113].
To understand the trends in Table 3, we need to con-
sider first the different contributions to the binding ener-
gies of ions. There are many techniques for analyzing
the nature of the bonding of adsorbates to cluster models
of metal surfaces [141]. One such method is the so-called
constrained space orbital variation (CSOV) method
[142,143], which allows the decomposition of the binding
energy of adsorbates into its many contributions. In
general, the contributions to the binding energy of anions
arise from the following processes: the repulsion
originating from the nonbonding overlap ofthe occupied
orbitals of the adsorbate and the metal cluster (this inter-
action is known as the Pauli repulsion and its effect is to
lower the binding energy), metal polarization induced
by the adsorbate, donation of charge from the surface to
the adsorbate, polarization of the adsorbate, and charge
transfer from the adsorbate to the metal surface. Except
for the Pauli repulsion, all the other contributions
increase the magnitude of the binding energy. We can
classifY these interactions as chemical and electrostatic.
Pauli repulsion, metal polarization, and adsorbate
polarization are electrostatic interactions, whereas
charge transfer processes are associated with chemical
bonding.
Electronic Structure Calculations 73

A CSOV investigation [113] of halogen anions 400 - , - - - - - - - - - - - - - - - - - - - ,

C Ag(110)
adsorbed on silver surfaces showed that the main contri- 350 o Ag(100)
butions to the binding energy of the ions arise from the L;, Ag(111)

Pauli repulsion, the metal polarization, and the charge ~ 300·

transfer to the metal surface. For the Cl-, Be and r- 13.>< 250
anions, the Pauli repulsion was found to increase with
the number of electrons of the adsorbate, whereas the
->- 200
C>
Q;
co"3
c
8 coo"
e: .C:I> 4
metal polarization showed the reverse trend [113]. For 'e:"
C>
150

these anions, the charge donation contributes between "0 100

HCO'
• 3
e: \
10 and 15 kcal/mol to the binding energy [113]. These :0 HOO. 0
50 •...--1'0;
trends are also observed in the data of Table 3. On a given
H 2 &>4 ""CIO.
crystal face, the highest binding energies are obtained 0
on hollow sites for those adsorbates with a high -1 0 2 4

coordination to the surface, whereas the lowest binding q' I a.u.

energies are obtained for on-top sites. The site stability

follows the order of polarizability because hollow sites
are more polarizable than on-top sites [113]. Table 3 also
shows a correlation between the binding energy and the
charge transfer to the metal. For example, on the hollow
site of Ag(lI1), sulfate has a binding energy of 154 and
129 kcal/mol for the eclipsed and monocoordination
adsorption modes (Table 3) and the charge transferred
to the metal is 0.42 and 0.28 electrons, respectively.
The same is observed when comparing mono- and
bicoordinated carbonate on the hollow site of Ag(IOO)
and Ag(lIO). In the case of phosphate, virtually one elec-
tron is transferred to the metal. Thus, we see that both
chemical and electrostatic interactions contribute to the
binding energy. Therefore, it is important to evaluate the
magnitude of the contribution of each interaction to the
binding energy ofthe anions. From a classic point ofview,
the polarization that a point charge induces in a metal is
represented as an image charge appearing within the
metal. This interaction scales with the square of the
charge according to Coulomb's law. The linear relation
between binding energy and the square of the ions effec-
tive charge shown in Fig. 10 effectively indicates that the
metal polarization is the main contribution to the binding
energy as the ionic charge increases. However, the scatter
in the data of Fig. 10 indicates that the metal polarization
is not the only contribution. Carbonate ion, for example,
has higher binding energies than sulfate on all crystal
surfaces and this is because of a higher charge transfer
to the surface (Table 3) and possibly to lower Pauli
repulsion (carbonate has 32 electrons, whereas sulfate
has 50) as is the case for the halogen ions [113].
For comparison purposes, we also plotted the binding
energy of sulfuric acid in Fig. 10. It has a value of
26 kcal/mol and corresponds to bicoordinated H 2 S04
adsorbed through the double-bonded oxygen atoms on
the hollow site ofAg(lOO). For this adsorbate, there is only
a charge transfer of 0.08 electrons to the surface. In com-
Figure 10 Anions binding energies (for the most stable
coordinations on each crystal face) as a function of the square
ofthe anions effective charge.
parison with the isoelectronic bisulfate and sulfate
anions, the binding energy ofsulfuric acid is considerably
lower, indicating that the metal polarization is the most
important contribution to the binding energy. The dotted
line in Fig. 10 shows that for the isoelectronic series
H 2 S04 , HS0 4, and SO~-. there is a very good linearity
between binding energy and square of adsorbate charge.
For this isoelectronic series we expect a similar Pauli
repulsion with the charge density of the metal.
The charge transfer processes involved in the chemical
bonding to the surface shown in Table 3 have also been
observed experimentally. As we outlined above, the
charge backdonation leading to the accumulation of elec-
tron density around the sulfur atom has been observed
for (bi)sulfate adsorbed on Pt(ll1) [15], Au(ll1) [49], and
Rh(lll) [52]. On the other hand, the charge donation
toward the surface has been indirectly observed in the
so-called displacement experiments [14] using I [13] or
CO [144]. In these experiments, the CO or I introduced
in the cell strongly adsorbs on the surface displacing the
specifically adsorbed anions. Therefore, the charge
transfer during the desorption of the ions is the opposite
to that during adsorption. In the case of (bi)sulfate
adsorbed on Pt(lll) and Au(lI1), displacement exper-
iments [13] yield reductive transients (there is flow of elec-
trons from the electrode to the adsorbate) that shows
when the ion adsorbs there is a charge transfer toward
the surface as indicated in Table 3. However, the
(bi)sulfate chemical bonding to the surface does not seem
to be strong enough as to modifY the band structure of
the metal. Shi et al. [55] evaluated the impact of sulfate
adsorption on the band structure of gold for the 111 sur-
face (in a second harmonic generation study) and found
,.
a negligible mixing ofthe electronic states ofthe adsorbed
ion and the metal. This indicates that the main contri-
bution to the bonding is electrostatic.
Table 3 shows that the binding energy ofperchlorate is
10 kcal/mol lower than that of bisulfate, and this cor-
relates with the fact that on many metals (except on Rh
[52]) the perchlorate ion does not seem to specifically
adsorb. On Pt(lll), for example, the electrode sulfate
coverage is not affected if perchlorate ions are in solution
[15]. Why does perchlorate have a lower binding energy
than bisulfate? We need to investigate the different contri-
butions to the binding energy for each ion to answer this
question. Table 3 shows that perchlorate and bisulfate
have the same effective charge of ca. 0.8 electrons and
transfer 0.2 electrons to the metal. Therefore, the metal
polarization and charge transfer contributions to the
binding energy are the same for both ions. Also, because
they are isoelectronic species (50 electrons), the Pauli
repulsion contribution is also the same. Concerning the
anions polarizability, it has been recently shown that they
are also similar [145]. As we outlined above, the donation
of charge from the surface to the adsorbate
(backdonation) also contributes to the binding energy.
For sulfate and bisulfate, this backdonation leads to an
increased electron density around the sulfur atom (Fig.
7). But for perchlorate, a similar plot to that shown in Fig.
7 showed much less accumulation of charge around
chlorine atom. Therefore, the difference in binding ener-
gies of bisulfate and perchlorate arises from the different
degree of backbonding. The lower backdonation for per-
chlorate is to be expected because this anion has a higher
HOMO~ LUMO gap than bisulfate [145]. These consider-
ations apply when the ions adsorb on the metal from
vacuum. But in the electrochemical situation where the
reference state is the hydrated ion in solution, the specific
adsorption of an ion involves the loss of part of the
hydration shell. But for perchlorate and bisulfate ions,
hydration effects [15] do not account either for the
observed adsorption specificities. Thus, even in solution,
the difference of adsorption properties of bisulfate and
perchlorate arise from the different backbonding.
v. ANIONS UNDER AN EXTERNAL ELECTRIC
FIELD
In this section we investigate the effect of externally
applied electric fields on several adsorbate properties
such as geometry, group vibrational frequencies, binding
energy, and charge transfer to the metal. Different electric
fields perpendicular to the surface in the range
± 0.01 au = ± 5.2 x 107 V jcm were applied to simulate
the environment of the electrochemical double layer.
ran:ut:~ VIHt:Ta t:l al.
These fields are comparable with those present in an elec-
trochemical cell, because an externally applied potential
of I V creates an electric field of ~ 10 7 V jcm at the elec-
trode surface [146]. We first review the different tech-
niques used to simulate electrochemical conditions in
ab initio calculations and then present electric field effects
for several anions.
A. Polarization of the Metal Cluster
To model adsorption processes in electrochemical
interfaces, the potential of the metal electrode has to be
taken into account. Several approaches have been con-
sidered in the literature. In semiempirical methods such
as the ASED method, in which the most important par-
ameters are the orbital ionization potentials (OIP), the
electrode potential is modeled by shifting the OIPs, which
produces a change in the energy levels ofthe metal cluster
[147,148]. In the case of ab initio calculations, the elec-
trode polarization can be treated as an external uniform
electric field applied in a direction perpendicular to the
metal surface. This approach has been used in the study
of adsorbates such as CO [149,150], CN [150], NO [151],
and atomic oxygen coadsorbed with ions [152]. Another
approach considered for ab initio calculations has been
to renormalize the electron density matrix so that a metal
cluster can have a fractional charge [153]. This approach
has been used with small metal clusters (Hg3 [153] and
Pt3 [154]), because for clusters with three or more atomic
layers there can be an important redistribution ofthe sur-
face charge [153]. An interesting aspect of this method is
that it allowed a quite reasonable estimation of the metal
contribution to the double-layer capacity. In the case of
mercury, a value of -151lF jcm 2 was obtained [153]. The
modeling of electrode polarization must take into
account the change in the electronic work function of
the metal and the shift of the electronic tail with applied
electrode potential. These two aspects were considered
in Ref. 153. Because in the case ofionic species large metal
clusters with several layers are required to obtain reliable
binding energies, the method described in Ref. 153 does
not seem adequate to treat ionic adsorption. Therefore,
we modeled the electrode polarization applying external
electric fields to the metal cluster-anion system.
For the large clusters used in the calculation ofbinding
energies, both the energy of the cluster HOMO and the
cluster surface charge were found to vary linearly with
the applied electric field. The surface charge was com-
puted from the differences in the Mulliken populations
ofthe surface metal atoms with and without applied elec-
tric field. A plot of the change in the HOMO energy with
surface charge for different electric fields is linear as
Electronic Structure Calculations 75

8£ I eV ,...-- ---, 190

(a)
1.0 180

~ 001
170
0.5 ·0.0075
(;
-0,005 160
E
·0.0025
0.0 0.0025 ~
~ 150
~ noneclipsed

-0.5 0.0075 140

--
eclipsed
0.01
130
-1.0
120 monocoord.

-15 -10 -5 o 5 10 15 -6e+7 -4e+7 -2e+7 Oe+O 2 ... 7 4e+7 6... 7

F I Vern"
Surface Charge j IlCj cm2
(b)
Figure 11 Change in the HOMO energyofthe 66 metal cluster 2.5
eclipsed

of Fig. 9 as a function of surface charge for different electric

fields.
~
~ 2.0
shown in Fig. 11. The slope of Fig. 11 gives the contribution
j
of the metal to the capacity of the double layer [153]. We o
"0 monocoord.

obtained a metal capacity of -12,uF/cm2 , which is a 15

reasonable value compared with the -15,uF /cm 2
reported for mercury [153], taking into account that silver
is less polarizable than mercury. Therefore, we conclude
that large clusters are adequate to describe the main fea-
tures of electrode polarization in presence of external
electric fields.
B. Binding Energies, Charge 'n'ansfer, and
Adsorbate Relaxation
Figure 12a shows the variation of the sulfate binding
energy with applied electric field for three sulfate
coordinations on Ag(l1 1). In the case of noneclipsed
sulfate, positive electric fields increase its binding energy
up to 25 kcallmol with respect to the zero field binding
energy. The strengthening of the sulfate-metal bond as
positive electric fields are applied leads to a decrease of
the sulfate-metal distance (Fig. 12b). As expected, Fig.
12b shows that monocoordinated sulfate penetrates more
into the hollow site of Ag(111) than the tricoordinated
anion (either eclipsed or noneclipsed). The bonding to
the surface also affects the S-O bonds for both the
coordinated and uncoordinated oxygen atoms. The bond
length between sulfur and the noncoordinated oxygen
atoms decreases (Fig. 13a), and the S-O bond length
involving the coordinated oxygens increases (Fig. 13b).
This is a general trend also observed for other anions [155]
and is coherent with the conversation of bond order on
metal surfaces [5]. As the surface bond is formed between
1.0 +-----r---_--~--_--___.--___1
-6e+ 7 -4e+ 7 -2e+7 Oe+O 2e+7 4e+7 6e+7
F/Vern"
Figure 12 Variation of (a) binding energy and (b) distance
between coordinated oxygens and the surface with electric field.
the metal and the coordinated oxygens, the bond between
these oxygens and the sulfur atom weakens and conse-
quently the S-Ocoord distance increases. As a conse-
quence of the weakening of the bonding between sulfur
and the coordinated oxygens, the S-Ouncoord bond
strengthens and its bond length decreases (Fig. 13a).
For a monobasic anion such as bicarbonate, the elec-
tric field not only affects the C-O bond lengths in the
same way as for sulfate but it also affects the orientation
of the ion on the surface as a consequence of the interac-
tion between the bicarbonate dipole moment and the
external field. In the absence of external electric fields,
the CO] fragment remains nearly perpendicular to the
surface and the coordinated oxygens are in the middle
of the hollow site of Ag(lOO). But when positive (Fig. 14a)
or negative (Fig. 14b) electric fields are applied, the ion
tilts in different directions. In all cases, the atoms of the
CO] fragment remain in the same plane, indicating that
the electric field does not affect the hybridization of the
carbon atom.
 1.49 -I
---------------~---=:--;;:=_ll
1 48
(a) ! .~

~
-4:
--
1.47

14e
----""-----------------------.
~ /7;;;;;;;;;;
-
i
~
monocoord

..,'J;I 145

~ ---~~ 15.210'
~~~~
V1cm
144

rr.,
1.43

I
1 . H-6e+7
#
'»»»;»> --~
no,~
i
,
.... e+ 7 -20+7 oeTO 2e+ 7 4e+7 6... 7

F/Vcm- 1
1.82
(b)
monocoord
1.80

.«
1.58

/p;;;;//;»;
~~--------------------
~-~.~.
156
i
0
..,'" .....--...---

--
1.54

...
..../ "ii:hW .,._ . nooeclipsed
1.52
, / ------k- .. -.-~ •

1.50 A--~------------------------~--
...-:-__ ,__ ~ __----------.----_ _ -
edipsed

146 I -l
- 6e+ 7 -4e+ r ·2e+ 7 Oe+ 0 2e+7 49... 7 6e+ 7

FIVcm

Figure 13 Variation of c-o bond lengths with electric field

for the bonds indicated in the insets. 1-5.210' Vlcm

The electric field also influences the charge transfer

process towards the surface. Figure 15 shows the charge
transferred to the metal as a function of the field for
sulfate, carbonate, and bicarbonate. For the most positive
fields, sulfate and carbonate lose nearly 0.6 electrons that
are transferred to the metal. Thus, one may wonder about
the nature of the adsorbed species. In this respect, the
data in Fig. 13 indicate that the geometry of adsorbed
sulfate is very close to that of sulfate salts that have an
S-O bond length of 1.49 A [156]. CEELS experiments
Figure 14 Side view of bicarbonate equilibrium geometries
also show that the chemical statc of the adsorbate is that
on Ag(lOO) when (a) positive and (b) negative electric fields are
of a typical sulfate, because the sulfur valency is +6 applied.
[15,49,52]. Similar plots to those in Fig. 13 for carbonate
also show that the c-o bond lengths are around the
value of 2.3 A observed in Ag 2 C0 3 [156]. Therefore, the bicarbonate: The C0 3 fragment remains always in the
adsorbed species has a structure compatible with that of same plane (see Fig. 14) and the COR angle is in the range
the corresponding salt irrespective of the magnitude of 110-119° for the electric fields investigated.
the charge transfer to the metal. The same holds in the The adsorbate geometry optimizations were
case of bicarbonate. Irrespective of the electric field, the performed by keeping the metal atoms fixed according
anion has a structure that is compatible with that of to the bulk metal geometry. Although divalent and
Electronic Structure Calculations 77

06 - , - - - - - - - - - - - - - - - - - - - - - , 1140,-------------------,

eclipsed OO~·
1120
0.5
::i
<Ii 1100
Vso I em-1 eclipSed
.! 0.4 monocoord. OO~- / . . . ;;>;>;;»
II> 1060
c:
~
~ 0.3 1060
nonecllpsed
co
-5
1040
0.2

1020 +-""--...,_--~---_--...,_----I
-4e+ 7 -2e+ 7 Oe+O 2e+ 7 4e+ 7 6e+7
0.1 -1----,-----,--,----.,..----,-----,--,-------1
-6e+7 -4e+7 -2e+7 Oe+O 2e+7 4e+7 6e+7 8e+7 1e+8 FI Vem'
FI Vem-'
Figure 16 S-Ononcoord vibrational frequencies for trico-
Figure 15 Sulfate, carbonate, and bicarbonate charge transfer ordinated sulfate on the hollow site of AgOI!) for two different
to the metal as a function ofelectric field. adsorption geometries.

Frequency shifts induced by an external electric field F

trivalent anions have large binding energies, we do not
expect a large contribution to the binding energy from
the metal relaxation because of the nature of the
anion-metal bonding. Because this bonding is mainly
electrostatic, it is delocalized over the entire metal cluster
[125]. Even the anion relaxation has a small contribution
(between 4 and 10 kcallmol) to the binding energy [125].
This is not the case, however, for the localized covalent
bonding involved in the binding of organic radicals on
metal surfaces, for which the metal relaxation has been
measured [157].
c. Group Vibrational Frequencies for Sulfate
In this section we investigate the frequency shifts
induced by applied external electric fields,. Frequencies
were calculated at the SCF level. Figure 16 shows the
SO stretching frequency for the SO group perpendicu-
lar to the surface of tricoordinated sulfate. The increase
in the frequency of the SO group indicates the strength-
ening of this bond and is consistent with the decrease
of its bond length shown in Fig. 13a. The frequencies
were calculated for both noneclipsed (Fig. 1) and
eclipsed sulfate (rotated 60 degrees with respect to
noneclipsed). Figure 16 shows that the SO frequency
and its rate of change with the electric field are sensitive
to the sulfate coordination, although sulfate binding
energies for these coordinations are similar: 154.4 and
159.3 kcallmol for eclipsed and noneclipsed sulfate,
respectively.
can be expressed in terms of the surface potential rp
according to
dv dv dF d<I>
--- (3)
drp dF d<I> drp
where <I> is the work function of the metal. In the case of
cluster models of metal surfaces, the changes in the work
function are directly proportional to the changes in the
HOMO energy of the metal cluster. Therefore,
dF dF
(4)
d<I> ds HoMo
In the electric field range investigated, the HOMO energy
for the anion-cluster system decreases linearly with
increasing electric fields. d<I>/drp in Eq. (3) equals -1
because the change in the work function of a metal, A<I>
(in eV), is related to the change in the surface potential
Arp (inV), according to [158]
A<I> = eArp (5)
In the case of sulfate we obtained dv/dF = 9.69 x 10- 7
and 1.23 x 10~6cm-l/(Vcm-l) for the eclipsed and
noneclipsed coordinations, respectively (see Fig. 16).
For dF/d<I> we obtained 5.04 x 10 7 and 4.82x
107 V cm- 1leV for the same coordinations. With these
values, the rates of frequency change in terms of surface
potential, dv/d¢, are 48.8 and 59.3 cm- I IV for the
eclipsed and noneclipsed coordinations. Although there
are no IR studies on silver, we can compare these results
with IR data measured on gold in which sulfate has a simi-
lar binding energy to that on silver [125]. On Au(lll)
Edens et al. [58] obtained a frequency shift with potential
of about 80 cm- 1IV, whereas Weber and Nart [70]
reported a value of 44 cm- 1IV on polycrystalline gold.
Therefore, good agreement is achieved with the
experimental results, taking into account that our calcu-
lations correspond to the low coverage limit in which
there are no lateral interactions neither with other anions
nor with solvent molecules. Thus, we see that even in the
absence of lateral interactions, the effect of the electric
field accounts for a large part of the frequency, shift
observed under experimental conditions. The main effect
of coadsorbates and the hydration layer will be to change
the local electric field around the anion and thus induce
different frequency shifts as compared with those in the
zero coverage limit considered in this chapter.
VI. CONCLUSIONS AND FUTURE
PROSPECTS
In this chapter we investigated the bonding of polyatomic
oxyanions on metal surfaces by means of ab initio quan-
tum mechanical calculations performed at the
Hartree- Fock +second-order perturbation level of
theory. Metal clusters with 50-100 atoms were used to
model different adsorption sites on the Ill, 100, and
110 surfaces of silver. The agreement between
thermodynamic and ab initio binding energies obtained
for simple ions indicates that this level of theory together
with the large clusters used to describe the surfaces is
appropriate. Special emphasis was put on the sulfate ion
because its adsorption has been widely investigated.
There are chemical and electrostatic contributions to
the binding energies of anions. The main electrostatic
contribution is the metal polarization. This contribution
leads to a linear increase in the binding energy with the
square of the anion effective charge. The chemical contri-
butions to the bonding are the donation of charge from
the adsorbate to the metal and the backdonation to the
empty levels of the anion. Mainly, the sand p bands of
the metal are involved in the bonding with only a minor
participation of d orbitals. In the case of sulfate, the
charge donated to the metal comes from the nonbonding
electron density localized around the oxygen atoms,
whereas the charge backdonated to the anion leads to an
increased electron density around the sulfur atom whose
orbitals contribute the most to the sulfate LUMOs.
The different contributions to the binding energy ofthe
ions allowed us to rationalize the magnitude oftheir bind-
ing energies. For the isoelectronic bisulfate and perchlor-
ate anions, the only difference in the bonding was found
in the degree of backbonding, which is lower for
perchlorate. This explains the fact that the binding energy
of the anion is 10 kcallmollower than that of bisulfate.
Carbonate has a higher binding energy than sulfate due
to a higher charge transfer to the surface and probably to
a lower Pauli repulsion.
The relaxation of the anions is coherent with the con-
servation of bond order on metal surfaces: the bond
length involving the coordinated oxygen atoms with the
central atom of the anion increases as a consequence of
the bonding with the surface. In turn, the bonding
between the central atom and the noncoordinated
oxygens strengthens and its bond length decreases.
When positive external electric fields perpendicular to
the surface are applied, anion binding energies increase
and charge is transferred to the surface. This leads to
shorter anion - metal distances and to an enhanced anion
relaxation. However, the anion geometry is always very
similar to that of typical salts. This indicates that the
adsorption process does not greatly alter the chemical
state of the adsorbate.
In the case oftricoordinated sulfate, the strengthening
ofthe S-Ononcoord bond with positive electric fields leads
to an increase in the vibrational frequency for this group.
The tuning rates of 48.8 and 59.3 cm- 1IV obtained for
the eclipsed and noneclipsed coordinations account for
a large part of the frequency shift observed under
experimental conditions. The main effect of coadsorbates
and the hydration shell of the anion will be to change the
local electric field around the ion and thus induce differ-
ent frequency shifts as compared with those in the zero
coverage limit considered in this chapter.
As we outlined in the Introduction, understanding the
structure of the electrochemical interface implies the
knowledge of the interactions of the components of an
electrolytic solution among each other and the metal
surface. Of all these interactions, we have considered in
this chapter anion - metal interactions in the zero cover-
age limit. This certainly represents only the first step in
the understanding of anion-metal interactions under
electrochemical conditions. To understand the energetics
ofanion - metal bonding under electrode potentials more
positive than the potential of zero charge, interactions
between adsorbed anions need to be considered. For
example, several studies [56-62] have shown that in the
case of sulfate, an ordered layer with a (.)3 x .)7) sym-
metry is formed at high potentials on the III surface of
fcc metals. The surface coverage of 0.2 corresponding to
this structure is difficult to understand, taking into
account the coulombic repulsions among the sulfate
anions. Therefore, the hydration layer around each ion
must play an important stabilizing role. Indeed, recent
studies [159-161] show that water molecules bridge
adsorbed sulfate anions. Thus, to simulate more
Electronic Structure Calculations 79

realistically the adsorption of anions under electro- 16. PW Faguy, NS Marinkovic, RR Adzic. Langmuir 12:243,
chemical conditions, the anion hydration layer has to be 1996.
considered.Work is being done in this direction. However, 17. PW Faguy, NS Marinkovic, RR Adzic. J Electroanal
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ACKNOWLEDGMENTS Electroanal Chern 350:297, 1993.
21. GAAttard, A Ahmadi. J Electroanal Chern 389:175, 1995.
ppa. thanks the support from the Fundacion Antorchas, 22. S Manne, PK Hansma, J Massie,VB Elings, AA Gewirth.
Republica Argentina, for Grant No. A-13434/l-000112 Science 251:183, 1991.
and the support from the Consejo de Investigaciones de 23. C Chen, SM Vesecky, AA Gewinh. J Am Chern Soc
la Provincia de Cordoba (CONICOR) for AIF Grant 114:451. 1992.
No. 4401. M.P. thanks the Fundacion Antorchas, 24. H Matsumoto. 1Oda, J Inukai, M Ito. J Electroanal Chern
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28. Z Shi, J Lipkowski. J Electroanal Chern 364:289, 1994.
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1992. 144. JM Orts, FR Gomez, JM Feliu, A Aldaz, J Clavilier.
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Introduction to Advanced Electronic Structure. New 145. ST Howard. GA Attard, HF Liebermann. Chern Phys
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Methods in Chemistry. New York: Springer-Verlag, 1991. 147. P Paredes Olivera, EPM Leiva, EA Castro. AJ Arvia. J
121. JL Whitten, H Yang. Surf Sci Rep 218:55,1996. Electroanal Chern 351:65,1993.
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THEOCHEM 388:209, 1996. Electroanal Chern 369:131,1994.
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1996. Rev Lett 58:559, 1987.
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380:264,1997. 152. G Pacchioni, F lllas, S Neophytides, CG Vayenas. J Phys
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6
Quantum Chemical Modeling of Electrocatalytic Reactions,
Including Potential Dependence: Beginning Stages
Alfred B. Anderson
Case Ttestern Reserve University, Cleveland, Ohio
ABSTRACT
Three possible approaches to calculating potential
dependent properties of redox and electrocatalytic
reaction are discussed. First, it is described how the
self-consistent calculational modeling ofsurface adsorp-
tion and reactions as already used in surface chemistry
studies might be extended to include changes in electron
chemical potential by adding charges to the surface
model. Problems here center on the limitation on poten-
tial adjustment that relates to model size and electrolyte
composition and structure. In the second approach, the
potential variations are made by modifYing electrode sur-
face atom ionization potentials so that the Fermi level as
given by semiempirical cluster or band calculations
shifts. This approach focuses on adsorbed molecules
and their interactions with the electrode surface, for
which changes in potential affect the donor-acceptor
bonding interactions. Within semiempirical atom
superposition and electron delocalization molecular
orbital theory, predictions of potential dependent
decomposition of adsorbed water molecules and
adsorbed carbon monoxide oxidation reactions over
platinum electrodes have been made in this way. The effect
of electrolyte molecules in this approach is manifested
through steric and covalent bonding interactions only.
For the third approach, the focus is on calculating
mechanisms for oxidation and reduction reactions of
species either in solution or adsorbed. In this case
self-consistent ab initio calculations are performed for
the reacting system with a remote noninteracting electron
donoror acceptor species present. As the reacting system
traverses the reaction surface, a structure is reached
where its electron affinity matches the donor's ionization
83
potential so that the reacting system and the donor are
in equilibrium. The ionization potential of the donor
determines the potential of the reduction reaction. The
transition state structure may come before or after the
electron transfers; in recent studies of outer sphere O 2
reduction, these have been found to coincide. Oxidation
reactions are treated in the same way with an electron
acceptor present: At the electron transfer equilibrium,
its electron affinity corresponds to the potential. Such
studies can also be accomplished without donors or
acceptors by the equivalent approach of analyzing
the intersections of reactant and product
Born-Oppenheimer potential energy surfaces. For
reactions outside the Helmholtz plane, the electron
potential is well defined, but, as for the semiempirical
Fermi level shift approach, for studying reactions of
adsorbed molecules away from equilibrium in the over-
potential region, often the case for electrocatalysis,
setting the correct electron potential requires knowledge
of the change in electrochemical potential that occurs
through the double layer.
I. INTRODUCTION
Heterogeneous electrocatalytic reactions can be
evaluated using quantum chemical means in the same
way as heterogeneously catalyzed nonelectrochemical
reactions but with one major and interesting com-
plication: the variable electrochemical potentials of elec-
trons or holes that are available for reaction at the
electrode surface. The adjusting and fixing of this
potential, seemingly easy from the experimental view-
84 Anderson

point once the resistances throughout the electrochemi-

cal cell are understood, has been little studied
theoretically. This chapter has three objectives relating
•.. . c 2 +

to advancing the theoretical understanding of

electrocatalysis: E
1. To determine how to modifY the ab initio cluster .....Q)
C/)
IP+
model approach used for studies of chemisorption
~
and heterogeneous catalysis for use in studies of
electrocatalytic reactions and their potential depen- ~
C/)
........../ ' c+
dencies by adding charges to the surface model; o
2. To review the semiempirical electrode valence band ~
shift approach to studying potential dependent e>
electrocatalytic reactions;
3. To present an ab initio approach in which electrons or
Q)
c 9° EA
IP!················l.l EA
.
holes may be introduced at desired potentials to the W
redox site without adding charges to the surface
C-/
•........*---1
•
model.
cv
-2 -1 0 1 2
II. AB INITIO APPROACH TO MODELING Charge of system
ELECTRODE POTENTIAL CHANGES WITH
Figure 1 Energyofa cluster or primitive unit cell, U, as a func-
THE ELECTROLYTE OMITTED
tion ofcharge. Lengths ofarrows correspond to first and second
ionization potentials, IP and IP+, and first and second electron
A. Determining the Electron Chemical affinities. EA and EA-.
Potential

Modeling of potential changes can be accomplished volume (see e.g., [1]):

quantum chemically by adding or subtracting electrons
and using a wave function ofdesired accuracy. This entails
approximations in practice. A major one is that when a
J1=EF = (-aG)
an T.P
(aE)
=-
an s.v
(I)

cluster of atoms is used to model the surface, as is often

the case in heterogeneous catalysis studies, consisting
of, say, 2-40 atoms, as consistent with laboratory com-
puters, the potential changes will be stepwise instead of
continuous. Furthermore. the electrons or holes on the
cluster will repel one another so that the electronic charge
density distribution function will become polarized with
excess charges building up on edge and corner atoms,
obscuring the meaning of calculated adsorption bond
energies and other properties.
To expand the issue of incremental potential changes,
consider applying the definition of electron potential to
an extended surface or an associated cluster model. The
vacuum scale electron chemical potential, J1, and the
Fermi energy, E F , are both the partial derivative of the
Gibbs energy, G, ofthe system with respect to the number
of electrons, n, in the system at constant temperature
and pressure; alternatively, J1 is the derivative of internal
energy, E, with respect to n at constant entropy and
The differential quantity (AE/ An) in the limit of adding
one electron, for which An = 1, is the negative of the elec-
tron affinity, EA, in the low temperature limit. Another
value for AE/ An could be determined by ionizing the
cluster so that An = -1. In this case AE/ An is the negative
of the ionization potential, IF. Neither - EA nor - IP is
the electron chemical potential. Ionization potentials
are larger than electron affinities, so when E is plotted as
a function of charge, the three points do not lie on a
straight line but will be generally as in Fig. 1. As will be
seen below, the electron chemical potential in the low
temperature limit is the average of the two slopes:
-EA - IP
J1= (2)
2
This J1 is the electron chemical potential ofthe uncharged
cluster, and three calculations are needed to determine
it, one for the metal cluster, one for the negative cluster
Quantum Chemical Modeling of Electrocatalytic Reactions
with an electron added, and one for the positive cluster
with an electron removed. To find how much the electron
chemical potential decreases when the cluster charge
changes from 0 to +1, it is necessary to calculate the
second ionization potential. The resulting electron
chemical potential is given by
-IP+ - IP
fl+ = - - - - (3)
2
The potential change being modeled by removing an elec-
tron from the cluster is then
(4)
Thus, it would take four self-consistent ab initio calcu-
lations on the cluster to determine the potential change
that one is approximating by removing one electron from
the cluster or adding an electron to it. For small clusters
there will be an increase of many electron volts because
IP+ will be »EA + IPin Eq. (4). Nowconsiderthepoten-
tial change when an electron is added to the neutral
cluster. The chemical potential for the cluster with the
added electron is given by
-EA- -EA
fl- = - - - - - (5)
2
The potential change being modeled by adding an elec-
tron to the cluster is then
(6)
Because for a small cluster IP+ » EA and IP» EA-,
the shift will be several electron volts. It is therefore con-
cluded that it will be impossible to model either exper-
imentally or with ab initio calculations continual
potential changes by means of changing the number of
electrons in small cluster models for macroscopic elec-
trode surfaces. If the cluster model of the conductor is
made larger and larger, the measured and calculated
value for IP and EA and therefore fl will converge toward
the bulk surface limits.
Consider infinite two-dimensional slab calculations
using a repeating primitive unit cell of some size. Such a
cell will have atoms on two surfaces and the interior and
will represent a two-dimensional slab of the material.
A model could be chosen that is sufficiently thick, say
10 layers or so, to represent the bulk electronic band
structures satisfactorily close to convergence to the
three-dimensional bulk limit. Because of computational
restrictions, there is only a small number ofatoms on each
surface in the primitive transitional unit cell. Then,
85
adding an electron to the primitive cell will cause large
shifts in the calculated ionization potentials and electron
affinities just as discussed previously for cluster models.
Furthermore, the quantum mechanical hamiltonian will
have to include the long-range components of the elec-
tronic potential due to cells that are far removed (for
further discussion see [2]).
B. Electron Chemical Potential and
Equilibrium
Setting the electron chemical potential of a system equal
to the negative of the average of its electron affinity and
ionization potential is more than just a mathematical
approximation to the derivative (aE/anhy in the low
temperature limit [3]. Suppose a system is in equilibrium
with a contact material with electron chemical potential
fl as shown in Fig. 2. Electrons are exchanging back and
forth at the interface and there is no net charge buildup.
Making the potential of the contact material equal to
-(EA + IP)/2 for the system accomplishes equilibrium
because then the energy change for an electron from the
material rising to the contact at potential fl = E F is the
same as for an electron from the contact material inde-
pendently rising to the system. This is similar to
Mulliken's argument, only he called (EA + IP)/2 the
electronegativity of the system [4].
For a metal, EA is less than IP because an electron
bonds less strongly to an uncharged surface than to a sur-
face of + I charge. In band structure diagrams for metals,
this distinction is sometimes not made because in the
Koopmans' approximation EA and IP are the same for
~
Q')
:l0-
a>
c
UJ -EA - EF = EF + IP
Figure 2 Schematic picture ofequilibrium between a contact
material with electron chemical potential Jl = E F and a material
with electron affinity EA and ionization potential IF.
86 Anderson

them. For semiconductors and insulators EA is calcul-

ated to be less than IP in the Koopmans' approximation
and the Fermi energy, E F , is, in the low temperature limit,
modeled by the middle of the calculated band gap. The
Fermi - Dirac distribution law places the Fermi energy tt
in the gap between - EA and - IP at low temperatures as P
illustrated in Fig. 2. o - gap
Ionization measurements by fast local probes, as is
>-
0>
possible by photoemission of electrons, may yield, for
I...
Q) n tt
inhomogeneous surfaces, local IP values. Such values c m+ +
UJ
would be the consequence offorming electron holes that Itt tt
have not had time to reach their most stable surface or
bulk locations. While EA are rarely measured for k + +
surfaces, analogous local values could exist for them too. jtt tt
The thermodynamic work function of a surface, which itt tt
equals - /1, can be averaged over the whole surface, as with
the Kelvin probe surface capacitance approach, or
locally by, for example, analysis ofthe temperature depen- metal in limit semiconducter in limit
dencies of electron currents created by thermionic emi-
ssion and photoemission. state (.. 'i 2 j2 k~ 12 ma 00 pO ... )
Figure 3 Depictions ofstates for a metal and a semiconductor
in terms of occupations of orbital energy levels before the bulk
c. One-Electron Picture and Its Limitations
limit ofa continuous density ofstates is reached. This particular
The single determinant of electron spin orbitals is the state is a "double excitation."
least complicated function that is antisymmetric with
respect to pairwise permutations, thereby satisfYing the
symmetry property of fermions. The band picture for
energy states comes from this model and is widely used, >-
/empty----U
but its approximate, model, and nature are sometimes ~
overlooked. The one-electron picture is the outcome of Q)
EF-- ..-- }gap
t.TI I EF--

this approximate wave function and Koopmans' assump-
tion concerning ionization and state changes.The ground
state ofa cluster ofatoms that forms a closed-shell system
can be represented by (... , P,i. k 2 , [2, m 2 , nO, pO, ... ),
where the labeling scheme has the orbital energies
increases to the right. A small gap in energy between m
and n suggests that the cluster is a model of a metal and
a large gap suggests it is a model of a semiconductor or
an insulator. Figure 3 shows an energy level diagram for
excited states ofthese systems and Fig. 4 shows how these
one-electron electronic structures evolve into the bulk
band limit. Koopmans'approximation is the assumption
that the shapes and energies of the one-electron orbitals
as calculated for the ground state are unchanged when
the spin orbitals are reoccupied to correspond to other
states of ionization or electron excitation. Thus, in this
approximation, E F is the energy of the highest occupied
band orbital for a metal and it lies in the middle of the
band gap for a semiconductor or insulator, as depicted
in Fig. 4. Metals EA and IP are the same numbers in this
approximation and can vary by several electron volts from
the measurables that are depicted qualitatively in Fig. 2.
~OcCUPiedJI
metal serniconducter
Figure 4 Band picture based on Koopmans' model.
For the semiconductor, the energies for removing an elec-
tron from the top of the valence band or adding an elec-
tron to the bottom of the conduction band are also
rough approximations to the respective IP and EA that
would be found by measurement.
The first correction to the rigid band one-electron
approach could be correcting the Koopmans' theorem
approximation by relaxing the orbitals ofthe ionized sys-
tems that are formed when an electron is added during
the calculation of EA or removed during the calculation
of IF. Further corrections to this would require
multiconfigurational electronic wave functions for all
Quantum Chemical Modeling of Electrocatalytic Reactions 87

states of the system: ground neutral, negatively charged,

and positively charged. Ultimately, the description of
Fig. 2 would be attained.

D. Factors Influencing EA and 'P in a Simple

Model System

Not surprisingly, chemical modifications ofthe surface of

Q cr*
a metal or semiconductor may change its chemical poten-
tial. An illustrative example that could be modeled rela-
tively easily with ab initio cluster or band calculations is
the adsorption of potassium atoms on platinum. For +
single-crystal III surfaces, work function measurements
as a function of increasing K coverage show a decrease
from the Pt value of about 6 eV to the potassium value
of 2.3 eV [5]. Between 0.1 and 0.2 monolayer coverage
surface, the work function passes through a minimum at
1.2 eV A reasonable model for this dependence is charge
donation at low K coverage [6] so that, in terms of the
one-electron picture, the valence s orbital of each
adsorbed K atom has donated most of its electron density
to the Pt conduction band as shown in Fig. 5. The
stabilized bonding counterparts will have large substrate
Pt metal amplitudes. Pt atoms around the K will gain
charge density. At 0 K the charge distribution might be
represented as in Fig. 6.Whether K can donate a free elec-
tron depends on the electron affinity of the Pt surface,
the IP ofa K atom (4.339 eV), and the adsorption energy
of K + on Pt, in the series of reactions
K K1Pt Pt
Figure 5 Schematic diagram to illustrate charge transfer and (J
K(g) -+ K+(g) + e- IP(K) bonding when K binds to a Pt surface. Occupied band region
Pt + K+(g) -+ K+(ads) Eads(K+) (7) is hatched.
e- -+ e-(ads) - EA(Pt)

K(g) + Pt -+ K+(ads) + e-(ads),

!J.E = IP(K) + Eads(K+) - EA(Pt)
There may also be an equilibrium between free electrons
in the surface conduction band and trapped states shown
in the complex of Fig. 6. There is experimental evidence

~-
for Kon Ni that has been interpreted to mean the complex
in Fig. 6 was not dissociated, so that the ionization process
was as in Fig. 7. There were local surface ionization
measurements. Assuming that this is also true for K on Figure 6 Schematic cross section of the K+ IPt surface
Pt, let us write the complex as K+Pc .Then the ionization complex. (See Ref. 6.)
potential for the process,

(8) from the Haber cycle

is given by
K+ IPC -+ K + Pt -+ K+ + Pt + e- -+ K+ IPt + e-
(9) (10)
88
So the IP depends directly on the bonding energies of K
and K+ to the surface. Because small coverages of K
decrease the work function from the bare Pt surface value
and it drops further as coverage increases, it is concluded
that Eads(K) - E(ads)(K+) decreases from 1.7 to -2 eVat
the high K coverage limit. It is reasonable for the adsorp-
tion energy of K to decrease because strong ionic Pt ~ K
bonds at the surface are being replaced by weaker
covalent K~K bonds. It is likely that the adsorption
energy of K + increases as the coverage ofK on the surface
increases because K+ ~K bonds are more ionic and
consequently stronger than K+ ~Pt bonds. The changes
in coverage and potassium charge that accompany the
decreasing work function are ilIustrated in Fig. 8.
To determine the electron chemical potential as a
function ofcoverage from IF, it is necessary to determine
EA. This is not easily accomplished spectroscopicalIy
even for the clean Pt surface. For the K-covered surface,
one could contemplate the cycle
K/PC --+ K- + Pt --+ K + Pt + e- --+ K/Pt + e-
(11 )
for which
EA = Eads(K -) + EA(K) - Eads(K) (12)
Though EA(K) is known (0.50 eV) [8] and Eads(K) is
available from thermal desorption studies, Eads(K -) is
difficult to measure. The adsorption of other electron
carriers, that is, negative ions A - , could be used to deter-
mine electron affinities of surfaces according to Eq. (12)
provided Eads(A-), EA(A), and Eads(A) are available.
It is expected that the factors that cause the ionization
potential of the surface to weaken as the K coverage
increases also cause its electron affinity to weaken. The
electron chemical potential should then increase, and
the measured electrochemical potential (V) ofthe surface
should therefore decrease as the K coverage increases.
Evidence, discussed below, suggests that in at least some
cases IP and EA both change the same amount with a
given change in applied potential.
hv
~e-
< -- ~~7
C0
0+
Figure 7 Schematic cross-sections ofinitial and final states for
the photoionization ofthe K + /Pt- complex. (See Ref. 6.)
Anderson
E. Band Bending and Measurements of
Electron Potential
Consider a contact between two different
semiconducting materials with different band
gaps. Atoms in each phase near the interface wilI
accept or lose charge until an equilibrium is established
for electrons hopping back and forth across the interface
as illustrated in Fig. 9a. As shown in Fig. 9b, the material
on the left has a higher Fermi level than the material on
the right and the interface polarizes, setting up the
space-charge regions. Fast local measurements of the
electron chemical potential in the left phase at the inter-
face and in the right phase will yield Fermi energies of dif-
ferent values and in the interface intermediate values
wilI be measured, as shown in the upper band structure
diagram. However, the Fermi energy ofthe whole system
is the negative average of the electron affinity of
the system, which is that of the right phase, and the
ionization potential of the system, which is that ofthe left
phase. For slow measurements, then, the two bands
should be superimposed and the result is a system elec-
tronic structure and Fermi energy as shown to the right
in Fig. 9b.
In discussing electron transport through the interface,
the band bending picture is used. In it the equilibrium
chemical potentials, that is, Fermi levels of both phases
in contact are the same. Local measurement ofthe poten-
tial with external probes perpendicular to the interface
cross-section will produce the results in Fig. 9b, but for
electron equilibrium through the interface the Fermi level
is constant, which is why bands are drawn bent. This
bending represents the work done on or by a charge mov-
ing through the interface, through the space-charge
region. If one phase is a metal and the other a
semiconductor, there will be no space charge in the metal
and charge will be localized on a thin layerofmetal atoms
at the interface. The metal is then said to be "pinned!'All
the work is done in the space charge region of the semi-
conductor phase. Figure 9 illustrates band bending with
the left-band phase pinned. The band bending in the
right-hand phase illustrates the work that must be done
on an electron that moves from the left-hand phase
through the space charge region. This work cancels the
decrease in chemical potential the electron would experi-
ence if no equilibrium space charge region had formed.
An electron traveling from right to left through the inter-
face does work as it travels through the space charge
region, essentially spending the increase in chemical
potential that it would have in the right-hand phase ifno
equilibrium space charge region had formed. In Fig. 9,
because the left-hand phase is also a semiconductor, it
Quantum Chemical Modeling of Electrocatalytic Reactions 89

Figure 8 Schematic cross-sections of changes in charge distributions as the coverage of K is increased on Pt.
90 Anderson

e- potential. The energy ofan electron at 0 Von the electro-

(a) ~ chemical scale is -4.6 eVon the physical (vacuum) scale

left phase : II: right phase

[9].
For the sake ofgenerality, it is interesting to note that if

~... . inTerlaCe
. .
I .. 7
.. .. ... ...
all the !1Go work is done by the proton in the electrolyte,
meaning the electron conductor has no resistance, then
the proton potential of the electrode in question is

vacuum Vpr = VO (14)

(b) --level......
In this case the potential of protons increases by Vpr in
passing through the electrolyte from the anode to the cat-
~ I ~ --.~-EF-~ hode. The energy to remove a proton to vacuum at the
standard hydrogen electrode surface is about 11.3 eV [9,
fast local slow system p. 492]. Thus, it may be said as for electron ionization that

(c)
measurement

o ..
vacuum
measurement the proton ionization energy of a standard solvated
hydronium ion is 11.3 eV and the standard proton has the
energy -11.3 eVon the physical scale. At the reduction

11 ===c ------
~
level
---- - E band bending
F model
electrode its energy will be (-11.3 - !1Go jnFV) eV
If protons were sent through proton conducting wires
to do work, it would be sensible to refer to the proton
W"~
potential of a cell. For the standard hydrogen half-cell,
pinned the Vpr would be 0 V and the proton energy would be
- 11.3 eV on the physical scale.
Figure 9 (a) An interface at equilibrium between left phase, It is also possible in principle for all the work to be done
with higher electron chemical potential, and right phase, with at the cathode by generation of heat or light or chemical
lower potential. (b) Comparison ofresults offast local measure- potential energy in the reduction reaction there. This
ments and slow system measurements of EF , lp, and EA. could happen ifthe electron and proton conducting wires
(c) Band bending model for interface. Occupied band regions
both had vanishingly small resistance and no work was
are hatched.
performed along them.
In the usual circumstance, wires of good conduction
are used as electron current carriers to devices where
electromagnetic or resistance work is done and the
will probably not be pinned and will bend up at the proton conducting electrolyte in the cell has some
interface. resistive work done on it by the flowing protons that is lost
as heat. The electron potential of the cathode is reduced
according to
F. Electrochemical Potential Scale
V
Vel = VO - proton work - (15)
eV
The electrochemical potential scale is based on assigning
o V as the potential, U. of the standard hydrogen where the proton work is in eV units. This reduction will
electrode. !1Go, the change in Gibbs energy, for the redox apply to fuel cells that use acid electrolytes.
reaction on this electrode is also assigned the value of Standard reversible potentials are for standard con-
zero. The reduction potential for any other standard elec- ditions and are corrected to nonstandard activities with
trode is, providing the electrolyte offers no resistance to the Nernst equation and to other temperatures by other
charge transport, thermodynamic formulas.

Vel = VO = -!1Go jnF (13) G. EA and ,Po' Emmersed Electrodes that

Were Under Potential Control
When !1Gois less than zero, the reduction is spontaneous A number of work function or IP measurements have
and the electrode is a cathode with positive potential. been made on emmersed electrodes under various initial
When !1Go is greater than zero it is an anode with negative applied potentials. For example, studies of emmersed
Quantum Chemical Modeling of Electrocatalytic Reactions
Au, Pt, and Ag electrodes have shown that the IP vary
with a slope of 1.0 ± 0.1 eV/V between ~O and 1.2 V [10].
These emmersed electrodes retained essentially intact
double layers. The EAwere not measured, but they should
show a similar potential dependance as the surface IF
Let /1 be the difference between the EA and IP at potential
f.1.Then
(16)
and
EA = -f.1-/1/2 (17)
In the well-defined region positive ofH 2 evolution, the Pt
work function appears to be 0.1 or 0.2 eV less than for
Au for the same initial emersion potentials. Though EA
were not measured, from Eqs. (16) and (17) it may then
be deduced that EA for Pt are ~0.1 eV greater than EA
for Au over this potential range. At lower potentials the
data become scattered, perhaps due to hydrogen evol-
ution disrupting the double-layer structure relative to its
relaxed value after emmersion.
In another study involving emersion, it was estimated
that at around I V on the electrochemical scale a
monolayer of oxide formed on the surface of an Ir elec-
trode [11]. The IP continued to increase as the potential
increased despite this. It was found that a thick oxide film,
generated by anodic cycling, was stable, and measure-
ments showed it to be a new electrode system with an IP
about 1.1 eV greater than that of the nonoxidized Ir sur-
face at each potential. Although the reason for this
behavior was not known, from the present perspective,
the implication is that EA of the surface decreased 1.1 eV
upon oxidation.
The difficulties of modeling such measurable systems
with ab initio theory are formidable not only for the
reasons discussed earlier, but because electrode surface
ionization potentials and electron affinities depend on
the electrode surface and electrolyte compositions and
structures, which are generally unknown and would have
to be assumed and chosen to model the potential of
interest.
H. Other Viewpoints and Approximations on
Surface Potentials
Nuclear and electronic charge distributions at a surface
give rise to electric fields, and these are often used to gen-
erate electrostatic potentials that an infinitesimally small
nonperturbing test charge would see. Such potentials,
based on rigid charge distributions of neutral or charged
systems, have been used to interpret ionization spectra
of surface systems, such as the effect of coadsorbing K
91
on the valence p ionization potential of Xe on Rh as
measured by ultraviolet photoemission spectroscopy
[6; Janssens et al.; 12]. Such electrostatic modeling is a
qualitative classic picture that could be construed to be
the first term in a quantum mechanical perturbation
theory approach. It may connect with qualitative trends
that are subject to correction by a quantum mechanical
treatment of the relaxed ionized system. The final state
relaxations of ionized systems are reliably calculable
only by an accurate self-consistent treatment of the
initial system and the ionized system. To find E F , the
electron affinity must be similarly calculated and used
with the calculated IP in Eq. 2. Estimates of surface
potential or of the potential dependence of surface
properties will, when based on model electric fields, be
approximate.
Potential differences between electrodes have been
described in terms of various interfacial components
that are based on models. For a full discussion see Ref.
9 (p. 71).
III. ATOM SUPERPOSITION AND ELECTRON
DELOCALIZATION MOLECULAR ORBITAL
(ASED-MO) BAND SHIFT MODEL
The ASED-MO theory is a one-electron approach that
uses an adjustable hamiltonian that makes it possible to
model potential changes for electrode materials using
clusters or two-dimensional slab band models. It is a pure
play in potential, something that, as explained above,
is practically unachievable for ab initio models using
electrode surfaces. Approximation exists due to the
non-self-consistent Hamiltonian, the model size, and
any assumptions about surface and double-layer compo-
sition and structure that are made. For a cluster of metal
atoms, a change in potential in this approach is given as
the change in the negative of the energy of the highest
occupied molecular orbital at the top of the filled part of
the valence band. Thus, to model an increase in eletrode
potential, the valence band is moved down on the energy
scale, and to model a decrease the band is moved up.
IdentifYing a particular band position with 0 V on the
standard hydrogen scale is approximate. A spectroscopic
property that is characteristic of potential and calculable
by the theory would provide a means of alignment. For
reasons to be discussed in the next section, the potential
at the surface of the electrode, and hence its
donor~acceptor capability, is also a function of any
potential drop or increase in the double layer. Adjust-
ments to the amount ofband shift that is necessary to cor-
respond to a given change in applied potential will be
possible when details of the double-layer potential
92 Anderson

~
change are known, but so far a linear relationship where a
change of 1 eV in band position is assigned to a change
of 1 V in applied electrochemical potential has been
assumed.
Perturbation theory [13,14] is useful for understanding
the results of the ASED-MO band shift calculations. A
change in potential changes the extent of donor and
acceptor interactions between the surface and an
*
adsorbate, as shown schematically in Fig. 10. Both the
electrode surface and the adsorbate have donor and Ed
acceptor orbitals. When two-donor orbitals, such as two
occupied lone pair orbitals, overlap, a closed-shell
repulsion interaction exists, as shown in Fig. II. The
destabilization of the antibonding counterpart, Ed, is
greater than the stabilization, E s , and the change in elec- *0
tron orbital energy is destabilizing, as is the total energy.
This might occur when an H 20 molecule is near an oxy-
gen anion of an oxide surface. When two empty acceptor
orbitals overlap, no bonds form (unless there is an occu-
pied donor orbital close enough to participate), as shown
o E*1' S

in Fig. 12. An example might be the overlap ofempty 2 p

orbitals on two Li atoms. In this example, the p orbitals
will hybridize into the (Js orbital, stabilizing it, and the (J
orbital of mainly (J p character will have (J s mixed into it
in an antibonding way, destabilizing it. The (J; and (J;
():>
orbitals mix similarly. Figure 10 focuses on the behaviors
Figure 11 Atomic orbital-molecular orbital correlation dia-
gram for the formation of occupied a and a* orbitals from the
overlap oftwo occupied lone-pair orbitals. E s and Ed are orbital
electrode band stabilization and destabilization energies.
--....-....--..
of bonding and antibonding counterpart orbital energy
levels as the electrode surface valence band moves. As
the filled part ofthe electrode valence band, which is often
-- -..,.
- ,

!1
/' a partially (e.g., over Pt) or completely (e.g., over Au)
.",.//
~E,, F filled dband moves down, away from the acceptor orbital
(e.g., an empty CO n* orbital), the stabilization of each d
/acceptor band orbital due to mixing of the acceptor orbital
becomes less because it is given by the second-order per-
turbation theory term

2
E(2) _ 1('¥dI H 'I'¥ a )1
~~ d _ (18)
~e~ Ed - Ea
~o
.~l?>
0"".... where '¥ d is the wave function of the dband orbital, 'I' a is
\~
G~e the wave function ofthe acceptor orbital on the adsorbate,
increasing donation H' is the interaction Hamiltonian, and Ed and Ea are the
4 d and acceptor orbital energies. If ('I'dl'l'a) is zero, 'I'd
increasing back donation
.- and 'I' a have the wrong symmetry to interact and E~2) is
Figure 10 How donor and acceptor adsorbate orbitals mix zero. The stabilization becomes smaller as Ed becomes
with electrode surface orbitals as functions ofapplied potential. more stable as occurs with increasing potential. As Ed
Occupied band regions are hatched. approaches Ea , that is, approaches the resonance con-
Quantum Chemical Modeling of Electrocatalytic Reactions
-@()
@()-
Figure 12 Formation of empty a and a* molecular orbitals
from the overlap ofempty atomic p orbitals on different centers.
dition, E~2) becomes large in magnitude but the
second-order term becomes a poorer approximation
and higher order terms are needed. At resonance, simple
first-order degenerate perturbation theory applies. The
coefficient of mixing of the acceptor orbital with the d
orbital is given to first order as
c(l) = ('¥dIH'I'¥a)
(19)
Ed - Ea
According to Eq. (19), mixing of the adsorbate acceptor
orbital with the surface d orbital increases as the potential
decreases. This corresponds to polarizing the occupied
surface orbital to extend into the region ofthe adsorbate,
that is, to transfer charge to the adsorbate. Large overlap
between '¥d and '¥ a also contributes to a large
polarization. There will be many orbitals of proper sym-
metry to mix with the adsorbate acceptor orbital.
Typically, overlaps between adsorbate orbitals and d
band orbitals are relatively large, but there is also per-
turbation of empty surface s-d band orbitals by the
adsorbate. Their density of states distribution function
will be changed in shape and they will, as symmetry
allows, mix in with the adsorbate-surface bonding
orbitals.
The perturbation theory treatment of adsorbate-
donor interactions with a surface and their potential
dependence follow an outline that may be anticipated
93
from the acceptor-surface discussion. In this case the
surface, not the adsorbate, is the acceptor and the
adsorbate. not the surface, is the acceptor, and Eqs. (18)
and (19) may again be applied.
Antibonding counterpart orbital energy levels are
shown in Figs. 5, II, and 12. These are viewed through Eqs.
(18) and (19) as surface orbitals being destabilized by
antibonding mixing of the wave function of the more
stable orbital with that for the less stable one. The resulting
molecular orbital is destabilized and antibonding
because of the change in sign of the energy denominator
in the equations. Although Eq. (18) states that the
destabilization of the antibonding counterpart is the
same as the stabilization of the bonding orbital, the
destabilization is in fact larger, as a variational treatment
would show, and the unequal splittings shown in Figs. 11
and 12 are correct.
For applications of the ASED-MO band shift
method to the electrochemical potential dependence
of vibrational spectra of CN- on Ag and CO on Pt,
CO adsorption sites on Pd and Pt surfaces, C=C and
C-H bond activation on Pt and Fe surfaces, dissol-
ution of FeOH+ from Fe, and generation of O 2 on
SrFe03, the reviews of Ref. 13 should be consulted. In
each of these cases the donor-acceptor properties of
the electrode surfaces and the adsorbed molecules
and the potential dependencies of the chemical bonds
at the interfaces determined the outcomes. In these
studies, clusters represented the electrode surfaces
and the only species interacting with them were the
adsorbate molecules. In some cases the steric environ-
ment due to other adsorbed species will need to be
considered. These might include additional CO in CO
adsorption studies or the electrolyte and its derivatives,
such as H 2 0(ads), OH(ads). and H(ads). It has been
satisfactory to omit steric effects in answering ques-
tions such as why does the CO vibrational adsorption
peak shift to lower energy as the potential applied to
a Pt electrode is decreased? Why does the
equilibrium structure of CO on Pt shift away from
low-coordinate and toward high-coordinate surface
sites as the applied potential is decreased? What is
likely to happen to the stabilities of C=C and C-H
bonds in chemisorbed unsaturated hydrocarbon mol-
ecules at various potentials? What is a plausible mech-
anism for reducing water to oxygen over a surface
transition metal cation site in SrFe03?
Steric effects were, however, found to be important in a
study of the mechanisms for the removal by oxidation of
the CO(ads) poison that forms on Pt anodes during the
operation of methanol (as well as hydrogen and other
organic) fuel cells. The oxident is probably OH(ads),
94
formed according to the mechanism [15]
H20(ads) ---+ OH(ads) + H(ads) (20)
This is believed to be the rate-determining step on the
anode and its activation energy was calculated to
decrease at higher potentials. The CO(ads) oxidation
step, which goes by the mechanism
CO(ads) + OH(ads) ---+ CO 2 + H+(aq) + e- (21)
was calculated to have an activation energy that was high
and it increased at higher potentials. In fact, the surface
should be quite crowded with other CO(ads) molecules,
H20(ads), OH(ads), and possibly anions from the
electrolyte. Modeling this with ~l!2 monolayer of
CO(ads) or with ~l!2 monolayer of OH(ads) showed
reduction of the activation energy for (21) to an accept-
able value. Further analysis showed that the crowding
considerably reduced the strength of the bond between
CO and the surface so that it more easily adjusted its pos-
ition and orientation to approach the adsorbed OH.
About 15% of the steric repulsion was due to
through-space orbital overlap with the other adsorbed
CO molecules and the remaining ~85% was due to
repulsive coupling through the metal bonds. Further
work showed that substitutional surface Ru atoms in the
Pt electrode attracted and activated OH(ads) formation
by (20) at a lower anode potential [15]. Assuming that (20)
is the rate-limiting step on the fuel cell anode, this
explains the well-known catalytic effect of alloying Ru
with the Pt.
Finally. a note concerning the applicability of the
ASED-MO band shift technique to outer Helmholtz
plane oxidations and reductions. This non-
self-consistent method is usually useful only for ana-
lyzing changes in bonding in a system in the absence of
charge transfer to or from the system. Although one could
apply it naively to outer sphere electron transfer reactions,
errors in calculated structures and energies are to be
expected.
IV. AB INITIO TUNABLE ELECTRON/HOLE
SOURCE FOR REDOX STUDIES
A method is under development in this laboratory, [16,17]
for calculating the mechanisms and potential dependent
activation energies for outer Helmholtz plane redox
reactions and inner Helmholtz plane electrocatalytic
reaction that circumvents the problem of electrode
charging that was explained earlier. It is outlined in this
section and illustrated with the O 2 reduction problem.
Anderson
A. Potential at the Transition State
To model quantum chemically a reduction reaction
taking place out in the solution phase, that is, taking place
outside the Helmholtz plane, the electrode will be
regarded as a remote electron source with ionization
potential IP on the vacuum scale. As a reactant
undergoing reduction changes its structure due to
thermal motions, its electron affinity also changes. Let
the system have structures where its electron affinity
-4.6 eVequals the potential U ofthe electrode multiplied
by the electron charge, e. Then assume there is an equili-
brium between the electrode and the reactant, R, for these
structures. A search of these structures and the paths
leading to them and from them to products will yield the
activation energy, E a , for reduction at this potential. Simi-
lar calculations at other electrode potentials will generate
points for a curve of Ea vs. U In this case the electrode is
modeled by a species such as a donor molecule, D, of
adjustable ionization potential. At equilibrium, the
potential is given as above because there is, at the point
just before stepping onto the reduced product
Born--Oppenheimer potential energy surface, an equi-
librium
D+R~D++R- (22)
Noting that
D - D+ = e-(O) - IP (23)
where IP is in electron-volt units and the electron has zero
energy on the physical scale, Eqs. (22) and (23) yield
e-(O) - IP + R ~ R- (24)
Because this is at equilibrium, we have
J1 = -IP (25)
or, on the electrochemical scale,
U = (IP/eV - 4.6)V (26)
This technique has been applied in determining poten-
tial dependent activation energies for the four steps in
O 2 reduction to H 20 in acid solution, with satisfactory
results [17]. The adjustable ionization potential electron
source was either a Li or a Be atom with one coordinated
H 20 molecule. The IP was tuned by changing the
coordination distance.
To study an oxidation reaction, an electron acceptor
species of adjustable electron affinity, EA, is used. This
could be an ionized donor of the type just mentioned.
The process offinding the potential dependent transition
states and activation energies would parallel the
Quantum Chemical Modeling of Electrocatalytic Reactions
reduction process and would focus on finding the lowest
energy pathway through an equilibrium ofthe form
(27)
where A is the acceptor species and, on the electrochemi-
cal scale, the potential at equilibrium would be
U = (EAleV - 4.6)V (28)
In the case of O 2 reduction, the electron transfers
essentially coincided with the reaction transition states
because ofbond order changes that occurred at each elec-
tron transfer step. In general, electron transfers need not
coincide with transition states and could occur before or
after the transition state (maximum energy along the
reaction path) structures are reached.
It is possible to eliminate the donor or acceptor func-
tion from the calculation by making a careful analysis of
the intersections of the reaction Born -Oppenheimer
potential energy surface with that for the reduced or
oxidized product. Having the donor or acceptor in the
calculation is a matter of convenience only.
This approach embodies the radiationless tunneling
model of Gurney [18] for electron transfer from
electrodes. It focuses on the premier parameter for under-
standing homogeneous and heterogeneous catalysis, the
activation energy. It is straightforward to introduce the
catalytic perturbation and to thereby address the struc-
ture and electronic factors that are at the heart of the
understanding of catalysis. The majority of previous
theoretical studies ofelectron transfer kinetics formulate
rate constants as integrals over the product of donor and
acceptor state densities along with a tunneling factor
from model Born -Oppenheimer energy surfaces. All
factors affecting the total current are included but little
effort has been directed to disentangling the interesting
structure and electronic factors. For a review, see Chapt.
4 of Ref. 9.
B. Double-layer Potential and Overpotential
In the equilibrium limit where no current flows, the elec-
tron potential will be equal to the applied potential at
the electrode surface and through any surface complexes
or double layer to the bulk electrolyte. In this limit U
known wherever the redox reaction occurs, whether
within or outside of the Helmholtz plane and the band
shift and adjustable electron source or sink models are
unambiguously applicable. When there is a net current
flow through the interface, there may be a potential drop
across the interface. The following discussion aims to give
a qualitative understanding of this drop.
95
At the potential ofzero charge (PZC) the electrode sur-
face is essentially uncharged and no electrostatic work is
done when charged species pass through the region
between the electrode surface and the bulk solution. At
potentials away from the PZC there is excess charge on
the surface and a distribution of compensating ions
through the double layer region. The charge can be found
by capacitance measurements, but its distribution in the
double layer is not easily determined. Redox reactions
involving electron transfer between the electrode surface
and the bulk of solution outside the outer Helmholtz
plane will occur as prescribed by the potential applied
to the electrode, but if a reactant enters the double layer
region prior to oxidation or reduction, the effective elec-
trode potential will be different from the applied value.
Take the reduction of R to HR in aqueous acid at applied
potential U:
R(aq) + H+(aq) + e-(U) ---+ HR(aq) (29)
Let the PZC be positive of U so that the electrode surface
bears a net electron excess and there is a double layer
across which an electron charge would experience when
passing from the electrode to the bulk position, a poten-
tial increase ofUill. Outside of the double layer region
the reaction in Eq. (29) will be able to take place when
the R· .. H+reacting complex is thermally agitated to a
structure wih an electron affinity given in Eq. (28). There
is an activation energy to reach this structure, and let the
complex be denoted as RH H . Now suppose Rand H+
move to a position in the double layer region and form
the same RH+* structure. Assuming a monotonic poten-
tial change through the double layer, the RH+* complex
is stabilized by aUilleV/V where 0 < a < 1. This energy is
lost as heat and contributes to the overpotential. In this
location the electron affinity of RH H is reduced by a Uill,
which is the electrostatic work to bring an electron from
the solution level to this position in the double layer.
Equivalently, for RH H at this position the electrode is a
weaker reducer and it is as if the electrode potential has
been increased a Uill compared to reducing RH+* in the
bulk solution. There are now two ways to initiate electron
transfer to the RH+* complex. One is for it to be thermally
agitated to a higher energy structure with its electron
affinitiy increased by aUilleV/V The other is to decrease
the electrode potential by a Uill to enhance its reducing
capability. The former illustrates the effect of a a Uill on
slowing the kinetic rate, and the latter is another contri-
bution of a Uill to the overpotential.
If the PZC is negative of U so that the electrode surface
is positively charged and the electrostatic potential
change through the double layer region is again
96
monotonic, the RH+- complex will be destabilized by
b UJ; at position b in the double layer and an electron
coming to this position from the solution will be
stabilized by b UJ;. The former effect contributes to the
activation energy for reduction and the latter corre-
sponds to an increase of the electron affinity of the
complex by b UJ; or a decrease of the electrode potential
by b UJ; compared to the value in the bulk solution. Elec-
tron transfer can therefore occur when the complex has
a smaller electron affinity, corresponding to less thermal
agitation and a lower activation energy at site b. The net
effect involves some cancellation and the implication of
a smaller double layer contribution to overpotential when
the electrode is positive ofthe PZC then when it is negative
of it. The effects of double layers on oxidation reaction
overpotentials are the same as above, respectively, when
the PZC is negative of and positive of U.
The double layer structure and capacitance depend on
the electrode potential and all the ionic species in
solution. Treatments based on simplifYing models imply
that potential changes at the outer Helmholtz plane are
small ( < 0.1 V) when ionic activities are high (Chapt. 3,
Ref. 9) and chemical interactions between reactant and
double layer molecules will be in all probability more sig-
nificant to the understanding of electrocatalysis there.
v. CONCLUSION
Of the three approaches described in this chapter, the
semiempirical ASED-MO band shift model should con-
tinue to find application to explaining the electrochemi-
cal potential dependencies of spectroscopic and
reaction prospects of adsorbed molecules. The tunable
electrochemical potential electron donor and acceptor
model shows significant promise for understanding the
potential dependencies of redox and electrocatalytic
reactions through the use of ab initio quantum
calculations. Both methods, but especially the latter, will
be applied more accurately as more is learned experimen-
tally about double-layer properties.
ACKNOWLEDGMENT
I am grateful for support of this work by ARPA through
ONR Contract No. N00l4-92-J-1848.
Anderson
REFERENCES
1. P Atkins. Physical Chemistry, 6th ed. New York: W H.
Freeman, 1998, p. 167.
2. C Pisani, R Dovesi, C Roetti. Hartree-Fock Ab Initio
Treatment of Crystalline Systems. Lecture Notes in
Chemistry 48. Berlin: Springer-Verlag 1988.
3. Past discussions take the viewpoint that Eq. (2) is a
finite-difference approximation to (3Ej3nh.v. For an
entry into the literature, see RG Parr, Y Yang.
Density-Functional Theory of Atoms and Molecules.
New York: Oxford U. P, 1989, p. 24.
4. RSJ Mulliken. Chern. Phys. 2:782, 1934 as pointed out in
Ref. 3.
5. M Kiskinova, G Pirug, H P Bonzel. Surf Sci 133:3211983.
6. This early suggestion, due to I Langmuir and KH
Kingdom (Phys Rev 21:381, 1923) is currently debated,
based on modern calculational and experimental results
sometimes thought to run contrary. For recent entries into
this literature, see PS Bagus, G Pacchioni. Phys Rev B
48:15262,1993; GK Wertheim, DM Riffe, PH Citrin. Phys
Rev B 49:1994, 1994; and TVW Janssens, JW
Niemantsverdriet, RA van Santen. Chern Phys 101:2995,
1994. Much ofthe problem lies in the fact that the K + and
M- "ions" are not spherical. Instead, the K + core rests on
a bed of electron density in the interface that is described
by atomic basis functions of both K and M.
7. J Lee, J Arias, CP Hanrahan, RM Martin, HJ Metiu. J
Chern Phys 82:485, 1985.
8. RC Weast, ed. CRC Handbook of Chemistry and Physics.
Boca Raton, FI: CRC Press Inc., 1986.
9. JO Bockris, SUM Khan. Surface Electrochemistry:
Molecular Level Approach. New York: Plenum, 1993,
pp.78,493.
10. ER Katz, H Neff. KJ Muller. J Electroanal Chern 215:331,
1986.
II. ER Katz, H Neff. Surf Sci 160:517,1985.
12. TVW Janssens, GR Castro, K Wandelt, JW
Niemantsverdriet. Phys Rev B 49:14599, 1994.
13. For earlier discussions ofthese ideas as applied to electro-
chemistry, see AB Anderson. J Electroanal Chern 280:37,
1992; and AB Anderson. Proc-Electrochem Soc 92-11:1,
1992.
14. For the early development of the application of per-
turbation theory to bonding, see R. Hoffmann. Accounts
Chern Res 4: 1, 1971; and references therein.
IS. AB Anderson, EJ Grantscharova. Phys Chern 99:9143,
9149,1995.
16. AB Anderson, D-B Kang. J Phys Chern 102:5993,1998.
17. AB Anderson, T Albu. to be published.
18. RW Gurney. Proc Roy Soc A 134:137,1931.
7
Theory and Computational Modeling: Medium
Reorganization and Donor-Acceptor Coupling in Electron
Transfer Processes
Marshall D. Newton, S. W. Feldberg, and J. F. Smalley
Brookhaven National Laboratory, Upton, New York
ABSTRACT
Rate constants for electron transfer between weakly
coupled donor (D) and acceptor (A) sites are formulated
theoretically in the context of a broad kinetic framework
capable of accounting for homogeneous processes and
interfacial processes involving metal electrodes. Particu-
lar emphasis is placed on two crucial kinetic parameters,
the solvent reorganization energy (Es ) and the D/A
coupling element (HDA ). The results of model calcu-
lations are described, which show how the behavior of
these quantities may be evaluated and analyzed theoreti-
cally and then successfully related to results inferred from
electrochemical kinetic measurements. The theory
underlying the calculations allows the formulation of
compact models of predictive utility that are valuable in
suggesting critical new experimental tests of theory.
I. INTRODUCTION
Electron transfer (ET) kinetics plays a central role in a
broad array of processes in the physical, chemical, and
biological sciences in both homogeneous and hetero-
geneous environments [1-4]. The description of these
processes involves a number of fundamental issues in
chemical energetics, dynamics, and geometric and elec-
tronic structure.
Present day mechanistic understanding of ET is
reflected in theoretical models of rapidly increasing
sophistication [5-9]. The evolution of these theories has
benefited immensely from close interaction with
97
numerous experimental efforts, which have experienced
their own spectacular growth in recent times. Of particu-
lar interest for the present volume is the recent success
in probing interfacial ET mechanisms by exploiting elec-
trochemical techniques (e.g., as applied to film-modified
electrodes [10-15], a primary focus of the present
chapter).
On the theoretical front, the long and successful tra-
dition emanating from the seminal ideas of Marcus [16]
has recently been enhanced by a number of theoretical
and computational advances that permit detailed treat-
ment of the various electronic and heavy-particle modes
of complex ET systems (including both discrete solute
species and surrounding medium) at quantum
mechanical, semiclassical, or classical levels, as dictated
by the nature of the relevant competing time scales
[5-9,17-25]. Typically, one identifies and treats quantum
mechanically, local molecular donor (D) and acceptor
(A) sites, and then formulates the manner in which the
effective coupling facilitating the ET process is
mediated by the energetic and electronic features of the
intervening medium [the "bridge" (B)] and the surround-
ing environment. The energetics and dynamics associ-
ated with activation are treated with either classic or
quantum mechanical models. Molecular dynamics
techniques, in conjunction with large-scale computer
simulation studies, are playing an increasingly valuable
role in probing mechanistic details at the molecular level
[9,19].
98
~--------~~:f~--------~
"-- ______ - - - -
I
/l"
Medium
(Solvent)
'l'j ~ {DBA} (initial state)
'l'f ~ {D+BA- } (final state)
Figure 1 Generic electron transfer system, DBAI D+ BA-,
comprising local donor (D) and acceptor (A) sites, the inter-
vening bridge (E), and the surrounding medium (or solvent).
In the two-state approximation (TSA), the kinetics may be
modeled in terms of initial (l/J;) and final (l/Jf) state wave
functions, in which the transferring charge is localized primarily
on the D and A sites, respectively. (From Fig. I of Ref. 27b,
reprinted with permission. Copyright [1997] Elsevier Press.)
A schemetic depiction of a generic DBA system is
offered in Fig. 1, which applies either to intramolecular
ET [where D and A are covalently linked by a molecular
bridge (B)] or intermolecular ET [where, e.g., the "bridge"
(B) could be solvent]. We use the convention whereby the
donor (D) donates an electron to the acceptor (A). An
example of central importance is the case of interfacial
ET between a redox species [RIO, which may exist in the
reduced (R) or oxidized (0) state] in contact with solution
and separated from a metal electrode (M) by a film (F).
In this example D, B, and A in the DBA entity (Fig. 1)
correspond, respectively, to M, F, and 0 for a reductive
(cathodic) process, with the roles of D and A being
reversed for the corresponding oxidative (anodic) process
(i.e., D =RandA =M).
The theoretical models play two important roles: lead-
ing (in conjunction with modern computing power) to
realistic computational implementation and allowing
analysis ofthe results ofsuch calculations (and those from
experiment) in terms of compact predictive models
grounded in simple concepts of chemical structure and
bonding. The power of the current array of theoretical
tools for confronting the challenges posed by ET
dynamics is underscored by their typically generic
applicability: e.g., to ground-state or photoinitiated pro-
Newton et al.
cesses [18], both homogeneous and interfacial [16c,26]
(e.g., at electrodes). The continuing goal, of course, is to
convert the rapidly accumulating mechanistic infor-
mation about ET kinetics (often representable in terms
of simple rate constants) into precise tools for fine-tuned
control of the kinetics and for design of molecular-based
systems that meet specified ET characteristics.
The present treatment will be limited to the kinetic
framework defined by the assumption of transition state
theory (TST). Situations beyond TST, in which medium
dynamics (either diffusive or inertial) contribute to or
dominate the bottleneck in ET processes, have been dealt
with extensively in the recent literature [5,25]. With the
above background in mind, the primary objective of this
chapter is to report recent advances in the theoretical
formulation, calculation, and analysis of energetics and
electronic coupling pertinent to ETin complex molecular
aggregates. The control of ET kinetics (i.e., enhancing
desired processes, whereas inhibiting others) involves,
of course, both system energetics [especially re-
organization energies (Er ) and free energy changes
(AGo)] and electronic coupling of local D and A sites,
which for thermal processes is most directly relevant only
after the system has reached the appropriate point (or
region) along the "reaction coordinate" (i.e., the
transition state) [1,8].
In the following sections we first discuss TSTrate con-
stant models [1-4,8,16,27a], emphasizing generic features
common to both homogeneous and interfacial processes
but also noting some special features arising when metal
electrodes are involved. We then turn to a consideration
of detailed aspects of medium reorganization and
donor-acceptor coupling. With these theoretical tools
in hand, we examine the results of recent applications to
complex molecular systems using the techniques of com-
putational quantum chemistry and electrostatics,
together with detailed analysis of the numerical results
and comparison with recent electrochemical kinetic data
[14,15].
II. KINETIC FRAMEWORK
A. Two-State Model
When the ET process ofinterest is dominated by two elec-
tronic states (e.g., the DBA and D+ BA- states displayed
in Fig. 1), whose energy separation is small relative to the
gaps separating them from all other electronic states, it
is often a reasonable approximation to invoke the
so-called two-state approximation (TSA) [1,2,8,27a]. At
this level (in which other states play at most a "virtual"
role), the golden rule yields the following unimolecular
Donor-Acceptor Coupling in Electron Transfer Process 99

rate constant (in inverse time units), valid in the limit of

sufficiently weak D/A coupling [1-3,8,27a], the situation
dealt with in this chapter:

where the overall rate constant is displayed as a sum of

contributions from all initial (Vi) to all final (Wi) vibronic
states, belonging, respectively, to the initial (ljJ,) and final
(ljJi) electronic manifolds. Each initial state (Vi) is
weighted according to P v, (generally taken as a
Boltzmann factor), energy conservation is imposed by
the delta functions, the VV;Wj is a vibronic matrix element
with respect to the full system Hamiltonian (H), and
h = 2nli is Planck's constant. Invoking the Condon
approximation, where we assume that the electronic
matrix element,
- - - - - - - - - - - - - - - - - -....
~ R

(2) Figure 2 Effective energy profiles along the reaction

varies slowly with respect to nuclear coordinates (at least
in the vicinity of the transition state), we may factor Hif
coordinate (R) for the initial [Vi(R)] and final [Vf (R)] diabatic
states, indicating the reorganization energy (E,\ activation
energy (E and reaction driving force (-<"100). In a linear
Q
\

system, with parabolic profiles of equal curvature (as implied

out ofthe summation in Eq. (1), yielding
k TST = ( 2n lli)(I H ifI 2 )(FCWD)
where "FCWD" is the conventional notation for the
so-called thermally weighted Franck-Condon density
of states (with respect to energy). In general, FCWD
implicitly contains quantal effects associated with
nuclear tunneling. However, in the classical or
high-temperature limit (where relevant nuclear
vibrational frequencies are small relative to k BT 1Ii,
where k B is the Boltzmann constant), considerable
simplification is possible. To illustrate this result, it is
necessary at this point to define some energy quantities
pertinent to theTST model (Fig. 2). The free energy pro-
files as a function of progress along the reaction
coordinate (R) are displayed for the diabatic states ljJ i
and ljJI' corresponding, respectively, to the generic
charge-localized valence bond structures DBA and
D+ BA -. These free energy profiles serve as effective
potential energy curves for nuclear motion and are
denoted here as VieR) and Vi (R), respectively, for the
initial and final states. The crossing point of the energy
profiles defines the activation energy (EQ) and the net free
energy change is denoted LlGo (equivalently, the driving
force is -LlGo). For a given state, the reorganization
energy (E;) or (E[) is given by the energy difference in
going from the minimum energy point (i.e., equilibrium)
to the nonequilibrium point defined by the minimum
energy point for the other state. Finally, the magnitudes
by the figure), the free energy change <"100 can be equated to
the gap between the minima of the two free energy profiles [35]
(3)
(a near equality is expected in general) and the vertical energy
gap (E~) at the equilibrium configuration for the initial state
(DBA) is equal to E[ + <"10° [I]. Correspondingly, the final state
(D+ BA-) gap (-EO is given by E; - <"10°.
of the vertical gaps at equilibrium where (R = R~q or
R{q) are given by E~ == Ev(R~q) and E{ == Ev(R{q), where
the vertical gap at an arbitrary value of R is defined as
Ev(R) == Vi (R) - VieR).
In the common situation in which the two profiles may
(to good approximation) be taken as harmonic (i.e.,
parabolic), each with the same curvature, we obtain sev-
eral relationships:
E, = E; = E[ = (E~ - E{)/2 (4)
(5)
(6)
Furthermore, the vertical gap, E v , becomes a linear func-
tion of R, so that for convenience we may adopt E v as an
alternative definition of the reaction coordinate.
100
Returning now to Eq. (3), we find that for the harmonic
case discussed above,
k TsT = (2n/Ii)IHif I2p(0) (7)
where p(Ev ) is the normalized classical density of initial
states with respect to the gap E v (i.e., p(Ev)dEv is the prob-
ability of finding the initial state in a configuration corre-
sponding to a vertical gap in the range E v to E v + dey):
p(Ev ) = (exp- (E, + 11(f! -Ev)2 /4E,k B T))/(4nE,k B T)I/2
(8)
Thus, in the classical limit, the consequence of the
energy-conserving golden rule expression [Eq. (1)] is
simply to invoke the classical density of states at the
transition state (i.e., the crossing, where E v = 0), the point
to which a radiationless electronic transition is confined
due to the constraints of the Franck-Condon principle.
Equations (6) and (8) allow Eq. (7) to be reexpressed as
eST = (2n/Ii)IH!d(4nE,k BT)-1/2 exp( _Ea /kBT)
(9)
displaying a weakly temperature-dependent (T- 1/ 2 )
prefactor and a conventional Arrhenius activation factor.
B. Multistate Models
Although theTSA has been shown to give good account of
many classes of ET kinetics, there are, of course,
situations in which a high density of electronic states
makes it necessary to generalize the expressions given
by Eqs. (1), (2), and (7). A paramount example is given
by the case of metal or semiconductor electrodes, where
one must deal essentially with an electronic continuum
[10,16,26,28]; i.e., in terms of Fig. 2, each of the two elec-
tronic states is replaced by a nested continuum of states
[16c]. Other examples arise in the case of molecular sys-
tems with degenerate or quasi-degenerate states. In the
following treatment, we confine our attention to systems
comprised of metal electrodes coupled to redox species
in fixed configurations by intervening films (i.e., "rigid"
DBA systems), so that the ET kinetics may be treated in
terms of unimolecular rate constants. Adopting a
one-particle model characterized by a spectrum of elec-
tronic energy levels for the electrode (represented by the
continuous variable 8) and formal potential EO' for the
redox moiety coupled to the electrode, one may general-
ize Eqs. (5) and (6) so as to obtain analogs that are
Newton et al.
functions of 8 [10,26]:
I1GJ,b(8) = ±(( -eEO') - 8) (10)
EJ,b(8) = (E, + I1GJ,b(8))2/4E, (II)
where the subscriptsfand b are used to distinguish the
"forward" and "back" processes, corresponding, respect-
ively to reduction (of the oxidized form) and oxidation
(of the reduced form) of the redox species, e is the
magnitude of the electronic charge, and the quantity
-eEo, is the free energy change for the 0 + e ---+ R half
reaction; the quantities -eEo, and 8 are understood to
be defined with respect to a common zero of energy,
which cancels when the difference is taken in Eq. (10).
Defining kJ.~T by replacing E a in Eq. (9) with EJ.b (8) and,
for generality, introducing a state-dependent matrix
element (Hif( 8) [28]) and then integrating over the entire
spectrum E, we obtain
+OO
kJ.~T =
J -00 d8p'}\(8)kJ ,b(8) (12)
where the effective electronic density ofstates, pe/. b , may be
displayed as the product of a state density (per unit 8),
pel(8), and the fraction ofstates at a given 8 that are filled
[for the forward (reduction) reaction] or empty [for the
backward (oxidation) reaction], as given by Fermi - Dirac
statistics [the second factor in Eq. (13)]:
P;~b(8) = pel(8)(1 + exp (± (8 - 8F)/k B T))-I (13)
where 8F is the Fermi energy of the electrode, which may
be expressed in terms of the electrode potential, EF , as
8F = -eEF .
In implementing Eq. (12), pel(8) and IHif(8)1 2 are fre-
quently replaced by effective or mean values, pel and
IHifl2 (e.g., the values at the Fermi level) [10]. Selection
of the effective value of pel(8) is guided by the estimated
number of atoms of the metal electrode that are in
adequate proximity to the relevant portion ofthe attached
film (e.g., see [13b] and Ref. 23 of [10]). Studies taking
more detailed account of the 8-dependence of H iJ are
reported in Ref. 28. The theoretical models suggest that
under certain circumstances [28c,d], the electronic
coupling may display an appreciable dependence on elec-
trode potential. A recent experimental study based on
ET through self-assembled films [29] found the distance
dependence of the coupling to be nearly independent of
electrode potential.
Donor-Acceptor Coupling in Electron Transfer Process
Although the full evaluation of knT [Eq. (12)]
requires a numerical integration, compact closed-
form expressions ofuseful accuracy may be obtained for
certain limiting cases. These expressions are analogous to
Eq. (9), with the counterpartofthe driving force L1Go [e.g.,
as in Eq. (5)] being provided by
L1G~,h == L1GJ,h(C F ) = ±« -e£l')-c F) (14a)
where we use the functional form introduced in Eq. (10).
An equivalent expression in terms of the electrode
potential, E F , is given by
(14b)
Correspondingly, we may define the analog of E U [Eq.
(6)]
(15)
using the notation of Eq. (11). For cases of small driving
force (IL1GJI/E, « 1), a linear approximation may be
used:
EJ ~ E,/4 + 1X(L1GJ) (16a)
E% ~ E,/4 - (l - 1X)(L1~) (16b)
The constant IX may be obtained from a linear Taylor
expansion of EJ,h with respect to L1GJ. Evaluation of the
first derivative of Eq. (15) with respect to L1~ at
L1GJ = 0 yields the frequently used value, 0.5.
The Butler-Volmer approximations for kfTST .h may
now be expressed as [10]
kPT = kJST exp(IXL1GJ/k BT) (17a)
kr ST = kJST exp(-(1-IX)L1~/kBT) (17b)
where k;jST (the "standard" rate constant) is obtained
from Eq. (12) for the limiting case of L1GJ = O. Numerical
studies [14] ofthe temperature dependence of kJST reveal
(aside from a prefactor proportional to T 1/ 2) a simple
Arrhenius behavior, with activation energy within 1% of
E,/4 [as one might expect by analogy with Eq. (6) for
L1eD = 0], provided that E,/kBT » 1 [the T 1/ 2 behavior
ofthe prefactor noted above differs from the T- 1/2 depen-
dence in the two-state case (Eq. [9]) as a result ofthe inte-
gration in Eq. (12)]. This analysis is, of course, based
on the assumption of a temperature-independent
reorganization energy (Es ). Because Es is formally a free
energy, it may in general be expected to display some tem-
perature dependence. Nevertheless, such effects are often
101
found to be minor [1], and in particular, the experimental
data dealt with below [14,15] adhere closely to Arrhenius
behavior.
Detailed balance provides an important relationship
between the kinetic and thermodynamic quantities:
(18)
Equation (18) is easily seen to be obeyed by the
Butler-Volmer rate constants [Eq. (17)] and may be
straightforwardly shown also to be a property of the rate
constants in full integral form [Eq. (12)].
The preceding models for ETrate constants, either at
the simple two-state level appropriate for homogeneous
ET in solution [Eqs. (3), (7), and (9)] or at the extended
level required for heterogeneous ETwhen electrodes are
involved [Eqs. (12), (17), and (18)], display in concrete
fashion the manner in which reorganization (E,) and
D/A coupling (Hi!) control the kinetics. In the remainder
of the chapter, we consider detailed expressions for E,
and Hi! and then summarize some computational
applications that have been especially helpful in guiding
and interpreting experimental kinetic studies at
film-modified electrodes [14,15], with particular empha-
sis on the dependence of the kinetic parameters on film
thickness. As noted above, the treatment is carried out
in a framework appropriate for relatively weak D/A
coupling (i.e., nonadiabatic ET, as governed by the
golden rule [Eq. (1)] and its various elaborations
[1,2,27a]).
III. SOLVENT REORGANIZATION ENERGY
The reorganization energy (E,) is a consequence of the
Franck- Condon principle, which precludes inertial
motion during an electronic transition. In general, E,
has a number of additive (under the usual harmonic
assumption) contributions from different inertial modes
of the "solute" (DBA in Fig. 1) and surrounding medium.
In the applications dealt with below, the dominant contri-
bution (to which we confine our attention) is from the sol-
vent medium and hence denoted as E s (the same
quantity is often referred to as Aor E out in the literature).
Expressions for Es at the level of dielectric continuum
theory may be developed from the Poisson equation for
an electrostatic system [30,31] (for an example of a
molecular-level treatment, see [32]):
(19)
where p is a charge density and ¢eq is the electrostatic
potential of a system at equilibrium with p (for linear
coupling of p to the medium, ¢eq is a linear functional of
102 Newton et al.

p). The equilibrium free energy of the total system is then
given by
Feq(p) = 1/2 L cPeq(P)P de
where the integration volume is all space. Detailed analy-
sis then shows that E s may be expressed as [30]
E s = Feo:(!~'Pif) - F:~(!~Pi/)
where st and op denote, respectively, a system with full
dielectric response (characterized by static dielectric
constants est) and the hypothetical variant in which only
the high-frequency (optical) response is operative
(characterized by optical dielectric constants eOP = n2 ,
where n is the refractive index), and
I1.Pif =PI - Pi
is the change in charge density accompanying the ET pro-
cess (l/J i --* l/JI)' Thus, E s is displayed compactly as a
double difference: the differential solvation energy (i.e.,
the difference between total and optical solvation) of the
change in charge density.
Equation (19) is typically solved for a piecewise homo-
geneous model, in which different spatial zones have dis-
tinct values of EOP and Est. Efficient numerical
techniques permit Eq. (19) to be solved accurately for
zones of arbitrary shape, thus allowing dielectric con-
tinuum models to be realistically adapted to the detailed
structure ofthe ETsystem ofinterest [30,31]. For compari-
son with the results of exact implementation of Eqs.
(19)-(22), a useful point of reference is provided by the
familiar point-charge two-sphere model of Marcus [16c],
which in generic form accommodating examples of both
homogeneous and two-zone heterogeneous systems,
may be expressed as
D (taken as an ideal conductor), we adapt Eq. (23) by
assigning YD = 0, YA = 1, YDA = I, and "rDA" is now the
distance between the actual site (A) and its image in the
(20) electrode [33]. This distance is simply twice the
distance of A from the planar interface. If, on the
other hand, it is assumed that the metallic screening
is quenched, then there is no image term (i.e.,
YDA = 0) [33b]. Equation (23) yields the important
(21) prediction that E s is expected to increase linearly with
the inverse of rDA, both for homogenous systems and
(to the extent that ideal screening pertains) hetero-
genous systems with metal electrodes. We note that the
same result for E s [Eq. (23)] is obtained for the reverse
(anodic) process in which the roles of D and A are
interchanged.
More detailed consideration of image effects in the
context ofmolecular-level solvent models is given in Refs.
(22) 9b and 34. The presence of dielectric inhomogeneity
entails the occurrence of transverse and longitudinal
polarization fields, as discussed in Ref. 35.
We now consider the more general case of interest, a
redox species in solution in proximity to a film-modified
metal electrode surface [30]. Equations (19)-(22) were
solved analytically for the three-zone dielectric model
depicted in Fig. 3: a spherical redox species (in a cavity
of radius a, with a point charge at its origin undergoing a
change I1.q in the ET process) in solution (zone l),
separated by distance d from the edge of a film of
thickness L (zone II), in contact with a metal electrode
(zone III). Taking zone III as an ideal conductor, we

Es = (ilq)2(1le op - I lest)(yDI2rD + YAI2rA - YDAlrDA)

(23)

where local D and A sites are taken as spheres (with radii

rD and rA, respectively), each with a point charge at its ori-
gin [e.g., PD(r) = qDb(r - rD)], which changes by ±l1.q
=
in the ET process (l1.q I1.qD = -l1.qA), and where rDA
is the intersite separation [within the spheres, eOP = eSt, o d d+L
usually set at the vacuum value (1) or a typical optical
Figure 3 A schematic representation of a redox couple in a
value (~2)]. For the case of two redox species (D and A)
spherical cavity of radius a, separated from a film ofwidth L by
in a homogenous medium, YD = YA = YDA = 1. For the a distance d. The point charge shift at the redox site is I1q, z,
two-zone heterogeneous system, with an infinite planar and p are cylindrical coordinates, and Ci (i = I, II, III) are the
boundary, corresponding to a single redox species in sol- dielectric constants for the three zones. (From Fig. 1of Ref. 30,
ution [taken here as the acceptor (A =0) in a cathodic reprinted with permission. Copyright [1994] American Chemi-
process (see Sec. I)] and a metal electrode as the donor, cal Society.)
Donor-Acceptor Coupling in Electron Transfer Process 103

obtain [30]

E = (_1 _~) (/1q)2 _ (fI~rl _fill,!) (/1q)2

S eOP est
1
00
'I

+ '"(-1 t
~
2a
I eOP
ope op
en fin,!
(e op + e
1
)1-1
est

OP )2
1
4d
st( st )1-1) (/1 )2
_ en fln,1
(est + e
_._q_
st )2 d + n
£=1 n 1 n 1
(24)
where flij == (ei - ej)/(ei + ej).
Equation (24) may be viewed as reflecting the contri-
butions from an infinite number of image charges, /1qn,
located at points 2(d + £-L) along the z axis (Fig. 3), for
£- ::': 1. In the limit of vanishing film thickness (L = 0),
Eq. (24) reduces to the single-image two-zone result [Eq. -----------------.....,.~R
(23), with rD = a, rDA = 2d, 'YD = 0, 'YA = 1, bDA = 1,
and est and eOP corresponding to zone I]. More discussion Figure 4 Schematic representation ofoptical and thermal ET,
in terms ofimage contributions is given below in conjunc- corresponding, respectively, to the vertical transition with exci-
tation energy hv and thermally activated passage through the
tion with specific applications. It must be emphasized
transition-state (or crossing) region. In experimental studies,
that neglect of image effects for dielectric systems of the the thermodynamically stable state, which is the final state in
type depicted in Fig. 3 may lead to greatly exaggerated the thermal ET process, generally serves as the initial state in
values of E s and incorrect variation with d (for fixed L the corresponding optical process.
and a), as discussed in Ref. 30.
The simple point-charge-in-a-spheremodel discussed
above is of course a crude (although often very useful)
model. More elaborate implementations of Eq. (21) are A. Thermal ET
possible, using detailed charge densities based on quan- In thermal ET, the effective coupling element H DA may be
tum chemical calculations for complex DBA systems in taken as one-half of the vertical adiabatic energy gap at
solution [31]. its minimum value with respect to the reaction coordinate
(R) [8]. For symmetry-equivalent D and A sites, this result
corresponds to
IV. DONOR/ACCEPTOR COLlPI.ING
(25)
Because coupling between initial and final diabatic states,
which are many-electron quantities, can often be where E+ and E_ are the energies of the adiabatic states
adequately represented as a one-particle matrix element that are, respectively, symmetric and antisymmetric with
coupling localized D and A orbitals [8], we adopt the respect to the D and A orbitals. For cases in which D and
notation H DA for the coupling element Hi} in the A sites are not symmetry equivalent, the use of Eq. (25)
following analysis. Within the two-state approximation requires that the D and A orbitals are brought into
(see above), it is convenient to distinguish two basic resonance by some device (e.g., adjustment of the mol-
approaches for evaluating D/A coupling, both of which ecular geometry or application of a suitable external
obtain the desired diabatic quantities (i.e., H DA ) electric field [36]).
indirectly in terms of adiabatic states (i.e., those which
are diagonal with respect to D/A coupling and which we B. Optical ET
denote as If; 1 and If; 2)' These approaches, described below,
may be contrasted with an alternative approach in which In optical ET, H DA may expressed entirely in terms
HDA is evaluated directly from charge-localized diabatic of adiabatic quantities, using the Generalized
states [8]. The two approaches differ in that one is defined Mulliken-Hush (GMH) model [18,33b]:
only at the transition state for thermal transfer [i.e., at (26)
the diabatic crossing point (Fig. 2), where resonant
transfer is possible], whereas the other is based on the cor- where f1tr is the transition dipole moment coupling the
responding vertical optical process (both process are two adiabatic states, /1E 12 is the corresponding adiabatic
depicted in Fig. 4). vertical energy gap (generally quite similar to the diabatic
104
gap, hv, indicated in Fig. 4), and the diabatic dipole
moment shift, /1/iDA' may in turn be expressed in terms
of /itr and /1/i12 (the adiabatic dipole moment shift):
1/1/iDAI = (1/1/inl 2 + 41/i~rl)I/2 (27)
The use of Eq. (27) obviates the need to approximate
1/1/iDA I as erDA, where rDA is an assumed D/A separation
distance (e.g., based on structural data). In the general
case when the various dipole vectors in Eqs. (26) and (27)
are not collinear, a reference direction must be adopted
(e.g., based on /1/id and then the components of the
vectors along this direction may be used in Eqs. (26) and
(27).
c. "Electron lUnneling"
The D/A coupling embodied in H DA is often described as
an effective "electron tunneling" process [27a]. To focus
the discussion, we consider specifically the dependence
of H DA on the D/A separation distance (r DA) and compare
the prediction of two quite distinct models [37,38], each
ofwhich yields exponential decay:
(28)
HDA(rDA)OC exp(-(f312)rDA)
[the decay coefficient is defined so that the rate constant in
Eq. (3) decays with coefficient 13]. Although rDA is in gen-
eral not uniquely defined, a convenient definition may
be obtained as 1/1/iDA II e, taking 1/1/iDA I as defined by
Eq. (27).
The phenomenological Gamow model [37] is based on
tunneling through an electronically homogeneous
medium represented by an effective one- dimensional
rectangular barrier of height /1 G and width r DA:
f3G = 2(2m e /1 G)I/2 I Ii (29)
where me is the mass (actual or effective) of the tunneling
electron. More general treatments of effective homo-
geneous tunneling barriers are given in Refs. 28c and 39.
Most modern treatments of bridge-mediated elec-
tronic coupling do not involve tunneling in the literal
sense of the Gamow approach and use electronically
inhomogeneous superexchange (SE) models [38], which
take detailed account [8,27] of the electronic structure
of the DBA system (Fig. 1). In implementing these models
one has the choice of how to subdivide the bridge into
subunits. The optimal choice involves various trade-offs,
including transferability among chemically similar sys-
tems (favoring small subunits), compactness of represen-
tation when it comes to synthesizing the overall
coupling, H DA (favoring larger subunits), and theoretical
considerations such as the applicability of perturbation
Newton et al.
theory (here the trade-off is complex but often favors
larger subunits [27a]). As a simple example for
illustration, we adopt the McConnell model [38a] based
on a bridge consisting ofa homologous sequence ofunits,
each of which is represented by a single orbital with
energy /1 relative to the common energy of the D and A
orbitals and with nearest-neighbor (NN) bridge orbitals
coupled by the "hopping integral" t. From this model,
for Itl/11 « I we obtain
f3SE = -2(1n Itl/1I)/(/1r) (30)
where /1r is the width ofone subunit.
In comparison with the result from the homogenous
model [Eq. (29)], f3SE reflects the molecular and electronic
structure of B, not only through the hopping integral t
but also /1 and /1r, because the values ofall the parameters
depend on the specific choice of subunit [we also note,
in contrast to Eq. (29), that in Eq. (30) the electron mass
is implicit in t and /1]. Another important distinction lies
in the role of the gap /1 in Eqs. (29) and (30). In the latter
case, /1 (for a particular bridge subunit) is in principle
(and in some cases in practice) a spectroscopic
observable, whereas the phenomenological /1 G, which
represents the full bridge in Eq. (29), is not in general
directly accessible as an observable. Effective /1 G values
may, of course, be inferred from Eq. (29) on the basis of
experimental 13 values, but attempts to use experimen-
tally determined energy gaps (e.g., from redox potentials
or spectroscopic data) frequently lead to exaggerated 13
magnitudes [39]. Equation (29) is more usefully applied
to the direct or "through-space" D/A coupling when no
bridge is present. In this case, /1 G may be identified with
the relevant ionization potential of D [40].
It is important to recognize that E s frequently provides
an additional contribution to the variation of kTST with
rDA (see below). Thus, caution must be used in comparing
13 values inferred from rate constants with values based
on H DA [41].
D. Superexchange Models
Having introduced the McConnell superexchange model
in connection with Eq. (30), we now consider
superexchange models in greater detail. The complete
McConnell expression [38a], which corresponds to the
definition of H DA based on thermal ET [e.g., Eq. (25)], is
given as
H DA = (T 2I /1)(tl /1)m-l (31 )
Donor-Acceptor Coupling in Electron Transfer Process
derivedintheperturbativelimit(ITI.1.I, Itl.1.1 « 1, where
the notation T, t, and .1. corresponds, respectively, to T, t,
and D in [38a]) for a sequence ofm bridge orbitals, whose
terminal members are coupled, respectively, to the D
and A orbitals via hopping integrals T [the other par-
ameters were introduced above in Eq. (30)]. Among the
important features revealed by Eq. (31) are the predicted
exponential falloff with m [already invoked above in
characterizing pSE in Eq. (30)] and the possibility of sign
alternation with m (the basis of the parity rule [42]),
although the detailed sign behavior requires careful
analysis, including a clear definition ofthe phase conven-
tions adopted for the various local orbitals or states of
the system (D, A, and B) [8,27a]. Equation (31) also pre-
dicts that H DA is sensitive to variations of the gap .1., e.g.,
as obtained by chemical modification of the D and A
groups [43] or the bridge (B).
Equation (31) may be generalized in a number ofways,
including [14]
1. Distinct bridging units:
m-l
H DA = (TDl TmA I.1.d IT (tk,k+I!.1. k+d (32)
k=l
where the subscripts on Tand t denote NN pairs of
coupled orbitals, and .1.e denotes the gap between
the D1A level and the energy of bridge unit 1:.
2. Summation over multiple "pathways" of the generic
type exemplified by Eq. (32), taking advantage of
the additivity of the different contributions and
including non-NN and NN pathways. In addition,
there is, of course, the direct (so-called through-
space) pathway between D and A (TDA ), although
its quantitative importance is usually small in
comparison with that of other pathways in DBA
systems.
3. Involvement of more than one orbital on each site,
including both occupied and unoccupied types,
thereby leading to competitive (either constructive
or destructive) interference among "hole," "electron,"
and "hybrid" pathways. In Sec. VB. below, we deal
specifically with the combined roles of sigma- and
pi-type molecular orbitals of the bridge units in
facilitating overall coupling.
Exponential falloff with m is maintained (although
the details change) when the perturbative limits are
relaxed, provided that T /.1.1 remains small and the DIA
1 quite similar, and the inner-shell reorganization energy
level avoids resonance with any of the eigenstates of the
bridge (i.e., remains outside the bridge "bandwidth"
(4Itl)) [44].
105
Indirect DIA coupling of the superexchange type is
often referred to as "through-bond" coupling, although
in a formal and also quantitative sense, it also applies to
DBA systems in which D and A are not linked by a con-
tinuous sequence of covalent bonds [27].
V. COMPUTATIONAL APPLICATIONS
The computational evaluation of E s and H DA is reported
below for model systems designed to assist in the
interpretation of experimental electrochemical kinetic
studies of interfacial ET between a gold electrode and a
ferrocene group linked to the gold surface by intervening
self-assembled monolayer (SAM) organic films ofvari-
able thickness [10-15]. The films are comprised of hom-
ologous chain structures anchored to the gold substrate
by terminal sulfur groups. Two basic chain types were
used: alkane chains [oligo-methylene (OM=(-CH2-)n)]
and alternating benzene and acetylene units [oligo-
phenylene-ethynylene (OPE=(-pC 6 H 4 -C=C~)n)]' For
the OM chains n may be equated to m + I [e.g., as in Eqs.
(31) and (32), where m is the number of C-C sigma
bonding (or antibonding)] orbitals within the chain. The
counterpart of Eq. (32) for the case of the OPE chains is
presented in Sec.VB.2.
At the outer surface of the film, in contact with aque-
ous solution, some fraction (typically ~1O%) of the
organic chains are covalently linked to ferrocene (Fc)
groups (either directly to one ofthe cyclopentadienyl (Cp)
carbons in the case of OPE, or to a carboxy-substituted
Cp ring in the case of OM), whereas the remainder of
the chains (the "diluent") are terminated with -CH3,
-OH, or -COOH, groups (for OPEs [15]) or CH3
groups (for OMs [14]). Structural studies indicate a
close-packed ordered structure for the OM-based SAMs,
with the linear axis of the fully staggered chains tilted
~27° from the direction perpendicular to the gold
substrate (see citations ofstructural data in [30]).
A. Evaluation of E s
E s for the OM-based interfacial systems described above
was evaluated via Eq. (24) by adapting the three-zone
model of Fig. 3 as follows [30]. An effective radius (a) of
3.8 A was used for the ferrocene (or ferrocenium) moiety
[45,46] that was assumed to be in "contact" with the film
(i.e., d = a) and .1.q was equated to ± e. The equilibrium
structures of ferrocene and the ferrocenium cation are
is estimated to be very small ( :s 0.03 eV) [47]. For the
aqueous zone (I), e~t = 78 and e? = 1.8 [48], whereas
for an OM film (with an estimated specific gravity of
106 Newton et al.

~0.95 g/cc), based on a mean separation of5 A between 1.1

I b IIII

---- ----
close-packed alkane chains with 2T tilt angles relative ----
d =a =3.3 A
to the normal to the metal surface, a value of
sn = s~f = 2.25 was assigned [30], similar to values
\;
1.0) / -
inferred for the bulk solid [49] (to good approximation /
/
d =a =3.8 A -
these values may also be applied to OPE films, especially
\
because E s is quite insensitive to the value of Sn in this
magnitude range as long as sn ~ s~f). For the metal elec-
:e </)
0.9I
I
I
"V ~
LLJ
>. I d =a =4.3 A
trode (taken as an ideal conductor), srh = s~fr = 00. In Cl
~
Q,) I
I
/ ~-- I- .-
all calculations, convergence of the sum in Eq. (24) was c:::: 0.8

il ".....- ~--
LLJ
very rapid [30]. c::::
o
Although the pertinent experimental work has been ~ v/
.!:::! 0.7
carried out with a finite ionic strength (I) in the aqueous c::::
phase, this effect was ignored in the calculations because
CI:l
Cl
~ VI
Es is not expected to be strongly affected by ionic strength
[16c].
o
Q,)
a::
0.6 / eb =78, e~
I
=1.8
I
Figure 5 presents the calculated E s values as a function e~ = e~ =2.25
offilm thickness L. As expected, the absolute magnitudes
0.5
~ el"-e" l
-
of E s are sensitive to cavity radius (variation of ± 0.5 A
relative to the estimate a = 3.8 Aare displayed). However,
the L dependence is invariant in the sense that plots of
°f-~I -
-
-
0.4
Es(L)/Es(L = (0) are nearly independent of the value of a 10 20 30 40 50 60
a. Variation of E s magnitude with L is appreciable; e.g.,
over the range L = 5-15 A, Es increases from 0.75 to Film Thickness L (A)
0.86 eV for a = 3.8 A. For cases near the thermoneutral Figure 5 Es (eV) plotted as a function of the film thickness L
limit (i.e., where E F ~ EO', in which case the activation (A), with the cavity in contact with the film [d = a (Fig. 3)] [30].
energy is ~ E s /4 [see Eqs. (15) and (16)]), this variation The solid curve is based on cavity radius a = 3.8 A. The broken
corresponds to a mean contribution of ~0.1 A-I to the curves are based on alternative values ofa (3.3 and 4.3 A). (From
overall exponential decay coefficient for the rate constant Fig. 2 of Ref. 30, reprinted with permission. Copyright [1994]
k o [see Eqs. (17) and (18)]. For longer range transfer, the American Chemical Society.)
effect is substantially reduced (e.g., for L = 15-25 A, a
change of ~0.03 eVin Es contributes only ~0.03 A-I to
corresponding to the e = 1 term in the summation. In
the overall decay coefficient).
fact, with YIn, I = 0, calculated E s values are within 1% of
Figure 5 reveals that E s increases by a factor of about
the general two-zone result ofRef. 23 [the small departure
two in proceeding between the two-zone limits of L = 0
arises from the higher order image contribution to the
(no zone II) and L = 00 (where Es is independent of zone
static component of Eq. (24)]. Neglecting all but the
III). The L = 0 (two-zone) limit is accounted for by the
dominant image contribution gives a linear dependence
Marcus two-zone expression [16c] given in Eq. (21), with
of Es on 11 (L + a) with slopes,
YD = 0, YA = 1, and 'Y DA = 1 (i.e., full image response in
zone III). The L = 00 (two-zone) limit is given by the first
two terms of Eq. (24) and corresponds to the general
two-zone expression given previously by Marcus [33] [of
which Eq. (21) is a special case].
s=-[ (Sn +1s?)2 - (Sn +1 srt)2 1sn(~q)2 (33)

The form of Eq. (21) makes it of interest to explore the

variation of the more general three-zone E s expression
[Eq. (24)] as function of 11 (L + a). More insight into this
and other aspects of E s in various limiting cases is given
by detailed consideration of image charge contributions
to Eq. (24). Because s? srI,
« Es is dominated by the
optical contribution to Eq. (24). Furthermore, the
similarity of the values of s? and £~f (i.e., YI~fI « 1) leads
to the dominance of a single image charge contribution,
where Sn is the common value of s~f and assigned to sn
zone I!.
The data in Fig. 5 is plotted in Fig. 6 (solid line) as a
function of 1I(L + a), and indeed a very nearly linear
behavior is observed. The slope [Eq. (33)] based on the
dominant image charge, s = -0.129, with (~q)2 = 1 in
units of e2, is similar to that for the exact results, and the
small difference reflects primarily the distinct values of
Donor-Acceptor Coupling in Electron Transfer Process 107

assuming a fully staggered conformation for the

(Au)(S)( CHz)n backbone, still leaves some variability of

,, £11= 2.25
d = a = 3.8 A
o L(n) with respect to other conformational degrees of
freedom [30]. A detailed consideration of structural
models [30] yields the following relationship for the mean
I=' 31 f-----~rl-----+-----__1
height of the Fc iron atom above the gold surface,
1Il hFe-Au(n):
~ , linear fit
en
LU
>. .~\ (5 = -0.120) hFe-Au(n) = 6.00 + 1.12n(A) (34)
Cl
~
Q)
c::
LU
c::
<>/
26 I--------f---.~' - - + - - - - - - - l
The model given in Fig. 3 for the case of "contact" (i.e.,
d = a = 3.8) thus implies the result:
o
~c:: L(n) = 2.20 + 1.12n (35)

'"o
Cl
~
Q)
a::
21 1-------+-----p.,,..--4.--------j
linear (single image)
(5=-0.137)
0.1 0.2 0.3
1/(L + a) (,A.-1)
Figure 6 Es (kBTat room temperature) plotted as a function
of l/(L+a). At room temperature k BT=0.026 eY. [Note the
inadvertent use of k BT units for E s, instead of the intended eV
units, was belatedly discovered after the proofs were set; for ease
ofcomparison with Fig. 5, the indicated conversion to eV should
be carried out. - - , Exact results [Eq. (24)]: - -- -, linear fit with
dominant image charge contribution [n = I term of Eq. (24)];
- - - -, best linear fit. The slopes s are given in parentheses in units
of (~q)2, as in Eq. (33). The value ofs for the single-image case
is given by Eq. (33). (From Fig. 3 of Ref. 30, reprinted with
permission. Copyright [1994] American Chemical Society.)
B~f and B~P, which lead to l1~fI = 0.11 (see above dis-
cussion). The optimal linear fit is excellent and may be
viewed as defining an effective single image charge.
To relate the model continuum results specifically to
the OM-based systems, one requires an estimate, Uri), of
the dependence of film thickness (L) on the number of
CH 2 units (n) in the constituent OM moiety. In particular,
we focus on the experimentally studied systems based
on films with redox-active (Au)(S)(CHzMOzC)(Fc) com-
ponents diluted with (Au)(S)(CH z)n-I(CH 3 ) units.
Adopting standard bond lengths and bond angles,
including 1.82 A for fes, 2.80 A for fAuS, 100° for
LAuSC, and 114° for L SCC, and a tilt angle of 27° rela-
tive to the direction normal to the surface [50] and
Because most of the film involves the methyl-terminated
chains, an independent measure of L(n) is the mean
height of these methyl groups. The height of the methyl
carbon atom, hAu-dn), is estimated as 1.90 + 1.12n, (A),
a result quite close to that provided by Eq. (35), and thus
supporting the value ~ 3.8 A for the effective radius of
the Fc redox group. The film thickness implied by Eq. (35)
is in rough agreement with most previous estimates based
on experimental probes or molecular models [50,51].
Although the assumption of regular close-packed struc-
tures appears reasonable for the OM films dealt with here,
we emphasize that in general it is important to investigate
the role of structural fluctuations, using molecular
dynamics computer simulations (e.g., [52]) and
experimental probes.
With Eq. (35) and the linear fit to calculated E s values
(Fig. 6), we obtain,
E,,(n) = 0.95 - 1.72/(6.00 + 1.12n) (36)
where E,,(n) is in eV units. Thus, EsCn) is predicted to vary
by ~O.l eVover the n = 5-25 range. Converting these
variations to contributions to the variation of In k o
with film thickness due to E s (i.e., positive increments
to f3 values based on H DA ), we obtain 0.08
A-I (n = 5-10),0.04 A-I (n = 10-15), and 0.02 A-I
(n = 15-25)[30].
It is clearly of interest to ascertain whether these
modest variations of E s (a consequence ofthe assumption
of ideal metallic screening) are compatible with
experimental estimates of E s . A comparision of calcul-
ated [30] and experimental [14] results is displayed in Fig.
7. A slight tendency ofthe experimental values to increase
with n is apparent, and this behavior is confirmed by
additional reorganization energies measured for fer-
rocence attached to gold by other types of "bridges"
(J. F. Smalley, et aI., unpublished results). However,
uncertainties in both the measurements and the theoreti-
cal estimates preclude an unequivocal conclusion
108 Newton et a1.

1.2 i i i i i i i I (25) or (26)] or from calculation [e.g., via Eqs. (25) or (26),
using the results of ab initio or semiempirical molecular
orbital (MO) calculations], but their underlying roles in
1.0 the overall coupling may be exposed by suitable analysis
of detailed electronic structure results [27]. A given SE
model, and any practical procedure for evaluating HDA,
0.8 entails a decision as to what finite portion of an extended
condensed-phase system constitutes the bridge (B) and
> where the "surrounding" medium begins. An example of
~ 0.6 an approach to this question is provided by model theor-
w
etical studies of alkane (OM) chains comparing f3 values
0.4 [Eq. (28)] from in vacuo results with those in which sur-
rounding solvent is included. The DBA systems are the
fully-staggered radical cation or anion species, 1 n(m), as
0.2 displayed in Fig. 8: (CH2)(CH2)m+l(CHf), where the
CHf group serves as the D( -) or A ( +) site and the ter-
minal CH 2 group is the corresponding A( -) or D( +) site.
0.0 I I i i i i i I i I I
For a given homolog m, the OM bridge (B) contains a
o 2 4 6 8 10 12 14 16 18 20 sequence of m covalent bonds [e.g., as in Eq. (31)]. The
n (number of CH 2 units) results in Table 1allow us to examine the possible role of
solvent in modifYing the in vacuo f3 values for the radical
Figure 7 Plot of E s vs. n: 0, values computed from slopes of cation and anion systems [27]. The long-range interaction
Arrhenius plots based on ILIT results (indirect laser-induced of a polarized aqueous solvent (as represented by a
temperature jump) for n = 5-9; e, values computed from
dielectric continuum model [31]) has no perceptible
slopes of Arrhenius plots based on chronoamperometric data
effect, and even explicit quantum mechanical inclusion
for n = 12, 16, and 18; x, value computed from direct
chronamperometric measurement ofthe potential dependence of peripheral water molecules causes only a modest
ofk! and kb for n = 16. The solid line gives the calculated results, reduction of f3 for the radical cations (presumably due to
as fitted according to Eq. (36). The abscissa may be converted the role of H 20 lone pairs in accommodating hole
to a distance scale by using (for example), relations of the type transfer), with no effect on the radical anion ET processes.
given in Eqs. (34) or (35). (From Fig. 12 ofRef. 14, reprinted with On the other hand, in other model studies, in which the
permission. Copyright [1995] American Chemical Society.) B portion of the DBA system does not fill the space
directly between the D and A groups, the solvent has been
shown to playa dramatic role in the D/A coupling [54].
The common picture emerging from model studies of
regarding the dependence of E s on film thickness. The
this sort is that the spatial region most important for
limiting values of E s for large n based on theory and ex-
HDA (and thus most important for defining the effective
periment are seen to be in good agreement.
The counterpart of Eqs. (34)-(36) for the case of Fc
linked to Au by an OPE-thiol is straightforwardly
obtained from structural data given in Ref. 53, together
with the data pertinent to the relevant diluent oligomers
[15].
····'1'

B. Evaluation of H DA and its Dependence on

the Nature of the Bridge C2v m = 2Q, h1 C2h m = 2Q + 1. Q~o

1. Results for Model Systems
We noted in Sec. IVD. the utility of casting the effective
D/A coupling in terms of competing superexchange (SE)
pathways involving the various "units" of the intervening
bridge. The contributions of these pathways are implicit
in H DA values inferred from experiment [e.g., via Eqs.
Figure 8 ETsystems 1 n(m), consisting of n-type DIA orbitals
(the nonbonding orbitals of the terminal CH 2 groups) linked
by a staggered-alkane bridge [( CH2)m+d possessing m covalent
CC bonds (the covalent bonds connecting the D and A groups
to the bridge contribute little to H DA [20-23]). The even and
odd m members correspond, respectively, to C 2v and C2h
point-group symmetry.
Donor-Acceptor Coupling in Electron Transfer Process
Table 1 Effect of Peripheral Aqueous Solvent on Coupling
Through Staggered Alkane Bridges [l7r(m)]a
Decay coefficient, f3(A -1)b
Nature of hydration Radical cations Radical anions
Absente 0.85 0.95
Dielectric continuumd 0.85 0.95
Specific hydration e 0.81 0.95
«CH2)m+3(H2 0 )m+1 )±
a Based on ab initio SCF energy splittings [Eq. (25)] with the 6-3IG**
orbital basis [27b] and includingm in the range 2-6 (Table 6 of Ref. [27b],
reprinted with permission. Copyright [1997] Elsevier Press).
b Equation (28), based on a linearleast-squares fit of In IHvA 12 as a func-
tion ofrvA.
C In vacuo results from Ref. 31.
d Based on the dielectric cavity model described in Ref. 31.
e An H 20 interacts with each of m + I CH 2 triads for each (CH2)m+3
species, oriented so as to allow the H20 lone pairs to overlap optimally
with the carbon framework [as indicated in structure (2)]. with van der
Waals Co . ·0 contacts of 3.1 A
o
H
j\ H
bridge) is that more or less directly between D and A,
whether occupied by a covalent sequence, solvent, or
vacuum. The studies also indicate similar f3 values for
ET in radical cations and anions.
A systematic study ofthe influence ofconformation on
H DA is given in Table 2, for the radical ions of the 1 n(3)
system (Fig. 1) [22,27]. Table 2 reveals that H DA is quite
sensitive to the conformation of the DBA system, both
with regard to sign and magnitude. We emphasize that
the "in-plane" and "perpendicular" conformations of D
and A orbitals relative to the bridge lead to two different
superexchange mechanisms for D/A coupling, involving,
respectively, the sigma orbitals ofthe carbon atom frame-
work and the CH n-type bonds and the bridge (i.e., a
hyperconjugative mechanism). The sensitivity to con-
formation just illustrated for OM-based DBA systems
and found to be equally important (see below) for their
OPE-based analogs [15] underscores the crucial import-
109
Table 2 Conformational Dependence of H DA for (CH2)t
Radical Ions [b(3)]"
Conformation of
D and A orbitals Conformation Radical Radical
relative to bridgeb ofC 4 bridge cation anion
In-plane trans (C2h) -11.0 -8.4
gauche (C 2) -2.4 -4.5
cis (C2v) -0.3 -4.3
Perpendicular to trans (C2h) -l.l +0.3
plane gauche (C 2) +3.6 +2.0
cis (C2v) +7.9 +9.9
a H VA given in mhartree (I mhartree = 0.027 eV ~ kBT at room
temperature), based on energy splitting (Eq. (25) at the Koopmans'
Theorem (KT) level, using the 3-21G orbital basis [27]. The sign conven-
tion [23] is based on the phases of the D and A orbitals in the two MOs
of primarily D/A character and assigns a positive (negative) sign to the
quantity -HDA when the occupation of the "in-phase" ("out-of-phase")
MO is energetically favored [the positive sign for -HDA corresponds
to the "normal" situation in which in-phase ("bonding") orbital interac-
tions are characterized by a negative transfer integral]. For the (CH2);
systems, "in-phase" is taken as transforming according to ag , a, and
aj for, respectively, C2b , C2 and C2v symmetry in the case of
"in-plane" D/A conformers and au, a, and hi for the corresponding
"perpendicular" conformers (Table 2 of Ref. [27b], reprinted with
permission. Copyright [l997] Elsevier Press).
bAngle of the D(A) pi orbitals relative to plane formed by the carbon
atom of the terminal D(A) methylene group and the closest two carbon
atoms of the bridge.
ance of detailed structural information in the analysis of
ET kinetics in situations where conformational flexibility
exists.
Although the results for the model systems discussed
above are of interest in themselves, they have been shown
to give f3 estimates in generally good agreement with
values inferred experimentally for DBA systems in which
the actual D and A groups are complex molecular
moieties (e.g., [15] and [23]). In the model studies
summarized in Tables 1 and 2, the nominal D and A
groups (the sp2-hybridized terminal CH2- groups) may
be viewed as serving as surrogates for the Sp2 carbon
atoms by which the actual D/A groups (e.g., aromatic
rings or the Cp ring of Fc) are linked to the bridge. The
simple form ofthe NN pathway model of McConnell [Eq.
(30)] suggests that the f3values for the idealized model sys-
tem and the actual system of interest will agree to the
extent that the effective gap A between the D/A energy
level and the occupied or unoccupied band edge of B is
similar for the two cases. In detailed calculations, the
sensitivity of f3 to A may be significantly less than that
110
implied by Eq. (30) as a result of the fact that many differ-
ent pathways contribute to the overall SE coupling
[20-23]. It may, of course, be possible to induce a
sensitivity by forcing the effective gap to be small (e.g.,
fine-tuning by chemical substitution [21]), but for suf-
ficiently small gaps the assumptions entailed in the
underlying perturbation theory might well be violated,
so that the superexchange model would not be applicable.
At any rate, even in situations ofcomplex competition
among multiple SE pathways, the form of the simplistic
single pathway McConnell model can be quite valuable
for modeling the variation of H DA within a family of
DBA systems [28], as illustrated below.
2. Comparison of f3 Values: Estimates from Model
Calculations and Experiment
Recent experimental studies of interfacial ET kinetics at
film modified gold electrodes have provided a set of data
well suited to comparisons with the results of electronic
structure calculations [14,15]. The examples illustrated
in Sec. VB.!. were limited to electronically saturated
bridges. In the case of unsaturated bridges, the occupied
and unoccupied manifolds of the bridge are expected in
general to be energetically more accessible to the D and
A groups [20-23] [i.e., the gap A in Eqs. (30)-(32) is
expected to be smaller], thus suggesting an ~ppreciable
reduction in f3 relative to the value of ~ 1 A expected
(e.g., seeTable 1) for saturated bridges. The electrochemi-
cal studies (introduced first in Sec.VA. in connection with
estimates for E s ) provide important tests of these notions
because for a fixed generic assembly type [(Au)(S)(B)(Fc)]
they allow a direct comparison of D/A coupling mediated
by saturated (OM) and unsaturated (OPE) bridge types
[15]. As revealed by Fig. 9, qualitative theoretical expec-
tations about variation of f3 with bridge type are strongly
supported by the results of the electrochemical studies,
thus inviting more quantitative contact between theory
and experiment, the subject of the following discussion.
Although the SAM films are extended close-packed
arrays oforganic chains, various experimental tests have
indicated [10-15] (at least when the redox-active
oligomers are "isolated" by diluents) that the coupling
between a given Fc group and the gold surface is strongly
dominated by the oligomer to which it is covalently linked
(as opposed to more circuitous pathways involving
neighboring oligomers; a possible role for interchain
coupling is discussed in [12b]). This result is consistent
with conclusions from model studies [27] (which empha-
size the major importance of the region directly between
the D and A groups in mediating the coupling, as noted
in Sec.VB.!.) and indicates that meaningful comparisons
may be made between calculations based on isolated
Newton et aI.
30 i I
25
20
;;:-- 15
.£b
.><:
c= 10
5
o
-5 I I I I I I" I
o 5 10 15 20 25 30 35
£/t
Figure 9 Comparision ofln [ko] vs.! plots for ET through OPE
and OM-based films. OPE results [15] are displayed for two
(¢; n = 2) and three (. ; n = 3) OPE units; the OM results (0
and.) are as given in Ref. 14. Different diluents give very similar
results. The error bars are significantly smaller than the size of
the symbols. The abscissa e denotes the straight-line distance
from the terminal sulfur-bonded oligomer carbon to the
attached carbon atom ofFc, based on mean bond distances [52].
A linear oligomer axis was assumed for both OM and OPE
systems. (From Fig. 1 of Ref. 15. reprinted with permission.
Copyright [1997] American Chemical Society.)
DBA systems and experimental results for the extended
SAM systems. Furthermore, to the extent that Es does
not vary significantly with rDA (e.g., see [15]), one may
compare calculated f3 values based on H DA with
experimental f3 values based on In k o.We note the distinc-
tion between rDA (which is independent of the tilt angle
of the linear oligomers) and the vertical height of the Fc
above the electrode, the quantity that controls the
magnitude of Es and that varies with tilt angle for a given
oligomer (as noted in Sec.VA.).
The computational results displayed in Tables I and 2
were based on Eq. (25) for symmetry-equivalent D and A
groups, using ab initio molecular orbital calculations.
For the comparison ofOM and OPE oligomers, the semi-
empirical INDO/s (intermediates neglect of differential
overlap/spectroscopic parameterization) method [55]
was used for the electronic structure calculations. This
semiempirical method, which has been shown to give
results quite similar to those from ab initio calculations
in a number of comparative tests [56], allows a very
Donor-Acceptor Coupling in Electron Transfer Process
efficient scanning ofthe various conformers of interest in
the case of the OPE systems. Although coupling through
OM oligomers is quite sensitive to conformation (Table
2), the available evidence indicates that the chains in the
OM-based SAMs are in fully staggered conformations
[10-14,30]. Thus, the comparison with experiment for
the OM films used the model structures hem) in Fig. 8.
In contrast, little is known about the distribution of
dihedral angles ofthe phenylene groups in the OPEbased
films. Because these groups are separated by acetylene
units, the intrinsic rotational barriers are expected to be
quite small (an upper limit of ~0.6 kcallmol has been esti-
mated for diphenyl acetylene [57]), so that the dihedral
angles in the OPE films could be strongly influenced by
the environment (i.e., the diluent oligomers). A full resol-
ution of these structural questions would require a very
large-scale computer simulation effort and would also
entail electronic structure calculations over a broad range
of conformations. On the other hand, adequate account
of conformational effects is essential for any meaningful
treatment ofcoupling, because the mediation of coupling
via OPE bridges will clearly be sensitive to the angular
orbital overlap between the different units of the bridge
and between the bridge and the D and A groups. A work-
able compromise for accommodating these issues was
achieved [15] by carrying out electronic structure calcu-
lations for a limited sample of dihedral angles and then
interpolating the H DA results for any desired set of angles
by exploiting the form ofthe McConnell expression given
by Eq. (32), as described below.
Calculations were based on homologs [31l(n)] of the
type shown in Fig. 10, where n is the number of PE units
and where as for the saturated analogs, 11l(m), terminal
CH2 groups serve as D and A sites. In addition to these
latter groups and the repeat unit, the 31l(n) structures
contain an additional acetylene unit. This was included
for convenience in analyzing the molecular orbitals,
because the extra unit yields symmetry-equivalent D
and A sites for many conformers studied. The coupling
was evaluated at the level ofthe two-state approximation
on the basis of INDO/s CI calculations for the radical
ion (cation or anion) states of structures 31l(n), followed
by GMH analysis [15]. The superexchange coupling for
the cation and anion systems are expected [20-23] to
be dominated, respectively, by the participation of the
occupied ("hole" transfer) and unoccupied ("electron"
transfer) electronic manifolds of the bridge, and as for
the case of the saturated systems [11l(m)], it is of interest
to compare the corresponding f3 values.
To obtain a compact expression for the coupling, the
results of the calculations were fit to the form of the
superposition of McConnell type pathways [see Eq. (32)]
111
e
?
~-=-~-=~
n
Figure 10 ETsystems 3:n:(n), consisting ofthe same n-type DlA
orbitals as in the case of the l:n:(m) homologs (Fig. 8). The
dihedral angle between the common plane of the terminal
CH 2 groups and that ofthe kth phenylene group is denoted 8k.
displayed in Eq. (37). This expression includes pathways
involving a hole (for radical cations) or electron-attached
(for radical anions) virtual electronic state in either the n
or (J manifold of each phenyl group (thus yielding a
superposition of 2n pathways) and also allows the kth
phenylene group to be rotated by an arbitrary angle, 8k,
relative to the reference plane of the coplanar D and A
CH2 groups (Fig. 10):
(37)
where Xk == nk or (Jk and the NN McConnell parameters
are expressed as [15]
T~'l = (T~Do cos[8Jl (38a)
(38b)
"k,"k+l
tk,k+i = ( "ko"k+l) (
tk,k+l 0 cos [8] [8
k cos k+l
]
(38c)
+ sin[8k] sin[8k+ Jl), etc.
The parameters denoted by "zero" subscripts were
obtained by least-squares fits (± 10%) to the GMH
results for a sample of 12 different conformers spanning
a broad range of dihedral angles in the series n = 1-4.
The use of the cos (8) and sin (8) factors is an approxi-
mation motivated by the fact that, for the purpose of
rotation about the OPE axis, the relevant orbitals of ben-
zene have the nodal structure of 2pn orbitals with respect
to the OPE axis, in contrast to the situation involving
porphyrins linked by a biphenyl spacer (analyzed by
Helms et al. [58]). The 2pn nodal structure pertains not
only to the phenylene occupied and unoccupied Mas
belonging to the conventional "pi" manifold but also to
the analogous Mas of the same nodal type belonging to
112 Newton et aI.

Table 3 Exponential Decay Coefficients distribution of dihedral angles. For homogeneous

p(A -I) Calculated a kinetics to be obtained in the case of the uniform dis-
p(A-I) tribution, interconversion among the dihedral angles
Tether repeat unit Anion Cation Experimental b would have to be rapid compared with the rate of electron
transfer [59]. Alternatively, the dihedral angles may be
A. staggered 1.00 0.83 0.9 ± 0.1 d
narrowly distributed about an intermediate value that
(-CH 2 -CH 2 -)C
gives an H1A value similar to the average value of H1A
B. (-C 6 H 4 -c=c-)e for the uniform distribution. Neither possibility can be
Perpendicular Uh =n/2) 0.99 0.95 ruled out on the basis of available data, because the
Uniform Fh distribution f 0.54 0.51 0.57 ±0.02g barriers to rotation are quite likely to be very small (see
Planar Uh = 0) 0.43 0.39
above). We note that a distinct set of dihedral angles can
C. trans (-CH=CH -) 0.32 0.31 0.2 h be observed in the solid state [52].
a GMH [18] and INDO/s [54] results based on In IHDA 12 vs. rDA.
b Results based on In [kol vs. e(see Fig. 9). The distance ediffers by a con-
stant from the distance between the Fc iron atom and the gold surface
at the point ofattachment to the OPE chain. VI. CONCLUDING REMARKS
e See Fig. 8.
d From Ref. 10-14.
The examples of calculated results presented in the last
e See Fig. 10. The Bk are the set of dihedral angles of the phenylene rings
section underscore the important role of computational
relative to the reference plane of the D and A groups [I :'0 k :'0 n for
31t (n)]. chemistry in establishing productive contact between
f {J is based on the rms values of H DA . A small torsional barrier (e.g., a theoretical and experimental investigations of electron
value of ~kBT at room temperature found for the related diphenyl acety- transfer kinetics in condensed phases. In the context ofa
lene system [56]) would yield somewhat large rms values of H DA and broad kinetic framework (albeit one limited to the case
smaller values of {J.
of weak D/A coupling) capable of accounting for homo-
g From Ref. 15.

h From Ref. 60.

Source: Table 2 of Ref. 15, reprinted with permission. Copyright [1997]
American Chemical Society
the "sigma" manifold (i.e., MOs of 2pn nodal structure
comprised of suitable linear combinations of the
phenylene sigma bonds). It is seen that the integer n in
Eq. (37), the number of PE units, is the counterpart of
m in Eqs. (31) and (32), because the superexchange
couplings involve in effect one orbital from the "pi"
manifold of each PE unit and one from the "sigma"
manifold.
Results for three limiting conformational cases are
displayed in Table 3. The calculated values of In [H1A] vs.
m exhibit linear behavior (regression coefficient ::,:0.99)
within a homologous series of a given conformational
type; the corresponding f3 values (Table 3) reveal a strong
dependence on spacer conformation, with similar results
for the radical anion and cation models. Note that the
agreement with experimental values is quite good for
both the staggered saturated (~CH2CH2~) and trans-
unsaturated (~CH=CH-) bridge units.
The experimental value of f3 for the OPE spacer is seen
to be intermediate between the calculated values for the
perpendicular and coplanar ring geometries and in
closest agreement with the calculated value for a uniform
geneous processes and interfacial processes involving
metal electrodes, we have placed particular emphasis
on two crucial kinetic parameters, the solvent
reorganization energy (Es ) and the D/A coupling element
(H DA ), showing how the behavior of these quantities
may be evaluated and analyzed theoretically and
successfully related to results inferred from electro-
chemical kinetic measurements. The theory underlying
the calculations allows the formulation of compact
models of predictive utility, suggesting critical new
experimental tests of theory and helping to identifY
principles that will be important in the design of new
materials with specified redox characteristics. Results of
the type illustrated in Table 3 suggest that the INDO/s
quantum chemistry model in conjunction with the gener-
alized Mulliken- Hush model for D/A coupling offers an
especially promising approach for efficient treatment of
a broad array of ET systems in a quantitatively reliable
manner.
ACKNOWLEDGMENT
This research was carried out at Brookhaven National
Laboratory under contract DE-AC02-98CH10886 with
the U. S. Department of Energy and supported by its Div-
ision of Chemical Sciences, Office of Basic Energy
Sciences.
Donor-Acceptor Coupling in Electron Transfer Process
APPENDIX
A further technical comment is in order with regard to
Eq. (37). Clearly, the superexchange model assumed for
the purpose of fitting the numerical results (with D and
A identified with the terminal CH2 groups) does not take
explicit account of the "extra" acetylene unit of the 31l (n)
homologs (Fig. 10). As a result, the T D and T A parameters
may be interpreted as corresponding to a generalized
D and A pair (relative to their nominal definitions as
terminal CH2 groups), which implicitly include the
influence of the extra acetylenic group.
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 8
Interfacial Electron Transfer in Electrochemistry and In Situ
Scanning Tunneling Microscopy
Esben P. Friis, Marianne Hallberg Thuesen, Jingdong Zhang, and Jens Ulstrup
Technical University ofDenmark, Lyngby, Denmark
ABSTRACT
Established and new elements of the theory of electron
transfer at electrochemical interfaces are overviewed.
This extends particularly to current-overvoltage
relations at metal, semimetal, semiconductor, and
high-temperature superconductor electrodes in the
diabatic limit of weak interaction between the electrode
and reacting molecule. A simple view of the conditions
for the prevalence ofthe adiabatic ordiabatic limits is also
introduced, and attention to the electronic tunneling
factor is given. The latter exhibits a new feature different
from electron transfer in homogeneous solution, i.e., the
electron density of the metal electrode expands on nega-
tive and contracts on positive surface charging. This
facilitates and hampers the tunneling process,
respectively.
Views of electrochemical electron transfer can be
extended to the two-electrode configuration of in situ
scanning tunneling microscopy (STM) of redox
molecules. The potential Gibbs free energy surfaces in
electron transfer modes of a large redox molecule
such as a transition metal complex or a redox metallo-
protein in the in situ STM configuration are
constructed, and it is shown that this configuration
offers approaches to experimental distinction
between different mechanisms for tunneling through the
adsorbed molecule. The mechanisms are particularly
sequential two-step electron transfer and coherent or
resonance tunneling. It is finally shown that recent in situ
STM data for adsorbed and covalently bound
metalloporphyrins and for adsorbed azurin (a blue
single-copper protein) exhibit features according to these
views.
115
i
I. INTRODUCTION
Chemical and biological electron transfer (ET) in
homogeneous solution has reached an impressive
level of characterization [1-12]. Central and now
well-known notions are localized electronic states [7,8],
strong electronic- vibrational coupling [7,8], the
diabatic and adiabatic limits [7,8], and long-range
ET through intermediate matter [9-12]. Other
important issues in more recent focus are, for example,
fluctuational tunnel effects [13-15], multilevel coherent
and resonance ET [16,17], and self-consistent
electronic-vibrational interactions and non-Condon
effects [18].
Similar detail in interfacial ET between metal,
semiconductor, semimetal and superconducting elec-
trodes and molecular redox centers in the interfacial
region has been more elusive. Fundamental similarities
and differences from ET in homogeneous solution were
recognized early [19-23]. Central analogies are first that
the ET process is in both cases a quantum mechanical
transition between two molecular electronic- vibrational
states, coupled to an environmental vibrational con-
tinuum, and to local vibrational modes. Free energy
relations can also be constructed in both cases. In homo-
geneous ET these are based on the notion of series of
closely related processes. The driving force in interfacial
ET is the overpotentiall], i.e., the actual potential relative
to the equilibrium potential. I] is thus positive for anodic
and negative for cathodic processes. A broadly valid form
over limited ranges of I] is the Butler - Volmer equation (cf.
116
below):
where J(rJ) is the current at the overvoltage rJ, Jo the
exchange current, (j, the transfer coefficient, whereas the
activation Gibbs free energy G°-j. incorporates all the
nuclear activation features. "Work terms," i.e.,
interreactant activation Gibbs free energy, are, finally,
important in both cases, where the electrochemical
analogues appear as "double-layer corrections," them-
selves functions of the overpotential. Among the most
conspicuous differences is first that the electrode now con-
stitutes a virtual continuous manifold of electronic states,
whereas only a single pair of states is involved in homo-
geneous ET. Consequences ofthis such as the absence of
an inverted Gibbs free energy region in interfacial ET
processes at metallic electrode surfaces, are discussed
elsewhere [8,24]. The view of overall interfacial ET as
independent transitions from all these levels is adequate
in the diabatic limit of weak electrode-molecule interac-
tions but needs modification when the interaction is
strong and the adiabatic limit approached. The
electrode-electrolyte interfacial region is, finally,
exposed to strongly different forces from the two bulk
regions and to strong electric fields. Solvent molecular
orientation, ionic charge distributions, solvation
patterns, and so on are therefore different from the bulk
and the simple view of a planar boundary between two
isotropic uniform media is inadequate when molecular
detail is approached.
Theoretical and experimental detail has been fraught
with difficulties in finding suitable approaches to the elec-
tronic and molecular structure and dynamics of the
inhomogeneous anisotropic interfacial environment.
Neither have straightforward analogues of molecular
quantum chemical approaches to the electronic tunnel
factor and the electronic-vibrational coupling features
in interfacial ET been available. New theoretical
approaches to the structure of the metal- solution
interface, sophisticated technology, and new and
nontraditional interfacial tunnel systems now, however,
offer more detail also in the fundamental interfacial ET
process. Theoretical approaches have been based on dens-
ity functional methods for the metallic surface electronic
structure interacting with the contacting solvent and sol-
ute molecules [25-30]. Density functionals can be con-
verted self-consistently to electronic wave functions of
the surface [31-33]. The electrochemical rate constant
can also be recast in terms of electronic densities rather
than wave functions [34]. This is because the dominating
levels over broad overpotential ranges are grouped in a
Friis et al.
narrow range around the Fermi level. Experimental
approaches to new and nontraditional interfacial ET
systems are based particularly on long-range ET across
variable-length self-assembling films [35-41] and on the
evolution ofscanning tunneling (STM) and atomic force
microscopy (AFM) as technologies for structural and
electronic imaging to submolecular resolution of individ-
ual adsorbate molecules directly in their natural func-
tional aqueous medium (in situ STM/AFM) [42-44].
The long-range electrochemical ETsystems are charac-
terized precisely enough that the electronic tunnel factor
and nuclear coupling parameters can be disentangled
and studied in detail. In addition to the structural
mapping of solute adsorbates, in situ STM/AFM has
also come to offer prospects for functional imaging.
Current/distance [45], current/bias voltage, and
current/overvoHage relations [46-48] of in situ STM are
such examples. Interpretation of these new important
cases of single-molecule spectroscopy can be interfaced
with interfacial electrochemical ET theory suitably
extended to in situ STM. Single-molecule AFM
spectroscopy has also been reported, for example in the
context of biological macromolecular conformational
changes illustrated by enzyme-substrate complex forma-
tion and unfolding patterns ofproteins and nucleic acids
[49-51]. In this chapter we provide a brief overview of
some of these new initiatives and ofsome of their further
perspectives [52].
II. ELECTROCHEMICAL PROCESS
Figure 1illustrates a broadly valid view of the fundamen-
tal electrochemical ET process [7,8,19-22]. Cathodic ET
is explicitly shown. The single most important
assumption is that the observable current is
composed of independent contributions from all the
individual electronic levels on the electrode side. This is
appropriate when the interaction between the solute
molecule and the electrode is weak and the diabatic
limit applies. Relaxation of this assumption is
addressed below. The electronic levels in the
electrode are weakly affected by the solvent, but the
tunnel factor involving the electronic density tail
protruding into the solution can be strongly affected.
The local molecular level is strongly coupled to the
environment. The equilibrium position of the initially
vacant level is thus well above the Fermi level.
Environmental polarization fluctuations must therefore
bring the level to match the populated levels where
significant current flow begins. These levels are located
around the Fermi level for metal and semimetal
electrodes but near the conduction or valence band edges
 Electron Transfer at Electrochemical Interfaces 117

[7,8,53]:

fee) = (I +exp[(e-ep)]}-l;
(3)
p(e) = (Vm;/2 /1i 3 n 3 )J2(e - eb)
where ep is the Fermi energy, V the volume of the
electrode, me the mass of the electron, and Eb the energy
at the bottom of the conduction band. k B is Boltzmann's
I
I
constant, 2nli Planck's constant, and T the temperature.
I
I
I Wee; IJ) in Eq. (2) is, finally, the rate constant (transition
U(q) I
I
I probability per unit time) for ET from the level of energy
I
I
I
I
e to the molecular level.
I
1-,
I Equation (2) is a general basis for a broad range of
(a) I (PRO) I (P) q
I PO specific systems. It applies to metal, semimetal,
semiconductor, and superconductor electrodes, where
differences are the range of e levels effectively con-
tributing, and the electrical potential distribution across
the interface. W( e; IJ) also incorporates all the many soph-
-1 e,IF',o) isticated features of electronic-vibrational coupling,
conduction band
nuclear tunneling, and so on. With a view on newly
------- .""01 --- •
} no electronic
observed features, we consider presently specific but
transition
broadly valid models for the interfacial ET process mostly
at metallic surfaces. One of these addresses the
valence banCl
electronic-vibrational interactions and nuclear
fluctuational features of the solute molecular part. In
another model, focus is on a simple representation
(b) (jellium) of the metallic electronic density and the reflec-
tion of this quantity in the electronic tunnel factor and
Figure 1 (a) Electronic energies (left) and nuclear potential its sensitivity to the overpotential variation.
(Gibbs free) energy surfaces (right) for electrochemical The following representative rate constant form is now
(cathodic) electron transfer at metal electrodes. (b) Same dia- in focus:
grams for semiconductor electrodes.

(4)
for semiconductor electrodes, and near the density band
gap edges at superconducting electrodes. The following
transparent current density form applies, broadly
independently of details of the electronic spectrum on or
the electrode side and of the solute molecular
electronic- vibrational interaction

.
j
j(lJ) = Jdep(e)f(e)j(e; IJ); (2)
(5)

j(e) = eCox(z*)~z Wee; IJ)

Cox(z*) is the concentration of the oxidized molecule at
the distance z* from the surface ( ::::; the contact distance)
and ~z a narrow z-range around z* where EToccurs.f(e)
is the Fermi function and p(e) the electronic density, for
which the following free electron forms are appropriate
E R is the total environmental and local classic
reorganization Gibbs free energy and ~Go(e; IJ) the
driving force relating to the individual electronic level of
energy f, whereas Weff is the effective vibrational
frequency of all the nuclear modes reorganized [7,8].
118
Kel is, finally, the transmISSIOn coefficient coupling
electronically a given electronic level in the electrode with
the molecular redox level. Equations (4) and (5) represent
electrochemical ET for many specific molecular models
of the electrode-electrolyte interface as long as the
electronic- vibrational interaction remains linear and
the electrode-molecule interaction is weak. New statisti-
cal mechanical molecular models would, for example,
be covered by this formalism. Other features such as
nuclear tunneling, nonlinearity and anharmonicity
modes, double-layer effects, or work terms can be added
as warranted.
A. Current- Voltage Relations at Metal,
Semimetal, Semiconductor, and
Superconductor Electrodes
Equations (2)-(5), with available extensions constitute
the current-voltage relations of the fundamental
single-ET process. This formalism holds important and
long-recognized but still often overlooked implications
[7,8,19-22].
Levels around the Fermi level dominate for broad er/
ranges at metal electrodes. The current then takes the
quadratic form
The exchange currentjo = j('1 = 0) is
jo ~ [nep(£F)/ Ii]y! Cox Cred (2k B T / E R ) 1/2
x ~z[TDA(£ ~£F; '1 = O)f exp( -ER/4k BT)
where Ced is the concentration of the reduced molecule.
The concentration factor in the pre-exponential part
arises from the Nernstian concentration part of the
equilibrium potential [7,8]. The transfer coefficient IX is
1 e'1
IX = -k B Tdlnj/d(e'1) = 2" + 2E (le'1l < ER )
R
Equations (7) and (8) apply in the "normal" overvoltage
range where le'1l < E R . In the activationless range
-e'1 > E R ('1 < 0 for a cathodic process) and broad
ranges of levels below the Fermi level dominate at metal
electrodes. An implication of this is that electrochemical
ETat metal electrodes has no inverted Gibbs free energy
region, in contrast to ET in homogeneous solution
where only a single pair of electronic energy levels is
available.
Equations (2)-(5) also apply to semimetal,
semiconductor, and superconductor electrodes. The
dominating £ ranges are, however, different here and Eqs.
Friis et aI.
(6)-(8) must be modified. The level densities of
semimetals is small and increase notably on either side
of the Fermi level. p( £) for the electrochemically broadly
used graphite thus exhibits a pronounced minimum at
£F [54], implying that levels above and below £F are
important. The dominating levels at semiconductor elec-
trode surfaces are the levels at the lower edge of the con-
duction band for electron transfer, £~ and at the upper
edge of the valence band for hole transfer, £;(Fig. Ib).
The surface potentials at the electrode are, moreover,
approximately independent of '1 due to the small charge
carrier concentrations. The '1 dependence of electron
transfer is therefore largely reflected in the level popu-
lation in the conduction band, whereas the hole transfer
current is independent of the overvoltage. The currents
for electron (e) and hole (P) transfer from the electrode
take the forms
(9)
with the exchange currents
(7)
(10)
where ~cp 0 is the equilibrium potential difference between
the bulk and the surface of the electrode, whereas ~e
and ~p are the gaps between £F and the lower edge of the
conduction band and the upper edge ofthe valence band,
respectively (Fig. Ib). The appearance of the equilibrium
(8) surface potentials in Eq. (10) reflects the bending of the
conduction and valence bands in the surface region (Fig.
Ib). The exponential factor exp[-(e'1 + ~e + e~¢o)/
k B T] in the first line represents, moreover, the population
of electron carriers in the conduction band given by the
Fermi function at the lower edge of this band at the
surface.
High-temperature superconducting electrode mat-
erials such as YBa2Cu307-b, YBa2Cu3(1-x)Znx 07-b,
and other mixed oxides have recently become available
[55,56]. These undergo a phase transition from a normal
electronically conducting to a superconducting state at
a critical temperature Tc , slightly above 100 K. They have
been introduced as electrode materials in connection
 Electron Transfer at Electrochemical Interfaces 119

with the solid electrolytes AgfJ' -alumina and frozen

HCI0 4 . 5.5H20. Electrochemical processes are U(q)
Ag+ -reduction and dihydrogen evolution, for both of
which a conspicuous feature (maximum or shoulder) in
the current-temperature relation appears at Te [55,56].
In "classic" superconductivity theory (the Bardeen-
Cooper-Schrieffer theory), superconductivity is associ-
ated with electron pair formation and an energy gap,
A, in the density near the Fermi level. A follows the
relation

below T e and vanishes above Te . Several views ofthe elec-

trochemical process, including both single-electron
transfer and electron pair transfer, have been forwarded
[57]. Single-electron transfer is conceptually the simplest
and follows the pattern for semiconductors below T e .
The exchange current would particularly be suppressed
by a factor of the form exp[ -aA(T)jk B T] and exhibit
a kink in the T correlation at T e . When the
electronic-vibrational coupling is weak (ER small), this
feature is converted to maxima as the molecular level
passes the band edges. The band maximum separation
closes at Te where the maximum height also increases.
The observed effects have so far been small, but
the area is still new and perspectives for larger
"supercatalytic" effects cannot presently be excluded.
B. A Simple View of Adiabatic
Electrochemical Electron 'n'ansfer
The discussion above rested on the view that the interac-
tion between the molecule and the electrode is, by some
scale, "weak." In the opposite limit of strong interaction
adiabatic behavior is approached but due to the macro-
scopic band state delocalization this concept is different
from ET in homogeneous solution. The virtual infinite
delocalization means that the overlap involving individ-
ual electronic states is always small. Individual
transitions are therefore strongly diabatic, but the
infinitesimal level separation means that the density of
states is high and that a macroscopically large number
of levels contribute. The diabatic or adiabatic nature of
the process is therefore determined by the combination
of the individual electron exchange factors and the level
density.
Different approaches to adiabatic electrochemical
electron transfer have been reported [7,58-62]. Figure 2
illustrates the character of this limit. Many-electron
effects in both the reactants' and products' states are now
important and give the two manifolds of states shown.
r As the molecular level approaches the potential surface,
q
Figure 2 Potential (Gibbs free) energy surfaces and system
trajectory for adiabatic electrochemical electron transfer at a
metal electrode. The bold line represents the manifold of
forward and reverse transitions involving individual electronic
energy levels.
crossing around the Fermi level a continuous manifold
of transitions in both directions begin. The potential
Gibbs free energy surface manifolds, spanned by the (set
of) nuclear coordinate(s), are
(12)
sand s' being the total energies ofall the metallic electrons
in the oxidized and reduced molecular state, respectively,
counted in such a way that
s - s' = s* - SF (13)
where s* is the energy of the electron transferred from a
particular Gibbs free energy surface.
UR(q) corresponds to the Fermi distribution of the
electrons in the metal and a vacant molecular state.
Up(q) corresponds to the Fermi distribution with one
electron less and an occupied molecular level. When
motion along q proceeds, transitions forward and reverse
between manifolds of level pairs begin, symbolized by
the bold "zig-zag" line in (Fig. 2). This is quantitatively
recast as the probability that the system is localized on
U Rf( q) and crossing to the particular surface UFe' (q),
and vice versa. A set of master equations in the two
probabilities constitutes the equations of motion that
have been set up and solved [58]. The following simple
consideration illustrates the result [8].
120
The probability ofET along VR/q) passing the energy
interval bs on the UN(q) manifold is
(14)
wheref(s-s') is the Fermi function that now depends on
the difference between the total electronic energies in
the metal before and after the transition. K€€, is the elec-
tronic transmission coefficient for transition between
thelevelssands'. For WEE' to approach unity, i.e., theadia-
batic limit, the condition
be' 0::::: [K€€,p(s)f(s - s')r l
(15)
and be 0::::: [K€€,p(s')f(s - s')r l
must apply for the s ---+ s' and s' ---+ s transItIons,
respectively. It follows from Eq. (15) that be' is large when
s' is above the Fermi energy where f(s - s') =
f( s* - SF) ---+ 0, but small below the Fermi energy where
be ---+ [K€€,p(S)r l . The opposite applies to be. The charac-
teristic energy range for both the Fermi function and
the nuclear activation factor is, moreover, k B T. The
transition probabilities throughout the characteristic
energy intervals are therefore small if the condition
(16)
holds. This is the diabatic limit corresponding to the pre-
vious sections. The adiabatic limit corresponds to the
inverse inequality of Eq. (16). The transition probabilities
in both directions near the Fermi level are here large
and the intervals bs and be' much smaller than k B T.
The precise description of the overall transition rests
on mapping of trajectories in the s,s'-plane [58]. The
resulting current in the adiabatic limit then takes the form
wad _ Werr (_ Gt-) (17)
DA - 2n exp kBT
where Werr is the effective frequency of all the classical
nuclear modes reorganized [cf. Eq. (5)]. The activation
Gibbs free energy, Gt-, is determined by the maximum
of the total adiabatic potential Gibbs free energy surface
[58]
Uad(q) = - kBTln{exp[-UR(q)/kBTJ
(18)
+ exp[- Up(q)/kBT]}
Friis et al.
C. Features of the Electrochemical Electron
lUnnel Factor at Metal Electrodes
Mechanisms for elastic, resonance, inelastic, and
thermally activated electron tunneling across thin oxide
and polymer films and through semiconductor band
bending were recognized early [63-66] and simple but
palatable formalism derived. The availability of new data
for long-range electrochemical electron transfer across
well-characterized, variable-length films [35-41] has
warranted new attention to the pre-exponential tunnel
factor, with more detail on the film properties and the
metal- film interface.
As for ETin homogeneous solution, the electrochemi-
cal tunnel factor is
T DA =TDA(S; 1])
= Jt/J€(s; Z, R; 1]) V(z)'Pmo1(z, R; a)dziR
(19)
where t/J€ is the metallic wave function at the level sand
overvoltage 1], 'Pmo1(z, R; a) is the wave function of the
reacting molecule at the position a, whereas V(z) is the
physical interaction between the molecule and the
electrode. V(z) incorporates a variety of effects, including
~larization, image charge effects, pseudopotentials, etc.
R is the lateral coordinate vector. Rather than using indi-
vidual wave functions, the electron exchange factor and
overlap can be recast as the density overlap [34]
2
---+ ---+
R; e; 1])'Pmol (z, ---+
M(s; 1]) =
J
dzdRt/JE(Z, R) 1
1
o:::::(i1zli~RIQ(z*)IIt/J€(z*;e; 1])1 2
---+ ---+ 2 * 2 ---+
= = l'Pmol(Z, ---+
Q(z)
J dR l'Pmol(Z, R)I R i1R 1
(20)
---+ ---+
where i1z and i1R are "effective" z- and R-ranges,
. ---+
~spectlVely, whereas z* and R * are the values of z and
R for which the integrand in M(s; 1]) is maximum. This
conversion is feasible because the z-integral is dominated
by a narrow range around z* and the energy levels
effectively contributing, over broad overpotential ranges,
are restricted to narrow ranges around the Fermi level.
The total metallic electronic density profiles at electro-
chemical interfaces are available from many recent
investigations. The density functionals can, finally, be
converted to the wave functions by self-consistent
schemes (the Kohn-Sham scheme). All this offers
attractive prospects for the use of electronic densities in
the description ofthe electrochemical process.
Electron Transfer at Electrochemical Interfaces
The quantity O(z*) length- 1 is the molecular elec-
tronic density. The metallic electronic density is
n(z; e; 1]) = p(e)f(e)ll/Je(z, ---+* 0
R ; e; 1])1-
The total density, n(z; 1]) to be represented by a density
functional, is
n(Z;I])=fden(z;e;I])~!'>en(z;e*;I]); (e*~eF)
where the second step rests on the observation thatf(e)
decreases rapidly with increasing e above the Fermi
---+
level, whereas Il/Je(z, R; e; 1])1 2 increases rapidly outside
the surface. Combination of Eqs. (20)-(22) with Eqs.
(2)-(7) gives
j(I]) = (ne/21i)be!'>zCox [V(z*)f M(I])exp[-G* /kBT]
be~J8kBTER;
M(I])~M(eF;I])~!'>z!'>R f dzIO(z)ln(z; eF)
Equation (23) is the current-voltage relation including
the electronic density overlap. The overvoltage and
interfacial charge dependence of the latter can be illus-
trated by the following specific density representations.
The molecular density is given by the exponential form
l'¥mol(Z, R; a)1 2 = (l /8n) exp{ _y[R2 + (z _ a)2]1/2}
O(z; a) = (y /4)(1 + i'lz - al) exp(-ylz - al)
where y is the orbital decay factor. Jellium is taken as a
representative of the metallic electron density
n(z) = n+ {1 -! exp[jJ(z - z)J}; z < z
n(z) =!n+exp[jJ(z-z)] z>z; Z = -(J/n+
where p-l is the inverse decay length in the interfacial
region, n+ (charge length-I) the bulk electronic density,
and (J (charge length- 2) the excess surface charge
density. Combination of Eqs. (24) and (25) with Eq. (20)
gives for the density overlap
n+
M(I]) = 4(p2 _ 1) {2exp[-jJ(a - z)]
+ p2{(p2 _ 1)[y(a - z) + 2] - 2}
x exp[ -yea - zm
p =jJIY
121
This equation has some interesting implications, with
no immediate analogue in long-range ET in homo-
geneous solution [34]:
(21)
1. Jelliumapplies to"simple" (s-p), electronically lighter
metals. By suitable extensions it can brought to apply
also to heavier metals more appropriate to electro-
chemical systems.
2. The simple form in Eq. (26) can be brought to
(22) carryover from metal- vacuum to metal- electro-
lyte interfaces by variational calculus of the
interfacial Gibbs free energy functional with suit-
able energy terms from the solution side added.
This has accounted for properties such as the
inner layer capacitance and interfacial optical
responses.
3. The decay length of the metallic density depends
itself on the excess surface charge density. This
additional effect is significant and affects not only
the jellium front [z = -(J /n+, Eq. (25)] but also its
(23)
4.
shape.
In the context of electrochemical ET, an intriguing
implication is that as the electrode is charged
negatively, the electronic density expands on the sol-
ution side, facilitating electron tunneling. Tunneling
is similarly hampered on positive charging. As a con-
sequence, asymmetric current-voltage relations
would be expected, with current enhancement on
the negative side of the potential of zero charge, rela-
tive to the positive side. This effect can be converted
to current-voltage relations via the differential
capacitance.
(24) 5. The effect in 4 is more important the
(electronically) lighter the metal, the longer the
ET distance, and the stronger the electronic
localization on the molecular reactant [the larger
y, Eq. (24)]. The effect is insignificant at contact
distance for most common electrode materials.
(25)
The two effects could, however, be comparable for
metals such as silver, even at moderate ET dis-
tances (say 10 A or so).
6. The effects in 4 and 5 are strongly reflected in the
current-distance relations. These are approxi-
mately exponential (cf. the following subsection)
with a decay factor that decreases (increases) with
increasing negative (positive) electrode charge
density.
7. The concepts, formalism, and implications above
(26) have disregarded a number of other physical effects.
One of these is the possible repulsive interaction
between the expanding metallic electron density
and the reacting molecule. This would obviously
122
counteract the density lability effects in the overlap
factor at fixed distance of the reacting molecule
from the electrode surface.
D. Some Experimental Observations
Reports of several well-characterized electrochemical
ET systems have appeared recently [35~41] based on
electrochemical electron exchange of simple redox
systems such as Ru(NH 3 )6f+/3+ and ferrocene/
ferrocinium across variable-length alkylthiol films
self-assembled on gold electrodes. These systems are
characterized in sufficient detail that the electrochemi-
cal rate constant can be disentangled into the
pre-exponential factor and the activation Gibbs free
energy. Some observations are:
1. The current-overvoltage relation is approximately
quadratic [35,39] with E R 0::::: 0.5 eV. E R follows a
characteristic distance dependence approximately
in line with electrostatic models of the three-phase
metal/dielectric film/dielectric solvent system
[68,69].
2. The pre-exponential factor falls off approximately
exponentially with increasing alkyl chain length.
The decay factor (0::::: 0.8-1 A) is not far from similar
factors for bridge-assisted ET in homogeneous
solution, pointing to the expected much stronger
fall-off of the electronic density of the metallic gold
surface.
3. The decay is, interestingly, slower ( 0::::: O. 57 A-I) for a
n-conjugated spacer [41].
4. There are few cases of self-assembled alkylthiol
films where the overpotential dependence of the
tunnel factor has been determined. In one case,
notable asymmetry was, however, noted but with
a slower fall-off on the anodic rather than the
cathodic side, i.e., opposite to the effect expected
from the simple views of jellium lability discussed
[37]. The cause of this observation is presently not
clear.
The surface charge density can be controlled by using
amalgam electrodes and varying the amalgam com-
position. It has been noted that the first step in the
reduction ofZn 2+ on In- and Tl-amalgam electrodes, i.e.,
Zn2+ ---+ Zn+ reduction in fact exhibits a charge density
dependence similar to the effects expected on the basis
of Eqs. (23) and (26) [70]. Charge density lability could
therefore deserve attention, but this particular process
might be far from simple ET.
Friis et al.
III. INTERFACIAL ELECTRON TRANSFER IN
IN SITU STM OF LARGE REDOX
ADSORBATES
In situ STM has come to offer a wealth of recognized
exciting new perspectives for imaging of metal-solution
surface structure and dynamics at the molecular and
submolecular level [42-45]. [n the context of interfacial
"long-range" ET, in situ STM offers particularly a new
dimension in the structural and functional properties
of large redox adsorbate molecules such as large
transition metal complexes or redox metalloproteins
[46-48,71]. This perspective reflects the following
observations:
1. In situ STM can image the redox molecules in their
natural aqueous functional environment. This raises,
however, a number of recognized issues relating to
potential control, adsorbate immobilization, and so
on.
2. The redox centers represent low-lying HOMO and
LUMO levels separated from environmental
electronic states but strongly coupled to the nuclear
environment. In this way, in situ STM is a new
approach for long-range, vibrationally, or con-
formationally coherent three-level ET [16,52,72].
3. Combination of in situ STM with in situ atomic force
microscopy (AFM) offers two kinds of insight into
the structural and dynamic behavior of large
adsorbates. Both STM and AFM offer real space
and time imaging with molecular and submolecular
resolution. In situ STM, however, also offers
single-molecule electronic conduction imaging,
complementary to the imaging oftopological surface
features (AFM).
4. Both in situ scanning probe microscopies hold clues
to the effects ofexternal factors such as the substrate
electrochemical potential. Force spectroscopic fea-
tures of AFM were noted above [49-51]. In situ
STM holds the additional perspective of
spectroscopy-like imaging of single-molecule elec-
tronic function, rooted in the independent control
ofthe potentials of the substrate and tip. In this way,
either the bias voltage, at fixed potential of one of
the electrodes toward a reference electrode, or the
overvoltage of both electrodes relative to a common
reference electrode, at fixed bias potential, can be
varied [47,48,52].
In situ STM of adsorbate molecules that can be
oxidized or reduced electrochemically offers other new
perspectives in interfacial ET. Approach to the electro-
 Electron Transfer at Electrochemical Interfaces 123

chemical rate constant has thus been proposed [73]. A

wider perspective is that different tunnel mechanisms U
~I
in principle can be distinguished, at least when the L

redox center of the molecule is separated spatially from 0---

the substrate and tip [52,71,72]. Large transition metal
complexes and even redox metalloproteins where the
transition metal centers are enveloped by ligands and
protein, respectively, are of interest here. Submo1ecu1ar
image features [74-76] and recorded functional tunnel t
patterns of such systems [47,48], in line with expec- eVbias
tations for vibrationally coherent tunneling, have,
moreover, been reported. We proceed to overview a few
elements of these mechanisms and some expectations
*
regarding observable current- voltage relations, with
emphasis on the bridge to electrochemical ETat a single
metal-solution interface [52,72].

(a)

A. Thnneling Mechanisms in the In Situ STM of

Large Redox Adsorbates
U(q)
Figure 3 shows schematically the energetics of electron
tunneling through a low-lying adsorbate redox level in
the in situ STM configuration. The substrate and tip elec-
trodes are represented by electronic continua, but dis-
crete electronic structural effects caused by finite tip size
can also be addressed. The vacant redox level in the equi-
librium configuration of the oxidized molecule is rep-
resented by a strong indentation in the tunnel barrier
constituted by the LUMOs of the aqueous or protein
medium. The redox level is, moreover, strongly coupled
to the nuclear environment so that nuclear con-
figurational fluctuations can take the redox level close to
populated electronic levels near the Fermi level of the
negatively biased electrode, CRF, where ET begins. Sub-
sequent to this step, several scenarios can be envisaged
[71]:
(b)
q
1. The electron can proceed directly to vacant levels in
the positively biased electrode, CL, in a three-level
resonance mode [72,77]. Figure 3 (a) Energy diagram for in situ electronic-vibrational
2. The temporarily filled (reduced) redox level can pro- STM of a molecule with a low-lying redox level. Electronic
ceed to full vibrational or conformational relaxation energy manifolds of the positively (£L, left) and negatively (£R,

r well below both Fermi levels. The second step, i.e.,

ET from the reduced molecule to vacant levels in the
positively biased electrode, then requires renewed
thermal activation. This is equivalent to two
consecutive, fully equilibrated, electrochemical
single-electron transfer steps. This limit is likely to
prevail when the electronic coupling between the
right) biased electrode are coupled via the (initially vacant) mol-
ecular redox level £d, in the tunnel gap. Fluctuations in nuclear
coordinate(s) q lower the redox level to values near the Fermi
level £RF where electron transfer predominantly occurs. Con-
tinued relaxation takes the filled (reduced) redox level to lower
values where electron transfer to the positively biased electrode
occurs before full vibrational relaxation. (b) Potential (Gibbs
free) energy surfaces corresponding to the electronic levels in (a).

r
I
124
molecular redox center and both electrodes (or the
equivalent tunnel factors) is weak (i.e., the strongly
diabatic limit) [71,72,74,75].
The limits in (1) and (2) have been analyzed previously
[71- 73]. Because each substrate and tip level is
only infinitesimally separated from continuous man-
ifolds ofother levels, the following patterns are, however,
appropriate for electronic molecule-substrate and
molecule-tip couplings of intermediate strength
[71,72,74,75] :
3. The molecular level is first filled by ET from CR and
then begins to relax vibrationally. Before full
relaxation has been reached, the second ET step,
however, occurs. This mode can be called
vibrationally or conformationally coherent two-step
electron transfer and is also represented by the
three-level potential surface configuration in
Fig. 3b. The environmental nuclear equilibrium
configuration is restored after the second ET step,
apart from the vertical displacement caused by the
bias voltage Vbias, i.e., by e Vbias( > 0) Similar con-
siderations apply to two-step electron transfer where
the initial state is the filled (reduced) redox level (hole
transfer). Patterns such as these in homogeneous
solution were addressed early [78-81] and have come
in recent more intense focus in new areas ofultrafast
(subpico and femtosecond time ranges) electron
transfer processes in chemistry and biology
[16,82,83].
4. Vibrational or conformational coherence acquires,
finally, a different character when the adiabatic
limit of strong interaction between the molecular
level and the substrate and tip electrodes apply in
the sense of the opposite limit of the inequality of
Eq. (16). The steady-state in situ STM current
maintains fully coherent two-step character, but
the tunnel factors no longer appear explicitly.
The following simple form approximately
applies instead, at given overvoltage and bias voltage
[84]:
ie l(Y1]) is the adiabatic single-electron transfer elec-
trochemical current density and Y the fraction of the
bias potential drop at the site ofthe molecular group.
The combination ~ P(cRP: 1])(e Vbias) » I represents
the total number of vacant levels in the positively
biased electrode in the overall coherent two-step
process.
Friis et aI.
B. Current-Voltage Relations in Coherent
Two-Step ET of In Situ STM of Redox
Metalloproteins
We now focus on the tunnel current in the two-step ET
mode in Fig. 3. The current is controlled by the bias
voltage, the total solvent, molecular, and protein
reorganization Gibbs free energy and the electronic
tunnel factors that couple the redox level with individual
electronic levels in the substrate and tip [cf. Eqs. (2)-(7)].
A unique feature of the in situ STM mode is further that
also the overvoltage ot: say, the tip relative to a reference
electrode at fixed bias voltage can be controlled. In the
frame of Fig. 3a this implies that the initial equilibrium
position of the redox level can be controlled relative to
the Fermi level of the negatively biased electrode.
It is shown elsewhere [52,74] that the following tunnel
current form for vibrationally coherent two-step ET
through the vacant molecular redox level then applies
~ u
Icoh(ll: Vbias) = 2 I
E Rli [kB TI UR.mol - UL.moll]J:
x J~oc dCR!(cR)P(cR)[TR,mol(8R;1]: Vbias)f
(28)
A similar form applies for electron transfer in the reverse
order (hole transfer), but this will be disregarded pre-
sently. Equation (28) holds several implications for the
physical nature of the STM process and the observable
current-voltage and current-distance relations:
1. T R.mol (8R; 1]; Vbias) and TL.mol(cL: 1]: Vbias) are the
electron exchange factors for electron transfer
between the local center and the negatively and posi-
tively biased electrode, respectively. Coherence is
reflected in the presence of both coupling factors
rather than the coupling factor solely of the
rate-determining step such as in sequential,
equilibrated, single-electron transfer transitions.
2. The electronic factors can be represented by the
metallic and molecular wave functions or by
density functional methods. The following cruder
tunnel forms are, however, broadly operationally
Electron Transfer at Electrochemical Interfaces 125

adequate: 1000
(a) ell = 0
[TR,mol(CR; '1; Vbias)]2 c:::::[T~.mo,f ell = 5
800
ell = 10
ex p {- ~ J2m e [U1 + e'1 + ye Vbias - (cr - cRF)]aR} ell = 15

(29) 600
B...
o 0
where me is the electronic mass, URthe barrier height .....
<: ...

400
for the transition from the negatively biased electrode
to the adsorbate at equilibrium ('1 = Vbias = 0), and
2nli Planck's constant. T~,mol and T'L,mol are energy 200
quantities independent of '1, Vbias, CR and CL, whereas
aR andaL are the spatial extensions ofthe tunnel gaps
(Fig.3a). 0
0 20 40 60 80
3. The preintegral factor reflects the intermediate state
relaxation process and depends weakly on the energy V
bias
quantities. U~.mol is, more specifically, the (Gibbs
free) energy at the first potential surface crossing 30
around CR C:::::CRF. Ul mol is, similarly, the energy at (b)
the second lower potential surface crossing, at
CL C:::::CLF·
4. The reorganization Gibbs free energy ER is smaller
than for electrochemical interfacial ET or ET in
homogeneous solution and depends characteristi-
cally on the gap extension and the tip radius. This is
discussed elsewhere [52].
Equations (28) and (29) represent the current-bias
voltage, the current-overvoltage, and the current-
distance relations for the coherent two-step in situ
STM electron transfer mode involving temporary popu-
lation of the intermediate redox level. One observation
is that by the particular in situ STM configuration, large
overvoltages, le'1l > E R - e Vbias, can be probed in a way
reminiscent of single-molecule spectroscopy. This is in 20 40 60 80
contrast to electrochemical ET in the activationless i
bias
overvoltage range where levels below the Fermi level
dominate and overpotential independent currents Figure 4 (a) Current-bias voltage relations for the in situ
STM configuration in Fig. 3, calculated from Eqs. (28) and (29).
emerge, with no inverted region.
The ordinate is the "normalized" tunnel current in the sense that
Accurate incorporation of broad currentlovervoltage
the preintegral factors, level densities, and the approximately
ranges exceeding le'1l > ER - e Vbias requires attention constant tunnel factors are disregarded. Energy quantities in
to a full set of master equations involving population units ofkBT. E R = 20. y = 0.5.The four curves correspond to dif-
and depopulation of the intermediate state. Such work is ferent overvoltages indicated to the right. The inflection points
in progress. Equations (28) and (29), however, illustrate follow the variation ofthe overvoltage. (b) Derivatives ofthe cor-
quite accurately important observable features of relations in a showing more clearly the structural feature as
current-voltage relations. Figure 4a shows the e Vb,., brings the redox level to cross the Fermi levels RF.
current - bias voltage relation at different fixed over-
voltages. The most distinctive feature is the inflection
point at a bias voltage where the molecular level that is approximately Gaussian for small overvoltage.
crosses the Fermi level of the negatively biased Figure 5 shows the current-overvoltage relation at
electrode. This is seen more clearly in Fig. 4b, which different fixed bias voltages. The most important
shows the derivative of the current- bias voltage relation feature here is the strong maximum at le'1l c:::::ER, which
126
40 r----,....-----r------,-------,
30
§
l::: OJ
20
10
60
Figure 5 Variation of the in situ STM current, normalized as
in Fig. 4, with the overvoltage at different bias voltages. Energy
quantities in units ofk B T. E R = 20. y =0.5. Increasing currents
correspond to the bias voltages 25, 50, 100, 150, and 200 mY.
The maximum is at el] ;:,oER for small bias voltages.
is again where the vacant molecular redox level crosses
the Fermi level of the negatively biased electrode.
The halfwidth of the maximum is a convolution of E R
with e Vbias and increasingly asymmetric as the bias
voltage increases. The spectroscopic features in Figs. 4
and 5 thus reflect important information about the
energetics of the molecular redox level and the potential
distribution in the tunnel band gap region.
C. Some Observations on lWo-Step ET
Mechanisms of In Situ STM of Adsorbed
Metalloporphyrins and Redox
Metalloproteins
Data to illustrate current-voltage patterns such as those in
Figs. 4 and 5 require high adsorbate stability. Such data
are scarce, but the following three systems accord in vari-
ous ways with expectations for the theoretical frames
above:
I. The current-overvoltage relation, at fixed bias
potential for in situ STM of iron protoporphyrin IX
adsorbed on HOPG, shows a maximum close to the
equilibrium reduction potential [48]. The halfwidth
is ~0.2 eV corresponding to a reorganization Gibbs
free energy of E R ::;:::0.3-0.4 eV. The maximum and
Friis et al.
the width accord with the notion ofcoherent two-step
ET, but a discrepancy is that the maximum appears
around the equilibrium reduction potential EO rather
than at EO - E R + 'Yleryl. Part of the discrepancy
could be associated with details of the potential dis-
tribution in the gap region, but the rest remains
elusive. This feature is also apparent in the other two
systems.
2. The STM current- bias voltage relations of several
metalloporphyrins covalently tethered to gold(lll)
in contact with an electrochemically inert solvent
(mesitylene) has shown an interesting structural
feature according with temporary population of
the redox level at the metal center [47]. The
observed derivative current-bias voltage relation is
broadly Gaussian. An interesting observation is that
the local environment of each surface-attached
molecule exhibits substantial inhomogeneous
broadening reflected in distributions of peak
potentials and widths of the Gaussian derivative
correlations at different parts of the surface.
Such broadening is perhaps not unexpected as
individual molecules are followed and not
statistical assemblies such as in electron transfer at
electrochemical interfaces and in homogeneous
solution.
3. Azurins belong to the class of blue single-copper
electron transfer proteins [85]. High-resolution
three-dimensional structures and a wealth of
physical chemical properties of wild-type and
mutant proteins are available. Of particular
importance in the present context is that the
molecule is ellipsoidal, with the copper atom
located in one end of the molecule and a
surface disulphide group in the other end. Facile
long-range electron transfer through the protein,
from reduced disulphide to the eu-atom, can also
be brought to occur [86]. The disulphide group is
suitable for linking of azurin to surfaces of gold
and other electronically soft metals. In situ STM
and AFM of adsorbed azurin on Au(llI) has
been reported [74,75,87,88]. Images are robust
over 0.5 V across the standard reduction potential.
Submolecular resolution shows, moreover,
consistently a smaller central area with an
apparent height two to four times larger than
closer to the molecular periphery [74,75]. This
would be in line with tunnel enhancement by the
local redox level of the copper atom and with the
reported observations for adsorbed redox
metalloporphyrins. Investigations of current-
voltage relations are in progress. I
[
1
Electron Transfer at Electrochemical Interfaces
IV. CONCLUDING OBSERVATIONS
The theory of interfacial electron transfer warrants new
attention. This is prompted by better understanding of
the electronic and structural properties of the
metal-solution interface, comprehensive theory of
electron transfer in homogeneous solution, the advent
of new and well-characterized long-range electro-
chemical electron transfer systems, and by new and
interesting electrode and electrolyte materials. To this
could be added new electrochemical ET phenomena such
as phase transitions and critical phenomena in electro-
chemical surface layers [89]. In situ STM and AFM
finally holds quite new perspectives for following
single-molecule electronic processes, directly in space
and time, and in the natural functional aqueous medium.
The discussion above has indicated some ways of
extending electrochemical electron transfer theory to
incorporate details of the interfacial metal-solution
region. Emphasis was on electronic density views. These
can be improved to incorporate a variety of physical
effects and converted to wave function formalism by
available procedures. Other approaches are available
and include, for example, Newns-Anderson theory of
adsorption where the adsorbate is in the solute state
[59,60].
Perspectives in such combined experimental and
theoretical efforts are first to lift the theory of interfacial
electron transfer theory, including theoretical frames for
electron transfer in nontraditional systems, to a level that
may ultimately approach the present level of the theories
of ET in homogeneous solution. Other perspectives are
illustrated by the relation between electrochemical
single-electron transfer and electron transfer in molecu-
lar nanoscale systems where in situ STM stands forward
prominently. In situ STM framed by formalism such as
the one discussed above holds clues to the distinction
between different tunnel mechanisms, such as coherent
and sequential two-step electron transfer specific to the
in situ configuration. Such distinctions rest on the mul-
tiple options ofexploiting the tunnel current dependence
on bias voltage and overvoltage. Wider perspectives are
offered by the prospects of following single-molecule
reactive behavior in the in situ STM and AFM modes,
such as initiated by the reports by Han et al. [47] and Tao
[48] for in situ STM and by Radmacher et al. [49] for
AFM. Intriguing approaches to the interplay between
macroscopic interfacial ET kinetics such as in electro-
chemistry or homogeneous electron transfer kinetics
and stochastically distributed single-molecule electron
transfer reactivity are held by these new research areas.
127
ACKNOWLEDGMENT
Financial support from the Danish Natural Science and
Technical Science Research Councils and from the
Carlsberg, Lundbeck, and Novo Nordisk Foundations
is acknowledged.
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'f
9
Electrochemical Processes Involving H Adsorbed at Metal
Electrode Surfaces
Brian E. Conway
University of Ottawa, Ottawa, Ontario, Canada
ABSTRACT
The role ofadsorbed atomic H in the electrochemistry of
various processes involving hydrogen is reviewed. A brief
survey of involvement of H in Hz evolution reaction
(HER) mechanisms provides the background for dis-
cussion of the role of chemisorbed H in electrocatalysis
of the HER at various metals, temperature depend-
ence of Tafel slopes of the HER, thermodynamics and
kinetics of underpotential deposition (UPD) of H
at single-crystal surfaces in relation to the recent
outstanding developments in electrochemical surface
science, metal-to-H bonding in UPD of H and the
entropy and volume of electrosorbed H, chemisorbed H
as the source of H sorbed into transition metals, and par-
ticipation of electrosorbed H in electrochemical hydro-
genation processes. The unique situation of the HER as
a model reaction for electrode kinetics and electro-
sorption is emphasized.
I. INTRODUCTION
A. Involvement of H in Electrode Processes
Electrochemical reactions involving hydrogen, both as
Hz and H, have served as model processes for the subjects
of electrode kinetics [1-5], electrocatalysis [5] and elec-
trochemical surface science [6,7] and, with D, the basis
for studies ofH/D kinetic isotope effects and their origin
[8-9,10]. Additionally, the chemisorbed H intermediate
in the cathodic Hz evolution reaction (HER) is intimately
involved in electrochemical hydrogenation [11,12] and
sorption ofH into transition metals [13,14].
131
On the applied electrochemistry side, the HER is
involved in commercial water electrolysis, as the cathode
reaction in anodic F z and Cl z production [15,16], and
in wet corrosion of base metals in Oz -deficient
environments [13,14], whereas its reverse is the process in
Hz fuel-cell operation [17,18].
On the fundamental side, studies ofthe HER provided
the early basis [2] for treatment of multistep electro-
chemical reactions involving an overpotential-
deposited (OPD) chemisorbed intermediate, H, and the
first treatment of electron transfer in terms of wave
mechanics by Gurney [19]. Through the works of
Horiuti and Polanyi [20] and of Butler [21], the basic
principles of electrocatalysis (the role of chemisorption
of H at the substrate cathode metal) were enunciated.
Complementarily, a major area of electrochemical
surface science has been developed concerning
so-called underpotential deposition (UPD) of H at the
catalytic noble metals, before the onset of Hz evolution,
and the role of double-layer effects in electrode kinetics
[4,22].
II. PROTON SOURCES IN UPD OF H AND IN
THE HER
In aqueous solution work the states and sources of
protons leading to chemisorption of UPD and OPD H
are the hydrated H 30+ ion in acid medium or the
HzO molecule in alkali, both in the double-layer
constituting the electrode interphase [3-5,23]. H 30+ is a

132
very stable molecule-ion [24,25,15], isoelectronic with
NHt but further hydrated to H 90t [26]. In H 30+, the
positive charge is delocalized among the three Hs,
whereas in H 90t, the proton is mobile through a
"Grotthus" jumping mechanism. The overall hydration
energy of H+ is ca. 1,150 kJ mol-I, which has to be
provided in discharge of the ion [19,21], forming
adsorbed H [21] but is compensated by the gain of minus
the energy of ionization of H.
Proton transfer and discharge can also take place
from proton sources other than H 20, e.g. carboxylic
acids, HF [15,16], alcohols, and so on, in the anhydrous
state.
III. MECHANISMS AND STEPS IN THE HER
Mechanistic studies ofthe HER have historically formed
a major plank of H electrochemistry, including coverage
by adsorbed H [5,15,16] and solvent effects [23]. The
reaction steps are
followed by either
MH ads + H 30+ + e (in M) -+ M + H 20 + H 2
(11)*
or
2MH ads -+ 2M + H 2 t (III)
In I and II, the state of the electron (e in M) is that at
the Fermi level of M for a given electrode potential,
<D ± EV At various transition metals and alloys such
as LaNi s , the adsorbed H involved in steps I, II, or
III in the HER can become sorbed [13,14] into the
metal:
MHads -+ MHabs (near surface) -+ MH abs (in bulk)
(IV)
* In earlier literature [27], instead of II, an H;-ion discharge has
been considered. Also, I and II can proceed from H 20 in alka-
line solutions.
)
Conway
IV. MOLECULAR-LEVEL MECHANISM OF
ELECTROCHEMICAL PROTON TRANSFER
AND DISCHARGE, FORMING
CHEMISORBED H
At the "molecular level," the discharge of the hydrated
(H 30+ ,nH 20) or solvated proton and its transfer to
an adsorption site, M, on a cathode metal surface is
fundamental in processes such as I or V (see p. 135)
and also in step II. The earliest model of electron
transfer to the proton in solution was that treated by
Gurney [19] and Fowler [28] where wave-mechanical
concepts were first introduced into electrochemistry,
together with the idea of a transfer coefficient [2,3], "r:t,"
using the Gamov equation [29], antedating the seminal
works of Weiss [30], Marcus [31-33], and Hush [34].
However, transfer of a neutralized proton as H [21] to
an adsorbed state at the metal was, surprisingly,
neglected so that metal dependence of the transfer
process was an aspect not considered in Ref. 19. The
omission was qualitatively rectified in terms of
potential-energy curves (for H+ in H 30+ and for the
metal-to-H adsorption bond) by Horiuti and Polanyi
[20] in 1935. In the important paper of Butler [21] in
1936, this representation of step I was more quantitat-
ively calculated, with applications to Hg or Ni. Such
diagrams gave a molecular-level basis for differences
of energy of activation in proton -electron transfer with
chemisorption of H at various metals, thereby provid-
ing the first basis for electrocatalysis [5,35] in the HER.
The molecular mechanics of process I are very
complex [36] and involve a model [24,26,36] for the
proton-source ion, H 30+, and its -OH+ vibration
[21,37]; a model for further hydration of H 30+ and
H 9 0t [25,26]; implicitly a model for the coupling
between proton transfer along the reaction coordinate
[21,38,39] toward an adsorption site [21,26] and the
proton solvation; and finally a potential function for
the M-H chemisorption (in the presence of
coadsorbed H 20 molecules in the double layer) result-
ing after electron transfer. Superimposed on these for-
mal constituent processes is the adiabatic [40] transfer
of the electron to a vibrationally excited, solvated
H30+ complex [36,41], treated in the theoretical work
of Conway et al. [36] and in later spectroscopic
[infrared (IR), mass spectrometry, and nuclear
magnetic resonance] studies on H 30+ (for reviews,
see Refs. 24, 25). Proton tunneling through the barrier
can also take place as a parallel process from various
distributed levels [8-10,41], e.g., in multidimensional
phase-space [41]. Special cases arising in the potential-
energy diagram treatments for extreme conditions were
1,
H Adsorbed at Metal Electrode Surfaces
referred to by Krishtalik [42] as "barrierless" and
"activationless" discharge, corresponding to limiting
values of the symmetry coefficient, {3 = I or O.
V. ROLE OF H CHEMISORPTION IN
ELECTROCATALYSIS IN THE H 2
EVOLUTION REACTION-
Electrocatalysis in the HER [and also in the H 2 oxidation
reaction (HOR), important for fuel-cell electro-
chemistry] is intimately related to the states and binding
energies of chemisorbed H. In the HOR, the reverses of
steps III and II are usually the rate-determining
processes.
The kinetics of the HER at, e.g., Hg and Ni or Pt
cathodes are characterized [5,21,36] by widely differing
values of the exchange current density, io, and also by the
extents of H coverage (8 H in the steady state of the HER
or of UPD H). Such differences (for Hg and Ni) were
recognized in the seminal paper of Butler [21].
Empirical relations between the exchange current
densities, io, and metal properties, e.g., the metal's work
function, <1>, were investigated [43,44], e.g., by Ruetschi
and Delahay [43]. In a significant paper [41], Conway
and Bockris showed that the relations oflog io to <1> (and
other properties) for the HER really originated on
account of demonstrable correlations between <1> and
MH chemisorption energy. The latter was derived by
means of the Eley- Pauling relation
expressed in kcal mol-I, where D represents the indicated
diatomic bond dissociation energies and X the
electronegativities of M and H. The (XM - XH)2 factor
turns out [44] to be an important factor relating log io
values to metal properties, reflecting the polarity of the
MH bond that leads to a coverage-dependent <1> due to
pairwise repulsion between MH dipoles.
A major further advance was made by Parsons [45] in
1958 paralleled by a somewhat similar paper by
Gerischer [46]) who showed that "volcano-type" curves
should actually arise when log io values for a series of
metals are plotted vs. the standard Gibbs energy of
* The term "electrocatalysis" is attributed to Grubb and
Niedrach, arising from their fuel-cell work at General
Electric Company. However, a more general and earlier
definition was given by Busing and Kauzmann [35] in terms of
the dependence of the standard rate constant of a process on
the electrode metal.
133
f
Pt
• • Re
a:: 3
W Rhl
I Ir
-\-
o
~5
IE
Au.
Cu.
N'
'c~
·Fe
u
~
07
.:..=.
e-
o
1
9
125 209 293 375
M-H Bond Strength/kJ mol- 1
Figure 1 Volcano relation for electrocatalysis in the HER in
terms oflog i o plotted as a function of heat of adsorption of H.
Note that the valve-metals on the r.h.s. branch ofthis plot prob-
ably bear nonreducible, thin oxide films. (From Ref. 47.)
chemisorption of H, ~~. The relations demonstrated
by Conway and Bockris [44] corresponded (for some
metals) to regions on one side or the other of the maxi-
mum ofsuch volcano curves. A well-defined volcano plot
(Fig. 1) with the active noble metals lying around its vertex
arises using best available data [47].
Briefly, the principles ofthe calculation ofParsons [45]
were as follows: io values were expressed in terms of the
product of the coverage 8H .r and free-site, 1 - 8H ,r,
fractions at the reversible (r) potential raised to the powers
{3 and 1 - {3, respectively, and including an exp function
of the difference of activation energies for the forward
and reverse directions of the supposed rds at zero
metal/solution p.d. The critical aspect of Parsons'
treatment originates from the above product,
8~ yO - 8H.r)l-fJ, which has a maximum at 8H ,r = 0.5
(when the barrier symmetry factor, {3, is 0.5). Because
8H ,r is directly determined by an exp function of ~G~,
the plots oflog io vs. ~G~ also exhibit a maximum, actu-
ally at ~G~ = O. Weak or strong H chemisorption
corresponds to positive or negative values of ~G~,
respectively.
His analysis gave a good account ofthe volcano-curve
behavior of electrocatalysis in the HER. However, it has
to be recognized that additionally to the 8H factor, the
activation energies for the HER (derived from d In
io/ d( 1/ T), where available, differ quite appreciably, being
ca. 80 kJ mol- 1 for Hg and ca. 40 kJ mol- 1 for the HER
134
I
! I!
I I
1(9 I I
I I
/ I
I I
HIM
//
II
/ /
IJl 1 /
.0 1/
.0 ~=~//
(9
Reaction Coordinate
Figure 2 Schematic potential-energy curves for proton dis-
charge and H adsorption for progressively weaker H
chemisorption: effect of different anharmonicities of the MH
bond vibration. (From Conway, unpublished.)
at Ni. Such effects can arise from differences of
anharmonicity of MH bond vibrations, depending on
MH bond strength (Fig. 2).
Conway pointed out that the data for the
electrosorptive Pt metals (Pt, Rh, Ir), at or near the top
of the volcano plot [47], seem anomalous because such
metals have the largest (negative), rather than zero, ener-
gies of H chemisorption (assuming the - T AS~
component of AG~ is « the AG~) leading, in fact, to
strongly bound UPD H [48-54]. He proposed that the rel-
evant AG~ for H adsorption at the Pt metals is not, in fact,
the AG~ for adsorption of H at the bare Pt metal but
rather the lower AG~ for the extra OPD H, which is the
kinetically involved adsorbed intermediate in the HER
and is deposited, on or commnually among, the UPD H
adatoms already fully occupying the initially bare or
otherwise available Pt sites. The mechanism of the HER
at the platinum metals on which H is underpotentially
chemisorbed is thus qualitatively different from that at
most or all other metals in terms ofthe surface-chemistry
involved. This is an important new conclusion for
electrocatalysis of the HER. Thus, the strongly bound
UPD H has the effect of indirectly raising the log io
for the HER much above what is would be if that
UPD H (for 8H < I) was the kinetic intermediate. The
contrary view, argued by Markovic et al. [55], that the
UPD H is an inhibitor of the HER, is thus difficult to
entertain. Coadsorption of HSO; ion is also a factor
[37,44-48].
Conway
VI. TRANSFER COEFFICIENT (ex) AND THE
BARRIER SYMMETRY FACTOR (13) FOR
PROTON TRANSFER AND H ADSORPTION
As we emphasised in earlier papers, theTafel slope values
for the HER (determined by 13 or ex) are as important
as io values in determining practical electrocatalytic
performance, i.e., at appreciable current densities,
especially when behavior over appreciable temperature
ranges is involved. Thus, a low Tafel slope can outweigh a
poor log io is providing practically high i values at rela-
tively low '1 (see Fig. 12 in Ref. 5).
A. Phenomenology of Behavior of ex and 13
Determinations ofmechanism(s) of the HER at various
metals have been traditionally based (e.g., [2]) on evalu-
ation of Tafel slopes, b, ( = d'1 fd In i) and their interpret-
ation in terms of 13 (the electrochemical Bronsted
coefficient [56]) or ex where b = RTf f3F or RTf riF
depending, respectively, on whether a first or later step
in the reaction sequence is rate determining at a given '1.
13 has the significance of an electrochemical BreJnsted
coefficient [56].
In recent years [57-60] it became recognized that
values of b for the HER did not depend on T in the
classically expected way (varying as T 1) but were in some
cases independent of T, or b involved some constant
together with a T 1 component factor [62], so that 13 or ex
are themselves dependent on T Agar [61] made a prelimi-
nary suggestion, in interpretation of Stout's results on
azide discharge at Pt (which occurs on a Pt-oxide film
[63]), that this behavior arose because ofan effect ofpoten-
tial on the entropy of activation, AS*, component of the
AG*.
Conway, et al. [57] made a detailed study of the tem-
perature dependence of b for the HER at Hg and Ni and
confirmed a T dependence of 13, giving, in limiting cases,
independence of b on T This and later work [58,62]
implied a major rethinking of the basis of potential
dependence of electrochemical reaction rates and their
temperature dependence and consequently the signifi-
cance of Tafel b values. Another example of dependence
of ex on Twas found by Yeager et al. [59] for the reduction
of 02.
B. Theoretical Treatment of TDependence of
13 or ex
In a series of papers [57,58,60,62], Conway et al. made an
extended analysis of the suggestion of Agar [61], includ-
ing studies with proton sources other than H 3 0+ or
H20. On the basis that ASo'!' could be '1 dependent, as
H Adsorbed at Metal Electrode Surfaces
well as ,1H° ct , he showed that Pcontained additive com-
ponents PH and T Ps leading to a Tafel slope of b =
RTf PF=RTfF(PH + TPs)' This relation applies exper-
imentally to the HER for some cases [51,57,62], with sig-
nificant or dominant TPs values. Other factors than
the conventional ones [21,37] should be taken into
account [62,64,65,66] as also treated by Gorchev and
Bockris [67,68]. For example, Kirowa-Eisner and
Gileadi [64] stressed that interpretations of temperature
dependence of Por b values must allow for temperature
dependence of double-layer l/Jj potential effects in the
electrode kinetics in a rigorous analysis of the kinetics
of NH 20H reduction at Hg. 17 Dependence of ,1S°ct
can arise on account of the effect of solvent dipole
orientation [65] in the double layer on the transition
state.
VII. UPD OF H: H ATOM CHEMISORPTION
A. Definitions
So-called UPD of H arises at electrodes when the
Gibbs energy of binding of H atoms of the surface
is numerically greater (actually more negative) than
half the bond energy in H 2 , i.e., I,1G MH I < I,1GI~H2'
so that UPD equilibria, H + M +e ~ MH (at
various 8H), are established at potentials more
positive than that of the HER equilibrium
!
H+ + M + e ~ H 2 .
Formally, the UPD of H is represented by
+ e (in M) ~ MHads + H 2 0 (V)
V 8H
for a potential Vand proton concentration CH+; 8H is the
site occupancy fraction for adsorbed Hand 1-8 the cor-
responding vacant site fraction with, 0 < 8H < 1. The
simplest electrochemical thermodynamic relation for
process V is then
(2)
which is the electrochemical Langmuir isotherm for V.
Alternatively,
is a Nernst equation for the H electrosorption reaction
(V) at equilibrium, at 8.
135
Differentiation of Eq. (3) leads to the pseudo-
capacitance [69,70], Cq" associated with the potential
dependence of 8H:
Cq, = -qlF . 8H (l - 8H )
RT
(4)
qlF KHCWexp[-VF/RT]
RT . (l + K H Cw exp[- VF / RT])2
where ql is the charge for monolayer deposition ofR. Cq,
is directly recordable asf(V) by cyclic voltammetry [71]
because, for a potential sweep rate ofsVs-I, the response
currenti(V) = Cq,(dV/dt) == Cq,or Cq, = i(V)/s.
When there are pairwise lateral interactions in the H
ad-layer, K H at 8H is KH,eH~O . exp ±g8 H [69], then Eq.
(2) takes the form ofa Frumkin isotherm.
B. Phenomenology of UPD of H
The first observation of UPD of H can be traced to the
(dis-)charging curves of Bowden and Rideal [72] and
Frumkin and Slygin [73] at Pt where a constant-current
transient, taken from just below the H 2 reversible poten-
tial at Pt, showed two arrests between 0.05 and 0.35 V
(RHE) before the double-layer charging region, also
resolvable by electronic differentation [74]. Such distinct
states ofUPD ofH are most sensitivity displayed in cyclic
voltammetry [71], e.g., down to 1% ML.
The study of UPD of H at the catalytic noble metals
(Pt, Rh, Ir, Ru, and Pd), especially at Pt, has established
the major recently developed area of so-called electro-
chemical surface science, * especially at well-ordered
single-crystal surfaces of Pt and Rh [48,75]. Related
studies on surface oxidation (0 and OH film formation)
have also been extensively made [76] at Au and Pt, includ-
ing single-crystal surfaces.
C. Multiple-State Chemisorption in UPD of H
Following the potentiodynamic experiments of Will and
Knorr [71] at polycrystalline Pt, electrosorption of H in
two principal states was confirmed by many workers
[72,73], through a so-called "anomalous" third state
(observable on anodic sweeps in aqueous H 2 S04) was
recognized and attributed to HSOi ion readsorption
[48,50].
* Strictly speaking, virtually all electrode process work, which is
intrinsically interfacial in nature, falls within the description
of "electrochemical surface science," but the latter term is cur-
rently used to refer to high-level research on well-prepared
surfaces, usually of single-crystals.
136 Conway

Considerable controversy arose concerning whether N

I,..
the multiple states of chemisorbed H on Pt arise due c:
u
simply to polycrystallinity or for other more fundamental «::J...
reasons; both factors seem to be involved. Conway et al.
...... 3
[77] argued that multiple states of chemisorption of H
and also of metal adatoms (in UPD of metals, e.g., Pb
on Au [78]) could arise intrinsically (even at single-crystal
surfaces [81]) on account of progressive overlay lattice
development with order/disorder transitions [79]* and
also due to (electronic) induced heterogeneity [80]
involving work-function (<I» changes as 8H ---+ 1.

D. Studies of UPD of H at Single-Crystal Pt
Surfaces
Following the first exploratory experiments on H UPD at
Pt single-crystals by Will [82], results by Hubbard et al.
[83] were "state-of-the-art" for some years until the
outstanding works of Clavilier [48,84] were published,
showing that very well-ordered surfaces could be pre-
pared from beads ofPt melted from a wire and thermally
annealed in H 2 - Ar, or in air, and examined directly in
clean cells [85,86] using very pure H2S04 or HCl0 4
electrolytes in "Milli-Q" distilled water. Previously, Con-
way et al. [85] emphasized the importance ofhigh purifi-
cation of solutions, cells, and electrode surfaces (see also
review by Kozlowska [86]) for obtaining meaningful
results on UPD processes.
The principal-index planes of Pt single-crystal
electrodes, prepared by the Clavilier procedure,
exhibited clearly distinguished voltammograms for
UPD ofH that provide characteristic signatures for such
surfaces and indications ofany imperfections, when they
arise, as may be seen complementarily by means of
LEED. Examples are shown in Fig. 3, curves 1, 2, and 3,
and have been reproduced, virtually exactly, in a number
of laboratories including the author's in studies of the
kinetics of UPD and OPD processes at single-crystal
surfaces [81] (see also [141]). Importantly, these
surface-specific voltammograms are substantially differ-
ent from those recorded previously in other works [82,83].
The high degree of specificity of the voltammograms
to surface geometry (short-range coordination arrange-
ments and associated electronic properties [<1>] and
hybrid-d-orbital emergence [87,88] indicates specific
dependence of the strength and type of bonding of H
to such Pt surfaces. Overall, the electrochemical
Gibbs energy of chemisorption, derived from the
* Note that such structures, in metal UPD, can now be visually
recognized at atomic resolution under the scanning tunneling
microscope.
l
Figure 3 Examples of the cyclic voltammograms for well
ordered single-crystal surfaces of Pt in aq. 0.5 M H 2 S0 4 :
Pt(lll): 1, Pt(lOO): 2, and Pt(llO): 3 obtained by the Clavilier
procedure.
voltammograms, varies from close to zero (relative to
~H2) to about +0.35 V (i.e. -33.6 kJ mol-I) as
1 > 8H (uPD) ::: O. This corresponds to a free energy of
bonding ofH to Pt of about -249 kJ mol-I, comparable
with the value for chemisorption ofH from the gas phase
(note: dissociation energy of! H2 == 215 kJ mol-I).
On the (111) surface, chemisorbed H could reside in
two alternative hole sites, one with or one without another
Pt atom beneath, with coordination numbers of 4 or 3,
respectively. The adsorption or desorption charge
determinations, from voltammograms, show that only
one ofthe two types ofsites on the (111) plane ofPt is occu-
pied by H or the accommodated H sits atop of individual
Pt atoms.
These types of assignment are complicated by the
important observations of Clavilier that about 33%
of the apparent monolayer occupancy charge
(210 JiC cm-2) is, in fact, associated with electrosorption
of bisulfate ions exhibiting a degree of charge transfer
H Adsorbed at Metal Electrode Surfaces
equivalent to that of 33% of a monolayer of H. Hence, the
earlier supposed full coverage of the (111) plane ofPt cor-
responding to ca. 210 JiC cm- 2 really corresponds to
about 66% coverage by H. This conclusion was reached
by Clavilier using the displacement procedure of Conway
et al. [49,89] but using CO insteadofCH 3CN or thiourea.
Over the potential range of UPD ofH, the charge associ-
ated with H displacement currents is positive (anodic H
displacement effect [49]) but only for ca. 66% of a
monolayer at Pt(111), whereas the remaining species
detectable in the voltammogram is displaced in a negative
charge transient, corresponding to desorption of HSOi
previously adsorbed as an almost neutral species. This
was a surprising but important result and one that is con-
sistent with the splitting ofthe "butterfly" voltammogram
for Pt(111) in the aqueous H 2S04 into two separated
regions with increasing dilution of the acid. The electro-
sorption ofH+ itself, as H, is associated with almost com-
plete charge transfer [90, cf. 91].
For the other principal-index surfaces ofPt, it is not so
clear whether coadsorption of HSOi ions is appreciable
or not, although the recent AV and voltammetry exper-
iments of Morin et al. [81] indicate the part of the
voltammogram for Pt(100) behaves different kinetically
from the first part associated with strongly bound H.
Apart from the displacement experiments by Clavilier,
using CO, there are important independent indications
of sulfate (or bisulfate) ion adsorption at Pt from the
works of Wieckowski [50-54,92] using radiolabeled
S-containing suIfate ions. These experiments showed that
SO~- jHSOi ion adsorption at Pt persists significantly
into the OHIO oxide formation region at Pt before com-
petitive desorption sets in, whereas as much less positive
potentials, "cathodic" desorption takes place just before
H 2 evolution (depending on the ion concentration).
Savich et al. [54] (see Savich, Ref. 93) examined whether
HSOi orSO~- is the principally adsorbed species, taking
into account the equilibrium HSOi + H20 ;=:
SO~- + H30+. A further factor is the possibility ofa Wien
field-dissociation effect in the high fields of the
double-layer promoting HSOi dissociation.
In earlier works (e.g., [85]), Pt surfaces were cleaned, in
situ, by voltammetric cycling between 0.05 and lAO V
(RHE). However, LEED studies by Ross et al. [94-98]
showed that this procedure leads to reconstruction and
faceting due to oxide-film formation and reduction [76].
Polarization up to higher potentials, ~ 2.2 V, leads
[76,99] to thicker film formation and further disordering
on reduction. The thorough study of Mooto and Furuya
[100] on a wide range of stepped Pt surfaces rationalized
the above effects through control of step-height to
terrace-length ratios.
137
VIII. KINETICS OF UPD OF H
Unlike the process ofproton discharge and H adsorption,
which takes place as step I in the HER (the so-called
Volmer reaction) and which can be studied continuously
at any overpotential, UPD ofH cannot proceed in a steady
state because its rate becomes eventually limited by
8H ---+ 1, just at the hydrogen reversible potential. Hence,
UPD can be examined kinetically only by
non-steady-state methods such as cyclic voltammetry
(CV), alternating voltage (AV) impedance, or pulse relax-
ation procedures using appropriate analyses ofthe results.
The first AV studies on adsorption of H were conduc-
ted by Dolin and Ershler [101] at Pt who treated their
results in terms of Temkin's heterogeneity model. Using
the impedance method to study the kinetics of UPD of
H, Breiter [102] found dispersion of H response currents
with frequency, with a limit around several kHz, corre-
sponding to rates at which H discharge and ionization
can just keep up with the modulation frequency.
In modern surface electrochemistry, the principal
interest in kinetics of UPD of H is its surface specificity
in relation to the distinguishable states of H adsorption
[84,100] and kinetics of OPD of H. Meaningful kinetic
studies require well-ordered single-crystal surfaces of,
say Pt [84], as in the case ofCV, using high purity solutions.
Durand [103] evaluated kinetic parameters for UPD of
H by impedance spectroscopy up to 1 MHz at Pt
monocrystal sphere electrodes, with facets at various
orientations, especially 111. The kinetics both ofH UPD
and the HER were investigated at nonactivated and
anodically pretreated Pt electrodes. In another publica-
tion [104], Durand determined the electrosorption
valency [90] for H adsorption from 1 mol dm- 3
NaS04 + 0.01 mol dm- 3 H2S04. Recently, Harrington
[105] investigated the UPD of H on Pt as a model reaction
to validate his extension of impedancy theory to the tech-
nique ofa.c. voltammetry, and Lasia [106] discussed vari-
ous modulation techniques for the study of H UPD at
polycrystalline Pt electrodes.
Although most studies at polycrystalline Pt involve
surfaces having both macroscopic and microscopic
structural differences (e.g., roughness factor, mixture of
more active versus less active sites), the results obtained
have been largely in mutual agreement. A charge-transfer
resistance (Ret) of about 0.05 Q cm 2 was observed at
SO mV (vs. RHE) and 20 for 1mol dm- 3 H 2S04 solutions,
and corresponds to an apparent rate constant of approxi-
mately 5 x 10- 6 mod S-I; the Ret at SO mV for
0.5 mol dm- 3 H2S04 solution is 0.06 n cm 2 (i.e, corre-
sponding to a rate of charge transfer of 4 x 10- 6 mol S-1
cm- 2 .
138 Conway

Using potential-step relaxation, Woodard et al. [107] (a)

concluded that UPD ofH involved "instantaneous" sur- 4000
C p I /IF cm 2
face equilibration between several coexisting but differ-
ent adsorption states. This model, they argued, was 3000
supported by the dependence of the adsorption kinetics Q

on electrode crystal face, electrode potential, and pH. 2000 ;

B
However, it seems that a better model is one in which, at
each coverage, with increasing potential new communal
arrangements of adsorbed H atoms arise [108] corre-
sponding to communal changes of the electronic proper-
ties of the metal surface with increasing 8H as
recognized in Refs.108-ll0. (b) 200
In the case of single- crystal Pt electrodes. Oelgeklaus 160
et al. [lll] determined the rates ofH and iodine adsorp- 120
tion on polycrystalline and Pt(lll) electrodes but, 80 00

surprisingly, found no influence of iodine adsorption on 40 9 BBDOQO

lJ 0 DB 0

the kinetics of UPD of H on a polycrystalline electrode, o+--+--t--t-----l---+--+---+---+---l

whereas the rates were appreciably lower on Pt(lll). (c) 2.5
Nishihara and Nozoye [1l2] examined the kinetics of the
processes (probably anion adsorption [48]) that arise at 2.0
Pt(lll) in 0.5 mol dm- 3 H 2 S04 over 600-800 mY, RHE. 1.5
a
The desirability ofcomparative kinetic measurements 1.0 a

on several single-crystal surfaces led Morin et al [81] to a a a

a
perform complementary AV and CV studies on 0.5 0 Q

well-ordered Pt(lll), (100), and (1l0), together with o0 0.1 0.2 0.3 0.4
the stepped plane, (5ll). Their high-purity impedance
experiments included resolution of the kinetics of E / V (vs. RHE)
HSOi adsorption, especially at the (Ill) plane. The Rct, Figure 4 Equivalent-circuit components for the H UPD pro-
the double-layer capacitance, Cdl, and the H cess Vat Pt(lOO) as a function ofpotential in aq. 0.5 M H 2 S0 4 ,
pseudocapacitance, Cp , (cf. Ref. 105) were evaluated T = 293 K. (From Ref. 81.)
using two equivalent circuits [81] (the second for parallel
response due to anion adsorption).
By following a treatment by Harrington and Conway The faradaic impedance is thus
[113], the Faradaic admittance is obtained by dividing
the modulated current, lei) by the modulated E e, CEe), 1 1 1 1
Zr
.
= -Yr = -A = }w(AjB) = R ct + }wC
-- (7)
and introducing the resulting modulated 8, (e), giving p

These relations enabled Ret, Cdl , and Cp to be

Yr = -F(~) _[F(~)(Fjq)(~) ] = A _ ~ evaluated over the UPD range of potentials, e.g., for
Pt(100). Considering the first equivalent circuit, Cdl and
. 3Ee }W-(Fjq)G;) Jw+B Cp become additive when ZR.et « ZCp and are then not
separately resolvable. Because only Zc components are
(5) w dependent, the above condition is reached at some suf-
ficiently low w, depending on Cpo For the (100) and (3ll)
surfaces, this limit was found to be ca. 1 kHz. For (Ill)
where A = - F( 3v j 3Ee) and hence is equal to 1j Reb and 110, however, it was much higher so that Ret was not
B = -(Fjq)3vj3Ee and v is the rate of the process V The determinable in the accessible frequency range nor in
H adsorption pseudocapacitance is obtained as experiments at lower temperatures (274 K).
Some results for the equivalent-circuit components,
accessible at the (100) and (311) surfaces, are shown in
C- q (~)
p - aEe -
- q (38)
av (~)
aEe -:i
- B (6) Figs. 4 and 5. In Fig. 5, a dashed line separates two regions
assignable to adsorption at the (Ill) and (100) sites of
H Adsorbed at Metal Electrode Surfaces 139

(a) standard reversible potential. They supposed, and their

5000 calculations showed, that at potentials sufficiently dis-
Cp / p.F em-'
placed from E a , the log[kinetic parameter] would vary
4000 linearly with E in a Tafel-like function with slopes deter-
(100)
3000 sites mined by the transfer coefficient for the kinetics.
However, we believe this modeling is incorrect, because
2000
(Ill)
sites . displacements of potential from the maximum of the Cp
1000 .• .
• 0
profile do not result in aTafel- type change ofrate constant
but rather, simply, a change ofrate or Ret due to the poten-
I.
0 , tial-dependent change of equilibrium coverage accord-
(b) , ing to some electrosorption isotherm. Thus, a transition
200 Cd' / p.F em-'
I
I to Tafel-type behavior would not be expected because E
160 I
I diverges appreciably from £0 but rather because S » So
120 I
[114] or equivalently at high w. Hence, a minimum in ReI
. I . .• • .....
I
80 I
I " I
or log Ret is not necessarily to be expected for kinetic
40 1... ·1 ...
I
reasons in modulation experiments except at sufficiently
0 I high frequencies or large sweep rates, S » So.
(c) R.:, / 0 em' The kinetics of UPD of H can also be quantitatively
2.5 characterized in CV by determining the onset of
. irreversibility in the deposition/desorption response
2.0 03
.• ...;-. .-: • currents and related peak potentials. This procedure was
1.5
02

o 1 . I
I
. I
I
I
• '. . applied to polycrystalline Pt by Kozlowska and Conway
[114], who determined the displacement of CV peak
1.0 0 0
I potentials with log[sweep-rate, s] from the respective
I
0.5 I reversible potentials for three UPD H states as S was
1'~I"i\ •
§ E / V(vs. RHE)
0
increased.When S > So, the limiting sweep rate for main-
0 0.1 0.2 0.3 0.4 tenance of reversibility, the Evs.logs relation becomes a
Tafel relation and, in fact, dE /dln s, gives a for the electro-
Figure 5 As in Fig. 4, but for the Pt(311) surface. Adashedline sorption process. Thus, So has the same significance as io
is drawn on the figure to separate the UPD of H C.) in two
and, in fact, io = Cq,.rev x So, where Cq,.rev are the adsorp-
regions corresponding to adsorption at the (Ill) and (100) sites,
tion pseudocapacitance values for H at equilibrium for
as shown. (From Ref. 81.)
various 8H s.

the (311) plane. At the latter, components of Ret due to H

and HSOi adsorption [the latter beyond
E(RHE) = 250 mY] are resolved (. for H, 0 for
HSOi). The total capacitance (points) profile from the
impedance measurements at Pt(3ll) in 0.5 M H ZS04 is
compared with that determined from CV (solid line; this
line is not drawn as a fit to the array of points).
In Fig. 4 before the influence ofHSOt adsorption [at
Pt(lOO)], Ret is almost independent of potential over ca.
a 0.3 -Vrange. This may seem unexpected (contrary toTafel
behavior). However, over the UPD range, this AV is
modulating a series of states of adsorbed H that are
virtually at equilibrium with H30+ ions as the H coverage
changes. Hence,Tafel behavior at Ret is not to be expected
except when S » So [114] in CVexperiments. In the paper
of Woodard et al. [107], correlations between Cp (written
in their paper as Cq,) and log Rei (written as log RJ ) were
shown in which log RJ exhibited a minimum at the Cp
maximum, the potential E a of which they identified as a
IX. ENERGY OF ADSORPTION OF UPD H AN D
ITS ENTROPY AND VOLUME AT
ELECTRODE SURFACES
A. Enthalpy of Adsorption and Bond Energy
The process Vor its equivalent for alkaline solution has
attracted great interest in electrochemical surface science
for many years and especially more recently [81,84] at
single crystals, e.g., ofPt, where distinguishable bonding
energies of H can be resolved.
The question of the energy with which the UPD H is
chemisorbed, e.g., at Pt, was examined first by Breiter
[102] in relation to the enthalpy of gas-phase adsorption
(!Hz + M ;= MH ads ). From the temperature depen-
dence of the Gibbs energy of adsorption expressed in
terms of a Nernst equation, he found the enthalpy of
adsorption of H at Pt to be comparable with that for dis-
!
sociative chemisorption of gas-phase H 2 , notwith-
140
standing the ubiquitous presence ofH 20 dipoles. The H is
evidently small enough not to suffer any appreciable inter-
actions with water in the double layer, although such
effects were found in IR spectroscopic measurements by
Bewick and Russell [115]. From the ilH value, the H-to-M
bond energy was easily evaluated.
A more direct procedure for evaluation ofthe enthalpy
of adsorption (and then the binding energy) of UPD H
is analysis ofthe T dependence ofpotentials ofthe current
peaks in cyclic voltammetry of Pt electrodes over the
UPD range. The potential ofany given peak, correspond-
ing to a given state of electrosorption of H at its
half-coverage, gives the standard Gibbs energy of that
state relative to that of! H 2 at the equilibrium potential,
i.e., H2 + M (site) ~ MHads for H in an UPD state.
From such measurements, the entropy of adsorption of
H can be evaluated, as in the work of Conway et al. [116]
and thence the enthalpy ofUPD H in various distinguish-
able states (cf, Ref 102) through their Gibbs energies.
An important hidden factor, which was taken into
account [116] in such measurements on process V, is the
temperature dependence ofthe single hydrogen electrode
reference potential.
B. Entropy of Electrosorbed H
On this basis, Conway et al. [116] evaluated the entropies
of adsorption of UPD H in the states distinguishable
at polycrystalline Pt. By means of statistical-
thermodynamic evaluation of the entropies of H
adsorbed in a 2-d immobile or mobile condition, they
concluded that the two main states ofUPD H, commonly
observed at Pt, must be mobile. (The calculated differ-
ences between S~ for mobile and immobile ad-species
are large and without any appreciable uncertainty.) The
T dependence of the third "anomalous" peak (on anodic
sweeps) corresponded to a much less mobile situation
that these authors attributed to adsorbed HSOi ions.This
seems to be consistent with the later assignment [48] of
33% of the UPD charge at Pt(l1l) to HSOi
adsorption/desorption.
This matter was recently further considered by
Zolfaghari and Jerkiewicz [1I7), who examined the T
dependence of the charge for UPD of Hand
coadsorption ofsulfate species on a Pt(ll1) surface, using
CV The overall adsorption/desorption charge-density
decreases by 25 I1C cm- 2 over the Trange 275-338 K,
whereas the anion adsorption component changes by
only 5 I1C cm- 2. The potential of the sharp peak associ-
ated with onset of HSO; adsorption (or completion of
its desorption) has a temperature coefficient of
0.57 x 10- 3 V K -I that would correspond to an appar-
Conway
ent standard entropy of the process involved (?
rearrangement or reconstruction) of ca. 55 J K -I mol-I,
possibly associated with change in the structure of the
water-dipole film at low coverages.
Similar studies of H UPD were made at various tem-
peratures at the (100) surface ofPt. In this case, the poten-
tial of the sharp main peak decreases linearly with
temperaturewithaslopeof-0.05 x 10- 3 VK-1,i.e.,of
opposite sign to that of the result for Pt(l1l). This must
be due to qualitatively different processes being involved:
HSOi adsorption at Pt(l1l) and H adsorption at the (100)
plane, indicated by different signs of the entropy changes
involved.
Following the procedure of Ref [116], Zolfghari and
Jerkiewicz [117-121] also determined the standard
entropies and enthalpies of UPD of H at polycrystalline
Pt and Rh, and later for Pt(l1l) as a function of H
coverage. Corresponding to the main two distinguished
states of electrosorbed H usually observed in cyclic vol-
tammetry at Pt, the ilS~ds (UPD) and the ilH~ds (UPD)
exhibited two maxima or minima, respectively (Fig. 6a
and b) in plots against the UPD H coverage, both having
appreciable negative values.
C. Metal-to-H Bond Energy
Comparison between electrosorption of H in the UPD
process and from! H 2 in the gas phase was specifically
examined by Jerkiewicz and Zolfaghari [118-121], using
a thermodynamic analysis of adsorption isotherms for
Hat polycrystalline Rh. The enthalpy of adsorption cal-
culated with respect to H gave the metal-to-H bond
energy at Rh as treated by these authors in Ref 118, the
value being comparable with that for dissociative chemi-
sorption from H2, as for Pt(l02).
In the latter works [118,121], the authors introduced
interesting 3-d diagrams (Fig. 7a) of ilG~ds (UPD H)
values plotted vs. the UPD H coverage, e H and the tem-
perature (275-338 K) for three concentrations of
H2S04 in water 0.05, 0.1, and 0.5 M. The isothermals for
ilG~ds (UPD) as ![eH(UPD)] change appreciably in
shape as T in increased from 275 to 338 K, indicating a
change of 2-d interactions, probably associated with
T-dependent coadsorption of HSOi and H20-dipole
orientation. Figure 7b shows a corresponding diagram
for ilH~ds'
These authors also evaluated the dependence of the
(apparent) standardentropyofUPDHon e H (UPD) that
becomes appreciably less negative as the H coverage
fraction tends to 1. Note, these ilSo data, as well as the cor-
responding ilGo, refer to the process of deposition from
aqueous H+ (cf. Ref 116), not from gas-phase H or! H2.
H Adsorbed at Metal Electrode Surfaces 141

0-,--------------,-----------,

....,
....,~
-20

- ,
a
f2 -40
28

24
""":l (a)
20
""-
Q -60
"'9'
16
~ !

~ -80 12

~
~ " -100 280
270
""l 2/3 4 .. " '.'~ ,"
'. '" . ' . . . . 300 290
0.2

-120
/'
+--r-----r--,---------,----.--,---'--T---,----,--------1 (a) 0.8
..... 310
320 '\: I
~

1.0 330
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

70 , - - - - - - - - - - - - - - - , - - - - - - - - -

-
....,
60 ...... 46 • • . "'"",,-,, x ri."

~l ::1:.·:··'
I

a
f2 (b)
~
""-
50
········ ...
Q
~
40
0000
00
0000
:: • ' ." . I(~....tJ.r&'lIt::J"""u
2S. 34 .'
~ 0
oc
~ 32
~ 30 ::r::<:l

" "'i 30 .. ' ..... 2m

~
280
28 290
20 2/3 0.2 ........ 310300 ~
'. 320 '\: I
(b) 330
10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

e'HUPD
Figure 6 Standard entha1pies (~H~dS) and entropies (~S~dJ
for UPD of H at pte III) as a function of H coverage, BH , in aq
H 2S0 4 . (e) refers to 0.05 M aq H 2 SO; (.) refers to 0.1 M aq
H 2 S0 4 ; and (,0,) refers to 0.5 M aq H 2S0 4. (From Ref. 119.)
D. Volume of Electrosorbed H at Pt
Conway and Currie [122] conducted voltammetry at Pt
electrodes at a series of high pressures up to 10 kbars
using a cell in a high-pressure vessel under, but well
isolated from oil, to avoid contamination. Good
Figure 7 3-d Diagrams for (a) ~Gads and (b) ~Hads for H UPD
at pte111) as a function of BH and temperature. (From Ref. 121.)
"pure-solution" voltammograms were shown to be
obtainable under these conditions. The derivatives, with
respect to pressure. ofvoltam metric peak potentials, were
evaluated that enabled, via a Nernst-type equation, the
volume change ~ VH associated with electrodeposition
of H from H 3 0+ in aqueous solution (volume =
5.6 ± 0.9 cm 3 mol-I). This value is close to that
(5.5 cm 3 mol-I) for the volume of H in a CH 2 group,
suggesting covalent bonding of H chemisorbed to Pt
rather than accommodation of a surface interstitial pro-
ton. Corresponding studies at single-crystal surfaces
142 Conway

would be interesting. Comparative studies of sorption of 2.0 E - 7 r - - - - - - - - - - - - - - - -

H into Pd ({3 PdH phase) gave a smaller value,
2 cm3 mol-I, consistent with a more protonic state of H.
(0 )
1.5 E - 7

x. H ATOM SORPTION AND DIFFUSION IN l(fl

TRANSITION METALS N 1.0 E-7

IE
Closely related to the H adsorption processes in the HER tJ
v, "---- __
at transition metals, e.g., Ni,Ti, Fe, Pd, and various alloys, o ,..----
E 0.5 E - 7 / V4 <,"
.......

is the phenomenon of cathodic absorption of H into the ......

> /
,
v\.."'-
, "
metal lattice. This behavior has been known for many ",' ? ~).,:-::.':";'-..-.. - -
years and a very large literature (e.g., [13-16]) exists 0.0 EO tr-;--;·_·-;-·-(~·:·····, , I " I '-----1--
on the electrochemistry, materials science, and -8 -4 0 4 8
metallurgical aspects of this phenomenon, e.g., log tis
corrosion, "metal-hydride" battery technology. On the
fundamental side, the microscopic mechanism of H 2.0 E - 7 r - - - - - - - - - - - - - - - _
sorption involves surface electrochemistry: The H sorbed
must originate from discharge ofH+ and by transfer into
1.5 E- 7
the metal from the adsorbed state into the near-surface
region (process IV) [123] followed by bulk (and I
(fl
grain-boundary) diffusion [124]. Alternatively, proton
~ 1.0E-7
injection [125] from the double-layer directly into the E
tJ
metal can be envisaged, analogous to processes of Li
o
intercalation into layer-lattice materials, coupled with E 0.5 E - 7
desolvation. ......
>
The large extent ofearlier and contemporary activity in
this field limits its coverage in this brief review. Lasia 0.0 EO
and Gregoire [126] treated a general model of electro- -8 -4 o 4 8
chemical H sorption into metals for conditions of log t / s
potentiostatic and galvanostatic charging. Finite and
semi-infinite diffusion conditions were considered for Figure 8 Modeled rates of electrochemical H transfer and
planar, spherical, and cylindrical (cf. Ref. 124) diffusion diffusion into a metal as a function oftime, t, taking into account
fields. Numerical solutions were obtained for the coupled the interfacial H-transfer step, process IV. Subscripts and 2 refer
electrode-kinetic/diffusion equations and plotted as to the Volmer and Heyrovsky partial reactions of the HER,
and 4 to the H transfer, respectively. (a) k4 = 10- 7 mol cm- 2
f(1og t) for the variables treated. Several examples are
s-I and (b) k4 = 10- 5 mol cm- I S-I. Other conditions:
shown in Figs. 8-10, wherein subscripts 1, 2, 3, and 4 refer,
k l = 10- 11 , k_ 1 = 10- 10 , k 2 = 10- 12 , k_ 2 = 10- 13 mol
respectively, to the Volmer, Heyrovsky and Tafel steps in cm- 2 S-I. (From Ref. 126.)
the HER together with the important interfacial H
transfer step, MHads -+ MHabs, denoted as process IV
An important series ofplots showed the relation between ation that might be expected to lower the tendency for H
the surface coverage, 8H , and the occupancy fraction, to become sorbed. Possible qualitative explanations for
X o, just inside the metal host, expressed asf(1og t). The the enhancement of absorption were summarized by
Xo determines the transfer rate and the subsequent Subramanyan [127] and in Ref. [123], but none seems
diffusion into the bulk metal. realistic, and the matter is still unsettled and contro-
Conway and Jerkiewicz [123] stressed the relation versial [127-131].
between the chemical potential of adsorbed H and the In the paper by Conway and Jerkiewicz [123],
thermodynamic driving force for its sorption into the expressions were derived for the chemical potentials of
metal. They identified a puzzling effect that adsorbed adsorbed H in the absence and presence ofa co-adsorbed
catalyst poisons that, at various transition metals, poison, P, according to Langmuir-type adsorption
enhance sorption ofH yet actually substantially diminish isotherms:
the 2-d coverage by H at the host cathode surface, thus
diminishing the chemical potential, }1, of the H, a situ- (8)
H Adsorbed at Metal Electrode Surfaces 143

1.0 r - - - - - - - - - - - - - - - - - - - - - - - , 1.0 , - - - - - - - - - - - - - - - - - - - - - - - ,
(a)

0.8 0.8

0.6
0.6
o o
X 0.4 X
';:0.4
Cb
0.2
0.2

0.0 ~.----~--~
-8 -4 a 4 8
log t /5 -8 -4 a 4 8 12 16
log t / 5
1.0
(b) Figure 10 Dependence of0 and X oduring potentiostatic dis-
charging from an initial potential 'Ii = -0.5 V, in the conditions
0.8 /
of semi-infinite linear diffusion; - - , at final potential
,,
/

I
'If = 0 V and k 4 = 10- 7 ; - - -, at 'If = 0.2 V and k 4 = 10- 5 ;
I
I - - - -, at 'If = 0.5 V; and k 4 = 10- 5 mol cm- 2 S-I; other con-
0.6
0
I ditions as in Fig. 9. (From Ref. 126.)
I
X
. I
I
I

CbI 0.4 I

I
I basis of assumed Langmuir adsorption because the
I
presence of P only then affects the statistics of lattice
0.2
I
/X o occupancy but not the bonding energy or possible lateral
/
J
interactions. However, if the latter are included through
/

0.0 a Frumkin-type isotherm, then enhancement of the

-8 -4 a activity of adsorbed H by P can arise leading to more
4 8
facile transfer of H into the metal. This effect, however,
log t /5
has to be balanced against the competition between P
Figure 9 (a) Dependence of 0 and X o as a function of time and H for surface-site occupancy.
during the application a potential step to '1 = -0.5 V in the con- Related to the thermodynamic analysis ofConway and
ditions of semi-infinite linear diffusion. Rate constants: Jerkiewicz [123] were several significant papers by
k 1 = 10- 11 , k_ 1 = 10- 10 , k_ 2 = 10- 12 , k-2 = 10- 13 mol cm- 2 Protopopoff and Marcus [128,129]. They introduced the
S-I. - - , k 4 = 10- 7 ; - - -, k 4 = 10- 5 mol cm- 2 S-I,
clever idea of scaling the H coverage in terms of the sites
L 4 = 2k 4 . (b) As for Fig. 9a but for a constant current pulse at left available, (1 - 8p ), for H adsorption after some
2.95 xl 0- 3 A cm- 2 under conditions of semi-infinite diffusion;
adsorption of poison had taken place. For such con-
k4 = 1O-7 mol cm- 2 S-I. (From Ref. 126.)
ditions they concluded that the activity of the H actually
adsorbed under such conditions would be enhanced for
and sorption. However, a reexamination [129,131] of their
equations reveals that they have the same limitation as
(9) that of the Langmuir functions for PH in Ref. 123 and, in
fact, are equivalent to them, so no enhancement can arise
together with
just on the basis oflattice-occupancy statistics.
(10) The effects ofco-coverage by P in diminishing 8H were
experimentally determined in several papers by Conway
to examine if the presence of P could raise the chemical et al. [132,133] in studies ofeffects ofAs- and S-containing
potential of H. After detailed analysis of the above and poisons, e.g., thiourea, cysteine, and diethanolsulfide,
further related thermodynamic equations that are by means ofpotential-relaxation transient recording, a.c.
involved, it turns out that P cannot enhance PH on the impedance, and Tafel relations for changes of GPD H
144
coverage and by means ofcyclic voltammetry for UPO H
site occupancy. In the overvoltage region, HER kinetics
are inhibited with corresponding decreases of OPH {]H.
In some cases, e.g., with thiourea at Pt, increase of
overvoltage at Pt results in progressive reductive
desorption of the poison, leading to unusual Tafel slopes
for the HER [132,134].
Although still only qualitatively understood, the
enhancing effect of adsorbed poisons on H sorption
seems to be due to an influence on the actual kinetics of
transfer [126] (process IV) between the state of H
adsorbed ({]H) and that absorbedjust inside the metal (site
fraction X o). This is a subtle "surface chemistry" effect,
possibly connected with a change of surface potential or
equivalent field due to P adsorption. Alternatively, a com-
plete change of mechanism to direct proton injection
has been suggested [125,128] and/or restructuring of the
surface geometry on the atomic scale.
Comparative investigations at Pd by Barber and Con-
way [132] and Barber [134] with thiourea as the poison
revealed, somewhat unexpectedly, that this poison
inhibited the otherwise easily measurable H sorption.
When H had been presorbed into an initially clean Pd
electrode, its anodic desorption, after poisoning the
surface, was also found to be inhibited; this is presumably
because sites on the outside of the electrode, onto which
H could be transferred from the bulk (actually the
near-surface region) into an adsorbed state where anodic
ionization could take place, were no longer available,
being blocked by thiourea or its reduction product, H 2S.
Desorption or sorption only took place if the
thiourea-covered Pd surface had been polarized to ca.
1.2 V, leading to oxidative desorption of the thiourea,
then allowing facile ionization of the sorbed H.
XI. SPECIFICITY OF H 2 EVOLUTION
KINETICS TO CRYSTAL FACE
ORIENTATION AT PT
A. Kinetic Measurements and Results
In Sec. VII it was explained how UPO of H is highly
specific to surface geometry at single-crystal planes of
various crystallographic orientations at Pt and Rh
[48,84,117-121] as are also the kinetics of the UPO and
desorption of H [81]. Of great interest, therefore, is the
question whether the kinetics ofthe OPO ofH and H2 for-
mation at finite overpotentials (/1) are similarly surface-
structure dependent. Unlike studies on UPO, CV is not
a procedure that can be usefully employed to answer that
question because steady-state H 2 currents are normally
much greater than those due to potential-dependent
Conway
changes of OPO {]H. Hence, transient or AV modulation
methods are required. In earlier and recent works, Con-
way with various coworkers (e.g., in Ref. 144) showed
how potential-relaxation transients, digitally recorded
over some six decades of time after interruption ofvari-
ous previous steady cathodic polarization currents, could
be analyzed to derive the pseudocapacitance, Cq" associ-
ated with the /1-dependence of OPO (]H. This gave some
of the first reliable estimates of OPO H coverage as!(/1)
for the HER at Ni and Pt. This procedure provides
response data in the time-domain, complementary to
that for the frequency-domain obtainable from AV
modulation, a procedure that was also used [132,141].
From the known major dependence of log io, on
cathode metal properties [5,42-46] and the recently
found [81] dependence ofthe kinetics ofUPO ofH on sur-
face lattice structures of Pt, it is surprising that what
results had earlier been obtained [135-138] on the influ-
ence of surface structure of Pt on the H2 OPO kinetics
indicated no significant dependence. Contrarily,
electrocatalysed reactions of small molecules at Pt are
substantially sensitive to the crystal surface geometry,
e.g., oxidation ofHCOOH.
This unexpected result for the HER, and the contrary
trends for the kinetics of UPO H [81], has led to new
detailed studies of the dependence of the kinetics of the
OPO processes in the HER by means ofcomplementary
a.c. impedance spectroscopy and d.c. polarization
measurements at several single-crystal surfaces of Pt
having different geometries. Contrary to previous results
[135-138], substantial specificity has now been found in
recent works [55,139,140]; the opposite conclusions
reached in earlier work seem to be due to the real kinetic
dependence on surface structure being obscured by
effects associated with supersaturation by H 2 in the
diffusion boundary-layer region [102] that arises at clean
and thence active Pt cathode surfaces. By means of elec-
trochemical impedance spectroscopy (IS) measurements
at rotated electrode surfaces, these complications due
the H2 diffusion can be factored out, as in the recent work
of Barber et al. [141], revealing the true dependence of
the reaction kinetics on crystal geometry.
The H2 diffusion effect is associated with development
of a supersaturation region of H2 in the diffusion layer
at kinetically active clean Pt surfaces, which sets up a
quasi-Nernstian potential. This can depend on current
density giving rise to an apparent Tafel slope around
30 mV that can be confused with the slope associated with
rate-controlling H + H recombination in step III. This
situation had been examined by Breiter [102,142] and by
Losev [143]. The diffusion effect can obscure the identifi-
cation of the actual kinetics of whatever is the rate-
H Adsorbed at Metal Electrode Surfaces
determining activation-controlled step in the HER at
such active electrode surfaces. Usually, this problem is
much more severe at Pt in acidic than alkaline solutions
because the activation-controlled kinetics in the latter
medium are slower. However, it is well known that good
kinetic results are more difficult to obtain in alkaline than
in acid solutions due to problems of purity of NaOH or
KOH and ofdissolution of silicates or borates from glass
when glass cells are used. It should be noted that the
diffusion effect involves diffusion of H 2 away from the
supersaturation region near the electrode surface so that
the phenomenon involved is not "diffusion control" in
the usual sense.
The diffusion effect can be mitigated by rotation of the
electrode [55,139,141,144] or can be factored out by use of
impedance spectroscopy analysis [141].When this is done,
a clear dependence of HER kinetics on crystal-surface
geometry is revealed [134,141] in a way then consistent
with the general trend [44,47] of electrocatalysis in the
HER with metal properties (see Sec.V).
Markovic et al [55,139, and Chap. 46] made a detailed
study of the HER at Pt(111), (110), and (100) surfaces in
aqueous H2S04 and KOH, using rotated electrodes
but only over the small potential range 0 to -0.17 V
(RHE) and anodically for H2 oxidation (HOR) from 0
to +0.9 V (RHE). The results gave clear evidence for
surface-structure dependence of the HER (as well as
the HOR) as manifested in Tafel plots. However,
experimental points were not shown on their curves.
In the HER region, some small but significant
rotation-rate (w) dependence of the cathodic currents
arises, whereas, ofcourse, in the HOR range the currents
follow the Levich- Koutecky relation in w, in the
expected way.
From their polarization measurements, the order of
increasing activity of Pt (hkl) planes for the HER was
determined as (lll) < (100) < (110). Because of the
intrinsically slower kinetics of H 2 evolution from H20
in alkaline solutions, where the proton source is H 20
(Sec. II), results can be obtained [145] mainly free from
the effects of H 2 diffusion that complicate interpretation
of results from measurements in acid solutions [141].
In work commenced in 1993, Barber [134] with Morin
and Conway [141] made a systematic examination of the
HER in acid medium (0.5 M H 2S04) at the principal
index planes ofPt and the stepped planes (511) and (1911),
as well as at (100), annealed by two different procedures
(cooling in H 2 + Ar or in air, Sj and SII), following the
now well-known crystal preparation procedures of
Clavilier. Ultra-high-purity experimental procedures
[85,86] were used in this work, the necessity for which is
now generally recognized.
145
Because of the substantial influence of effects of
diffusion ofH 2away from the electrode interfaces at active
Pt surfaces, explained earlier in this section, IS measure-
ments coupled with electrode rotation and d.c. Tafel
polarization experiments were required to factor out the
effects arising from H 2 diffusion. The IS results, plotted
in the complex plane, enabled the diffusion effect to be
clearly distinguished (it behaves according to the finite,
bounded, diffusion model rather than to the Warburg
case), but the extent of its role depends on the kinetic
activity of each Pt face for the HER. The true
activation-controlled kinetics, evaluated in terms of the
Faradaic resistance, Ret, could then be determined for sev-
eral of the surfaces. At others [(111), (110), and (100) SIll,
it was too low (kinetics too fast) to give a reliably resolved
high-frequency response, hence evaluation of Ret [141]
The impedance behavior was analyzed according to
the kinetic treatment of Harrington and Conway [113].
The periodic material flux equations (related to currents,
i) were written for electron transfer (ro), H coverage
change (rI) and mass-transfer (of H2) (r2), and the
Faradaic admittance, Yr, derived from the determinants
of the three differential-flux equations [ef. Eq. (5)]:
AB
Yr
.
= ft.// ft.E = A = - - - - - - - ; , - - -I-B
----=---
iw C + -,----------;==---,------;:=
I - E.J7WScoth.J7WS
(11)
where A = -F aro/aE, B = (-aro/afi)/(arJ/afi),
C = qt(F arJ/afi), E = D/(L ar2/aCs), S = L 2/D is the
(finite) diffusion length and D the diffusion coefficient of
H2 in solution.
The overall impedance, including the double-layer
capacitance, is then
(12)
The kinetic behavior of the HER at Pt (hkl) surfaces
was then characterized by the values of A, B, C, and E
derived by optimized computer fitting; details of these
calculations are given in Refs. 134 and 141. The com-
plex-plane plots showed clear dependence on surface
orientation (2-d structure) leading to surface specificity
ofthe values of A, B, C, and E as illustrated in Figs. 11-13.
From the derived rate constants, Tafel relations were
constructed for the kinetics free from the effects of
H 2 diffusion. Major dependence on 2-d geometry is
observed as shown in Fig. 14, contrary to the conclusions
ofearlier works.
Unfortunately, for the (111), (110), and (100) Sn faces,
kinetic relaxation response, corresponding to the
high-frequency Faradaic resistance (IIA), was not
146

-0.09

-0.08

-0.07
>
-- -0.06

~ -0.05
~ -0.04
r-l
-0.03

-0.02

-0.01 o -8E-5 L-_"--_'----''--'~ ........_ _'__ _'__~_....J

0.00 L~--1.~ ",,-................."""":':""'....L._..::....._......._~_-J 0.00 -0.01 -0.02 -0.03 -0.04 -0.05 -0.06 -0.07 -0.08 -0.09 -0.10
2 6 7 8 9 101
Evs.RHE / V
A / n- I cm-2 Figure 13 As in Fig. 12, but for the parameter C in Eq. (5).
Figure 11 Pt surface-geometry dependence ofthe kinetic par-
-0.20 r - - - - - - - - - - - - - i r - , .------,,-----...,.,
ameter A in Eq. (5) for the HER at Pt single-crystal surfaces in
0.5 M aq. H 2 S0 4 • (From Ref. 141.) ,.i ;.:
i
i
i
i
-0.15 i
-0.10 r-----r----,-------,,..,----------r------, i
i
i
i
-0.09 i
i
i
-0.08 ~ -0.10 i
i
i

i
-0.Q7 i
> ~ (IOO)SI / / (111) i .,/' (511)
r-l
-- -0.06

_._:.~~:': ,.>//
r-l -0.05
~ -0.05

~ -0.04

r-l -0.03 0.00 '='=:w.-'-===:........

10-3 2 3 10-2 2 3
"--==::...........100. . .
10- 1 2 3
. . - l.........................o-...........J
2 3 10' 2 3

-0.02 2
current-density / A cm-
-0.01
Figure 14 Tafel relations constructed from the a.c. impedance
0.00 L~'----'~_ ........_~ _ _'_~__'_.......:....::::..::..._........:~'----'.I....._.....I
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 1.0 parameters for the HER for indicated single- crystal Pt surfaces
in 0.5 M aq. H 2 S0 4 . (From Ref. 141.)
B

Figure 12 As in Fig. 11, but for the parameter B in Eq. (5). 1.0 1 -----------:-::::::-===--======1
(From Ref. 141.) 0.9

a! 0.7
~
0.8

0.6
h(l1l) .'
(110)

,,'
""",

..................
.........................

detectable in the frequency range that could be covered

~~ 0.5 .' . ~~OO)SI
. (511)
(i.e., the kinetics are very fast on these faces). At inter- <> , •

~ ~.~ ::::<~:~::.../ . /
mediate frequencies, the relaxation process is that of
adsorbed H (8), represented by parameters Band C
[Eq. (11)], whereas the low frequency relaxation is that
for oscillation of the interphasial H 2 concentration.
As seen in Fig. 14, the order of increasing kinetic 0.0 L ........ -'- ----l

activity ofthe Pt surfaces for the HER, free from the com- 0.0 -0.1 -0.2 -0.3

plications of H2 diffusion, is 100 S, < (111) < (511) Evs.RHE / V

< (110) as shown by that derived Tafel relations. The data Figure 15 OPD H coverages as a function of potential at the
also enabled the OPD coverage by H to be evaluated as a indicated Pt single-crystal surfaces, corresponding to the
function ofoverpotential (Fig. 15).These relations are also behavior ofthe derived kinetic parameters plotted in Figs. 11-14.
clearly dependent on crystal-face geometry. (From Ref. 141.)
H Adsorbed at Metal Electrode Surfaces
B. Relation Between UPD Hand OPD H
Considerable interest and discussion has arisen around
the question of the relation between the UPD and the
OPD H, e.g., in regard to kinetics of the HER and to mat-
ters such as electrochemical hydrogenation (Sec. XII)
and H sorption into metals.
Markovic et al. [55] regard the strongly bound H as an
"inhibitor" of the HER; however, in relation to the
position of the Pt metals on the volcano plot (Fig. 1),
Conway (Ref. 5 and Sec. V) argues for an opposite
conclusion. For example, on Pt(110) they [55] consider
that the troughs in the "railed" structure accommodate
the UPD H (cf. Ref. 152), whereas the H atoms
involved in recombination to H 2 reside on top "Pt-pair"
sites. A related distinction was drawn in the paper of
Barber et al. [141], who noted that the (lll) face has
twice as many hollow sites as the (100) so that at "full"
UPD H occupancy the (lll) face would have half of its
hollow sites vacant, whereas the (100) face would have
almost all of its hollow sites filled. The OPD species may
then fill the remaining hole sites, enabling a larger
qr(OPD) charge to be realized for the (lll) than for the
(100) face. The alternate explanation, with the on-top
active for OPD of H, could also explain their results. Note
that on the (Ill) face the trigonal holes are of different
kinds: those with and those without an immediately
underlying metal atom of the 3-d structure. Kita et al.
[138] regarded the UPD and OPD H states as essentially
different, which is justifiable if complete coverage by
UPD H species is attained when the hydrogen reversible
potential is reached.
A further and significant possibility is that the
extra OPD H beyond the "monolayer" of UPD H is
accommodated in a new communal noncommen-
surate lattice arrangement. Although the formal
chemical identities of UPD and OPD H are, of
course, the same, their electronic, bonding, and
coordination relations on the surface lattice must be
different once nominal full coverage, "BH = 1," is
exceeded.
It should be mentioned that the extent of "full
coverage" by UPD H in relation to the onset of
deposition of the OPD H intermediate in the H 2
formation reaction is to some extent arbitrary in the
sense that the H 2 reversible potential could be made
more negative at H 2 pressures greater than the
standard value or, in the opposite direction, for lower
p(H 2). Then it could be expected that larger UPD cover-
age might be attained up to the H 2 reversible potential if
experiments could be conducted up to, say, p(H 2 ) ;:::; 100
or 1000 atm.
147
Finally, it is of interest that H sorption into Pd or Ru
can take place already from the H UPD region and thus
does not require H to be generated under 0 PD conditions
for which it is less strongly bound.
The behavior of the Pt(lll) surface requires special
comment beyond the recently demonstrated [55,84] fact
that ca. 33% ofthe 210 JiC cm- 2 charge is associated with
electrosorption of HS0 4 ions. The remaining 66% of
charge (for UPD of H) is passed with an almost constant
voltammetric current density (pseudocapacitance) over
ca. 0.25 Vofpotential range. Discussions of this fact have
involved the idea that lateral interactions would explain
this behavior but have failed to indicate why similar effects
would not arise at the 100 and 110 faces. Also (cf. Ref. 69),
such interactions would have to be extremely strong to
give an almost flat CV profile that then should extend (see
Ref. 69) over some 0.9 V instead of 0.25 V! A more
realistic explanation is that the (lll) H profile is really
composed of three overlapping, almost Langmuirian
(69) peaks, for three lattice-array structures having differ-
ent standard potentials.
XII. ADSORBED H IN ELECTROCHEMICAL
HYDROGENATION
Electrochemical hydrogenations have been carried out
since the beginning of the century, e.g. as in Refs. 11,
147-151, and the role ofadsorbed H was early recognized
[151]. Tafel's workon H, in fact, originated from his studies
of electrochemical reduction of strychnine [152]. Such
processes provide good examples of "electrocatalysis"
[5]. Electro-organic reductions in aqueous media take
place either by electronation followed by protonation
steps (at noncatalytic metals) or by an hydrogenation
mechanism involving the adsorbed H in steps I, with II
or III, in the HER at transition metals where BH can be
appreciable. Catalytic hydrogenation can also be
performed indirectly at the exit side of a thin Pd
membrane cathode by transfer of atomic H, generated at
the cathodic side of Pd.
Some advantages of electrochemical hydrogenation
over regular catalytic hydrogenation with H 2 are that the
kinetic barrier for dissociation of H 2 is completely
avoided and mass transport of the poorly soluble H2 mol-
ecule is bypassed because reagent H is directly produced
at the electrode surface. Additionally, selectivity in the
reduction pathway and resulting product can be achieved
at different potentiostatically controlled electrode
potentials [153-156] (which determine H coverage) as first
found in Haber's classical studies on nitrobenzene
148 Conway

reduction or at different cathode metals (cf. the volcano 31. RA Marcus. Annu Rev Phys Chern 15:155-202,1964.
relations discussed earlier). Recent leading work is that 32. RA Marcus. J Chern Phys 29:1858-1871,1963.
by Lessard et al. [153-156]. 33. RA Marcus. J Chern Phys 39:1734-1742, 1963.
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35. R Busing,W Kauzman. J Chern Phys 20:1129-1142,1952.
36. BE Conway, JO'M Bockris, H Linton. J Chern Phys
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10
Reconstruction of Gold Surfaces
A. S. Dakkouri* and D. M. Kolb
University of Ulm, Ulm, Germany
ABSTRACT
Surfaces of flame-annealed gold single-crystal elec-
trodes are reconstructed in very much the same way
as those gold surfaces heated in an ultrahigh vacuum
chamber. The electrochemical conditions are given
under which a reconstructed gold surface is stable in
contact with an aqueous solution. A potential-induced
surface reconstruction (in contrast to the thermally
induced one) is shown, and its consequences for elec-
trochemical studies with gold electrodes are
demonstrated. Charge- and adsorbate-driven struc-
tural transitions between reconstructed and
unreconstructed surfaces, which can be initiated by
potential changes, are presented. Finally, the electro-
chemical properties of reconstructed gold surfaces
are briefly discussed.
I. INTRODUCTION
As has been described in several chapters of this
book, there is a strong influence of the structure of
metal surfaces on many electrochemical reactions.
For a detailed understanding of such effects, however,
it is almost mandatory to use single crystals with
structurally well-defined surfaces, because those of
polycrystalline material are far too complex to allow
a mechanistic interpretation. Only from measure-
ments with single-crystal electrodes we first learnt
about the pronounced structure sensitivity of electro-
* Current affiliation: University of Erlangen - Nuremberg,
Erlangen, Germany.
151
chemical reactions such as the oxidation of organic
fuel [I], the reduction of oxygen [2], and the forma-
tion of thin metallic overlayers [3,4]. With the use of
single-crystal material it is assumed tacitly that the
atoms at the surface retain their bulk positions and
hence the surface structure can be derived directly
from the bulk structure that is well known. Although
many metal surfaces fulfill this expectation, some do
not. The reason for this deviation is the break in
translational symmetry at a surface and the highly
asymmetric environment of surface atoms due to
missing neighbors. Therefore, atoms at surfaces
experience different forces than atoms in the bulk,
which very often leads to a rearrangement in the top
layer with respect to the bulk structure [5-7]. (1)
Quite often, small variations in the bond length nor-
mal to the surface are found for atoms in the surface
region in response to the changed environment.
Typically, there is a contraction of the spacing
between the first and second atomic layer (of the
order of a few percent of the bulk spacing), followed
by an expansion between the next two layers. This
effect is called surface relaxation. (2) There may also
be local bond breaking and new bond formation
within the surface that we call surface reconstruction.
In this case, surface atoms undergo a lateral displace-
ment that is driven by a lowering of the surface
energy and is often connected with phase transitions
to markedly different surface structures. (3) It is also
possible that a clean surface can undergo large-scale
changes facilitated by surface diffusion over distances
that are much greater than atomic spacings. Such a
152
surface restructuring-which is called surface
reshaping-can cause macroscopic changes in the
surface topography (e.g., creation of steps, surface
roughening, and faceting).
A. Some Observations Obtained from
Ultrahigh Vacuum Studies
It is well established from numerous ultrahigh vacuum
(UHV) studies that all three low index faces of a gold
single-crystal reconstruct when they are subjected to a
heat treatment [5-17]. This reflects the tendency of
creating densely packed surfaces. For example, the
Au(100) surface reconstructs into a hexagonal close
packed (hcp) form (Fig. la) [8-10] that will be called in
the following "(hex)" structure. This Ill-like surface is
slightly buckled because the top atoms are no longer in
registry with the underlying bulk [10]. The 110 surface
of gold typically reconstructs into the (1 x 2)-
"missing-row," in which every second row of atoms has
been removed to yield narrow Ill-microfacets in the 110
direction [11-13] (Fig. Ib). Occasionally, a (l x 3) or
(l x n) (with n = 5,7, ... ) reconstruction is observed
with correspondingly deeper grooves and larger
Ill-microfacets. Even Au(Ill), which is already densely
(a) AU(100) (1x1) (hex)
(b) AU(110) (1x1)
• (1x2)
(e) AU(111) t/3x22)
(1x1)
Figure 1 The structure ofunreconstructed and reconstructed
gold single-crystal surfaces.
Dakkouri and Kolb
packed, reconstructs into a so-called (.J3 x 22) structure
that consists ofa slight lateral compression of the surface
atoms in one of the three 110 directions by about 4.4%
[14-17]. This causes every 23rd surface atom to be in
register with every 22nd atom of the underlying bulk.
Correspondingly, the unit cell of this reconstruction,
about 6.3 nm in the long direction, is rather large (Fig. Ie).
Surface reconstruction is usually driven by an
enhanced lateral attraction in the surface, which is
created by an increased electron density between the sur-
face atoms. Accumulation of extra charge density
between the ion cores of the surface atoms of a metal
results from the so-called Smoluchowski effect that
describes the smoothing of the electron density
corrugation along the surface to lower the kinetic energy
of the sp electrons [18]. An alternative explanation using
directional bonds is based on the redistribution of elec-
tronic charge in the surface due to the missing neighbors
[19]. Both models are sketched in Fig. 2. The (hex) struc-
ture of the reconstructed Au(100) surface and the
missing-row structure of reconstructed Au(llO) can be
understood as an increase in the surface coordination
number [in the case of Au(lOO) even at the expense of sur-
(a)
(b)
Figure 2 Models explaining the increased electron density
between surface atoms. (a) Accumulation of charge between
the surface atoms due to the Smoluchowski smoothing effect.
The square lattice represents the Wigner -- Seitz cells. (From Ref.
18.) (b) Redistribution of charge in the surface bonds due to
missing neighbors. (From Ref. 19.)
Reconstruction of Gold Surfaces 153

face atoms leaving their four-fold hollow sites], whereas

the (,J3 x 22) reconstruction of Au(lll) is a direct result
of stress relief [20].
It has been frequently observed that the reconstruction
is removed by adsorption of atoms or molecules [7]. This
has been rationalized by the fact that adsorption is
energetically more favorable on the structurally more
open (1 x 1) surface than on the densely packed
reconstructed surface. Hence, if the difference in the
heats of adsorption for reconstructed and
unreconstructed surfaces is large enough to over-
compensate the gain in surface energy due to
reconstruction, the surface structure reverts to the
unreconstructed case [21]. In addition, the adsorbate
could be thought to substitute for the missing neighbors
at the surface and to create a bulklike environment for
the substrate surface atoms.
Although the bare reconstructed surface is thermo-
dynamically more stable than the unreconstructed one,
there is an activation barrier that prevents spontaneous
reconstruction at room temperature [21]. This activation
barrier can be quite substantial in height [Fig. 3, which Figure 4 STM image of an unreconstructed Au(lOO) surface
shows the energetic situation for the (1 x 1) and (hex) in 0.05 M H 2 S04 at E = +0.4 V Ys. SCE, recorded shortly after
lifting of the (hex) reconstruction. 500 x 500 nm 2 •
forms of Pt(lOO)], because in some cases reconstruction
involves bond breaking and a transport of atoms rather
than a simple displacement ofsurface atoms within a unit
cell. Therefore, the unreconstructed surface is generally Structural transitions due to surface reconstruction
trapped in its metastable state after room temperature cause a change in the number of surface atoms, hence a
desorption of the adlayer, which had removed the change in surface density. For example, the reconstructed
reconstruction, and the sample must be heated again to Au(lOO)-(hex) surface with its hcp structure contains
restore the reconstructed surface. about 24 % more atoms than the unreconstructed
Au(lOO)-(l x 1) surface. Because the excess of surface
atoms is expelled during the structural transition
(hex) -+ (1 x 1), lifting of the reconstruction inevitably
(1x1 ) (hex) causes a certain degree ofsurface roughening. In the case
of Pt(lOO) [22] and Au(lOO) [23], it has been shown by
scanning tunneling microscopy (STM) studies that the
expansion ofthe surface lattice, due to the (hex) -+ (l x 1)
Pt(100) + COgas transition, leads to the formation of small monoatomic
high islands created by the 24% excess of surface atoms
~
that coalesce by surface diffusion. A typical STM image
"-
CD of a Au(lOO) surface after removal of the reconstruction
c::
CD is shown in Fig. 4.
It has been reported in the literature that metal
surfaces such as Cu(llO), Ag(llO), or Pd(llO), which do
not undergo thermal reconstruction in the clean state,
Pt(100) + C0adS can be reconstructed into the (l x 2) form by adsorption
of small amounts of alkali metals [24-26]. This has been
interpreted as a surface-charge induced reconstruction.
Figure 3 Energy diagram for reconstructed and Surface energies depend on the surface charge, and in
unreconstructed Pt(l00), illustrating the influence ofan adsorb- model calculations it was shown that a negative surface
ate (CO).I1E ~ 42 kllmol; E* ~ 96 kllmo!' (From Ref. 21.) charge will favor reconstruction [27,28]. The result of such
154 Dakkouri and Kolb

1.5 3.4

(a) , 3.2 (b)

1.4
Ag(11 0)
,, , 3.0 Au(110)
,,
1.3 2.8
(1)<2),,,
2.6
1.2
,," .........(1X1)
'1' , '1'
2.4
....,E 1.1
I.
E
-,... 1.0
l.

-,...
...:, 2.2

2.0

1.8
0.9 --(1x1)
1.6 ----(1)<2)
...... (1x3)
0.8
1.4

0.7 1.2
0.10 0.05 0 -0.05 0 -0.04 -0.08 -0.12 -0.16

Induced charge per surface atom Induced charge per su rface atom

Figure 5 Calculated surface energies of reconstructed and unreconstructed Ag(llO) [28] and Au(IlO) [29] as a function of a
field-induced surface charge. The arrows in b mark the transitions between (l x 2) and (I x 3) (left) and between (l x I) and (l x 2)
(right).

a calculation is given in Fig. Sa, where the surface energies
of Ag(110)-(l x 1) and Ag(llO)-(l x 2) are plotted against
surface charge. Whereas for uncharged Ag(llO) the
unreconstructed form is seen to be the thermo-
dynamically stable one, which is in agreement with
experimental observation, the situation reverts for nega-
tive excess charges exceeding 0.03 electrons per surface
atom. The alkali-induced reconstruction of the 110 faces
ofCu, Ag, and Pd [24-26] has been explained along these
lines [18]: The alkali atoms donate charge to the substrate
and hence cause surface reconstruction that otherwise
would not occur for the uncharged surface.
A corresponding calculation of surface energies for
reconstructed and unreconstructed Au(llO) is shown in
Fig. 5b [29]. For uncharged Au(110) both reconstructed
surfaces, the (l x 2) and (l x 3), are energetically favour-
able over the (l x I) structure, again in full agreementwith
experiment. We note in passing that theory predicts the
(l x 3) structure to be marginally more favorable than
the (l x 2) structure. At positive charges the energetic
situation changes in favor ofthe unreconstructed surface,
but very large excess charges are required (about -0.08
electrons per surface atom) until clean unreconstructed
Au(llO) becomes the most stable form.
We have now seen that adsorption and surface
charging have an influence on the stability of re-
constructed surfaces. We point out here that the same
phenomena will occur at the metal-electrolyte interface
[30]. However, in the latter case, surface charging and
(specific) adsorption are strongly interrelated. This often
makes it difficult, if not impossible, to unequivocally
separate out the contributions ofadsorbates and charging
to lifting the reconstruction. We return to this point later.
B. Is Surface Reconstruction Relevant to
Electrochemical Studies?
From the above-described UHV work on surface
reconstruction, the general picture emerged that only
bare surfaces reconstruct (if they reconstruct at all) and
that adsorption usually lifts reconstruction. Therefore,
when electrochemistry with single-crystal (particularly
Reconstruction of Gold Surfaces
gold) electrodes started it was by no means clear whether
those reconstruction phenomena observed under DHV
conditions would playa role for metal surfaces in con-
tact with an aqueous electrolyte. Specifically and
nonspecifically adsorbing ions and the overwhelming
amount of water molecules could well have rendered
reconstructed surfaces unstable. Despite this, surface
reconstruction has now and then been postulated in the
past to explain certain features in cyclic voltammograms
ofsingle-crystal gold electrodes [31]. However, conclusive
evidence about the existence of reconstructed surfaces
in an electrochemical cell was only obtained after elec-
trochemists had more structure-sensitive techniques at
hand. Yeager et al. [32,33] in a pioneering study showed
by coupling an electrochemical cell to a DHV chamber
and using low-energy electron diffraction (LEED) on
emersed electrodes that a reconstructed Pt(llO)-(l x 2)
surface, prepared by sputtering and annealing in UHY,
was stable in the aqueous electrolyte and even survived
potential cycling in the double-layer charging and
hydrogen adsorption region. Soon after, similar studies
were performed systematically with all three low-index
faces ofgold electrodes [34,35] which soon demonstrated
the widespread influence of reconstruction phenomena
in interfacial electrochemistry (see, e.g., Ref. 36).
II. PREPARATION OF RECONSTRUCTED
GOLD SURFACES
A. Sputtering and Annealing in UHV
Initially, the safest and most direct way of preparing
reconstructed gold surfaces of high quality was that
routinely chosen in surface science: to apply cycles of
sputtering and annealing to the sample in a DHV
chamber until the desired surface structure emerges.
Structure and cleanliness could be checked unequivo-
cally in subsequent measurements by electron diffraction
[LEED or reflection high-energy electron diffraction
(RHEED)] and Auger electron spectroscopy,
respectively. Typical conditions for such cycles are room
temperature sputtering with argon ions for 45 min at
5 x 10- 5 Torr and thermal annealing by resistive heating
for 20-30 min at about 450-550°C. The number of
sputtering and annealing cycles strongly depends on the
state of the surface, ranging between 10 for mechanically
polished samples and I for a quick reconditioning of the
surface between two electrochemical experiments. The
samples were moved between DHV chamber and electro-
chemical cell via a closed-transfer system [37]. To retain
155
the reconstructed surface during and after contact of
the electrode with the electrolyte, certain precautions
have to be met that are described in Sec. III.
B. Flame Annealing
Because for most electrochemists UHVequipment is not
readily available for the preparation of single-crystal
surfaces, other and simpler means of preparing
single-crystal electrodes were searched for in addition.
The facets of a Pt single-crystal sphere, obtained by
melting one end of a Pt wire, often served as electrodes
in the 1960s and 1970s [38,39]. A major step forward was
done by Clavilier et al. [40], who introduced the so-called
flame annealing for preparing clean and well-ordered
planar Pt single-crystal surfaces obtained by polishing
down such spheres. This flame annealing has emerged
over the years as a very simple yet extremely capable
method for preparing single-crystal surfaces of high
quality that has been shown to work for different metals
such as Pt [41], Ir [42], Au [43], or Ag [44] and for different
types of electrodes such as bead or disc electrodes and
even for evaporated films on glass [45,46] (provided the
right kind of glass is used). In the following we describe
the preparation ofgold single-crystal electrodes by flame
annealing and discuss the structure of the resulting
surfaces.
The gold single crystal mounted onto a gold wire for
better handling is annealed at red heat in the small flame
of a Bunsen burner for a certain amount of time, which
ranges between 2 and 3 s up to several minutes, depending
on the size of the sample and the surface condition. The
minutes of annealing are achieved by constantly moving
the crystal in and out of the flame, restricting the heating
period to a few seconds only to avoid any danger of
melting. (For a better judgement ofthe temperature color,
the room should be darkened during flame annealing.)
Contrary to earlier practice [47], the hot crystal should
not be quenched in water immediately but held in a
stream ofnitrogen for some time until the red heat has dis-
appeared or, even better, until room temperature has been
reached [43]. The crystal is then dipped into a beaker with
clean (triply distilled or Milli Q®) water and transferred
with a droplet of water adhering to the polished surface
into the electrochemical cell. This helps to prevent surface
contamination by laboratory air. Immersion of the
flame-annealed sample is a critical step that has to be
done under strict potential control and at sufficiently
negative potentials to avoid anion adsorption. The
experimental conditions that ensure that the initial
thermally induced reconstruction is retained after con-
tact ofthe surface with the electrolyte, are given in Sec. III.
156
(a)
Figure 6 STM images of freshly prepared Au(100)-(hex) electrodes in 0.1 M H 2 S04, showing (a) the reconstructed surface with
atomic resolution at E = -0.2 V vs. SCE (10 x 10 nm 2) and (b) a larger-scale view of the reconstruction rows at E = -0.24 V vs.
SCE (44 x 44 nm 2).
The following observation concerning an improve-
ment in the preparation of high-quality single-crystal
surfaces may be worth mentioning. It was reported for
Au(100) that electropolishing ofthe surface in a cyanide
solution after mechanical polishing but before flame
annealing yielded large atomically flat terraces [43,48].
Whereas mechanically polished and flame-annealed
gold surfaces usually exhibit flat terraces that are several
tens of nm wide, separated by monoatomic high steps,
the additional electropolishing in cyanide solution yields
much larger terraces, about 0.1-0.5 11m wide and
separated by bunches of steps. Such large 11m-size flat
terraces makes a surface ideally suited for STM studies.
Gold surfaces that were treated in the way just
described are clean, of good single-crystallinity, and are
reconstructed. This has first been shown unequivocally
for Au(100) by RHEED [49] and later by in situ STM [50].
Figure 6 shows an STM image of freshly prepared
reconstructed Au(100) in 0.1 M H 2S04, in which the hex-
agonal arrangement ofthe surface atoms is clearly visible.
Because the top layer with its (hex) structure is no longer
in registry with the underlying second layer, the surface
becomes buckled. Most notable are the so-called re-
construction rows (they run vertically in Fig. 6) with a
corrugation length of 1.45 nm and a height of about
0.05 nm. These rows are a convenient sign ofa surface to
be reconstructed for all those cases where atomic reso-
lution cannot be obtained, and hence the (hex) arrange-
Dakkouri and Kolb
(b)
ment of the surface atoms cannot be seen directly.
Well-prepared reconstructed Au(100) surfaces show
large (hex) domains with the reconstruction rows being
aligned along monoatomic high steps.Yery often a terrace
is covered by one single domain.
Reconstruction of Au(111) manifests itself in the
appearance of double rows in the STM images, which
are separated from each other by 6.3 nm. This is shown
in Fig. 7a, which is an STM image of freshly prepared
Au(l1l) in 0.1 M H2S04 at -0.2 V vs. SeE.This particular
image reveals besides the reconstruction double rows
another feature that is well known from UHV studies:
The reconstruction rows run zig-zag, changing direction
always by 120° (herringbone structure). The (J3 x 22)
reconstruction of Au(1 11), a 4.4% compression ofthe sur-
face atoms along one of the three 110 directions, results
from the tensile stress in the surface. The energy differ-
ence between reconstructed and unreconstructed
Au(111) is obviously very small, and model calculations
were not always in favor of the reconstructed form [51].
Therefore, it was argued that the herringbone structure,
which leads to defects at the elbows (Fig. 8) and hence to
a further reduction of the tensile stress, was a necessary
requirement for Au(l1l) to reconstruct. However, it has
been reported recently that flame-annealed
Au(1ll)-(.J3 x 22) may show double rows without the
herringbone structure [52,53]. An example is given in Fig.
7b, which shows an STM image of Au(1ll)-(.J3 x 22) in
Reconstruction of Gold Surfaces
(a)
Figure 7 STM images of freshly prepared Au(lll)-( v'3 x 22) electrodes in 0.1 M H 2 S0 4 • (a) The reconstructed surface shows the
well-known herringbone structure. E= -0.2 V vs. SCE. 200 x 200 nm 2 • (b) For slightly different annealing conditions, the re-
construction rows are straight and aligned along steps. E = -0.15 V vs. SCE. 168 x 168 nm 2 .
Figure 8 A close-up of the so-called elbows in the
herringbone structure of Au(1ll)-(-J3 x 22). 0.1 M H 2 S0 4 •
E = -0.2 V vs. SCE. 42 x 42 nm 2 .
0.1 M H2S04 where the reconstruction rows are seen to
run straight, covering a large terrace in a single domain.
We note that the rows are usually aligned along a
monoatomic high step similar to the case of
157
(b)
Au(lOO)-(hex). A more systematic study about the flame
annealing process for Au(lll) seems to point toward the
temperature as a crucial parameter: The herringbone
structure is conspicuously absent when the temperature
of the flame was low (dark red), whereas the former was
reproducibly observed after high-temperature annealing
(bright yellow) [54]. It thus appears that both structures,
(.j3 x 22) with and without herringbone structure, can
be obtained at will. In Fig. 9, an STM image with atomic
resolution of reconstructed Au(lll) is given showing the
two soliton walls (the double rows) that separate hcp and
fcc sites [20].
Finally, a few words about the preparation of
reconstructed Au(llO) may be appropriate. Whereas the
preparations of reconstructed Au(lll) and Au(lOO)
surfaces are practically identical and straightforward, it
is more difficult for Au(llO), where the reconstructed
(l x 2) surface is known to undergo an order-disorder
transition at about 350°C on raising the temperature [55].
While in the flame, the Au(llO) surface is in the dis-
ordered state, and rapid cooling (i.e., by quenching the
crystal in water) obviously traps this state. Therefore,
cooling the crystal in air (or in a protective atmosphere
such as a stream of nitrogen or argon) instead of
quenching in water is almost mandatory for obtaining
reconstructed Au(llO) surfaces. Only in the first case were
~- superstructure streaks observed in the RHEED pattern
and usually none or very weak superstructures in the
158
Figure 9 High-resolution STM image of a freshly prepared
AuOll)-(,j3 x 22) surface in 0.1 M H 2 S04 at E= -0.2 V Ys.
SCE.lO x 10 nm 2 .
Figure 10 STM image of flame-annealed reconstructed
Au(llO) in 0.1 M H 2 S04 at E = -0.2 V Ys. SCE. 80 x 80 nm 2 .
latter case [49]. Only in the first case, in situ STM revealed
reasonably reconstructed domains, whereas in the latter
case the surface is only rough. The best results were appar-
ently obtained with extensive flame annealing below red
Dakkouri and Kolb
heat and cooling under a hut out of glass to reduce the
cooling rate. An STM image of flame-annealed
reconstructed Au(110) in 0.1 M H 2 S0 4 is given in Fig.
10. The (l x 2) structure (missing rows) is clearly
recognizable. Monoatomic high islands and mono-
atomic deep depressions are seen to have an extremely
anisotropic shape, all being aligned along the main
crystallographic 110 direction. In many cases the islands
consist ofone single row ofatoms only.
As we have seen from the discussion above, gold
surfaces flame annealed in air are reconstructed, with
large domains of well-aligned reconstruction rows. To
retain this thermally induced initial state of re-
construction during and after contact with the liquid
phase, two obstacles must be overcome: the temperature
ofthe sample must be low enough at the moment of touch-
ing the water and the electrochemical parameters such
as electrode potential and electrolyte composition must
be correctly chosen. We discuss both points further in
Sec. III.
c. Potential-Induced Reconstruction
Out of completeness of this section, which deals with
the preparation of reconstructed gold surfaces, we
briefly mention an electrochemical procedure that in
the case of gold single crystals unwillingly leads to
reconstructed surfaces. It was observed, initially for
Au(lOO) and later for the other two low-index faces, that
application of a sufficiently negative electrode potential
(or negative surface charge) to an unreconstructed bare
gold surface causes this surface to reconstruct [49,56].
This effect appears to be different from the
alkali-induced reconstruction of surfaces such as
Ag(llO) that normally do not undergo reconstruction.
In the case of gold, the bare unreconstructed surfaces
are in a metastable state, reconstruction of the
uncharged surface being prevented at room tempera-
ture by an activation barrier. Applying an electrode
potential negative to the potential of zero charge (PZC)
obviously reduces the activation barrier to such an
extent that reconstruction is restored within a short
time of seconds or minutes even at room temperature.
As discussed in more detail in Sec. IV, a
potential-induced reconstruction can be readily dis-
tinguished from the initial thermally-induced re-
construction by STM, because in the first case the
reconstructed domains are small and show different
orientations on one and the same terrace. This is dem-
onstrated in Fig. 11, where the STM image of a Au(100)
electrode is shown, the (hex)-structure of which was
obtained by applying a potential of E = -0.19 V vs.
Reconstruction of Gold Surfaces
Figure 11 STM image of Au(100) in 0.1 M H 2 S0 4 , showing
potential-induced (hex) reconstruction. E = -0.19 V vs. SeE,
92 x 92 nm 2 . (From Ref. 52.)
seE to the unreconstructed surface for some time
[52,53]. As pointed out later, the kinetics of this
(l x 1) -+ (hex) transition is strongly influenced by the
availability of surface defects, which in this case are rep-
resented by the monoatomic high gold islands created
during lifting of the reconstruction. From a comparison
of Figs. 6 and 11 it becomes obvious that the structure
and the properties of both surfaces are sufficiently dif-
ferent to justifY a distinction between thermally induced
and potential-induced reconstruction.
III. STABILITY RANGE OF RECONSTRUCTED
GOLD SURFACES
A. Some General Remarks About the Proper
Electrode Immersion
As we have noted before, the contact of the freshly pre-
pared reconstructed gold surface with water or an aque-
ous electrolyte is a crucial step and often detrimental to
reconstruction. The two decisive points, sample tempera-
ture at the time of contact with the liquid and electrode
potential during immersion, are addressed in the
following.
159
The impact ofthe temperature at which the gold crystal
is brought in contact with the liquid on the quality of the
reconstructed surface has been systematically investi-
gated for Au(lOO) [43]. It was found that the initial re-
construction due to flame annealing is fully retained
when the crystal is cooled in atmosphere to room tem-
perature (instead of being quenched in water) before it is
transferred to the electrochemical cell. STM images of
such surfaces have revealed that usually each terrace is
covered by just one single reconstruction domain as
shown, e.g., for Au(100)-(hex) in Fig. 6. Of course, this
procedure bears some danger of surface contamination
in air that in the case ofgold is often readily removed by
the contact with the aqueous electrolyte. (We stress the
point that for gold the impact of surface contamination
during cooling in air on the electrochemical performance
has been grossly overestimated.)
Earlier on, the crystal after flame annealing was
allowed to cool in air for a few seconds until the red heat
had disappeared before it was quenched in water (i.e., it
still gave a hissing sound). Such a treatment has been
routinely used in the past in our laboratory for the study
of reconstruction phenomena because it was considered
at that time as a compromise between minimizing the
heat shock and minimizing the danger of surface con-
tamination in air [36]. The result were surfaces that
showed large reconstructed domains (on the average,
70-80% of the total surface area were reconstructed)
but also showed some unreconstructed regions, particu-
larly in the vicinity of steps [43]. Overall, this treatment
yields surfaces that contain large areas of the initial rec-
onstruction and that therefore are still suited reasonably
well for the study of reconstruction effects.
When the crystal is quenched immediately after flame
annealing, as has been often advocated for reducing as
much as possible the danger of surface contamination, a
highly disordered surface in the unreconstructed state
emerges [43]. Obviously, it was fast quenching of the
Au(lOO) crystal that had prevented other groups 10 years
ago from detecting surface reconstruction effects [57]. It
thus appears that the heat shock during quenching is
detrimental to the reconstructed surface and that fast
quenching produces rough and structurally ill-defined
surfaces. (We mention in passing that the latter treatment
gradually destroys the bulk crystal, which is even more
apparent with Pt single crystals because of the higher
annealing temperature.)
Presently, in all our STM studies with gold single-
crystal electrodes, the samples are allowed to cool down
to room temperature in a gentle stream of nitrogen. For
this purpose, the flame-annealed gold sample rests on a
ceran plate, covered by a funnel through which nitrogen
160
is blowing. For large samples, the cooling period may last
for as long as several minutes; however, in this way the
initial reconstruction is fully retained.
We now turn to the second point, the proper immer-
sion potential. From the findings in UHV of an
adsorbate-induced lifting of reconstruction, one may
intuitively conclude that the specific adsorption of anions
will be harmful to reconstructed surfaces. This is indeed
the case, and consequently the immersion potential
should be chosen sufficiently negative as to prevent anion
adsorption [36,49]. Immersion under open-cell con-
ditions almost certainly will cause lifting of the
reconstruction. Although the proper immersion poten-
tial will now be dictated by the electrolyte composition
(for chloride-containing solutions it will be far more
negative than for sulfate solutions), we may recommend
in the case of Au(lOO)-(hex) and Au(1ll)-(J3 x 22)
-0.3 V vs. SCE for sulfuric and perchloric acid solutions
as a safe value for the immersion potential. This value is
about 0.5-0.6 V negative ofthe PZC! Although electrode
immersion under potential control is readily done with a
normal electrochemical cell, this may be tricky to achieve
with electrochemical STM cells, where the sample after
flame annealing and cooling is mounted onto the bottom
ofthe empty cell. The filling-in of the electrolyte (e.g., by
pipette injection) has to be fast and in such a way that
the growing volume of solution establishes contact first
with the reference electrode and then with the counter
electrode.
B. Au(100)-(hex)
Au(lOO) was the first electrode for which systematic inves-
tigations on the stability ofthe reconstructed surface were
performed, after it was discovered in ex situ RHEED
experiments that contact of the Au(lOO)-(hex) surface
with electrolytic solutions did not necessarily remove re-
construction [34]. Structure investigations on Au(lOO)
were initially done ex situ with LEED and RHEED
[35,49] and in situ with electroreflectance spectroscopy
[49,58]. In the latter case it was the presence or absence
of empty electronic surface states in the energy gap at X
of the two-dimensional Brillouin zone of Au(lOO)-(l xl)
[59] that was used as indication for the absence or
presence of the (hex) structure.
The lifting of the (hex) reconstruction is particularly
clearly seen in cyclic voltammograms, where the
(hex) -+ (l x 1) transition shows up in a pronounced cur-
rent peak. This is demonstrated in Fig. 12, which shows
the current-potential curve for Au(lOO) in 0.1 M H 2 S04.
Starting the potential scan with a freshly prepared
reconstructed Au(lOO) electrode at -0.2 V vs. SCE in
Dakkouri and Kolb
Au(1 00): (hex)-(1 x1)
40
')IE 20
u
II
-
<i::
<-
o
·20
-0.2 0.0 0.2 0.4 0.6 0.8
E SCE / V
Figure 12 Cyclic current-potential curve for Au(IOO) in 0.1 M
H 2 S0 4 , starting with a freshly prepared reconstructed surface
at -0.2 V vs. SeE. Scan rate: 50 mV . s-I. Lifting ofthe (hex) re-
construction during the positive scan is seen by a pronounced
current peak. The subsequent scan in negative direction reflects
the electrochemical behavior of Au(IOO)-(l x I).
positive direction, lifting of the reconstruction is clearly
seen on the first cycle as a pronounced current peak at
about +0.36 V vs. SCE, which marks the potential for
the (hex) -+ (l x 1) transition. It has been shown that the
charge under the peak depends strongly on the anion
in solution [49]. The subsequent reversed potential
scan reflects the electrochemical response of the
unreconstructed surface; so does the second scan in posi-
tive direction if the potential was not held for too long at
cathodic values. Otherwise, a small current peak at the
transition potential becomes discernable on the second
scan to positive values, indicating that potential-induced
reconstruction has started while the surface was exposed
to a negative surface charge [56]. The difference electro-
chemical response for reconstructed and
unreconstructed surfaces is also reflected in measure-
ments of the double-layer capacity. This is demonstrated
in Fig. 13, where the double-layer capacities of
Au(lOO)-(hex) and-(l x 1) in 0.01 M HCl0 4are given [58].
When the freshly prepared reconstructed Au(lOO) sur-
face is immersed into the electrolyte at -0.35 V vs. SCE
and the potential cycled up to +0.55 V, a double-layer
capacity C emerges that is quite similar to that for Au(lll)
(dotted curve in Fig. 13). From the pronounced minimum
in C(E), a PZC of +0.30 V vs. SCE is derived for
Au(lOO)-(hex) in perchlorate solution, which is about
220 mV more positive than the PZC of Au(lOO)-(l xl).
When the potential scan under the conditions shown in
Fig. 13 exceeds +0.60 V vs. SCE, the reconstruction is
Reconstruction of Gold Surfaces 161

50 .-----.--.------.--.------.--.------.--.------.--.---.------,

AU(1 00): (hex) ....(1x1 )

0.01 MHCI0 4
40

C)'
E
o
Li..
:::1.
30
.......
()

20
t
PZC
PZC Au(111) - (-,J3x22)
Au(100)-(1x1)
10 '---------'---_-'-----'---_-'-----'---_.l....-----'---_.l....-......L.._..L...-......L..-----J
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8
ESCE / V

Figure 13 Double-layer capacity as a function of potential for Au(IOO)-(hex) in 0.01 M HCl0 4 with transition from (hex) to (I x I).
Numbers show the sequence of scans. (...) capacity curve for Au(1l1)-(y'3 x 22). (From Ref. 58.)

lifted and the well-known capacity curve for the 14 ,.---,----.---.--.--,---,----.---.---,

unreconstructed Au(lOO) is obtained with its PZC Au(1 00)
around +0.08 V vs. SCE [60]. We thus know that the 12 (hex) ....(1x1)
(hex) ---+ (l x 1) transition of Au(lOO) is connected with a
10
shift of the PZC of220 mY, which simply reflects the cor-
responding change of 0.22 eV in work function to lower 8 ,
,
values. This sudden shift in PZC with lifting of the :I:
Q. ,,
reconstruction requires additional charging of the 6 ' 6

C~so.:pV//.O
electrode surface to maintain the applied potential 'x
4 ~
during the structural transition, and this gives rise to a 4- --
..!:!,.

~. ~
pronounced current peak (see Fig. 12) [49].
2 CIO. 2 Cl
From systematic studies of the above-described If
type (current-potential and capacity-potential o L.....l_---'-_....L_....L..-_.L.----I.......---'-_--'------J0
measurements), the following conclusions with respect o 0.2 0.4 0.6 0.8
to the stability of the (hex) structure were drawn [36]: ESCE IV
The reconstructed Au(lOO) surface is stable in aqueous
solution in a potential range where no specific adsorption Figure 14 Transition potential for Au(IOO): (hex) -+ (1 x 1) as
a function of anion concentration and pH. The (hex) structure
of anions takes place. Neither water nor solvated ions
is stable only at potentials to the left ofthe respective line. (From
remove the reconstruction. Although the anodic poten-
Ref. 36.)
tial limit of the stability range was dictated by the onset
of specific anion adsorption, no such limit was found at
the negative end of the potential scale, where cations are Because the specific adsorption of anions varies mark-
accumulated on the surface as counter charge. Even edly in strength with the chemical nature, it is not
Cs+, which is known to adsorb specifically, did not harm surprising that the stability ofthe (hex) structure strongly
the (hex) structure nor did extensive hydrogen evolution. depends on the type of anion. This is demonstrated in
162 Dakkouri and Kolb

Fig. 14, where the transition potentials as derived from

cyclic current-potential curves for freshly prepared Au(100) : (hex)-.(1x1)
Au(lOO)-(hex) in various solutions are plotted as a func-
tion of the anion concentration (of pH for the influence 25 Pyridine 10.01 M N~S04
of OH-). Be and 1- shift the transition potential even
more into negative direction [61], causing a significant
reduction of the stability range of the (hex) structure. 20 I
For an anion concentration of0.05 M, the (hex) --+ (l x I) 1-
transition for a freshly prepared reconstructed Au(lOO) !I
surface is at -0.62, -0.23, +0.02, +0.2, +0.33, and 15 n
+0.58 V vs. SeE for ]-, Br-, Ci-, OH-, HSOi, and 1/
CIOi, respectively. This sequence reflects the !!" A
E
well-established tendency of these anions to specific
adsorption at metal electrodes. It also demonstrates that
()
10 Ii!I /I

i ..II ."
trace amounts of Ci-, the most common impurity in
sulfate or perchlorate solutions, can severely reduce the
stability range of the (hex) structure [62].
- 5
;\
ii
I:
I I
II
, I
,
II

I
I :
\~
I

Although anions of the supporting electrolyte are the ..

I \. I \ t !oo'"'

most relevant adsorbates to interfere with surface f--::=:;:"-':-':":" .....I~:: . : _.,,'

reconstruction, other adsorbates, particularly organic
O~-----------+---l
adlayers, may be similarly interesting. Their influence
on the stability of the (hex) structure is of fundamental
importance for any adsorption study with gold ' ..
~

electrodes, which focuses on the role of the surface -5

structure. In this respect, one of the most prominent mol-
ecules is pyridine, for which the adsorption behavior on
a number ofdifferent electrodes, including the low-index
gold single-crystal faces, has been studied [63]. In Fig. 15 -0.6 -0.2 0.2 0.6
it is demonstrated by cyclic voltammetry how the
presence of pyridine in the electrolyte reduces the stab- ESCE IV
ility range ofthe (hex) structure [64]. As discussed in more Figure 15 Cyclic current-potential curves for freshly prepared
detail in Sec. VB., lifting of the reconstruction is con- Au(lOO)-(hex) with (hex) --+ (1 x I) structure transitions due to
nected with a structural transition within the pyridine pyridine adsorption. om M Na2S04+x M pyridine: (--)
adlayer, the molecules changing their orientation from x = 0; (- - -) x = 10- 5 , ( ... ) x = 10-4, (- .-) X = 10- 3 , (- .. -)
flat-lying on Au(IOO)-(hex) to upright standing on x = 10- 2. Scan rate: 50 mV . s-I . (From Ref. 64.)
Au(lOO)-(l x 1)[65].

The existence of reconstructed Au(11 I) surfaces in an

C. AU(111)-(V'3)( 22)
The reconstruction ofthe Au(11 I) surface, which consists
ofa ca. 4 % compression ofthe top layer in one ofthe three
110 directions [14-16], is a rather subtle effect on the sur-
face structure as far as change in surface symmetry or in
packing density is concerned, and hence reconstruction
phenomena were more difficult to study simply by
current-potential measurements [49]. In contrast to
Au(lOO), where many questions concerning the stability
of the reconstructed surface could be answered by cyclic
voltammetry, the more elaborate approaches of in situ
STM [66] and in situ x-ray diffraction [67] were necessary
to establish the stability criteria for Au(lll).
electrochemical environment has been demonstrated
by ex situ electron diffraction experiments [35,49]. Once
such a structure information was available, apparent
peculiarities in the electrochemical behavior such as
pronounced differences in the current response for
anodic and cathodic potential scans could be safely
attributed to reconstruction phenomena. In Fig. 16 the
cyclic current-potential curve is shown for a freshly pre-
pared, high-quality (low defect density), reconstructed
Au(11 1) electrode immersed at rather negative
potentials into 0.1 M H 2 S04 . The (~3 x 22) --+ (l x 1)
structural transition is reflected in a pronounced cur-
rent peak on the anodic potential scan at +0.32 V vs.
Reconstruction of Gold Surfaces
6 2
4 50
2 :::L
~ C,)
E
(,)
«::l. 0
- -2
Au(111)
-4
-6
-0.4 0.0 0.4 0.8
ESCE / V
Figure 16 Cyclic current-potential curve for Au(lll) in 0.1 M
H 2 S0 4 , starting with a freshly prepared reconstructed surface
at the negative end of the scan. Scan rate: 10 mV . S-I.
SCE, the counterpart of which is mlssmg on the
cathodic scan. We mention in passing that the current
spikes at about +0.78 V vs. SCE are due to structural
transitions within the sulfate adlayer [68]. The
double-layer capacity of a freshly prepared
reconstructed Au(ll1) electrode and its change with
lifting of the reconstruction in 0.01 M KC10 4 is shown
in Fig. 17 together with the corresponding
voltammogram [69]. It demonstrates that the PZC for
Au(111)-(J3 x 22) in that solution is at +0.32 V vs.
SCE, which is 0.09 V more positive than that for the
unreconstructed (l x 1) surface [36,49]. The structural
transition from (J3 x 22) to (l x 1) due to a potential
excursion beyond +0.4 V vs. SCE is clearly reflected in
a current peak and in a change of the double-layer
capacity, both of which result from the shift in the PZc.
It thus appears that the (J3 x 22) reconstruction is
lifted at potentials slightly positive of the PZC of the
reconstructed Au(ll1). A comparison of double-layer
capacity measurements in 0.Q1 M KCI0 4 with slow-scan
cyclic voltammetry reveals that the difference between
(J3 x 22) ---+ (l xl) transition potential and PZC is
only about 100 mY. Hence, very little irritation, either by
163
70
60
Au(111)
':'E 1 10 mM KCI04
0
c(
::I.
':'
E ~o
(J
u. 40
-1
-0.4 0.0 0.4
30 ESCEI V
20
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
ESCE IV
Figure 17 Double-layer capacity-potential curve for Au(lll)
in 0.0 1M KCl0 4 , starting with a freshly prepared reconstructed
surface at -0.6 V vs. SCE. Reconstruction is lifted around
+0.5 V vs. SCE, as indicated by a current peak in the corre-
sponding voltammogram (see inset).
surface charge or adsorbed anions, is needed to remove
the reconstruction. This makes it very difficult at present
to decide whether it is an adsorbate-induced or a
charge-induced lifting. Unlike Au(lOO), where recent
surface energy considerations strongly suggest an
adsorbate-induced removal of the (hex) structure [70],
both mechanisms appear feasible for Au(ll1).
Studies of Au(ll1) with in situ surface x-ray scattering
(SXS) [67] and with in situ STM [53,66] have revealed that
potential-induced reconstruction is a surprisingly fast
almost reversible process. This has to be taken into
account when the potential for a Au(ll1) electrode is
stepped or cycled across the transition potential: Not only
is the surface structure slightly different on either side of
that potential, but also with each lifting of the (J3 x 22)
structure monoatomic high gold islands are created that
increase the defect structure of the Au(ll1) surface.
D. Au(110)-(1)( 2)
The clean Au(110) surface after annealing is
reconstructed in such a way that every second row of
atoms in the 110 direction is missing (so-called
missing-row model, see Fig. lb). This has been shown by
electron diffraction, ion scattering, and STM experi-
ments [11-13,71-73].
Unlike for Au(100) and Au(111), no significant changes
in the double-layer capacity of Au(110) were observed
for transitions between (1 x 2) and (1 x 1). Hence, similar
164
2 correspond to the PZC of the reconstructed (l x 2)
Au(110)
1 0.1 M H2 SO4
~ and (l x 2) is so fast that the surface is fully reconstructed
E
()
« 0
- ~
-1
-2
-0.4 0.0 0.4 0.8
ESCE IV
Figure 18 Cyclic voltammogram for Au(llO) in 0.1 M H2S04.
Continuous cycling. Scan rate: 10 mV . S-L.
to Au( 111), our understanding ofreconstruction phenom-
ena for Au(llO) stems largely from the use of in situ
STM [74] and in situ SXS [75]. In situ STM studies of
flame-annealed Au(llO) electrodes in aqueous electro-
lytes [74] have revealed that the (l x 2) structure was
stable in essence at potentials negative of the PZC (which
is around -0.04 V vs. SCE [49]) and up to +0.05 V vs.
SCE for perchloric or sulfuric acid solutions. Positive of
that value reconstruction is lifted and the (1 x 1) phase is
formed. It has also been noted that the structural
transition from (l x 2) to (l x 1) that takes place between
+0.05 and +0.20 V vs. SCE is highly reversible, the (l x 2)
structure being restored rather quickly and to full extent
when the potential scan is reversed [74]. Conclusions
from earlier ex situ LEED measurements, that the (1 x 2)
structure is stable up to very positive potentials of about
+0.9 V vs. SCE, were obviously wrong, misled by the fast
and full recovery of the (l x 2) structure at 0 V vs. SCE,
the value at which the electrode was emersed for a struc-
tural characterization by LEED after the electrode poten-
tial had been cycled to various anodic limits [76].
Double-layer capacity measurements with freshly pre-
pared Au(llO) in 0.01 M HCI0 4 reveal a pronounced
minimum in CDL at about -0.04 V vs. SCE that should
Dakkouri and Kolb
surface. Scanning the potential in negative direction
from a region where reconstruction has obviously been
lifted, the double-layer capacity curve almost retraces
the anodic scan. This means that either the PZCs
of reconstructed and unreconstructed Au(llO) are
practically the same (which has been assumed in earlier
studies [49]) or the structural transition between (l xl)
again as the scan in negative direction reaches the poten-
tial of the capacity minimum. In the latter case, it would
not be possible to determine the PZC of Au(llO)-(1 xl).
In Fig. 18 the cyclic current-potential curve for Au(llO)
in 0.1 M H2S04 is shown. From in situ STM measure-
ments, it can be concluded that the current peak at
+0.05 V vs. SCE is related to the (1 x 2) -+ (1 x 1) struc-
tural transition [77]. However, much more information
is presently needed to establish a picture of the rec-
onstruction process as detailed as the one for Au(lOO).
IV. STRUCTURAL TRANSITIONS BETWEEN
RECONSTRUCTED AND
UNRECONSTRUCTED SURFACES
A. AU(100): (hex) -+ (1 )( 1)
The kinetics of the (hex) -+ (l x 1) transition has been
shown to depend strongly on the electrode potential,
the transition time ranging from minutes at low
overpotentials down to about a millisecond at high
overpotentials [58,78]. This transition is almost certainly
anion-induced (rather than charge-driven [70]) and it
follows a nucleation-and-growth mechanism [48,79,80].
For comparatively large overpotentials, the structural
transition from (hex) to (l x 1) occurs within
milliseconds, and this is conveniently studied by cur-
rent transients. Because of a change in PZC, the
(hex) -+ (1 x 1) transition requires additional charging
to maintain a constant potential, which is clearly seen as
a pronounced peak in the cyclic voltammogram (Fig. 12).
By stepping the potential ofa freshly prepared (hex) sur-
face from negative values where the reconstructed surface
is stable, to positive values, where the reconstruction is
lifted due to the specific adsorption of anions, a current
transient is obtained that directly reflects the rate at which
the surface is transformed into (1 xl) [78]. After correc-
tion of the measured current transient for mere
double-layer charging in the absence of any re-
construction effects, rising current transients are
obtained that can now be used for a quantitative evalu-
ation of the transition kinetics by, e.g., applying the stan-
dard models for instantaneous or progressive
 Reconstruction of Gold Surfaces 165

25 .....--.....----.-----r----,-----,----r-----, of the transition peak does no longer reflect the stability

limit of the (hex) structure but rather is determined by

,,
AU(100): (hex) --(1x1)
20 1\/0.63 V transition kinetics. Another interestingobservation made
\ 0.1 M HCIO. + 0.01 M H 2SO. possible by the STM refers to the dimensionality of the
:\, transition. It was found that the (hex) ~ (l xl) transition
':'
E 15 J;' r',/0.58 V is highly anisotropic and proceeds always along the rec-
u I: \ '.
ci:: I: \", onstruction rows, the "unzipping" of the (hex) structure

-
"<f
E
10 I:
,.I: \ '
048V
starting at the top ofthe reconstruction row, where the sur-
face atoms arein"on-top"positions [80].This is concluded
from the location of the gold islands after lifting of one

,.
5 , . 1 ' .. _.
': ,.' \ ". - - -( .
_..\:. - .. -.. ':~.: ~-."
0
'.'
,
.'
".
0 1 2 3
t/ms
Figure 19 Current transients /',.F!) for Au(lOO)-(hex) in 0.1 M
HCI0 4 + 0.01 M H 2 S0 4 due to potential steps from +0.24 V
vs. SCE, where the (hex) structure is stable, to the indicated
values, where reconstruction is lifted. The transients were
corrected for double-layer charging. (From Ref. 78.)
nucleation. An example is given in Fig. 19 for
Au(lOO)-(hex) in a sulfate-containing electrolyte [30].
An analysis ofthe transients led to the conclusion that at
high overpotentials (E > +0.53 V vs. SCE) instantaneous
nucleation occurs, whereas for low overpotentials a
mechanism with constant transition rate prevails (see,
e.g., curve for E = +0.43 V vs. SCE in Fig. 19) [78]. Such
a type of transition was also observed by optical
spectroscopy when the reconstruction was lifted over a
period of minutes [58].
The early stages oftheliftingofthe (hex) reconstruction
in sulfuric acid solutions were studied by in situ STM
[48,53,80] and an example is shown in Fig. 20. Although
kinetic parameters could not be derived from the
sequence of STM "snap shots" taken in minute intervals,
valuable insight into the local mechanism ofthe structure
transition could be gained. For example, it was demon-
strated that lifting ofthe reconstruction starts exclusively
either at substrate surface defects, which for
~ well-annealed electrodes are mainly the monoatomic
I
high steps, or at defects in the (hex) overlayer, which result
from improper flame annealing (Fig. 20a). As a con-
sequence, the kinetics of the (hex) ~ (1 x 1) transition
depends markedly on, e.g., the step distribution. Particu-
larly for very well-prepared surfaces with large atomically
flat terraces, lifting of the reconstruction may be
exceedingly slow and hence the transition peak in cyclic
voltammograms may be shifted considerably toward
more positive potentials [52,80]. In that case, the potential
single reconstruction row (Fig. 20e). Therefore, under
0.43 V
- ..~ .. _.. _. the present conditions for the STM investigation (i.e., at
--._-. very slow transition rate), lifting of the (hex) rec-
4 5 6 7 onstruction occurs quasi-one-dimensional, pretending
a zeroth order reaction kinetics [58]. The
one-dimensional growth of the (l x 1) area corroborates
with the unusual shape of the current transients at low
overpotentials for which a constant transition rate was
observed. We recall that the transients for high
overpotentials were described by instantaneous
nucleation [78] and the evaluation along Avrami's
equation, e = 1 - exp(-ktn ), yielded an exponent of
n = 2 that is typical for a two-dimensional growth, indi-
cating a transition from quasi-onedimensional to
two-dimensional as the overpotential is increased.
The important role ofsurface defects for the transition
kinetics has been demonstrated in a recent study using
stepped Au(lOO) surfaces [30,81]. The increase in the
transition rate with the number of steps was clearly
discernable.
B. Au(100): (1 )( 1) ~ (hex)
The potential-induced reconstruction of Au(lOO) is a
much slower process than the adsorbate-induced lifting
of the (hex) structure, and it appears to follow a
nucleation-and-growth mechanism [48,56,80].
As has been demonstrated in Fig. 20, lifting ofthe (hex)
structure leads to the formation of small monoatomic
high gold islands. STM studies have clearly shown that
the rims of these islands act as nucleation centers for the
reverse process. An example is given in Fig. 21a where
the reconstruction rows are seen to start at the rims of
the gold islands. As a consequence of the many islands
and hence of the many nucleation centers, the (hex)
domains are now much smaller than those for a thermally
induced reconstruction and the directions of the re-
construction rows are about equally distributed among
the two main crystallographic directions of the substrate
(Fig. 21b) [48,52,53,80].
166 Dakkouri and Kolb

(a) (c)

(b) (d)

(e)

Figure 20 Sequence ofSTM images (a-d) showing the (hex) ---+ (1 x I) transition for flame-annealed reconstructed Au(IOO) in 0.1 M
H 2 S0 4 at 0.28 V vs. SCE (a) and 0.47 V vs. SCE (b-d) 93 x93 nm 2 . (e) Very initial stages of this transition in 0.01 M H 2 S0 4 at -0.34
V vs. SCE. One single reconstruction row has been lifted l2x12 nm 2 . (From Refs. 53 and 80.)
Reconstruction of Gold Surfaces
(a)
(b)
Figure 21 Two STM images for Au(lOO)-(l x 1) in 0.1 M
H 2 S0 4 , showing the potential-induced (1 xl) --+ (hex)
transition. The gradual reappearance of the (hex) structure at
-0.2 V Ys. SeE is seen by the increasing number of recon-
struction rows with time. (a) 81 x 81 nm 2 . (b) 230 x 230 nm 2 .
167
STM studies have also revealed that the gold islands of
the unreconstructed surface do not only provide with
their rims the starting points for the (1 x 1) ~ (hex)
transition, they also supply by dissolution the additional
gold atoms that are needed for the formation of the more
densely packed (hex) domains. This is particularly clearly
seen in Fig. 21b, where the longish shape ofgradually dis-
appearing islands reveals donation ofgold atoms to newly
emerging reconstruction rows.
A comparison of the STM images for thermally
induced and potential-induced reconstruction of
Au(lOO) shows pronounced differences that justify the
distinction between both types of reconstruction: A
potential-induced reconstructed surface-which exists
only for the metal-electrolyte interface and which is
obviously caused by the negative surface excess
charge-has small reconstructed domains of different
orientation on one and the same terrace, whereas the
thermally induced reconstruction often shows one single
domain per terrace. In addition, potential-induced re-
construction is often incomplete [56,80], and hence such
a surface has a much higher density ofimperfections than
the thermally treated one.
Although the potential-induced reconstruction is a
comparatively slow process-it may take minutes to
transform a noticeable fraction of the surface into the
(hex) form-it may still be fast enough to complicate or
even invalidate measurements with Au(lOO) at negative
potentials, particularly measurements for which waiting
times at negative potentials are involved. For example,
during a slow potential scan in the range negative of the
PZC, Au(lOO)-(l x 1) inevitably will reconstruct, and
hence the surface structure will change dramatically. In
this respect it may be worth mentioning that electro-
chemical annealing [82-86] can offer a way out of this
dilemma: Once the monoatomic high gold islands have
disappeared due to extensive electrochemical annealing
[80], it seems almost impossible to have any significant
potential-induced reconstruction. Therefore, the gener-
ation of an island-free unreconstructed gold surface will
enable one to study more leisurely Au(lOO)-(l x 1) at
negative potentials, at least under certain precautions.
We return to this point in Sec.v.B.
c. Au(111): ( .....3 )( 22) -++ (1 )( 1)
As mentioned before, lifting of the (J3 x 22) re-
construction at potentials positive of the PZC and
potential-induced reconstruction are two rather fast pro-
cesses that both occur within a comparatively narrow
potential range of about 100 mV [87]. Like in the afore-
mentioned case of Au(lOO), the potential-induced
168
Figure 22 STM image of Au(lll) in 0.1 M H 2 S0 4 , showing
potential-induced (-/3 x 22) reconstruction. E = -0.15 V vs.
SCE was applied for 14 min to Au(lll)-(1 x 1).168 x 168 nm 2 .
(From Ref. 52.)
(,)3 x 22) structure is far less ordered than the thermally
induced one. This is shown in Fig. 22 where the double
rows are seen to run zig-zag in all three main
crystallographic directions [52,53]. Like for Au(lOO), the
monoatomichigh gold islands that were generated during
lifting of the (.)3 x 22) reconstruction are consumed in
the process of the potential-induced formation of the
(.)3 x 22) structure.
v. ELECTROCHEMICAL PROPERTIES OF
RECONSTRUCTED GOLD SURFACES
A. Potential of Zero Charge
Reconstruction phenomena can play an important role in
the study of electrode reactions for the following two
reasons. The first has to do with structure. As we have seen
before, reconstructed electrodes have a surface structure
that deviates often considerably from that of the
unreconstructed ones, i.e., from the one that is inferred
from the bulk structure. This is especially clearly seen
for Au(lOO), where reconstructed and unreconstructed
surfaces differ not only in their packing densities by about
24% but also in their symmetry. Reconstructed Au(lOO)
is very similar to that of Au(lll), i.e., hexagonal-densely
packed, whereas unreconstructed Au(lOO) has the
Dakkouri and Kolb
fourfold symmetry one expects from the bulk structure.
An additional complication is brought in by the
potential-induced reconstruction that occurs for
E < Epzc and that causes the surface structure to
become even potential dependent. This is particularly
important for adsorption reactions as will be demon-
strated in the next section. Furthermore, because of the
generally higher packing density of reconstructed
surfaces, lifting of the reconstruction momentarily leads
to a (1 x 1) surface that is covered by monoatomic high
gold islands constituting a high density ofsurface defects.
As has been discussed earlier, coarsening of the gold
islands, the rate ofwhich depends markedly on electrolyte
composition and electrode potential, leads to a smooth-
ing of the surface with time. This may cause seemingly
irreproducibilities in kinetic experiments, because the
number ofsurface defects will depend on time, a fact that
has not always been sufficiently appreciated in the past.
The second reason is regarding potential ofzero charge.
Reconstructed electrodes have PZCs that may differ
substantially from those of the unreconstructed ones.
This is quite natural because the PZC of a single-crystal
electrode correlates directly with its work function, which
in return relates to the packing density ofthe surface [88].
The PZCs of the three low-index faces of gold,
reconstructed and unreconstructed, are summarized in
Table 1 [36]. We may mention that the PZC of
Au(lOO)-(l x 1) in Table 1 refers to an island-free surface,
which was prepared by electrochemical annealing. Values
of the PZC obtained directly after lifting of the re-
construction are typically a few mV more negative, the
direction of the shift being consistent with expectations
for a stepped or roughened surface.
The differences of the PZCs between Au(lOO)-(hex)
and -(1 x 1) were shown to have a profound influence on
the reduction kinetics of highly charged species such as
Co(NH3)~+ and Fe(H20)~+ due to double layer effects
[89]. Their reduction on a Au(lOO) electrode in dilute
Table 1 Potentials of Zero Charge for Reconstructed and
Unreconstructed Gold Single-Crystal Electrodes in 0.01
MKCI0 4
Surface structure PZC (V vs. SCE)
Au(lOO)-(hex) +0.30
Au(lOO)-(l x I) +0.08
Au(1ll)-(-/3 x 22) +0.32
Au(lll)-(1 xl) +0.23
AuOlO)-(1 x 2) -0.04
Au(llO)-(l x I) (-0.02?)
Reconstruction of Gold Surfaces
supporting electrolytes was significantly different for
(hex) and (1 x 1). The change in the rational potential,
E - Epzc , during lifting of the reconstruction that
amounts to about 220 mY, can cause substantial changes
in the potential drop across the diffuse double layer (the
<fJrPotential), particularly in the vicinity of the PZC,
where this potential drop is rapidly changing with the
electrode potential [90]. Depending on the sign of the
double-layer field, the ions are repelled from the
double-layer region or attracted into it, leading to a
decrease or an increase in the current and to a concomi-
tant shift in reaction potential. Increasing the ionic
strength of the solution reduces the double-layer effects
and the differences in reaction kinetics for (hex) and
(1 x 1) structure indeed vanish [89].
B. Adsorption of Pyridine on Au(100)
Pyridine on gold has been thoroughly studied in recent
years by Lipkowski and Stolberg [63]. The adsorption
isotherms for pyridine on all three low-index faces ofgold
and the corresponding Gibbs energies have been derived
from charge measurements. For Au(111), a small disconti-
nuity in the charge-potential curve pointed to the occur-
rence of a first-order structural transition within the
pyridine adlayer, which was explained by a change in the
admolecule's orientation from a flat position at low
coverages to a vertical one at high coverages [91]. For
AuOlO) a broad one-step adsorption isotherm was
observed, indicating that on the very open 110 surface
pyridine is adsorbed in a vertical position from the very
beginning. For Au(IOO) the adsorption isotherm revealed
a discontinuity similar to but significantly larger than
for Au(111), which led to the conclusion that the same
structural rearrangement as for Au(l11) occurred also in
the adlayer on Au(100) [92]. However, as is now well
established, the surface structure of Au(100) is potential
dependent: As a consequence of potential-induced
reconstruction and adsorbate-induced lifting of the
reconstruction, the surface structure ofthe Au(100) elec-
trode is hexagonal close packed at negative potentials
and only at positive potentials the surface assumes the
bulk structure. A combined electrochemical and e1ectro-
reflectance spectroscopy study has revealed that the
adsorption of pyridine on Au(100) under the
experimental conditions used in all former investigations
started on Au(100)-(hex) because of the relatively long
time for which the potential was held at negative
potentials [65]. At the transition potential where the sur-
face charge as a function of electrode potential shows a
clear discontinuity and hence the current in cyclic vo1-
tammetry a pronounced peak (Fig. 23), the recon-
169
5
Au (1 00)
4
1 mM pyridine
+0.1 M NaCI0 4
3
'l'
E 2
u
-
et
~
1
0
-1
-2
-0.8 -0.6 -0.4 -0.2 0
ESCE / V
Figure 23 Cyclic current-potential curves for Au(lOO) in 0.1 M
NaCl0 4 + 1 mM pyridine for various negative potential limits.
Scan rate: 10 mV . S-I. The pronounced current peak at -0.06 V
vs. SeE reflects the (hex) -+ (l x 1) transition and the concomi-
tant change in orientation of the adsorbed pyridine. (From Ref.
65.)
struction is lifted due to pyridine adsorption that is
unequivocally shown by the optical response of the elec-
trode in the photon energy range ofexcitation into surface
states [65]. (We recall that the electroreflectance spectra
of Au(lOO)-(hex) and -(1 x 1) differ vastly due to the
absence or presence of surface states at X of the surface
Brillouin zone [49].) This is demonstrated in Fig. 24,
where the (hex) -+ (1 x 1) transition is reflected in an
abrupt change in I1R/R from a curve that is typical for
Au(111) to one typical for Au(lOO)-(l x 1). Concomitant
with the lifting of the reconstruction the pyridine mo-
lecules undergo a structural transition from flat
n-bonded on the densely packed (hex) surface to vertical
N-bonded orientation on the more open Au(lOO)-(l xl).
In retrospect it becomes evident that only a fraction of
the sudden charge increase at the transition potential
can be attributed to the structural rearrangement in the
pyridine adlayer, whereas a significant part ofthat charge
must be due to the lifting of the reconstruction and the
concomitant shift in PZc.
To study the pyridine adsorption on an un-
reconstructed Au(lOO) over the entire potential region,
the reappearance of the (hex) structure at negative
170 Dakkouri and Kolb

15 however, reconstruction effects have not been taken into

account, and hence many ofthe obtained data may refer
~,
to different surface structures, depending on the poten-
\ tial region.
AU(111) ......../
10 ,, \
\

~
, \
\
\
\ c. Phase'n'ansitions in Organic Adlayers on

-
a:
a:
-<:I
5
I
\
\
...
AU(100)

(')0 Au(100) - (hex) The adsorption oforganic molecules on solid electrodes

~
I has received increased attention in recent years mainly
0 because such adlayers may be used to specifically mod-
ify the chemical and electrochemical properties ofa sur-
AU(100) - (1X1) ............. / face [94]. Their potential applications range from

.. '.
tailor-made electrocatalysts to corrosion inhibitors. As
-5 is well known from numerous studies with the mercury
hanging drop electrode, many organic molecules
undergo structural rearrangements as their coverage is
-0.8 -0.4 o 0.4
increased, which can often be described by first-order
Esce/ V two-dimensional phase transitions [95]. Such
rearrangements are typically disorder-order transitions
Figure 24 Potential dependence of the electroreflectance or a change in the molecule's orientation from flat lying
effect !'1RIR of Au at nm = 3.0 eV for a scan in positive to vertical, as was discussed above for pyridine on
direction. - - , Au(lOO)-(hex) with transition to (1 x I) around Au(IIl). Phase transitions in organic adlayers on solid
-0.1 V vs. SCE; ... " Au(lOO)-(l x I); - - -, Au(lll). 0.1 M surfaces of gold or silver were readily observed on the
NaC104 + I mM pyridine. (From Ref. 65.) densely packed (Ill) faces that obviously allow the mol-
ecules to rearrange themselves freely in the desired
fashion [96-102]. Such rearrangements had not been
seen in the past for the more open 100 and 110 faces that
seem to lock the molecules in their hollow sites. It could
potentials has to be avoided. This has been achieved by be shown, however, by the use of freshly prepared
making the adsorption kinetics much faster than the reconstructed Au(100) electrodes that molecules such
restoration of the (hex) structure. At sufficiently high as coumarine [96], uracil [98], thymine, 5-chlorouracil,
pyridine concentrations (l mM or higher), waiting times and camphor [103] on Au(100)-(hex) undergo the very
ofa few seconds are enough to establish adsorption equi- same phase transitions as on Au(1Il). This is demon-
librium but are too short for allowing the (hex) structure strated for camphor on Au(100)-(hex) in Fig. 25, where
to be formed at any significant extent. Such studies the pronounced current spike around -0.25 V vs. SCE
revealed that the adsorption of pyridine on in the cyclic voltammogram of Au(100)-(hex) in 0.05
Au(100)-(1 x I) proceeds without any sign of a phase M Na2S04 containing 2.5 mM camphor indicates the
transition, very much like on Au(1lO) or Au(21O), occurrence of a structural transition within the camphor
suggesting that the molecule adsorbs on the more open adlayer [103]. At potentials positive of +0.4 V vs. SCE,
Au(100)-(1 x I) in a vertical position from the very begin- camphor adsorption lifts the reconstruction and the
ning [93]. As has been mentioned before, the kinetics following potential scan shows that the phase transition
of the (l x I) ---+ (hex) transition can be strongly influ- occurs even on the unreconstructed Au(100)-(1 x I)
enced by the defect structure (island structure) of the surface.
(l x I) surface. Electrochemical annealing of the From a number ofstudies performed in our laboratory
unreconstructed surface can inhibit the potential- [103] we are led to conclude that practically every mol-
induced reconstruction to such an extent that ecule that undergoes a structural transition on Au(1ll)
electrochemical reactions may be leisurely studied will show the same behavior on Au(100)-(hex), provided
on Au(100)-(1 x I) even at potentials negative of the the (hex) structure is stable in the potential range under
PZC [86]. In most studies with Au(100) in the past, consideration.
Reconstruction of Gold Surfaces 171

are of great importance in the study of adsorption

10 Au(lOO) reactions. The potential-induced reconstruction is
50 mMNa,SO.
especially worth mentioning, because the surface struc-
2.5 mM camphor
5 ture may change markedly [e.g., for Au(IOO)] with elec-
/
(I trode potential. This effect underlines the strong
e
tl
II
/1 influence that electrochemical parameters such as the
"": 0 ---
:::1. II '\
If surface excess charge can have on the structural and elec-
\I
II
1\ " tronic properties of a metal surface.
"
-5 \I
\I "
"
The gold - electrolyte interface has been studied very
I
"
"
intensively over the last 20 years with respect to surface
-10
i reconstruction, and a rather detailed picture about the
structure of flame-annealed surfaces and its change with
electrode potential (e.g., due to adsorbate-induced lifting
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
of reconstruction) has emerged. Similar effects are
expected for platinum single-crystal electrodes, particu-
Figure 25 Cyclic current-potential curve for reconstructed larly for Pt(100), which is known to reconstruct into the
Au(100)-(hex) in 0.05 M NaZS04 + 2.5 mM camphor (--), (hex) form when prepared in a UHV chamber [5-7]. Yet,
starting at -0.2 V vs. SCE in negative direction. Reconstruction very little is known about the structure offlame-annealed
is lifted around +0.4 V vs. SCE on the anodic sweep and the sur- Pt surfaces and the role of surface reconstruction in
face remains unreconstructed during the subsequent scan Pt(hkl) electrochemistry, despite the fact that Pt(llO)
(- - -). The occurrence of phase transitions in the camphor was the first electrode surface for which reconstruction
adlayer on Au(lOO)-(hex) and -(1 xl) is clearly indicated by cur- was verified [32,33]. It was only recently that ex situ
rent spikes. (From Ref. 103.) studies have demonstrated that Pt(lOO)-(hex) is stable in
an aqueous environment [104], although the require-
ments for a clean handling are far more stringent than
The situation is more complex with Au(100)-(l xl). those for gold. This may also be the reason why systematic
We recall that the (hex) -+ (l x 1) transition causes the in situ STM investigations with Pt(lOO) and Pt(llO) are
unreconstructed Au(100) to appear rough because the still lacking. Preliminary STM studies with
surface is covered with monoatomic high islands. This flame-annealed Pt(100) reveal surface structures that
apparent roughness obviously can play a role in the are greatly different from the well-known (hex) structure
observability of phase transitions on Au(lOO)-(1 x 1). For [104,105] and for which a 3.0-nm corrugation length
example, it has been shown for uracil that a structural rather than the expected 1.45 nm prevails. It is easily fore-
transition occurs on the island-free Au(lOO)-O xl), seen that reconstruction phenomena at the
which was prepared by electrochemical annealing in a platinum-electrolyte interface will receive increasing
chloride-containing solution [86], whereas such a attention in the near future, particularly in view of the
transition could not be observed to occur on the many open questions that still exist for adsorption
island-covered Au(100), i.e., directly after lifting of the reactions on Pt(hkl), e.g., for hydrogen adsorption on
(hex) structure. This finding emphasizes once more the flame-annealed Pt(lOO) [106] and which may be
important role ofdefects for surface structural transitions answered with the help ofdetailed structure information.
and the impact of reconstruction phenomena. So far,
phase transitions in organic adlayers on Au(100)-(l xl)
ACKNOWLEDGMENT
have been reported for uracil [86], thymine [101], and
camphor [103]. It is a pleasure to acknowledge the expert help ofL. Kibler
and M. Kleinert with high-quality gold surface prep-
aration and with high-resolution STM imaging.
VI. CONCLUSIONS AND OUTLOOK
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11
In Situ Surface X-Ray Scattering Studies of Electrosorption
Jia X.Wang, Radoslav R. AdZic, and Benjamin M. Ocko
Brookhaven National Laboratory, Upton, New York
ABSTRACT
This chapter reviews the application of surface x-ray
scattering techniques to the electrode-electrolyte
interface. Examples are provided for three types of
electrosorption phenomena: metal, halide, and
metal- halide adlayers on single crystal electrodes.
Recent results for Bi on Au(lOO) and Au(lW), Br on
Au(lOO) and Ag(lOO), and the coadsorption of TI with
Br or I on Au(lll) are given. Factors affecting ordering
of pure metal and halide adlayers and the metal-halide
surface compounds are discussed.
I. INTRODUCTION
At electrode-solution interfaces, various metal and
anion adlayers ranging from submonolayer to bilayer
can be formed under thermodynamic equilibrium. For
metal ions, this phenomenon, so-called underpotential
deposition (UPD), occurs when the adatom-substrate
bonding is stronger than the adatom-adatom bonding
so that the first one or two monolayers are deposited at
potentials positive of the Nernst potential for bulk depo-
sition [I]. For anions, the monolayer is formed by
chemisorption, usually called specific adsorption. This
process occurs over a wide potential range below anion
bulk oxidation or substrate dissolution potential, often
involving partial charge transfer. At intermediate
potentials, metal cations and anions can also coadsorb
on electrode surfaces. These adlayers play an important
role in interfacial electrochemistry because they pro-
foundly affect the kinetics of many reactions [2]. The
sensitivity of electrosorption to the substrate metal and
175
crystallographic symmetry is known from electrochemi-
cal studies on single crystal electrodes. This has motivated
structural studies using various methods to gain a micro-
scopic understanding ofelectrode-electrolyte interfaces
and to elucidate a wide variety ofsurface electrochemical
processes.
A true atomistic picture of these adlayers on single
crystal electrodes is emerging. This development has
been accelerated by the introduction of in situ struc-
tural methods, specifically scanning tunneling
microscopy, atomic force microscopy, and surface
x-ray scattering (SXS). X-ray scattering has long been
the most powerful technique for three-dimensional
structure determination of solids. Its application to
the study of two- dimensional (2D) structures at
surfaces had been limited before the advent of intense
synchrotron sources. In the past decade, SXS has
become an increasingly important technique in sur-
face science research [3,4]. Although most SXS studies
to date have been carried out under URV conditions,
the penetrating nature of x-rays, unlike electron
probes, allows studies to be carried out under
well-controlled electrochemical conditions. Since the
first successful synchrotron SXS study of an
underpotentially deposited metal monolayer a decade
ago [5], the technique has been applied to a wide var-
iety of electrochemical phenomena including metal
deposition, surface reconstruction, anion adsorption,
surface oxide formation, surface water, and electro-
catalysis. There are several reviews that describe the
applications of in situ SXS techniques to interfacial
electrochemistry [6,7].
176 Wang et al.

In this chapter results from SXS studies of metal and

halide adlayers on electrode surfaces are reviewed. For K (c)t
pure metal adlayers, we focus on the ordering of
• 0 .0.
close-packed monolayers on various substrate surfaces,
where the adatoms are significantly larger than the too 0 0

substrate atoms. Previous studies on close-packed (111) (0,1). 0 • 0 •

surfaces by Toney et al. [8] found that the

I~ 0 0 0 0

underpotentially deposited Tl and Pb adatoms form

incommensurate structures similar to their
~~~·H
vapor-deposited analogues. In Sec. III, studies of UPD
on more open surfaces, (100) and (110), are presented (d)
along with a discussion of the factors that affect the (b) I
ordering, symmetry, and the density of metal I 1.2
L I I

monolayers. In Sec. IV, studies of potential induced I

I
I
I
1.0 ,-
I I
second-order phase transitions for Br adlayer are pre- I I O.S§'
I I
sented and the results are compared with universal phase I I 0.6 G"'
I I
transition theories. In Sec.v, results from Tl coadsorption I I
a
211/c 0.4 ....,
with halides are presented, and these illustrate the effect
I
I
I
,, (")

211/b 0.2~
of partial charge on the structure and the stoichiometry
0
ofcoadsorbed adlayers. The quantitative results obtained 211/0 H
from in situ SXS are complementary to those obtained Log Intensity
with real space scanning probes.

II. EXPERIMENTAL Figure 1 Schematic illustrations of a (2 x 2) monolayer at a

A determination of surface structures with SXS involves
measurements of the distribution of scattered x-rays in
reciprocal space, (H,K,L), and a comparison of the
diffraction pattern and intensity distribution with
atomic models. To illustrate the relationship between
real and reciprocal space, a (2 x 2) adlayer on a
rectangular substrate is shown in Fig. 1. In reciprocal
space (Fig. Ib), the diffraction is a 2D lattice of rods.
Each rod is a line of scattering that is sharp in both
directions parallel to the surface (H and K) and diffuse
along the surface normal direction (L). The solid lines
show the crystal truncation rods (CTR) that pass
through the Bragg points of the bulk [9]. In addition,
surface rods (dashed lines) arise at half order positions
from the (2 x 2) adlayer. Typical rod profiles are shown
in Fig. Id. Whereas the intensity of a surface rod
monotonically decreases, the CTR intensity rises
sharply near the Bragg points where many layers con-
tribute to the scattering.
Information pertaining solely to the structure within
the surface plane is obtained with a grazing incidence
angle ('""1°), where L is small. From the in-plane
diffraction pattern (Fig. Ic), where the observed peaks
are shown in the (H,K) plane, the superlattice structure
is deduced. On the other hand, when the scattering
vector is aligned entirely along the surface normal direc-
tion (e.g., no in-plane component), the electron density
single crystal surface (a) and the corresponding 3D (b) and 2D
(c) diffraction patterns. The solid and dashed lines in (b) and
the filled and open circles in (c) represent the crystal truncation
rods and surface rods, respectively. Typical intensity profiles of
a crystal truncation rod (solid line) and a monolayer surface
rod (dashed line) are shown in (d).
profile normal to the surface is obtained, independent
of the specifics of the in-plane ordering. This geometry
is referred to as specular reflectivity because the angle
between the surface plane and incident wave vector is
equal to the angle between the surface plane and the
scattered wave vector [7,10]. Additional structural infor-
mation is obtained from the intensity distribution along
the surface normal direction at a fixed (H, K) position
corresponding to either the bulk crystal structure (i.e.,
the CTR) or to the surface structure (i.e., the surface
rod) [4].
A thin-layer x-ray scattering electrochemical cell
(Fig. 2) is usually used in SXS studies of electrode
surfaces. In our measurements, a 4-,um-thick plastic
x-ray window seals the cell, which makes a thin 10- to
20-,um solution layer between the crystal face and the
film. An outer chamber was filled with high purity
nitrogen gas to prevent oxygen diffusing through the
I Surface X-Ray Scattering Studies
polypropylene
film
x-rays
single crystal
\ .1~I"d.
\
reference
electrode
/
Kel-F cell
counter
electrode
Figure 2 Cross-section of thin-layer x-ray electrochemical
cell.
thin film during the measurements. Compared with
UHV measurements, the presence of electrolyte and
the plastic film significantly increases the background
signal and limits the ability to detect weak peaks.
Despite this limitation, diffraction from monolayers of
low Z atoms, such as CI, has been observed [Il]. A
reversible hydrogen electrode was used in acid solution,
especially for halide-free solutions and an Ag/AgCI(3M
NaCl) reference electrode was used for halide-
containing solutions.
The data reported here were obtained with focused
monochromatic synchrotron radiation at beam lines
X22A (). ~ 1.20 A) andX22B(A ~ 1.54 A)attheNational
Synchrotron Light Source at Brookhaven National
Laboratory. In the four circle geometry, the sample
was oriented through its Euler angles (), X, and cjJ
by a spectrometer under computer control [12].
The magnitude of the scattering wave vector is
Ikr - k; I = (4n/ Ie) sin(2() /2), where k; and kf correspond,
respectively, to the incident and scattered wave vectors
and 2() is the angle between these two vectors. Diffraction
measurements were carried out by measuring the
scattering intensity along paths in reciprocal space in
the "w = 0 geometry" [13]. Soller slits or an LiF(200)
analyzer crystal were used for achieving a high radial
in-plane resolution and for reducing the diffuse x-ray
scattering background from the film and electrolyte. For
reflectivity and rod measurements, regular slits were used.
They were located 600 mm from the sample, typically
2-mm wide within the scattering plane. The structure
factors were obtained after correcting the integrated
intensities for the variation of the Lorentz factor, the
effective sample area, and the resolution along the surface
normal direction [14].
177
III. METAL DEPOSITION: Bi ON Au(100) AND
AU(110)
The UPD processes often exhibit features in voltammetry
curves sensitive to the crystallographic structures of the
electrode [1,2]. Hence, it has been speculated that these
metal adlayers form ordered structures on single crystal
electrodes. Indeed, well-ordered superlattice structures
have been observed by using SXS for many UPD metals
(TI, Pb, Bi, Ag, Hg) on the least corrugated (111) surfaces
(Ag, Au, Pt, Cu) [8,15-24] and for Tl and on the more
corrugated (100) surfaces (Au, Ag) [25,26]. Complemen-
tary structural studies have also been carried out using
scanning probes. Many fundamental issues have been
addressed in these studies, but a general view on the role
of the substrate crystallographic structure in UPD has
yet to emerge. To evaluate the effect of substrate
corrugation on the ordering of close-packed UPD metal
monolayers, recent SXS results of the UPD of Bi on
Au(100) and Au(1lO) are presented and compared with
other related systems.
Figure 3 shows the voltammetry curves for the UPD
of Bi on the (111), (100) and (110) surfaces of gold in
0.1 M HCI0 4 solution. The major deposition peaks
shift to more positive potentials on the (100) and (110)
surfaces as compared with those on the (111) surface.
This is consistent with theoretical calculations which
show that chemisorbed adatoms prefer the highest
coordination (hollow) sites and the bonding energy
increases as the surface becomes more open [27]. The
deposition of a close-packed Bi monolayer at potentials
before the onset of bulk deposition can be ascertained
from the integrated charges for all three surfaces. To
obtain the charge, currents between 0.7 V and the low
potential limits were integrated for both the cathodic
and anodic sweeps. Averaging the integrals from both
sweeps gives 445, 472, and 357 ItClcm 2 for Au(111),
Au(100), and Au(1lO), respectively. Assuming Bi 3 + is
fully reduced, the charge required for depositing one
Bi atom per surface gold atom is 666, 576, and
408 ItC/cm 2 for the (111), (100), and (110) surfaces,
respectively. On Au(111), the Bi coverage is
445/666 = 0.67 monolayer, which is close to the cover-
age (0.646) obtained from SXS measurements at the
most negative potential [22]. The atomic density of the
uniaxially commensurate Bi monolayer (see the model
in Fig. 3) is 6% higher than that in the bulk environ-
ment (see Fig. 5 caption for the definition). Because
the charges measured by voltammetry for the (100)
and (110) surfaces are similar to that for the (111)
surface, the Bi monolayers on Au(100) and Au(1lO)
are expected to be close packed. SXS measurements
178 Wang et aI.

80
Au (111 )
K t Bi-c(px2)jAu(100)

1I/0~
e 0 e
60
40
20 (o,1)e
1 o

0 e 0 e
0
l (1/p,1/2)
-20 -e---,e-O--e__
I (1,0) H
-40
15 Au(100)
N-----
E 10
u K 1 Bi-(px1)jAu(110)
5
" ~ o.
'"---'
......
c
~
"--
0
-5
-10
(O,l)e\
i oe
(l/p,l )
o.
::l
u
-15 -e----De------o-e--
po
I (1,0) H
15 Au(110)
10 Figure 4 Observed in-plane diffraction patterns (left) and
5 corresponding real space models (right) for Bi monolayers on
, the Au(lOO) and Au(lW) surfaces at potentials close to the onset
o I '

of bulk deposition. The relative size of Bi and Au atoms in their

-5 bulk solids are represented by the size of the filled and open
-10 circles.
-15 L.-L~~-L-~----"-_~-'----~--'-_~-,--~_LJ

0.2 0.3 0.4 0.5 0.6 0.7 0.8

ERHE (V)
Figure 3 Linear sweep voltammograms obtained at 2 mYls
for the UPD ofBi on the three low-index gold surfaces in 0.1 M
HCl0 4 containing 2.5 mM Bi 2 0 3• Dashed line shows the onset
of bulk deposition. Inset: Atomic model of the close-packed
2Bi-(p x ../3) monolayer on Au(lll).
were carried out for the Au(lOO) and Au(llO) surfaces
to investigate the influence of the substrate lattice on
these Bi monolayers.
In Fig. 4, the diffraction patterns obtained for the
UPD of Bi on Au(lOO) and Au(llO) are shown with the
corresponding real space models. For Au(lOO), only one
of two symmetry-equivalent domains is shown. The
adlayer diffraction pattern (open circles) has the charac-
teristics of a centered rectangular lattice, i.e., the
diffraction intensity is zero at (mlp, n12) when the sum
of m and n is odd. Here, pis nonintegral, and thus the unit
cell is uniaxially incommensurate. This monolayer exists
within 40 mV positive of the onset of bulk deposition.
The Bi diffraction peaks shift slightly with potential
along the incommensurate direction; hence, the adlayer
lattice is uniaxially electrocompressible. The coverage
calculated from the lattice constants ranges from 0.798
to 0.776 relative to the atomic density of Au(lOO) surface.
The coverage calculated from the charge is
473/576 = 0.82, in reasonable agreement with the SXS
results.
On Au(ll0) the noninteger diffraction peaks are found
at (lIp,O), (l/p,l), and (2Ip,0) positions, as shown in Fig.
4 (bottom, left), where p changes from 1.148 to 1.142 over
a O.l5-V potential range. The corresponding coverages
(e = lip, where e varies from 0.871 to 0.876) are also
consistent with the calculated charge (357/408 = 0.875).
Because the surface is free of Bi at potentials positive of
0.7 V, the decrease in the (0,1) peak intensity with the
deposition of Bi indicates that the Bi adatoms diffract
out-of-phase with those from the Au substrate and must
be centered with respect to substrate unit cell along the
y-axis. The (l,Q) peak intensity changes much less over
the same potential range. This indicates that the Bi
adatoms do not have fixed positions along the x-axis,
where the adlayer is incommensurate with the substrate.
1
Surface X-Ray Scattering Studies 179

Based on these observations with Bi monolayers and
the behavior of other systems reported previously, the
major factors affecting the order of metal adsorbates can
be further elucidated. In general, when an adatom is sig-
nificantly larger than the substrate atom, an ordered
adlayer will often be incommensurate at full coverage.
From SXS studies of the UPD of Tl, Pb, and Bi
[8,15-22,25,26,28], 2D incommensurate structures have
been observed on the (Ill) surfaces of several metals but
not on any of more open and corrugated (100) and (110)
faces. On these two faces, ordered adlayers are found to
be commensurate with the substrate along at least one
direction, which allows the adatoms to reside between
the substrate rows. The atomic height is modulated along
the incommensurate direction and reaches a minimum
at the hollow site and a maximum at the bridge site. This
height modulation is smaller than that expected for a
two-dimensionally incommensurate phases on the same
surface. On the other hand, uniaxial commensuration
usually causes a symmetry distortion of the superlattice
from the ideal free-standing lattice, and this in turn
creates strain in the adlayer. Apparently, only when the
distortion-induced strain is small enough, the uniaxially
commensurate structure can exist. Therefore, disordered
phases are more common for the more open and corru-
gated surfaces.
The pronounced effect ofsubstrate corrugation can be
further illustrated by comparing the Bi monolayer struc-
tures on the Au(lOO) and Au(110) surfaces. The substrate
To compare Bi with other metal monolayers, the layer
densities for the close-packed monolayer structures of
Tl, Pb, and Bi formed on the three low-index gold surfaces
as a function of potential are summarized in Fig. 5. These
densities have been normalized relative to their bulk
values (see figure caption). On the least corrugated
Au(lll) surface, all of them form an ordered monolayer
with a potential dependent layer density ranging from
near unity to 1.06. On Au(lOO), both Tl and Bi form a
c(p x 2) uniaxially incommensurate structure, whereas
Pb appears to form commensurate c(2 x 2) adlayer with
small patches ofantidomain phases [28], i.e., orders only
in short range. On the more corrugated (110) surface, only
Bi forms an ordered close-packed monolayer. The Bi
layer densities are out of the normal range (1-1.06) on
both (100) and (110) surfaces. This again shows that Bi
monolayer phase behavior is distinctly different from Tl
and Pb, probably due to the more nonmetallic bonding
characteristics ofBi compared withTl and Pb.
1.2 TI 6s 2p 1 Pb 6s 2p2
3.456 'A 3.500 'A
1.15
\c(px2)
>,
1.1
~ x l-hex
:'=
(f) c(pxf3)

C(~X~~~~ bUlk-~
unit cell has the same 2.885-A spacings along the x-axis a3 1.05
on Au(lOO) and Au(110). If the substrate corrugation o
along the incommensurate direction did not playa pro- __
nounced role, then Bi would form the same c(2 x p) phase
on Au(110) as on the Au(lOO) surface, albeit with a differ- 0.95
ent value of p. This is not the case. Rather, a (p x 1) • Au(111)
structure, with the commensuration along the more cor- 0.9 • Au(100)
rugated y-axis, is formed. For this rectangular structure, .. Au(110) ~

the nearest neighbor spacing along the y-axis is 22%
larger than that along the x-axis. This asymmetry is
unusually large for close-packed monolayers. For
example, thallium, which also forms a c(p x 2)
monolayer on Au(lOO) [25], forms no ordered phase on
Au(llO). The lack of the (p xl) Tl phase is likely due to
the more metallic character of Tl than Bi and hence a
stronger tendency toward hexagonal symmetry. This is
supported by the difference in the bulk crystal structures
(hcp vs. rhl) [29] and the monolayer structures on the Ag
and Au (Ill) surfaces (rotated hexagonal for Tl [15,16]
and uniaxially centered rectangular for Bi [21,22]).
Therefore, the covalent bonding characteristic for Bi
appears to play an important role in the formation of the
(p x 1) Bi monolayer on Au(lIO).
0.85 (px1 )
-0.5 -0.3 -0.1 0.1 0.3 0.5
ERHE (V)
Figure 5 Layer density of the TI( > -0.4 V), Pb( > -0.18 V),
and Bi( > 0.25 V) monolayers on the three low-index gold
surfaces as a function of potential. The diameters given forTI
and Pb are the nearest-neighbor separations within the hexag-
anal layers in the bulk crystals [29]. For Bi, the "equivalent bulk
diameter" is calculated from the rhombohedral bulk crystal [29]
by assuming an fcc structure with the same unit cell volume.
The layer density is calculated from the hexagonal unit cell area
with the bulk diameter as the lattice constant divided by the unit
cell area measured for the monolayer.
180 Wang et al.

Besides the substrate geometry effects discussed c( J2x2J2)R45° c(2x2) or (J2xJ2)R45°

above, the specifics of the substrate-adatom interaction
also influence the structure of UPD metal adlayers. For
example, Tl forms a well-ordered bilayer phase before
bulk deposition on both Ag(111) [15] and Ag(lOO) [26]
but not on the Au and Pt electrodes. Platinum, as a
transition metal, is distinctly different: A high-order
commensurate Pb monolayer [19] and an aligned hexag-
onal Tl monolayer [17] are formed on Pt(l1 1) in contrast
to the incommensurate rotated-hexagonal monolayers
of Pb and Tl on the Ag( Ill) and Au(1ll) surfaces.
K t K t
IV. HALIDE MONOLAYERS: BROMIDE ON • 0
•0 • • • •
Au(100) AND Ag(100) 0 0 0 0
0 0
Halides (Cl, Br, and I), similar to the UPD metals dis-
cussed in the previous section, also form well-ordered
(0,1) •
0
• 0
• (0,1) • • •
monolayer phases below its bulk oxidation or substrate 0 0 0 0

dissolution potential. Synchrotron x-ray scattering

studies have shown that the structure of these phases
may be commensurate or incommensurate with the
underlying noble metal electrodes [11,30-37]. On the
Au(lll) surface, for instance, halide ions (Cl, Br, and I)
form incommensurate hexagonal monolayers that com-
press with increasing potentials [11,30,31]. In the case of
bromide, the nearest-neighbor separation decreases from
4.24 to 4.03 A as the potential is increased over a 0.3-V
range. Over the entire potential range, the adsorbed
bromide monolayer remains incommensurate.
As for many other adsorbates, the symmetry of the
underlying electrode affects the epitaxy of adsorbed
halides. On the square Au(100) surface, a commensurate
e(.j2 x 2.j2)R45° Br monolayer is formed at intermedi-
ate potentials (Fig. 6, top left), which becomes uniaxially
incommensurate and electrocompressible at the most
positive potentials. The distortion from hexagonal sym-
metry is reduced by the uniaxial lattice compression,
and the maximum coverage is similar to those found on
Au(111), showing a moderate effect ofsubstrate symmetry.
On Ag(lOO), however, a square e(2 x 2) Br adlayer is
formed where the Br adatoms are adsorbed in the fourfold
hollow sites (Fig. 6, top right). Because Ag has nearly
the same lattice constants as Au, this demonstrates that
the stronger chemical affinity between halide and silver
enhances the site-specific adsorption. The bromide
adlayers on both Au(lOO) and Ag(100) have the same 112
monolayer coverage despite their different symmetries.
The in-plane diffraction patterns observed from these
two adlayers are shown on the bottom of Fig. 6. Besides
the half-order peaks, e.g., (1/2,1 /2) and (3/2,112),
quarter-order peaks, such as (1/4,3/4) and (1/4,5/4)
peaks, were observed from Br on the Au(lOO) surface.
-. I
0
•
(1,0)
0
.---H -. I •
(1,0)
.---H
Figure 6 Top: Models of the e(,J2 x 2,J2)R45° and e(2 x 2)
Br adlayers on Au(lOO) and Ag(lOO). Bottom: in-plane
diffraction patterns for the above models. The solid circles rep-
resent crystal truncation rods, and the open circles and squares
represent the surface rods of the two symmetry equivalent
domains ofthe Br adlayers.
This diffraction pattern results from two symmetry
equivalent domains, where the long lattice constant lies
along, or vertical to, the (1,l) substrate axis. As the phase
becomes incommensurate at high potentials, the peaks
shift along the (1,1) or (1, 1) directions accordingly. Both
systems exhibit simple second-order phase transition,
an Ising-like order-disorder transition on the Ag(100)
surface [36] and a 10 commensurate-incommensurate
transition on the Au(lOO) surface [33].
For bromide adsorption on the Au(lOO) surface, the
potentials where new diffraction features appear are well
correlated with the peaks in the cyclic voltammogram
shown in Fig. 7. At potentials below PI, all diffraction
features are associated with the square pattern from
the underlying gold substrate. Positive of PI, additional
reflections appear, which correspond to a rectangular
commensurate e(.j2 x 2.j2)R45° unit cell, as shown
on the top left of Fig. 6 and in the inset of Fig. 8. Further
analysis of the diffraction reveals that the adsorbed
bromides are positioned on the bridge sites [33]. Over
the entire potential range between PI and P2, there is
no change in the symmetry or in the coverage of
bromides.
Surface X-Ray Scattering Studies 181

appears to be second order. The uniaxial compression

4
reduces the symmetry distortion of the quasihexagonal
P1 lattice, and when 8 = 0.13, the lattice is nearly perfectly
---.. c(l2x212) P2 c( I2xp) hexagonal. At the maximum coverage, the nearest-
N 2 neighbor separations are close to the value expected
E
u
........... on the basis of the Van der Waals radius and to the
~
......... measured value for bromide on Au(111).
0 Pokrofsky and Talapov [38] predicted that an
.......
c
Q)
l..-
incommensurate phase forms from the commensurate
I..-
::::l phase when entropically wandering noninteracting
u -2 P2' domain walls appear. They predicted that the
incommensurability should follow a power law with the
P1 ' reduced chemical potential with a critical exponent
-4 f3 = 1/2. The best fit to a power law form to the
-0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 incommensurability, as shown by the solid line Fig. 8,
gives a critical exponent f3 = 0.4, statistically smaller than
EAg/AgCI (V) the Pokrofsky and Talapov prediction. In addition, their
model predicts sharp domain walls rather than a uniform
Figure 7 Linear sweep voltammogram from Au(100) III compression. The absence of satellite peaks for Br on
0.05 M NaBr. Sweep rate, 10 mVis. Au(lOO), within the limits of the diffuse scattering
background, establishes that the compression is nearly
uniform and not a network of locally commensurate
At potentials above P2 (ca. 0.42 V), the bromide regions separated by domain walls [33].
monolayer is compressed uniaxially as shown in Fig. 8, We now turn our attention to the electrodeposition of
where p < 2v'2. The incommensurability, 8, is related to bromide on the Ag(lOO) surface. Here the surface exhibits
the inverse of p. In the commensurate c(v'2 x 2v'2)R45° an order-disorder phase transition at a critical potential
phase, 8 = O. In the incommensurate c(v'2 x p )R45° that corresponds to a transformation between a
phase, 8 varies continuously from 0 to 0.13, as shown in "lattice-gas" phase, with short-range positional order,
Fig. 8. The phase transition is nearly reversible and and a commensurate phase, with long-range positional
order. The order-disorder transition is predicted to be
second order and is isomorphic to the two dimensional
0.14 Ising model in magnetism [39]. The analogy to the Ising
model requires the adsorbate atoms to reside at lattice
0.12 c( J2x2J2)R45° sites and the near-neighbor lateral interactions to be rep-
>- ulsive. According to the Ising model, the order-disorder
~ 0.10
.D
o
transition occurs at a critical coverage of 0.368 and the
~ 0.08 order parameter should follow a power law with a critical
c exponentofl/8 [40,41].
E0.06 On the Ag(lOO) surface, under vacuum [40] and elec-
E
trochemical conditions [36], an ordered c(2 x 2) struc-
8c 0.04 ture is observed above a critical coverage where the
0.02 halides are situated in the fourfold hollow sites of the
underlying silver lattice. Although both the c(2 x 2)
o and the c(v'2 x 2v'2)R45° structures have the same half
0.2 0.3 0.4 0.5 monolayer coverage, the packing arrangement on
0.6 0.7
Ag(lOO) is square compared with the quasi hexagonal
EAg/AgCI (V) structure found on Au(lOO). Measurements of the
scattered intensity at the (1/2,1/2) position vs. the
Figure 8 The incommensurability vs. the applied potential applied potential from the Ag(100) surface in 0.05 M
for electrosorption of Br on Au(100). Insets: atomic models of NaBr (Fig. 9) reveal a phase transition at -0.76 V
the Br adlayers at potentials below and above the critical point associated with the development of long-range order of
ofthe phase transition. the adsorbate. The intensity is zero below this potential
182 Wang et al.

structure. The interference effects, however, are reduced

1.0 (1/2,1/2) because there are significantly fewer electrons for a chlor-
0.8 ide atom compared with the number in a bromide atom.
0.6 With chloride the intensity falls to 44 %, also in agreement
>,
:+:::: with the simple interference calculation described above
(f)
c
0.4 [36]. The decrease of the (0,1) scattering intensity, at
Q)

C 0.2 potentials more negative of the ordered phase, is consist-

ent with the interference expected for lattice-gas adsorp-
15 OLL_~---c~~~~~~=-=::::~~~~ tion at the fourfold hollow sites.
~ 1.0 ~Jlmlll:i;;:;::'~~'-----~---'--~-----'-~--'~ These results clearly indicate that electrodeposited
::;::; bromide on Ag(lOO) undergoes an order-disorder
3 0.8 (0,1) transition. Comparison with the Ising model confirms
c.n 0.6
the essential predictions of the model. The top panel of
0.4 Fig. 9 shows reasonable agreement between the data
0.2 (circles) and fitted model curve (solid line) obtained by
oL....L_~---"-----~ _ _'-~--'--_~---"-----~_L-J using the power-law form with a fixed Ising model critical
~ 15 ,-----,--r--__,__~-,-----~-----,-r--__,__-----r--,___, exponent of 1/8. In addition, the critical coverage of 0.35
~ 10 where the order-disorder transition occurs at -0.76 V
~
is in agreement with the Ising model prediction of 0.368.
~ 5
'----' 0
C -5 v. METAL- HALIDE COADSORPTION: TI- Br
~ -10 ] AND TI-I ON AU(111)
~ -1 5 '---L_~----,---_~~~---,----~--,---~---,---I
U -1,2 -1.0 -0.8 -0,6 -0.4 -0.2 The UPD ofmetals can be influenced by specific adsorp-
tion of anions. Unlike the systems described in Sec. III,
EAg/Agel (V) which do not involve specifically adsorbed anions,
strongly adsorbed anions can cause formation of
Figure 9 Results for the electrosorption of bromide on the coadsorbed metal-anion phases. For the UPD ofCu in
Ag(100) surface. The scattered intensities, after background the presence of sulfate, chloride, and bromide on Au and
substraction, are shown at (1/2,1/2) and (0,1) vs. the applied Pt surfaces [42-47], a bilayer forms with Cu directly con-
potential. The corresponding cyclic voltammogram curve tacting the substrate and the anion in the second adlayer.
(10 mV/s) is shown at the bottom, The anion adsorption is enhanced due to a stronger inter-
action ofthe anions with the partially charged Cu adatoms
than with the Au or Pt substrate. This in turn stablizes
and increases sharply at the potential corresponding to a the low-coverage Cu adlayers. An illuminating
cusplike current peak in the cyclic voltammogram, counterexample, with opposite anion-cation distri-
shown in Fig. 9. bution in the adlayer, is provided when alkali-metal cat-
In a SXS measurement, the registry of an ordered ions coadsorb with iodide on Au(llO) [48]. In this
adlayer or the adsorption sites in a disordered phase can system, the anion interaction with the substrate is much
be inferred from analysis of the crystal truncation rods. stronger than that of the metal cation, causing the forma-
By considering the scattering amplitude from the tion of coadsorbed adlayer with the anion chemisorbed
semi-infinite sum over the Ag(lOO) lattice, both with on the substrate and the cation being coadsorbed.
and without a half monolayer of bromide atoms at the In this section we present results for the coadsorption
fourfold hollow sites, it can be shown that the scattered ofTI with Br or I on Au(ll1). Here the cation-substrate,
x-ray intensity at (0, 1, 0.12) is expected to be 11 % of the anion-substrate, and cation-anion interactions are all
value obtained in the absence of bromide. The intensity comparable in strength over a wide potential region. A
indeed decreases to 11 % of its level with no bromide, as more complex phase behavior is seen, and the structures
shown in the middle panel of Fig. 9, when the potential of coadsorbed adlayers can be best understood in terms
increases from -1.0 V (no adsorbed bromide) to -0.3 V ofthe formation ofsurface compounds, where the partial
and supports the adsorption of a half a monolayer in the charge on the adions plays an important role in
fourfold symmetry sites. Exchanging the bromide ions determining the stoichiometry and the lattice symmetry
with chloride ions does not change the halide adsorbate [49,50].
Surface X-Ray Scattering Studies 183

For thallium - bromide electrosorption on the

Au(ll1) surface, three mixed and two pure adlayer
phases are formed at different potentials. The vol-
tammetry curve (Fig. 10) shows a multitude of reversible
peaks over a wide potential region. The peaks labeled
by the letters are associated with structural phase
transitions. Real space atomic models, corresponding
to the five ordered phases determined from x-ray
diffraction measurements, are shown in the potential Br Br
TI TI TIBr TIBr Br
range where they occur. The hexagonal bromide adlayer
disorders at about 0.9 V where thallium starts to ~n CXX2
coadsorb. As the potential is further decreased over a -100
O.7-V potential region, two well-ordered commensurate
and one weakly ordered incommensurate phases --.. 1.2 (.468,.468) (2/3.1/6) (9/13.3/13) 1.2
appear. At the most negative potentials a rotated- 1l 1 1
~
hexagonal Tl monolayer forms. .•.. . .•
~ 0.8 0.8 "0
The structuiefactpr analysis for the commensurate;/ <
phases shows the for~ation of TlBr2 and TlBr surface 5 0.6 00
0.6 ~
0
>, <0
compounds in the 3-CJT3 x.JT3) and 2-(3 x .J3) .i;i 0.4 0.4 ro
co
phases, respectively. For the 2TlBr-(3 x .J3) structure, ~ 0.2 0.2
the bromide ions are situated at the gold bridge sites
o 0
and thallium ions are situated near the hollow sites.
In addition, the top-layer Au atoms are displaced lat- -0.4 -0.2 o 0.2 0.4 0.6 0.8
erally along the .J3 direction. This results in a more
even separation between Tl and the three neighboring
Au atoms and an increase of the Br-Au separation. Figure 10 Top: Voltammetry curve for the UPD of Tl on
A discussion on gold surface relaxation is published Au(lll) in 0.1 M HCI0 4 containing I mM TIBr. Sweep rate,
elsewhere [50]. 20 mYls. Bottom: potential dependent diffraction intensities
The lower panel shows the potential dependent (0.5 mYls) at (9113, 3113), (2/3, 1/6), and (0.468, 0.468) positions
diffraction intensities for the three mixed phases at the for the (m x m), (3 x v'3), and c(2.14 x v'3) phases,
corresponding reciprocal space positions. These scans respectively. Coverages, in units of monolayers of the Au
identify the potential intervals of the observed phases. substrate, shown by the open and filled circles for Br and TI,
The characteristic of first-order phase transitions is respectively, are calculated from the adlayer lattice constants.
shown by the step changes in the coverages (circles).
The electrosorption reactions leading to the formation
ofthese phases involve a partial charge transfer. The posi- Figure 11 shows models of the 3TlBr2-(.JT3 x .JT3)
tive charge on metal adsorbates increases and the nega- and T1I 3-(3 x 3) structures, both hexagona\, with their
tive charge on adsorbed bromide decreases with corresponding in-plane diffraction patterns. The lattice
increasing potential. This leads to a phase transition constants and the azimuthal orientations are determined
involving a change of stoichiometry from TlBr to TlBr2 from the observed in-plane peak positions, and the ratio
and a lattice symmetry change from quasisquare to and arrangement of the two species within the unit cell
hexagonal. are deduced from the intensity analysis. The intensities
Similar phase behavior has been observed for the have been measured at grazing incidence geometry
coadsorption of Tl with I on Au(lll). Because iodide is (L = 0.2) by integrating the e rocking curves of each sur-
larger than bromide, the centered rectangular phase for face diffraction peak in the (H,K) plane. The results, after
TIl is 3TlI-(5 x .J3), which has a slightly lower coverage correcting for the variation of the Lorentz factor, the
(OJ monolayer) than that of TlBr (0.333 monolayer). At effective sample area, and the resolution along the surface
higher potential, a T1I 3-(3 x 3) hexagonal phase has been normal direction [14], are shown by the areas of the open
observed. Relative to TlBr2, the higher anion to cation circles in Fig. 11, c and d.
ratio occurs because iodide is more discharged than ForTlBr2, the primitive unit cell with oneTl ion at the
bromide. An analysis of the hexagonal phase x-ray data origin and two Br ions at the two triangular sites, depicted
is presented below. by the solid line in Fig. lla, was used for the calculation
184
K (C)
(!)
:0.1 ) G)
.. EB
.. H H
EB E9 1,0) (!)
G)
EB
EB
Figure 11 (a and b) Structural models where the Au (I 11) sur-
face atoms (2.885 A), Tl ions (2.98 A), and anions (Br 3.92 A, I
4.30 A) are represented, respectively, by the open, light shade,
and heavy shade circles (c and d). Observed in-plane diffraction
pattern from the (-/f3 x -/f3) and (3 x 3) phases, respectively.
The sizes (area) of the open circles are proportional to the
measured structure factor intensities and the sizes of the" +"
sign are proportional to the calculated values based on the
models shown above.
of structure factor intensity. As shown in Fig. 9c, the cal-
culated intensities, represented by the size ofthe" +" sign,
are consistent with those measured (circles). If only one
Br per Tl is assumed, the calculated intensity for the
first-order peak is at least 50% higher than the measured
value. Because this is far above the experimental
uncertainty, the TIBr model can be ruled out.
For the (3 x 3) phase (Fig. lib), two high-symmetry
models, TII 3 and T131, yield nearly identical intensity dis-
tribution pattern, though the absolute intensities are
higher for Tl3 I due to the higher Z of Tl than I. Because
it is difficult to measure the in-plane diffraction intensity
on an absolute scale, the data are normalized so that the
intensity for the first-order peak equals the calculated
value. Therefore, the agreement (Fig. lld) between the
data (size of the circles) and calculated values (size of the
"+" signs) supports both models.
To distinguish the two models and to determine the
adlayer spacing from the substrate surface, specular
Wang et at.
ideal
-TlI s
.---- Tis!
'-
o
:::::l
U
(])
0-
U1 10- 7
10-8
'--_-'----_-'--_...J-_--'--_-----'--_--'-_----'
o 2 345 6 7
L (units of CO)
Figure 12 Specular reflectivity profile obtained from the
T1I 3 -(3 x 3) adlayer on Au(ll1).
reflectivity measurements were carried out for the (3 x 3)
phase. Figure 12 shows the integrated intensities at differ-
ent L along the (O,O,L) rod, where the normalization
factor is obtained by fitting the data near the (0,0,3) Bragg
position. The data (circles) clearly differ from the
adsorbate-free Au(lll) reflectivity profile (dotted line)
and are analyzed using a real space density model that
incorporates an ideally terminated Au(lll) crystal, a
nonideal Au top layer, a thallium, and an iodide
monolayer. Each ofthese three surface layers is described
by an atomic coverage normalized to an ideal Au(lll)
plane, a layer spacing, a vertical root-mean-square dis-
placement amplitude, and a species-dependent atomic
form factor. Although the density of the Au top layer is
always fixed at unity, theTl coverage is held at either 0.11
or 0.33 with the I coverage fixed at 0.33 or 0.11, respectively.
The former corresponds to the TII 3 model and gives a
much better fit (solid line) than the latter, which represents
theThl model (dashed line). For theT1I 3 model, the layer
spacing between the Au top layer and the I and Tl adlayers
are 2.6 and 3.5 A, respectively. In contrast, bromide ions
in theTIBr2-( ffi x ffi) phase are found, from analysis
of specular reflectivity profile (not shown), to be in two
layers more than 3 A apart [50]. These results can be
understood by comparing the adsorbate sizes with the
lattice spacings. ForTIBr2 (Fig.lla), the nearest-neighbor
separation (3.47 A), calculated from a 2D lattice, is much
smaller than the diameter of bromide (3.92 A [29]). In
Surface X-Ray Scattering Studies
theT1I 3 adlayer, on the other hand, the iodide ion (4.3 Ain
diameter [29]) is slightly smaller than the in-plane
nearest-neighbor separation (4.32 A) (Fig. lIb).
The results discussed above demonstrate that
well-ordered surface compounds can be formed by
coadsorption of cations and anions. The stoichiometry
and the lattice structure of these compounds are influ-
enced by the substrate and applied potential. Further
studies of various metal-anion surface compounds will
enhance our understanding of the phase behavior of 2D
ionic adlayers.
VI. SUMMARY
This chapter demonstrates that in situ, SXS is well suited
for studying electrode surfaces because it provides a high
accuracy means for determining the density and com-
pressibility of incommensurate adlayers, a quantitative
measure ofpotential induced structural phase transitions,
and a reliable structural determination ofmixed adlayers.
The examples discussed, metal underpotential
deposition, halide electroadsorption, and metal- halide
coadsorption, were chosen to highlight these capabilities.
In general, the adlayer structures for pure metal and
pure halide adsorbates under electrochemical conditions
are similar to those found under UHV condition. These
facts and detailed quantitative structural information
obtained with SXS, especially on the potential dependent
phase behavior, have made electrode-electrolyte inter-
faces more accessible to theoretical studies. These
experimental and theoretical studies have enhanced
our understanding of adsorption and 2D ordering
encompassing both UHV and electrochemical
environments.
The formation of well-ordered surface compounds,
Tl-halides on Au(lll), have demonstrated that ordered
binary ionic adlayers can be systematically investigated
over a whole range of stoichiometry in the electrochemi-
cal environment. Analogous measurements under UHV
conditions would be nearly impossible. Further studies
will hopefully lead to a unified view of cation and anion
coadsorptions and continue to stimulate theoretical
research in 2D ionic adlayers.
ACKNOWLEDGMENTS
Supported by the U.S. Department of Energy, Divisions
of Chemical and Materials Sciences, under Contract
No. DE-AC02-98CH10886. We have benefited from col-
laboration and discussions with our collaborators Olaf
Magnussen, Thomas Wandlowski, Ian Robinson, and
Steve Feldberg.
185
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12
Atomic-Scale Aspects of Anodic Dissolution of Metals:
Studies by In Situ Scanning Tunneling Microscopy
Kingo Itaya
Tohoku University, Sendai, Japan
ABSTRACT
This chapter describes the anodic dissolution of various
metals, which occurs only at step edges under electro-
chemical conditions. The layer-by-layer process ofdissol-
ution results in the formation of atomically flat
terrace-step structures. The anodic dissolution of bare
Ni, sulfur-modified Ni, bare Ag, iodine-modified Ag,
iodine-modified Pd, Cu, Au, and Co is described in detail
based on in situ scanning tunneling microscopy
observations. It is reasonably expected that such an in situ
method will become one of the most useful techniques
for exposing well-defined surfaces of various metals in
solution.
I. INTRODUCTION
Since Binnig and Rohrer invented it in 1981, scanning
tunneling microscopy (STM) has quickly been estab-
lished as an invaluable and powerful surface structural
technique with atomic resolution in ultrahigh vacuum
(DHV) [1]. Sonnenfeld and Hansma [2] demonstrated
for the first time in 1986 that STMcan be used even in elec-
trolyte solutions, and several groups quickly realized
its importance for studying electrode-electrolyte
interfaces. The early experiments were carried out with
a two-electrode cell arrangement, in which electron
tunneling occurs between the sample and the tip without
potentiostatic control [2]. However, to elucidate electro-
chemical reactions in situ, it is absolutely necessary to
control the electrochemical potentials not only of the
substrate but also ofthe tunneling tip, with respect to a ref-
187
erence electrode. In 1988, we proposed a new procedure
for in situ STM using a four-electrode configuration, in
which the electrochemical potentials of the substrate
and the tunneling tip are independently controlled with
respect to a reference electrode [3]; in that year, other
groups also proposed similar potentiostatic STM
apparatuses [4-6]. In the last 10 years, many successful
experiments with STM and related techniques, such as
in situ atomic force microscopy (AFM), have been used
for surface electrochemical studies of various metal
electrodes; included in such studies were surface rec-
onstruction and the adsorption of inorganic and organic
chemical species. In situ STM and AFM allowed us not
only to determine surface structures but also to follow
various electrochemical reactions, such as the deposition
and dissolution of metals and semiconductors. An excel-
lent review article on applications of in situ scanning
probe microscopy for electrochemical studies has
recently been published [7].
One goal of investigating electrochemical reactions
is to obtain a correlation between the structure
and reactivity of electrode surfaces in the presence
of adsorbed ions and solvent molecules. For such
studies, it is of critical importance to prepare
electrode-electrolyte interfaces reproducibly and to
establish methods to observe those interfaces accurately.
Well-defined single crystalline surfaces must be used
to understand surface structure- reactivity relationships
on the atomic scale. It is difficult to examine electro-
chemical reactions, on the atomic scale, using poly-
crystalline electrodes.
188 Itaya

II. WELL-DEFINED SURFACES

Efforts have succeeded in producing extremely clean and
well-defined atomically flat surfaces ofvarious electrodes
made of noble metals, base metals, semiconductors, and
metal oxides in solution. Experimental techniques to
expose well-defined surfaces are summarized below.

A. Flame-Annealing and Quenching Method

A unique and convenient way to expose well-defined
clean Pt surfaces in aqueous solution was proposed by
Clavilier in 1980 [8]. He also established a method for pre-
paring a single-crystal Pt electrode by melting a Pt wire
in the flame. The mechanically exposed single-crystal Pt
was then annealed in a gas-oxygen flame and quenched
in pure water [8,9]. This technique was extended by 15.0
Hamelin for Au [10], by Motoo and Furuya for Ir [11],
and by Sashikata et al. for Rh and Pd [12]. It is well known
that the hydrogen adsorption-desorption reaction is a
very structure-sensitive reaction on Pt single-crystal
surfaces, as indicated by the characteristic shapes of 10.0
voltammetric curves for Pt [9]. Although Clavilier et al.
[9] quantitatively analyzed the binding sites of hydrogen
using systematically prepared stepped surfaces, more
recent work using a CO replacement technique clearly 1
5.0
indicated that part of the faradaic charges observed in
the hydrogen adsorption region included a significant
contribution from the adsorption and desorption of
sulfate- bisulfate ions [13].
Nevertheless, a direct evidence supporting the exist-
ence of a well-defined surface in solution was demon- o S.D 10.0 15.0
strated by Itaya et al. in 1990 using in situ STM [14]. (b)
Figure 1a shows the first STM image ofa flame-annealed
Pt(lll) surface in a sulfuric acid solution. The height of Figure 1 Large-scale (a) and atomically resolved (b) STM
each step is ca. 0.23 nm, in agreement with the images of a Pt(lll) in solution. (From Refs. 12 and 15,
monoatomic step height of 0.238 nm on the Pt(ll1) respectively.)
surface. The monoatomic steps observed on the surface
are usually located on nearly parallel straight lines or in
atomic image of Rh(ll1)-(l x 1) was routinely discerned
the direction forming an angle of approximately 60°, as
on the terrace as shown in Fig. 2b. The almost perfectly
expected for a surface with threefold symmetry. The
aligned hexagonal structure can be seen with an
terraces appear to be atomically flat. Later, it was shown
atomic distance of 0.27 nm. Flame-annealed Au single
by us that the terrace has a (I x 1) structure as shown in
crystals have been used widely by several groups [7] for
Fig. lb [15,16]. On the upper and lower terraces, the
various studies that included investigations of the
Pt(lI1)-(l x 1) structure was clearly discerned at
potential-induced reconstruction. It must be noted,
potentials near the hydrogen evolution region. The
however, that the technique developed by Clavilier can
nearest-neighbor spacing and the corrugation height are
be applied only to Au, Pt, Rh, Pd, Ir, and possibly Ag [17].
0.28 and 0.03 nm, respectively.
Figure 2 shows an example offlame-annealed Rh(lll)
in HF [16]. It is surprising that only a few monoatomic
B. UHV Electrochemical System
step lines were found in a large area of 500 x 500 nm,
indicating that the flame-annealing and quenching tech- It is well established in UHV that clean and ordered
nique produced an extremely well-defined surface. The surfaces can be prepared by cycles of Ar-ion bombard-
Anodic Dissolution of Metals 189

electrochemical system (UHV-EC), in which a chamber

for electrochemical measurements is attached to the
UHVapparatus [18,19], various well-defined substrates
are transferred into an electrochemical cell under
purified Ar atmosphere. This experimental procedure
was successfully applied to noble metals such as Pt,
Au, Pd, and Rh [18-20]. However, for some metals, such
as Ni [21] and Cu [22], surface oxidation takes place in
the electrochemical chamber before immersion of the
electrode into the electrolyte solution because of the
presence of trace amounts of oxygen and water vapor.
These results strongly suggest that the UHV-EC
approach is limited to the noble metals and cannot be
applied to more easily oxidizable metals such as Ni
and Cu.
As described above, the flame-annealing and
quenching method can only be applied to limited metals
such as Pt, Au, Rh, Pd, and Ir and cannot be used for
o 100 200 300 400 500nm more practically important metals such as Ni, Co, Fe,
and Cu, because they are heavily oxidized in the flame
(a) and in air. In the UHV-EC method, problems of
substrate oxidation occurring during the immersion
and emersion processes are still unsolved. In this regard,
it is important to note that iodine adlayers are known
to protect highly sensitive surfaces of metal single
crystals from oxidation and contamination in the ambi-
ent atmosphere, providing easy methods of preparation
and handling of well-defined surfaces during electro-
chemical measurements [18,19]. The iodine-CO
replacement is one of the promising methods for
exposing well-defined and clean surfaces in solution
[23]. The layer of adsorbed iodine on the surface can
be replaced by a CO adlayer. Clean surfaces are then
exposed in solution by the electrochemical oxidation of
CO from the surface.
This chapter deals with details of the anodic dissol-
ution of various metals, which occurs only at step edges
under carefully adjusted electrochemical conditions.
The layer-by-layer process ofdissolution results in the for-
mation of atomically flat terrace-step structures. We
believe that such an in situ method will become one of
o 1 2 3 4 5nm the most useful techniques for exposing well-defined
surfaces of various metals at least for electrochemical
(b)
studies. Although anodic dissolution has long been used
for "electropolishing" metals to prepare mirrorlike
Figure 2 Large-scale (a) and atomically resolved (b) STM
images of an Rh(lll). (From Ref. 16.) surfaces, not much fundamental knowledge is available
about the anodic dissolution on the atomic scale. The
anodic dissolution of bare Ni, sulfur-modified Ni, bare
ment and high-temperature annealing [18,19]. The sur- Ag, iodine-modified Ag, iodine-modified Pd, and Cu is
face structure and composition are usually described in detail based on in situ STM observations.
determined by low-energy electron diffraction (LEED) The anodic dissolution of Au(1l1) and Co(OOOl) is also
and Auger electron spectroscopy. Using a UHV- described briefly.
190 Itaya

III. ANODIC DISSOLUTION OF METALS
A. Bare Ni(111) Electrode
Because Ni is one of more important electrode materials
used for various industrial purposes such as elec-
trocatalysis, batteries, and electroplating [24], numerous
electrochemical studies have been performed for Ni
metal to understand its anodic dissolution, passivation,
and oxide formation. However, atomic-scale elucidation
of electrochemical oxidation processes on well-defined
Ni substrates is still an important subject that remains to
be investigated; this lack is almost certainly related to
the difficulty in the preparation of well-defined Ni
surfaces in solution. Chemical and electrochemical
etching techniques have been used most frequently in pre-
paring Ni surfaces for electrochemical studies [24]. In
the STM works of Ni(100) in alkaline solution,Yau et al.
[25] used surfaces initially prepared by chemical etching,
followed by cathodic polarization to remove oxide layers.
They presented an atomic STM image with a quasi-
hexagonal lattice obtained at an early stage of the
oxidation ofNi(lOO), which was attributed to the III plane
of NiO or the 0001 basal plane of Ni(OHh. An attempt
to image an oxide-free Ni(lOO) surface was unsuccessful,
probably due to a difficulty of removing spontaneously
formed oxide layers in alkaline solutions [25]. An ex situ
STM study in air also recently demonstrated the capa-
bility of STM to reveal atomic structures of
electrol:hemically formed Ni oxide layers [26]. Although
bare Ni(lIl) surface was anticipated to be unstable in
alkaline solutions even under cathodic polarization [25],
it was firmly concluded by MacDougall and Cohen
[27,28] that complete removal of Ni oxides was possible
only in acidic solutions of pH less than ca. 3.
Wang et al. [21] attempted to prepare well-defined
Ni(lll) in an alkaline solution using an UHV-EC system,
in which a well-defined clean Ni(lll) and an Ni(lll)
protected with a CO adlayer were prepared,
characterized, and transferred to an electrochemical cell.
The crystals were annealed in an H 2-filled (1 atm) quartz
tube at 1237 K for 3-10 h. The furnace was slowly cooled
down to room temperature under the H2 stream. To avoid
oxidation ofsurfaces caused by oxygen in air, the crystals
were dropped into hydrogen-bubbled water and mounted
on the STM cell [29].
1. Cyclic Voltammetry
Figure 3 shows a cyclic voltammogram (CV) of Ni(lll)
recorded at a scan rate of 20 mV S-l in 0.05 M Na2S04
(pH 3). The open-circuit potential (OCP) was found to
be -0.37 V. The first scan was made in the negative direc-
tion from the OCP to -0.8 V, at which the scan direction
was reversed. A small cathodic current can be seen during
the negative-going scan, which might be due to a slow
hydrogen evolution reaction. In the subsequent anodic
scan, the current abruptly increased at about -0.4 V,
formed a peak at -0.05 V, and rapidly decreased with
increasing positive potential. Upon reversing the scan at
0.25 V, no corresponding anodic current was found, indi-
cating that the Ni(IlI) surface was passivated by the for-
mation of an oxide layer. In the result shown in Fig. 3,
the anodic current, at least on the rising portion of the
peak, is expected to be due to simple anodic dissolution
of Ni to form soluble Ni 2+ species in solution. The
1200
1000
800
C'J
'E
0
«:l. 600
~
'(ii
c 400
"C
a>

The c(4 x 2)-CO adlayer on Ni(lll) was expected to 'E

!!? 200
protect its surface from the oxidation. Unfortunately, on :5
()
Ni(lll), the electrochemical oxidation of CO took place
in the basic solution; consequently, the Ni(lll) surface 0 ....................

was also electrochemically oxidized [21].

We carried out in situ STM of Ni(lll) in a solution of -200
Na2S04 acidified to pH 3.0; in this pH, Ni oxides can be
reduced by cathodic polarization [29]. The Ni single
crystals used in our study were subjected to thermal -0.8 -0.4 0 +0.4
annealing in an H 2 stream. Single-crystalline surfaces Electrode Potential! V VS. SeE
were polished metallographically, finished with 0.25
/lm diamond paste, and sonicated, sequentially, in Figure 3 Cyclic voltammograms on an Ni(lll) in 0.05 M
trichloroethylene, acetone, methanol, and pure water. Na2S04 (pH 3.0). The scan rate was 20 mVls. (From Ref. 29.)
Anodic Dissolution of Metals 191

cathodic current observed in the second cathodic scan

was clearly larger than that found in the first cathodic
scan, suggesting thatthe oxide layer formed at the positive
potentials can be electrochemically reduced to metallic
Ni. After the reduction of the oxide layer, the anodic dis-
solution peak appeared again in the subsequent anodic
scan with a similar magnitude of current density.
MacDougall and Cohen [27,28] reported that the oxide
film formed on polycrystalline Ni in Na2S04 solutions
was composed of NiO with nearly constant thickness
(0.9-1.2 nm) in the pH range of 2-8.4 and that the oxide
film could be completely removed by a negative scan in
solutions of pH less than ca. 3.

2. In Situ STM of Ni(111)

In general, STM images acquired on freshly prepared
Ni(lll) showed atomically flat terrace-step features,
indicating that our experimental procedure successfully
produced well-defined surfaces of Ni. However, we o 2.5 5.0 7.5nm
usually found some small islands on the atomically flat (a)
terraces on OCp, at which STM images showed a hex-
agonal atomic structure with a lattice constant of
0.29 ± 0.02 n m. Our STM images acquired on these
islands seemed to be similar to the image reported pre-
viously using an ex situ STM in air for electrochemically
passivated Ni(lll) [26]. Nevertheless, it was found in
our study that these islands disappeared when the elec-
trode potential was set at potentials more negative than
-0.5 V, where the oxide layer was electrochemically
reduced, as expected from Fig. 3.
Figure 4 shows two examples of in situ STM images
with atomic resolution obtained at -0.50 V in 0.05 M
Na2S04. The image of Fig. 4a shows that the surface
of Ni(lll) in the solution has an atomically flat
terrace-step structure. The monatomic steps shown in
Fig. 4a are in parallel to the atomic rows of Ni(lll),
but sometimes they form long twisting curves. Atten-
tion was paid to determining lattice parameters as
precisely as possible on Ni(lll) at -0.5 V, because
the oxide formed on Ni(lll) also exhibited a hexag-
onal lattice in STM images with an interatomic dis-
tance of ca. 0.29 nm, which is slightly larger than
o 2.5 5.0nm
that (0.25 nm) of the Ni(lll)-(1 x 1) structure. Figure (b)
4b shows an atomic image acquired on a relatively
Figure 4 Atomically resolved STM images of an Ni(lll) in
large terrace under such conditions. An almost perfect
7.5 x 7.5 nm(a)andin5 x 5 nmframes; respectively. (From Ref.
hexagonal lattice is seen with an angle of 60 ± 2° 29.)
between the atomic rows. It is also confirmed that
the atomic rows are parallel to the close-packed direct-
ions of Ni(lll) determined from the orientation of and 0.25 nm. We conclude that the surface structure
the crystal on the STM stage as shown by an arrow of Ni(lll) at -0.5 V is Ni(lll)-(1 x 1). This is the first
in Fig. 4b. The average value of the nearest-neighbor atomic image of bare Ni(lll)-(1 x 1) obtained in
distances in all atomic directions lies between 0.23 solution. To our knowledge, no STM image of clean
192 Itaya

Ni(1ll) has been presented even in UHV [30],

although the structures of Ni(100) and Ni(1lO) have
been revealed [31,32].
The Ni(lll)-(1 x I) structure was observed in the
potential range between -0.6 and -0.4 Y, indicating that
no oxidation took place in this range. However, the (I x I)
structure was also consistently observed even at
potentials near the foot of the anodic dissolution. This
result indicates that the anodic dissolution occurred with
the substrate structure (1 x I) being maintained at least
at the foot of the anodic dissolution peak. We acquired a
set of STM images of the same area at -0.3 V where the
anodic dissolution takes place slowly. The images shown
in Fig. 5 are two examples of those acquired with a 50-s
interval. The arrangement of atoms and the step lines
can be clearly discerned in these images. It is seen that
the step edge seen at the upper right corner of Fig. 5a is
retracted in the downward direction with time to expose
the underlying Ni(lll)-(1 x I) plane. No pit formed on
the terrace, indicating that the anodic dissolution took
place only at the step edge. The result shown in Fig. 5
o 7.5nm
(a)
clearly demonstrates that the anodic dissolution proceeds
in the layer-by-Iayer mode at the onset ofthe anodic peak.
We also investigated Ni(lOO) in the same solution [29]
and found that a well-ordered atomic arrangement
appeared with a fourfold symmetry. The lattice constant
of 0.5 ± om nm observed in the ordered domains was
twice as large as that ofNi(lOO). The rows ofadatoms were
parallel to the substrate Ni(100) atom rows. The adlattice
structure was designated as p(2 x 2). No Ni(lOO)-(1 x I)
lattice was found in the STM images acquired at -0.5 V
It has been demonstrated, by LEED [33] and more
recently by STM [32,34] in UHY, that oxygen adatoms
on Ni(100) form p(2 x 2) and e(2 x 2) structures. It is
noteworthy that the p(2 x 2) lattice was consistently
observed in the potential range between -0.4 and - 0.6 V
[29]. The p(2 x 2) oxygen adlayer seems to be a
thermodynamically stable phase that is difficult to reduce
electrochemically at -0.5 V We further attempted to
acquire an atomic image at a more negative potential of
-0.8 V but failed to achieve atomic resolution because
of the hydrogen evolution reaction [29]. When the poten-
o 7.5nm
(b)
tial was scanned more positively, the Ni(lOO) surface
was first covered with a hexagonal lattice and then Figure 5 Two successively recorded STM images ofan Ni(lll)
atomically roughened. The layer-by-Iayer mode observed being anodically dissolved at -0.33 V in 0.05 N Na2S04.
for the anodic dissolution of Ni(1ll) was not the case for (From Ref. 29.)
Ni(100) [29]. The surface ofNi(100) became rougher with
further progress of anodic dissolution. The Ni(lOO) sur- cal dissolution of the oxide layer might be followed by
face was expected to be covered partially or fully by oxides either the fast dissolution of Ni or the replenishment of
depending on the electrode potential even in the active the oxide layer. This heterogeneous dissolution seems to
region. Under such conditions, relatively fast dissolution be the case of roughening of the Ni(100) surface brought
might occur on the Ni(100)-p(2 x 2) surface. Slow chemi- about by anodic dissolution.
Anodic Dissolution of Metals 193

B. S-Modified Ni(100)
5
Among numerous electrochemical works on Ni, Oudar
and Marcus [35] previously reported an interesting effect
ofchemisorbed S on the rate ofanodic dissolution of Ni.
They found that the presence of a monolayer of S 4
C\J
increased the rate of dissolution of Ni substrates. The
passive potential region resulting from the formation of
E
()

Ni oxides significantly shifted toward more positive <C 3

E
potentials in H2S04 solutions when the Sadlayer was pre-
sent on the Ni surface. In other words, the corrosion rate
--...
>-
'00
of Ni and its alloys was drastically increased by the c 2
Q)
presence of S adlayers [35]. Potential pH diagrams for
Ni electrodes with S adlayers predicted that the S adlayer ...c
Cl

is strongly attached on Ni and is very stable in wide poten- ......

Q)

tial and pH ranges [36].
We used in situ STM to investigate the S adlayer
structure and the influence of S on the anodic dissol-
ution of Ni(lOO) single crystal electrodes at the atomic
scale [37]. The Ni(lOO) crystals were annealed in a
quartz tube under H2 atmosphere (l atm) at 1250 K
for 3 h, the conditions similar to those used for Ni(lll)
as described above. The S-modified electrodes were pre-
pared by two different methods after the thermal
annealing. One was similar to that previously described
by Oudar and Marcus [35]. After annealing in the H2
stream at 1250 K, the furnace was cooled down to
750-800 K, and H 2 gas (l atm) containing 200 ppm
H2S was introduced for 1 min. The cooling was con-
tinued to room temperature in pure H2 flow. The other
was a solution dipping method. The annealed crystals
were cooled to room temperature in the quartz tube
under H2 stream and then dipped into a
hydrogen-saturated 5-mM Na2S solution. The contact
with Na2S solution was carried out in the same quartz
tube under H 2 stream to avoid oxidation of clean Ni
surfaces by oxygen in air. The S-modified electrodes
were rinsed with an H2 saturated Na2S04 solution and
quickly transfered into an electrochemical cell.
1. Cyclic Voltammetry
Figure 6 shows CVs ofbare and S-modified Ni(lOO) elec-
trodes by dashed and solid lines, respectively. OCP for
both electrodes were found to be ca. -0.38 V. In the
anodic scan from OCp, the anodic current due to the dis-
solution of Ni increased and reached a peak at ca.
-0.05 Von the bare Ni(lOO) surface. The anodic current
then decreased at more positive potentials because of
the passivation by the formation ofoxides, which is simi-
1ar to what was observed with Ni(lll) in Fig. 3. On the
other hand, the anodic current surprisingly continued
to increase with potential beyond 0 Von the S-modified
:::J
()
o
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6
Electrode Potential I V vS.SCE
Figure 6 Cyclic voltammograms ofS-modified Ni(100) (solid
line) and bare Ni(100) (dashed line) in 0.05 M Na2S04. (From
Ref. 37.)
Ni(lOO) electrode in sulfide-free 0.05 M Na2S04 (pH 3)
as shown by the solid line in Fig. 6. This particular CV
was obtained using an S-modified Ni(lOO) electrode pre-
pared by the solution dipping method described above.
The anodic current was found to be enhanced by the S
adlayer consistently during many cycles in the potential
range shown in Fig. 6, suggesting that the S monolayer
remains on the surface during the anodic dissolution even
at such high current densities as 5 rnA cm- 2. A similar
remarkable increase in the dissolution current was first
observed in a sulfuric acid solution by Oudar and Marcus
[35] using S-modified Ni electrodes prepared in a gas
phase. An Ni(lOO) electrode treated in the gaseous
mixture of H2-H2S was also used in our study, which
yielded a CV with almost the same feature as that shown
in Fig. 6 (solid line), indicating that either method can be
used to form a monolayer ofS on Ni surfaces. The forma-
tion of S adlayers by similar solution dipping methods
was previously investigated and characterized on Pt and
Pd single-crystal surfaces using ex situ LEED [38,39]. It
is also noteworthy that the S monolayer was found to be
stable even during the hydrogen evolution reaction. The
remarkable stability of S monolayers on Ni was recently
194 Itaya

interpreted based on potential pH diagrams calculated

from standard Gibbs energies of formation of S adlayers
[001 1; jf,[OIl]
[36]. \L.....lOIO]
2. In Situ STM of S-Modified Ni(100)
Figure 7 shows a typical example of topographic STM
images of the S-modified Ni(lOO) electrodes acquired at
-0.45 V The scan area was 200 x 200 nm. All steps
observed were mostly monatomic with a height of
0.176 nm. Wide terraces extending over 100 nm were
usually observed on well-prepared S-Ni(100) electrodes
as shown in Fig. 7. A preferential orientation of step lines
is seen in the image acquired even before the anodic dis-
solution. The step lines seem to be nearly in parallel with
the [001] and [010] directions, which are rotated 45° off
from the close-packed direction ([011]) of the underlying
Ni(lOO).
Figure Sa shows an STM image with atomic resol-
ution obtained on an atomically flat terrace. It is clearly
seen that the S adlayer has a structure with fourfold
symmetry, i.e., a square lattice. The height of each S
atom was typically 0.04 nm. The atomic rows of S are
also rotated by 45° with respect to the close-packed
direction of the underlying Ni(lOO). The observed
lattice constant of ca. 0.35 nm corresponds to -/2 times I I
o 2nm
(a)
[001] [011]
\i:[010]

(b)
o Ni 0 S
o 100 200 nm
Figure 7 Large-scale STM image of S-modified Ni(lOO) in Figure 8 Atomically resolved STM image of S-modified
0.05 M Na2S04. (From Ref. 37.) Ni(100). (From Ref. 37.)
 Anodic Dissolution of Metals
the lattice constant of Ni(100), 0.25 nm. This structure
is designated as c(2 x 2) as shown in Fig. Sb. It is also
interesting to note that single-atomic defects of S were
sometimes observed in well-ordered S adlayers as
shown in Fig. Sa. Those single-atomic defects were con-
tinuously observed at the same relative locations in
subsequently acquired images for at least 30 min, indi-
cating that the surface mobility of adsorbed S atoms
was very small.
Figure 9 shows an STM image ofa relatively large area
(10 x 10 nm) with atomic resolution, including three
atomic layers. It is easily seen that the S adlayer forms
the c(2 x 2) structure over terraces. A single domain of
the S adlayer was found on each terrace. Phase bound-
aries were not usually observed on each atomically flat
terrace, suggesting that the S adlayer with a long-range
ordering formed on the Ni(lOO) surface. The image
shown in Fig. 9 also reveals detailed structures ofthe step
edge. Individual S atoms on the upper edge of the step
marked (a) can be clearly seen with the same corrugation
amplitude as observed at the center of the terrace,
suggesting that the S atoms along the step lines are also
located on the fourfold hollow site, similarly to those at
the center ofthe terrace. The step (b) is atomically straight
and parallel to the direction of the S atom row, whereas
the step (a) includes kink sites. As described in the
t mode or the so-called digital etching [40]. In the first
• (a)
t
1
1
i
ti • (b)
I
t
j smaller in width in the first 7 s but remained
I unchanged in subsequent images. This observation
5nm
Figure 9 Atomically resolved STM image of S-modified
Ni( 100) in the region including steps. The direction ofthe atomic
rows of the Ni(lOO) surface was indicated by the arrows. (From
Ref. 37.)
195
following section, the anodic dissolution seems to occur
preferentially along the [010] direction, starting from the
kink sites followed by row-by-row dissolution at the step
edges.
We pursued an investigation on the effect ofadsorbed S
on the dissolution at potentials near the onset of anodic
current. Soon after the acquisition of the image shown
in Fig. 9, the electrode potential was slightly shifted posi-
tively to follow the movement of the step line resulting
from the anodic dissolution. The c(2 x 2) structure was
consistently observed on the terrace even under the
anodic dissolution.
Figures 10, a and b, illustrates the time-dependent
etching process of S-modified Ni(lOO). These images
were acquired consecutively with a time interval of
7 s in an area of 20 x 20 nm. All lines seen in the
images shown in Fig. 10 were found to represent
monoatomic steps. We focused our attention to the
progressive etching of the topmost layer, marked T b
in the image shown in Fig. lOa. As described above,
the step lines are nearly parallel to the [001] or [010]
direction but they are not always straight, indicating
that some step lines include kink sites as shown in Fig.
9. As a general feature, it is clear that the anodic dis-
solution takes place preferentially at the step sites.
The steps continued to recede to dissolve the terrace
(T 1). No pit formation was found to occur on the
terrace, indicating that the dissolution of Ni on
S-modified Ni(100) proceeds by the layer-by-Iayer
7 s, relatively fast etching took place along the [010]
direction in the lower part of the terrace T 1, splitting
the continuous terrace into two domains. The step Sj
with a staircase shape also disappeared and was con-
verted to a relatively straight step line along the [011]
direction as shown in Fig. lOb. Note that the [011]
direction is parallel to the close-packed atomic rows
of the underlying Ni atoms. It was interestingly found
that the corner marked C 1 in Fig. lOa remained in all
subsequently acquired images, whereas the corner
marked C z was rapidly retracted in the first 7 s from
Fig. 10, a - b, forming a step line along [011]. It is also
important to note that the upper part of the terrace
marked A with the shape of a narrow strip became
strongly suggests that the etching rate along the [001]
direction is significantly slower than that along the
[010] direction. Such an anisotropic etching process
seems to be important in explaining the morphological
change in the shape of terraces during the dissolution
illustrated in Fig. 10.
196 Itaya

The anisotropic dissolution process can be further

o 20 nm
(a)
o 20nm
(b)
Figure 10 Two successively recorded STM images of
S-modified Ni(lOO) dissolving at -0.3 V. (From Ref. 37.)
elucidated by the structural models depicted in Fig. 11
[37]. Figure lla shows a model structure of the S adlayer
on Ni(lOO) including three step lines along [001], [010],
and [011] directions, respectively. The S adlayer was
drawn to scale using the interatomic distance (0.25 nm)
ofNi and van derWaals diameter (ca. 0.35 nm) ofS atom
[39]. The adsorbed S atoms on Ni(lOO) seem to form an
almost close-packed adlayer, because the diameter of S
is nearly equal to ,J2 times the lattice constant ofNi( I00).
All S atoms on the upper terrace should be located at
the fourfold hollow sites even near the step edges, because
the S atoms on the upper terrace along the step edges
appeared as spots with the same corrugation height as
that observed at the center of the terrace as described for
Fig. 9. According to the model structure shown in Fig. Ila,
neighboring S atoms along the step edges on the lower
terrace are located with different spaces depending on
the orientation of the steps. There is almost no space at
the step along the [001] direction. Each Ni atom located
on both the upper and the lower terraces along this step
is coordinated to an S atom. On the other hand, the steps
along the [010] and [011] directions provide larger spaces
near the step edge.
It is important to note that the step lines along the [001]
and [010] directions become nonequivalent because of
the presence of the S adlayer with the e(2 x 2) structure.
The S atomic rows should be shifted by a half space at
the step edge along the [010] direction as shown in Fig.
Ila. On the other hand, the S rows are continuously
aligned in the straight line along [001]. Such a difference
in the alignment of the atomic rows of S might be seen in
the STM image in Fig. 9. The S rows at the step edge along
[0 I0] were indeed shifted by a half space. Figure II b illus-
trates the atomic arrangement at a corner of the upper
terrace. This corner corresponds to that marked C 1 in Fig.

(a) [001] t ,,[011]

IL..rOIO]
(b)

JI-l
-- l-l
o,r'\o,C'I
J )( J-J J:l t:l 1:1)
) II 1: D
] J: I MD
O( I-l \7~ '\ ....."

J
I-l
-: r-
] :1 - - .......
:1 I)

'f
-, -J - ---
] J
-:
I)

Figure 11 Structural models ofS-adlayers on Ni(lOO)-(l x 1). (From Ref. 37.)

Anodic Dissolution of Metals
lOa, which was stable against the anodic dissolution as
described above. The nonequivalent step lines along [001]
and [010] can also be seen in Fig. lIb.
We proposed a model to explain the local anisotropic
etching process using the local atomic structures shown
in Fig. 12. The energy required to remove an Ni atom from
the surface can be estimated by a simple bond counting
model [41,42]. The single Ni-Ni bond energy (ENi-Ni)
is 0.365 eV [1/12 of the sublimation energy of Ni
(4.38 eV)]. The bond energy between Ni and adsorbed S
atoms (ENi - S ) can be estimated as 0.456 eV from the free
energy of the adsorption of S on Ni(100) (1/4 of 1.82 eV
[36]) in which the coordination number (4) of the
adsorbed Son Ni(lOO) is taken into account.
The energy to remove each Ni atom from the step edge
along [010] equals 6ENi-Ni + ENi-S, because one Ni
atom at the step edge has six neighboring Ni atoms and
Anodic dissolution
(a)
(c)
Figure 12 (a) and (b) Schematic illustration ofthe anodic dissolution process. (c-e) Local atomic structures in the square shown in
(a). (From Ref. 37.)
197
one S atom when the S atom, which has been coordinated
with the removed Ni atom, stays on the upper terrace after
the removal. However, if the S atom can slide down to
the lower terrace to find a fourfold hollow site during the
removal of the Ni atom, the total energy becomes only
6EN i-Ni. The movement of the S atom at the step edge
from the upper terrace seems to be a key factor in
determining the preferential etching process. The Ni
atom such as g in Fig. l2a at a step site along [010], except
the one at the corner such as that marked a requires the
energy of 6ENi-Ni + ENi-S for removal, because the S
atom cannot find a hollow site on the lower terrace due
to its van der Waals diameter. On the other hand, the Ni
atom a can be more easily removed from the upper
terrace, because the S atom attached on Ni a slips down
to the lower terrace during the removal of the Ni atom.
The neighboring Ni atom b should be easily removed
..
[001]
+ [011]
jf
1L-.[010]
(b)
(d) (e)
198
from the surface during or after the removal of Ni a,
because the Ni atom b is coordinated only with six
neighboring Ni atoms. Therefore, the simultaneous
removal of two Ni rows along the [010] direction is
expected to accompany the movement of the first S row
on the upper terrace to the lower one as illustrated in Fig.
12, a and b. After the dissolution of Ni atoms (a and b),
the Ni atoms (c and g) can then be easily removed in the
same manner, and the etching is propagated in the [010]
direction. The above mechanism explains the row-by-row
etching process along the [010] direction. The first
removal of the Ni atoms such as c and e needs the energy
of 7ENi-Ni, even though the S atom can slide down to
the lower terrace after the removal ofthese Ni atoms.This
explains the faster etching of Ni along [010] compared
with that along [001].
The instability ofthe steps along the [011] direction can
be explained as a consequence of the etching along the
[010] direction from the step edge along [011]. The
row-by-row etching mechanism proposed here also
explains the etching profile at the corner of C 2 in Fig. lOa.
The step line along [001] involving the corner C2 became
one ofthe steps along [011] as shown in Fig. lOb. This pro-
cess is expected to occur when the etching starts with
the corner atom by the row-by-row mechanism.
The model structure shown in Fig. lIb can explain the
high stability of the corner marked Cl in Fig. lOa. Both
Ni atoms marked by arrows in Fig. lIb need the higher
energy of 7ENi-Ni + ENi-S to remove because there is
no vacancy to accept the S atom on the lower terrace.
The high stability of this type of corners will terminate
further etching along the atomic rows in the [010]
direction. The propagation of etching along the rows
indicated by the dashed arrow in Fig. 11b will be
terminated at the corner.
c. Iodine-Modified Ag(100)
It is now clear that the adlayer plays an important role in
the anodic dissolution processes of metals. To reveal
the role of the adlayer, this section describes the anodic
dissolution of an iodine-modified Ag(lOO) [43]. A com-
mercially grown Ag(lOO) single crystal was
metallographically polished and sequentially sonicated
in acetone, methanol, and pure water. The single crystal
was then placed for 2 h in a quartz tube continuously
purged with purified H 2 and maintained at 1100 K.
The sample was cooled to room temperature under H 2
steam and subsequently brought into contact with
ultrapure water saturated with H2 and then transferred
into an electrochemical cell with a droplet of pure water
on it to mitigate surface contamination. For the prep-
Itaya
aration of the iodine monolayer on Ag, the clean surface
must be exposed to the KI solution under potential con-
trol; immersion at OCP leads to the formation of bulk
AgI and roughened surfaces [44]. It should be
mentioned that several recent studies on I-pretreated
Ag electrodes using STM [17] and x-ray photoelectron
spectroscopy [45] may have been complicated by the
presence of AgI multilayers because the I adlayers in
those studies were prepared by immersion at OCP. In
our study, the clean Ag(lOO) electrode was immersed
in a solution that contained 0.1 M HCI04 and 1 mM
KI at a specific potential in the double-layer region.
After 5 min, the electrode was emersed at the same
potential and immediately transferred to the electro-
chemical cell containing pure HCI0 4 for the vol-
tammetry and STM experiments.
1. Cyclic Voltammetry
Figure 13 shows CVs for the bare Ag(lOO) (Fig. 13a) and
I-pretreated Ag(lOO) (Fig. 13 b) electrodes in 0.1 M
HCI0 4 . Figure l3c shows the CVobtained in 0.1 M
HCI0 4 that also contained 1 mM KI. In the absence of
KI, the anodic dissolution of Ag commenced at ca. 0.5 V
(vs. RHE). The cathodic peaks at 0.55 Vobserved during
the cathodic scan correspond to the electrodeposition
of Ag metal from the initially formed Ag+ ions. It is clear
that the Ag dissolution-deposition reactions occur
reversibly at the same potential regardless of whether I
was present or absent at the Ag(lOO) surface. The case is
different, however, for the hydrogen evolution reaction;
this commenced at -0.15 Von the bare Ag(lOO) electrode
but at ca. -0.30 Von the I-Ag(lOO) surface (Fig. 13b).
A similar adsorbate-induced overpotential for the
hydrogen evolution reaction was found on I-pretreated
Au and Pt electrodes [46,47]. In Fig. l3c, the onset poten-
tial for the anodic dissolution current was at 0.1 V; the
overall reaction in the presence ofI- ions involves Ag dis-
solution to form Ag+ ions followed by immediate precipi-
tation of bulk AgI. Figure Bc shows that no bulk AgI
phase is formed in the potential range between 0.1 and
-0.2 V, the conditions used here in the preparation of
the I monolayers. It may be noted that the hydrogen evol-
ution reaction is further shifted to negative potentials
when iodide ions are present in solution.
It is important to mention that for Ag(lll), the CV in
the presence ofI- ions is characterized by small reversible
peaks at potentials slightly negative to bulk AgI forma-
tion [44]. Studies based on LEED and STM showed that
the peaks are due to rotational phase transitions in the
Ag(lll)-I adlayer. No similar peaks are found for
Ag(100) (Fig. l3c).
f Anodic Dissolution of Metals 199

5.0
~
(a)
E
t>
1. 0

-5.0

-0.5 o 0.5

5.0

~
(b)
E
t>
1. 0

-5.0

-0.5 o 0.5

5.0

~
E
t>
(c) o 50
nm
100 150
1. 0
(a)

-50

-0.5 o 0.5

E IV vs. RHE

Figure 13 Cyclic voltammograms of bare Ad(lOO) (a) and

I-modified Ag(IOO) (b) electrodes in 0.1 M HCl0 4 and in 0.1 M
HCl04 + 1 mMKI (c). (From Ref. 43.)

2. In Situ STM

(a) Bare Ag(IOO). Figure 14a shows a typical large-

scale STM image of the bare Ag(lOO) electrode in 0.1 M
HCI04 at 0.1 V [43]. Atomically flat terraces can be
seen that extend over a few hundred nanometers. Steps,
mostly monatomic in height, are characterized by
arc-shaped (rather than straight) edges; relatively large
islands are circular in morphology. A similar surface
morphology has been reported for real and quasiperfect
Ag(100) electrodes [48,49]. The shape and location of
the step lines observed in Fig. 14a were not significantly
changed in the potential range between 0.4 and -0.1 V,
suggesting the absence of potential-induced recon-
struction on the bare Ag(100) in contrast to that found o nm 3
on Au(100) electrodes [50,51]. Figure 14b shows a (b)
high-resolution STM image acquired on the atomically
flat terrace. It can be clearly seen that the Ag(100) surface Figure 14 Large-scale (a) and atomically resolved (b) STM
has a square lattice with an interatomic distance of ca. images ofbare Ag(IOO) surface in 0.1 M HCl0 4 . (From Ref. 43.)
200 [taya

0.29 nm along the [110] direction; the corrugation ampli-

tude ofeach Ag atom is about 0.05 nm. The image shown
in Fig. 14b demonstrates that under the present con-
ditions, the Ag(lOO) surface retains the unreconstructed
(1 x 1) structure, consistent with previous results [49,52].
Images obtained in the potential range between 0.4 and
-0.1 V also showed the (1 x 1) structure; the absence of
potential-induced reconstruction in this potential region
is thus demonstrated.

(b) I-Modified Ag(IOO). Figure 15 shows typical

large-scale (Fig. 15a) and high-resolution (Fig. 15b)
STM images ofthe I~Ag(lOO) surface in HCl04 at 0.1 V.
It is interesting to note that the monatomic steps now
run parallel to the [100] direction, rotated by 45° with
the respect to the atomic rows of the Ag substrate. The
change in the step direction may have occurred upon
exposure of the Ag(100) surface to the KI solution. The
interatomic I~I distance was found to be 0.4 nm, which
corresponds to ../2 times the lattice constant of Ag(100);
in other words, it can be concluded that the I adlayer
o nm 100
possesses a e(2 x 2) structure. Previous UHV- based (a)
studies on the chemisorption of iodine from 12 vapor
showed a e(2 x 2) LEEO pattern on Ag(lOO) [53]. Our in [001] [010]
V
situ STM result is thus in good agreement with the ex-situ
LEEO data. A more important observation is that the
e(2 x 2) structure was consistently found in the
double-layer region (from 0.5 to -0.2 V); at least under
the present conditions, no potential-induced structural
changes in the iodine adlayer are indicated.
It is important to view the potential independence of
the I~Ag(lOO) adlayer structure in the context of what
has been observed for the I~Ag(l1l) adlayer [54-56].
Our recent work on Ag(ll1)~1 adlayer by means of
tandem in situ STM and ex situ LEEO revealed a continu-
ous compression of the adlayer, from (../3 x ../3)R30°,
via e(p x "/3R300), into a rotated hexagonal phase in
acidic HI solutions [44], when the I coverage was
increased as a result of an increase in the applied
potential. In general, the 11l planes of Ag and Au exhibit
several incommensurate iodine structures [57]. The single
commensurate structure of I on the Ag(lOO) surface
may be explained by the difference in the coordination
numbers of the iodine adatoms on the 100 and 111
surfaces. Each iodine adatom on Ag(100) is expected to
be located on a fourfold hollow site; hence, each iodine
atom has a coordination number offour. In comparison, o nm 3
an iodine atom on a threefold hollow site on Ag(ll1) has (b)
a coordination number of only three. The exceptional
stability of I on Ag(lOO), due to a higher coordination Figure 15 Large-scale (a) and atomically resolved (b) STM
number, may explain the formation of the single com- images of I-modified AgOOO) surface in 0.1 M HCI04 . (From
mensurate e(2 x 2) structure. Ref. 43.)
f Anodic Dissolution of Metals 201

As was shown in Fig. 15a, the monatomic step-lines rows. Figure 16 shows a set of STM images acquired
found on the I-Ag(I00) are mostly parallel to the atomic sequentially after a time interval (32 s) at the onset of
rows of iodine atoms in either the [001] or [010] direction, (low-current) anodic dissolution. It can be seen that
rotated 45° with respect to the close-packed Ag atomic although the step lines remained nearly parallel to the

[010]

100 nm 100 nm
(a) (c)

100 nm
(b)
Figure 16 Time-sequenced STM images showing the etching process ofI-modified Ag(IOO) in HCI0 4 •The images were acquired at
the time intervals of 32 s. (From Ref. 43.)
202 Itaya

[001] and [010] directions, they were not always

atomically straight. This result indicates the presence of
[001 ]
kink sites along the step lines. For example, whereas the
step line marked Sj is almost perfectly aligned along the
[010] direction, the S2 step is not. The initial jaggedness
in the latter (S2) step lines was rendered smooth as a result
(a) L r0101
of the anodic dissolution; staircase-shaped edges were
formed as shown in Fig. 16c. The step edge marked by
the arrow in Fig. 16a also includes several kink sites of
various orientations. This step line was likewise con-
verted to a staircase-shaped step edge (Fig. 16c).
Although it has become clear that the etching of Ag on
I-Ag(lOO) takes place exclusively at the step edges, one
can recognize that the etching rate on I-Ag(100) along
the [010] direction is faster than along the [001] direction.
As an illustration of this anisotropic etching, it can be
seen thatthe step lines marked C 1 and C2 in Fig. 16 remain
unchanged, whereas the steps along the [010] direction
was progressively retracted. Several other sets of
time-dependent STM images were obtained in different
areas during the anodic dissolution; invariably, similar
anisotropic etching processes were found.
The anisotropic dissolution found on I~~Ag(lOO) can
be rationalized in terms of the surface structural models
shown in Fig. 17. These models are similar to those shown
in Fig. 11 but include three atomic layers with the step
along either [010] or [001] directions; the topmost layer (b)
is shown on the lower right-hand section. In the absence
of iodine, the step lines along [001] and [010] directions
are equivalent, but they are nonequivalent in the presence
ofthe e(2 x 2) adlayer. In the proposed model, all I atoms
on the terraces are located at the fourfold hollow sites,
even near the step edges. As shown in Fig. 17a, the
arrangement of I near the step edges is dependent on the
direction ofthe step edges: the steps along the [010] direc-
tion include larger spaces near the edge compared with
those along [001], the I rows are aligned in a straight line
across the three atomic layers along the [010] direction,
and in the [001] direction, the 1 rows are shifted by a half
space at each step edge. These differences in the align-
ment of the atomic rows had been clearly discerned by
high-resolution STM images of S-Ni(lOO). The
upper-to-Iower terrace diffusion of the first iodine row is
driven by the need to minimize the free energy change
during Ag dissolution along the step edges. Because of
its open structure, the anodic dissolution along the [010]
direction is expected to occur more easily than along the
[001] direction. The Ag atoms marked A and B in Fig
17a are thus the first to be dissolved accompanied by the
diffusion of the iodine atom from the upper to the lower Figure 17 Schematic depictions of anodic dissolution pro-
terrace. After dissolution of A and B, the same process cesses of Ag(IOO) with differently aligned e(2 x 2)-1 adlayers
is expected to continue along the [010] direction; this on the terraces. (From Ref. 43.)
f Anodic Dissolution of Metals
results in the propagation ofthe anisotropic etching along
the direction marked by the arrows in Fig. 17. It is import-
ant to note that the different alignments ofthe atomic rows
of iodine do not always extend through several atomic
layers. The I adlayer on each terrace has an equal proba-
bility to be shifted by a half space with respect to those
on lower and upper terraces; such shift may result in an
alternative alignment as shown in Fig. 17b.
In this case, the anisotropic etching of the topmost
layer is expected to proceed along the [001] direction as
indicated by the arrow. The etching of the second layer
must then propagate along the [010] direction. It should
be noted that this mode of anisotropic etching, rotated
by 90° with respect to a particular step-terrace con-
figuration, was observed on much higher or much lower
terraces (Fig. 16). Nevertheless, the overall features for
the anodic dissolution of Ag on I-Ag(lOO) can be
explained by the model structures shown in Fig. 17.
D. Iodine-Modified Pd Electrodes
Recently, Soriaga and coworkers [58-60] discovered
using the UHV-EC that the anodic dissolution ofPd(11l)
and Pd(lOO) single crystal electrodes in pure H2S04 sol-
utions was catalyzed by the presence of monolayers of
100
Pd( 100)----..
50
Pd(1lO)
C'l
I
0
8u
<
--
~
-50
-100
-150
o 0.5
E / V vs. RHE
Figure 18 Cyclic voltammograms obtained at I-free Pd(111), Pd(lOO), and Pd(llO) electrodes in 0.05 M H 2 S0 4 . (From Ref. 61.)
203
iodine chemisorbed on these surfaces. Large anodic
peaks were found for the dissolution even in noncorrosive
electrolyte solutions only when the surfaces of Pd were
modified by the iodine adlayer. In this section, we present
only our results based on in situ STM that extend our
understanding of the role of adsorbed iodine for the
anodic dissolution [61]. Iodine pretreatment was
accomplished simply by immersion of the clean
electrode, without potential control, in an aqueous I-mM
solution of iodide for 5 min. Unadsorbed iodide was
removed by rinsing with pure water.
1. Cyclic Voltammetry
The electrochemistry of iodine-free palladium is
expected to be dependent on the crystallographic
orientation of the surface in contact with the electrolyte.
Such a dependence was well demonstrated for the
oxidation of Pt single-crystal electrodes [62]. Figure 18
shows CVs of Pd(11l), Pd(lOO), and Pd(llO) in 0.05 M
H2S04. All three single-crystal surfaces exhibited sharp
anodic oxidation peaks at potentials E ox that increased
in the order Pd(llO) (Eox = 0.85V) < Pd(lOO) (Eox =
0.90V) < Pd(lII)(Eox = 1.l0V). In contrast, only a
broad undefined peakcan be obtained at a polycrystalline
Pd(11l )---...
• ~ [:
~ "
"
.. .I \1......\._-
~-~ _. .....
:':',..
1.0 1.5
204
500
400
Pd(lOO)-I ----... f
300
';'
E
u
200
1 observed at both iodine-free and iodine-pretreated
, Pd(lll). Atomic-resolution images showed that the
100
\[2,,/
Pd(lOO)----... ..:
0 nearest-neighbor atoms was determined to be
-100
0 0.5 1.0 1.5
E/V vs. RHE
Figure 19 Cyclic voltammograms of I-free and I-modified
Pd(lOO) electrodes in 0.05 M H 2 S0 4 . (From Ref. 61.)
surface [58]. The structure sensitivity of E ox almost cer-
tainly originates from differences in surface-atom
arrangements at the three low-index planes [62].
When the Pd electrodes were pretreated with iodine,
dramatic alternations took place in CVs recorded under
conditions identical to those in Fig. 18, as can be seen
in Fig. 19 for an iodine-coated Pd(lOO) surface. Two
more notable features are the suppression of the
surface-oxidation peak at E ox and the emergence of a
new anodic peak (E~x = 1.25 V) that yields a peak cur-
rent nearly an order-of-magnitude larger than that for
the I-free surface. If the potential is held at a value just
below, the current does not decay but remains essentially
constant, a behavior diagnostic ofa material-limited dis-
solution process. These results are very similar to those
found on S-Ni(lOO) as described above.
Previous work on polycrystalline and single-crystal
Pd electrodes, based on techniques that included
coulometry, atomic emission spectroscopy, electron
diffraction, and surface elemental analysis, has estab-
lished that the anodic peak is due to the two-electron dis-
solution reaction [58,63]:
(1)
Itaya
Similar CV features were observed for the dissolution
of I-Pd(lll), I-Pd(lOO), and I-Pd(llO) surfaces
in 0.05 M H 2S04 , slightly depending on the
crystallographic orientation [61].
2. In Situ STM
(a) I-Pd(lll). In 0.05 M H 2S04 and at potentials
within the double-layer region (OJ V < E < 0.7 V), wide
atomically flat terraces with monatomic steps that
intersected one another at an angle of 60 or 120 were
0
iodine adatoms were aligned along the {121} direction,
that is, along a vector rotated 30° with respect to
the substrate-atom rows. The distance between
0.47 ± 0.01 nm. The observed structure, Pd(lll)-
(,J3 x ,J3)R300-I, is identical to that reported earlier
based on LEED measurements [58].
The potential was scanned to and held at 1.05 V, a
potential at which metal dissolution is initiated. Figure
20 presents two STM images, in the same
(300 x 300 nm 2) domain, obtained at the beginning
and 25 min after the start of the anodic dissolution,
respectively. The progress ofdissolution can be monitored
via topographical changes in the terrace (designated by
a T) and the step edge (marked with an M) within the
rastered domain. It is easy to recognize that as the
low-current dissolution proceeds, the step edge retracts
upward, the area of the lower terrace increases, and the
(diminished) upper terrace and (enlarged) lower terrace
remain pit free. In addition to these obvious features,
one can also note the gradual dissolution of the islands
on the upper left- hand corner in Fig. 20a and the charac-
teristic jagged outline (contour) of the receding upper
terrace. The latter observation suggests a preferential
dissolution process along either substrate or ad-
sorbate atomic rows. The images shown in Fig. 20 clearly
point to a step-selective layer-by-layer dissolution
mechanism. It is noteworthy that high-resolution STM
of the postcorrosion terrace revealed an iodine
adlattice structure identical to that observed before the
anodic dissolution, that is, a well-ordered Pd(lll)-
(,J3 x ,J3)R300-I adlattice was retained after the
corrosion reaction. This observation is in consonance
with data reported earlier on the basis of UHV-EC
measurements [58].
(b) I--Pd (1 00). As with the Pd(lll) surface,
atomically flat terraces with monatomic steps were
observed at both the clean and iodine-coated Pd(lOO)
facets in 0.05 M H2S04 in the double-layer region. An
observed iodine adlayer structure was also observed at
Anodic Dissolution of Metals
I I i I
100 200 300
nm
(a)
Figure 20 Two successively recorded STM images ofl-modified Pd(lll); b was recorded 20 min after a. (From Ref. 61.)
flat terraces, typified by the high-resolution STM image
in Fig. 21. It is possible to ascertain that the iodine
adatoms are aligned along the [110] direction, 45° with
respect to the [100] direction; a nearest-neighbor distance
of 0.38 nm was measured. This interfacial configuration
is consistent with a c(2 x 2)-1 lattice structure previously
determined by LEED experiments [59].
Before the anodic dissolution, the surface morphology
was similar to that observed for the bare Pd(100). The
monoatomic steps were mostly parallel to the atomic
row of Pd(lOO). However, after removal of several layers
by the anodic dissolution, the direction of the step line
was drastically changed. STM images obtained after 5,
6, and 7 min at 1.05 V are shown in Fig. 22: Only
rectangular terraces with steps along the [100] edge and
its orthogonal direction are recognizable. All steps were
now only monatomic in height; that is, anodic dissolution
led to diminution of the step line parallel to the atomic
rows of Pd.
Closer inspection ofthe STM images in Fig. 22 reveals
that dissolution transpired only at step edges; corrosion,
via pit formation, was not observed at the terraces (T).
More significantly, it can be recognized that dissolution
occurred anisotropically. For example, the "narrowing"
(and subsequent disappearance) of the Tl, T 2 , and T 3
terraces developed almost entirely along the
205
I I
100 200 300
nm
(b)
[OOl]-directed step, with only minimal in the direction
perpendicular to it. Such anisotropic dissolution has
been observed for sulfur-modified Ni(lOO) in acid sulfate
solutions and for iodine modified Ag(100) as described
above.
The absence of pit corrosion at the terraces, coupled
with the selective dissolution at and the continuous
retraction of the step edges, provides evidence that the
corrosion of I-Pd(100) proceeds via a layer-by-layer
mechanism. In this regard, Pd(l00)-c(2 x 2)-1 behaves
similarly to Pd(1ll)-(.j3 x .j3)R300-1. The present case
of anisotropic dissolution may be understood in terms
of the schematic model as shown in Figs. 11, 12, and 17.
Removal of Pd atoms easily permits the iodine atom to
slide down from a fourfold site at the upper terrace onto
another hollow site at the lower terrace in a particular
direction depending on the arrangement of iodine atoms
near the step edges. The ease by which iodine moves from
a high-symmetry site from the upper to lower terrace also
seems to be the key factor for I-Pd(lOO) as the major
driving force in anisotropic dissolution.
(c) I-Pd (11 0). In contrast to the other two low-
index planes, wide atomically flat terraces were
not encountered with I-free Pd(110)-(l x 1) nor with
I-Pd(llO) surface [61]. The existence ofa handful of ran-
domly located pits, a few nanometers in diameter and up
206 Itaya

(a)

[001]

[O~

(b)

I
3.0nm

Figure 21 Atomically resolved STM image of Pd(lOO)-

e(2 x 2)-1. (From Ref. 61.)

to three atomic layers in depth, can also be recognized

during the anodic dissolution, resulting in a disordered
surface. The propagation of pit corrosion on the upper
terrace and inside the rectangular pits leads to (c)
progressive deterioration of the I-Pd(llO) surface, a
result that was initially indicated by the LEED data [60].
The formation ofthese pits is simply due to the dissolution
of more active Pd atoms on the Pd(llO) terrace plane. In
view of the aggressive reactivity of the I-Pd(llO) surface
relative to I-Pd(lll) and I-Pd(lOO), it may just be that
pit corrosion on I-Pd(llO) terraces cannot be com-
pletelyeliminated.

E. Dissolution of Cu in HCI
Suggs and Bard [64,65] reported detailed dissolution pro-
cesses of Cu(lll) and Cu(lOO) in HCl solutions using in
situ STM. It is well known that chloride ions are relatively
strongly adsorbed on Cu electrode, forming specific
structures depending on the crystallographic orientation
of Cu single-crystal electrodes. It was demonstrated by
them that the anodic dissolution of both electrodes pro-
ceeded by the layer-by-layer mode in HCI.
We are particularly interested in the anodic dissolution
of Cu(lOO), on which the adsorbed chloride forms the
c(2 x 2) structure [65]. As described above, the anodic
dissolution of Ag(lOO)-c(2 x 2)-1 and Pd(lOO)-c(2 x 2)-1
I I
40 80nm
Figure 22 Large-scale STM images of Pd(100)-e(2 x 2)-1
obtained after (a) 5, (b) 6, and (c) 7 min ofdissolution in 0.05 M
H 2S04 . (From Ref. 61.)
are similar to that of Ni(lOO)-c(2 x 2)-S. The striking
similarities observed for the three different 100-oriented
metal substrates (Ni, Ag, Pd) pretreated with different
adsorbates (S, I) but having identical c(2 x 2) structures
Anodic Dissolution of Metals 207

strongly suggest that adlayer structure plays a dominant

role in the anodic dissolution of 100-oriented metal
surfaces. In the in situ STM study of the anodic dissol-
ution ofCu(lOO) in HCl by Suggs and Bard [65], aniso-
tropic dissolution along [100] directions was also found.
Because the Cl-on-Cu(lOO) adlayer possesses a e(2 x 2)
structure, we anticipated that a rationale identical with
that proposed for Ni(100)-e(2 x 2)-S, Ag(100)-e(2 x 2)-1,
and Pd(100)-e(2 x 2)-S is operative in the Cl- -assisted
dissolution of Cu(lOO) [66].
Figure 23 shows two high-resolution images acquired
consequtively every 13 s in the same area in a O.OI-M
HCl solution. Each small spot corresponds to a chloride
ion adsorbed on Cu(100) with the e(2 x 2) structure. It is
surprising that the well-ordered e(2 x 2) adlayer can be
seen on all terraces in Fig. 23. Interestingly, it can be seen
that the chloride atomic rows are not shifted by a half
space and that they are continuously aligned along the
[010] direction through several layers.
o 15 nm
We focused our attention on the progressive etching of (a)
the terrace marked T2. A new step with four chloride
atomic rows appeared at the bottom ofthe terraceT2 , and
it developed along the [001] direction as shown in Fig. 23b.
This stepwasconsistentlystraightalong the [010] direction
during etching and finally merged into the step along the
[010] direction, forming a corner illustrated in Fig. 11b.
Figure 24a shows a magnified image near the step with
four atomic rows. It is more clearly seen that the atomic
rows along the [010] direction are not shifted by a half
space along the [010] direction at the step edge as shown
by the dashed line marked L\. On the other hand, the CI
atomic rows along the direction of [001] are indeed
shifted by a halfspace at the step edge as shown by the line
L2. Figure 24b illustrates the atomic arrangement near
the step edge. According to the models shown in Figs. 11
and 17, the etching should proceed by the row-by-row
mechanism along the [010] direction as indicated by the
arrow in Fig. 24b. It is now concluded that the anodic dis- o 15 nm
solution of the four different substrates (Ni, Ag, Pd, Cu) (b)
with the 100 orientation with different adsorbates (S, I,
CI) takes place by the same row-by-row mechanism. Figure 23 Two successively recorded STM images ofCu(lOO)
during anodic dissolution of an HCI solution. (From
unpublished result.)
F. Other Metals
(aJ Au (111). In early 1989, Trevor et al. [67] demon- on Au(ll!) significantly enhanced step motion. The
strated that the surface of a roughened Au(lll) became anodic dissolution of Au(lll) in a solution containing
atomically flat at potentials in the double-layer region chloride ions was proceeded by the layer-by-layer mech-
due to the surface migration ofAu atoms, or the so-called anism [68]. More recently, adsorbate-induced etching of
electrochemical annealing. Pit growth and disappear- Au(lll) was demonstrated using an organic molecule of
ance was explained by the diffusion of Au atoms at the tetramethylthiourea [69,70]. Such processes might be
step edge [41]. More importantly, Trevor et al. [67] and expected to occur on various metal surfaces, resulting in
Honbo et al. [68] discovered that the adsorbed chloride the formation ofwell-defined surfaces.
208 Itaya

(b) Co (0001). We recently carried out an in situ

[001] STM studyofa Co(OOOI) single-crystal electrode in a sol-
ution of Na2S04 at pH 3.0 to establish the possibility of
exposing a well-defined electrode surface in solution [71].
[0101) It was found that the anodic dissolution of Co(OOO I) pro-
duced atomically flat terrace step structure at a potential
corresponding to the onset of the anodic current in the
acidic solution of Na2S04. Freshly prepared Co(OOOI)
surfaces were usually atomically rough at OCP in 0.05 M
Na 2S04 (pH 3). Atomically rough surfaces were tran-
sformed to well-defined terrace-step features at
potentials near the onset of the anodic dissolution. After
the removal of several atomic layers by anodic dis-
solution, the electrode potential was set at a value in the
relatively narrow double-layer potential range.
Figure 25a shows a typical in situ STM topographic
image of Co(OOOI) in 0.05 M Na 2S04 (pH 3) [71]. An
atomicallyflatterrace-step structure is seen on the surface
with terrace widths of 50-100 nm. All steps observed
are with a height of 0.2 nm, which is consistent with
0.204-nm-high monoatomic steps on Co(OOOI).
Although only small terraces were usually obtained in
the beginning ofthe anodic dissolution, the terrace width
increased with time during the anodic dissolution by the
layer-by-Iayer mechanism. Figure 25b shows an STM
4nm image with atomic resolution obtained on an atomically
(a) flat terrace. Nearly perfect hexagonal lattices can be seen
clearly with an angle of 60 ± 2° between the atomic rows.
The observed lattice constant ofca. 0.25 nm corresponds
to the known lattice constant of Co(OOO1),0.2507 nm. It
is concluded that the surface structure is designated as
Co(OOOI)-(l x I). The STM image shown in Fig. 25b is
believed to represent the first atomic image of a clean
Co(OOOl)-(l x 1) obtained in a solution.

IV. CONCLUSION

The anodic dissolution of Ni(111), Ni(100), Ag(lOO),

Figure 24 (a) Magnified STM image near the step edge with
four atomic rows of adsorbed chloride ions. (b) Schematic
depiction of the atomic arrangement near the step edge.
Pd(100), Cu(lOO), Au(111), and Co(OOOl) in the absence
and presence of the adlayers of S, 1, and CI has been
investigated by in situ STM. Except for bare Ni(100)
and 1-Pd(110), all other metals are anodically dissolved
by the layer-by-Iayer mode, resulting in the formation
of well-defined surfaces. The striking similarities in the
anodic dissolution observed for the four different
100-oriented substrates (Ni, Ag, Pd, Cu) in the presence
of different adsorbates (S, I, CI) with the identical
adlayer structure [c(2 x 2)] indicate that the atomic
arrangement near the step edges plays a dominant role
in the anisotropic dissolution of 100-oriented metal
surfaces.
Anodic Dissolution of Metals 209

on Priority Area of "Electrochemistry of Ordered

Interfaces" from the Ministry of Education, Science,
Sports and Culture, Japan.

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60. WF Temesghen, JB Abreu, RJ Barriga, EA Lafferty, MP
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Soriaga, J Electroanal Chern 300:487-498, 1991.
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62. N Furuya, S Koide. Surf Sci 220:18-28, 1989.
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42. WK Burton, N Cabrera, FC Frank. Philos Trans R Soc
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Surf Sci 296:310-332, 1993. 431:277-284,1997.
13
Auger Spectroscopy of Electrode Surfaces
ArthurT. Hubbard
Santa Barbara Science Project, Santa Barbara, California
ABSTRACT
Auger electron spectroscopic (AES) studies of electrode
surfaces are described. AES is useful for identification
and quantitation of all elements present at the electrode
surface, except H and He. Limits ofdetection are typically
about I % of one monoatomic layer at the present time,
and the technology continues to advance. Although
AES requires evacuation, the experimental evidence to
date indicates that chemisorbed species remain at the sur-
face for identification and quantitation in vacuum.
Cationic species present in the emersed layer ofliquid or
in the electrical double layer can also be determined using
AES. However, anions, X-, present in the emersed elec-
trical double layer and solution, typically undergo
hydrolysis to volatile HX species, which are subsequently
lost to the vacuum. Recent applications of AES to the
study of electrode surfaces include monitoring of
the preparation of clean electrode surfaces; analysis of
the monoatomic, monoionic, and monomolecular
chemisorbed layer at an electrode surface; charac-
terization ofelectrodeposited metallic films; and investi-
gation of alloy and compound semiconductor electrode
surfaces.
I. INTRODUCTION
Pierre Auger made the exciting discovery that the cloud
chamber tracks of some ejected electrons correspond to
certain characteristic kinetic energies, which he correctly
identified as stemming from internal transitions within
the electronic levels of atoms [1]. Many years later, these
':A..uger electrons" were recognized as useful for elemental
analysis of the surfaces of solids [2]. The surface speci-
211
ficity of Auger electron spectroscopy (AES) stems from
the fact that an electron, traveling through a solid in the
kinetic energy (KE) range from about 20-1000 eV, has a
mean free path of only a few picometers before
undergoing inelastic scattering processes readily
detectable with conventional electron energy analyzers.
The Auger transition process begins with ejection of an
inner level electron, followed by an internal transition
that fills the original vacancy and ejects a second electron,
an Auger electron, at a characteristic energy. In fact, all
the elements except H and He exhibit Auger electron
emission, and thus AES is a source of surface elemental
analysis information for virtually all elements [3]. The
sensitivity of modern Auger spectrometers is such that a
fraction ofa monoatomic layer can be detected for most
elements at most solid surfaces [4-8].
As a result, the range of surface processes to which
AES is applicable is fairly broad: AES is useful for surface
elemental analysis in preparation of a clean surface of
some electrode material, particularly before identifi-
cation of the characteristic behavior of the clean surface
in other experiments such as cyclic voltammetry. AES is
an excellent technique for identification oftrace elements
at the electrode surface and is readily combined with x-ray
photoelectron spectroscopy (XPS) for identification of
the valence states of various elements at the surface [9].
After calibration of the spectrometer-sensitivity factors
with reference to a clean substrate and tabulations of stan-
dard spectra [3], AES is very useful for determination of
the molecular constitution of a chemisorbed molecular
layer at an electrode surface and for measurement of the
molecular packing density resulting from chemisorption
212 Hubbard

under a specific set ofelectrochemical conditions. AES is of a series of interesting adsorbed layer structures [5-8].
also suitable for investigation of surface thin films result- I For example, the Pt(ll1) surface reacts with aqueous KI
ing from electrodeposition or from oxidation, etching, solution to form a layer of adsorbed I atoms [20,21]:
annealing, and other processes occurring at elemental,
alloy, and compound electrode surfaces. Pt +r -+ Pt!+e- (I)

Discharge ofthe iodide ion during adsorption is signaled

II. EXAMPLES by a pulse ofcurrent in the external circuit.When adsorp-
tion is carried out at open circuit, the discharge of iodide
Now, let us consider some examples of the use of AES to
ions leads to reduction ofprotons:
characterize electrode surfaces.
(2)
A. Electrode Surface Cleanliness
The presence ofthe adsorbed I layer is readily detected by
Surface structures and processes are often sensitive to
AES, the doublet above 500 eV in Fig. 1. Other spectral
traces of adsorbed oxygen, carbon, sulfur, anions, alkali
features up to 400 eVare due to Pt.
metals, and other species [10] stemming from the
Quantification of the I atom packing density is rela-
electrolyte, solvent, laboratory environment, electro-
tively easy because the structure found from LEED [21]
chemical apparatus, vacuum enclosure, or species that
and STM [12-14] data at relatively negative potentials is
segregate from the electrode material during annealing
the primitive Pt(1ll)[,)3 x ,)3]R30° -I structure con-
or other pretreatment. The structure of the surface is
taining only a single iodine atom per unit cell, such that
sensitive to trace constituents. Accordingly, the remark-
the ideal packing density is
able sensitivity and specificity of AES for virtually all
elements is very useful in guiding the preparation and 8r = 1/CJ3)2 = 1/3 (3)
maintenance of clean electrode surfaces [4-8]. "Blank"
procedures, in which the electrode is examined by AES where 0 r is expressed in units of I atoms per surface Pt
after an identical procedure except for omission of the atom. Accordingly, the proportionality constant relating
intended adsorbates, are an important part of each I Auger signal to I packing density can be found from
investigation. Furthermore, the structure ofthe electrode
surface, including locally disordered regions of the (4)
surface, commonly influences electrode behavior. Thus,
Referencing the I Auger signal to a clean-surface Pt
the availability of instrumentation that combines AES
signal, such as at 170 eY, normalizes the results for
with structure probes, such as low-energy electron
instrumental factors such as multiplier gain. The packing
diffraction (LEED) [11] and scanning tunneling
densities corresponding to other observed structures
microscopy (STM) [12-15], is an important development.
can be found from Ir/Ipt by use of Eq. (4); for instance
In addition, many other techniques are compatible with
8r is about 3/7 for the Pt(lI1)(,)7 x ,)7)R19.l °-I adlattice
AES and afford a balance of direct fundamental
and 4/9 for the Pt(lI1)(3 x 3)-1 adlattice. Surface oxide
information concerning electrode surface state:
is absent under these conditions. Rearrangement from
infrared reflection adsorption spectroscopy [16] and
the ,)7 to the ,)3 double-layer structure is accompanied
high-resolution electron energy-loss spectroscopy
by narrow spikes in the positive- and negative-going
(HREELS) [17] for vibrational spectroscopic charac-
linear scan voltammograms.
terization of the molecular constitution/chemical bond-
When adsorption is carried out at relatively positive
ing in the surface region; XPS for surface valency, as
potentials, the AES signal due to adsorbed I decreases
noted above [9]; thermal desorption mass spectrometry
in favor of signals due to adsorbed oxygen, oxides, or
[18] for chemical dynamics and analysis of the surface;
hydroxides (Fig. 1). Coinciding with the appearance of
and an increasing armamentarium of surface
an oxygen signal is the emergence of a prominent signal
characterization strategies based on the use of
due to K near 250 eY. Evidently, K+ and other cations
synchrotron radiation [19].
are retained at the adsorbed 0 2- /OH- ions to a much
greater extent than the nearly neutral iodine adsorbed
B. Monoatomic Layers at Electrode Surfaces
layer.
Immersion of various relatively "noble" metal electrode When the electrode is removed from solution
surfaces, such as Pt, Au, Ag, or Pd into aqueous halide, ("emersed"), a layer of liquid adheres to the surface.
sulfide, or hydroxide electrolytes leads to the formation Under most conditions the thickness ofthe emersed layer
Auger Spectroscopy of Electrode Surfaces 213

(b) AFTER IMMERSION INTO

O.lmM KI (pH-7) at 0.1 Y

W
"U
"-
W
"U W
"- Z
"U
~
z PI
"U PI

100 200 300 400 500 100 200 300 500

KINETIC ENERGY (ev) KINETIC ENERGY (eV)

(C) 0.1 mM KI (pH-IO), -0.6Y

(d) 0.1 mM HI (pH-4l, 0.4Y

0.1 mM Phosphate (pH-4l, I.OY

W W
"U "U
"- "-
w w
z
"U
Z
"U

0
K

100 200 300 400 500

KINETIC ENERGY (eV)

Figure 1 Auger electron spectra of (a) clean Pt(111); (b) Pt(lll)(.J7 x .J7)RI9.1 °-1 adlattice prepared by immersion of Pt(111) into
O.l-mM KI solution (dilute HF/KF pH 7 buffer) at E = 0.1 V vs. Ag/AgCI reference; (c) Pt(111)(.J3 x .J3)R300-1 adlattice prepared
by immersion ofPt( Ill) into O.I-mM KI solution (pH 10 with KOH) at E = -0.6 Vvs. Ag/AgCI; and (d) pte111)(diffuse)-0, an oxidized
Pt surface prepared by anodization of an adlattice similar to (a) in 10-4 M pH 4 phosphate buffer for 6 min at 1.0 V vs. Ag/AgCI.
Experimental conditions: The incident electron beam was 1.0 J1A at 2000 eV kinetic energy, incident at an II ° angle from the surface
plane. (From Ref. 21, with permission.)

is large compared with that of the electrical double layer
[22]. As a result, the surface region analyzed by AES
includes all of the original contents of the double layer.
However, evacuation of the surface before analysis has
thelimitation that volatile constituents such as the solvent
are lost before analysis. Likewise, volatile adsorbates that
are weakly adsorbed or rapidly desorbed may go
undetected by AES. In particular, anionic species may
undergo hydrolysis to form volatile byproducts:
(5)
Loss of cations due to volatilization is negligible in many
cases, such as
K+ + OH- ---+ KOH(aq,nonvolatile) (6)
except when the cation is unstable in vacuum:
(7)
Accordingly, cations such as the alkali metals,
Li+· .. Cs+, and the alkaline earths, Be+· .. Sr+, can be
quantified by use of AES; these are useful as "tags" for
investigation of the emersed layer, the double-layer,
ion-exchange processes, and so forth.
Monoatomic anions such as F-, Cl-, Be, 1-, and S2-
and various simple molecules have been investigated by
use of AES and related techniques at Pt(111) electrodes
[21,23-30], at Pt(100) electrodes [31-34], various ordered
surfaces having steps and terraces [35,36], Ag(111) elec-
trode surfaces [37,38], Au electrodes [39--47], Pd elec-
trodes [48-54], Cu electrodes [55-59], Ru electrodes
214 Hubbard

o~
05 ~
Br 04 Ci)
o
(a) 03 ~
en
0.2 =i
-<
0.1 •
3.0
0.0 ~
4
~ 2.5

>=
~
pH iii 2.0
z
~
~ 1.5
k-f-L.-f-L.-f-I.....jf-t......y"'-''-l'---/- 10 i2
(.)
-04 -0.2 0 0.2 04 06 08
ELECTROOE POTENTIAL, VOLT VS. Ag/AgCl ~ 1.0

~ 0.15 05
.
)-
~

~ 0.10
Co
(b)

-0.4 -0.2 0 0.2 0.2 0.4

ELECTRODE POTENTIAL, VOLT YI. Ag/AgCI
pH

-04 -02 0 02 04 06
ELECTRODE POTENTIAL, VOLT Vs. Ag/Agel

Figure 2 Packing densities of (a) Br (b) Ca, and (c) 0 (OH, H20) from aqueous CaBr2 solutions at Pt(lll) as determined by use of
AES. Experimental conditions: 0.05 mM CaBr2, pH adjusted with HBr or Ca(OHh as indicated; electrode potentials are referred
to Ag/AgCI halfcell in I M NaCI.

[60,61], Celectrodes [62,63], Cr [64,65], Ni[66], Al [67,68],
Nb and Ti [69,70],TiO z [71-73], polycrystallinePt [74,75],
MoSez [76,77], Fe [78-80], Rh[81], Si [82], Li [83], Ru [60],
Ru oxides [84], mercury cadmium tellurides [85-88], In
and Sn oxides [89], PbO z [90], and Sn sulfides [91]. Some
illustrative results for CaBrz are shown in Fig. 2 [23].
The competition between Br- and OH- favors Br chemi-
sorption at electrode potentials near 0.3 V vs. Ag/AgCl;
note the maximum in eBr (Fig. 2a). Retention of cations
is stronger, however, at more positive potentials where
Pt oxides predominate. Indeed, eCa shows a minimum
near 0.2 V (Fig. 2b), where eBr is minimal. The Br
packing density maximum in Fig. 2a evidently corre-
sponds to a hexagonal layer of nearly neutral Br atoms
at a packing density of eBr = 4/9 Br atoms per surface
Ptatom.
Studies of Ag electrode surfaces at relatively positive
electrode potentials in solution containing X = Cl- , Be,
j- or pseudohalides such as X = CN- or SCN- indicate
that the AgX layer that forms can be substantially thicker
than the escape depth of the Auger electron and thus
appears to AES as a semi-infinite AgX phase rather than
Auger Spectroscopy of Electrode Surfaces 215

0.4

(b) Pt(l1l)(2 X 2) -SCN-

0.3

(a) PtOlI)(2J3 X 2J3)R300 -CW

8+ 0.3

®+
0.2

0.2
Cs+

0.1
Ca 2 +

0.1
Ca 2 +

~ 0
0 2 3 4 5 6 7 8 9 10 II
pH
0 I 2 3 4 5 6 7 8 9 10 II 12
pH
Figure 3 Cation packing densities, 0 cs + or 0 Ca 2+, measured by use of AES at a Pt(lll) surface containing an adlattice of
(a) Pt(l1l)(2y'3 x 2y'3)R30° -CN- or (b) Pt(1ll)(2 x 2)-SCN-. Experimental conditions: The adlattices were prepared by immersing
the Pt(lll) surface into I mM KCN (pH 9.2) or I mM KSCN (pH 6) for 2 min at open circuit. The surface was subsequently immersed
into 0.1 mM Cs+ or Ca 2 + solutions the pH of which were adjusted to the desired value by addition of HCI, CsOH, or Ca(OHh. The
open-circuit electrode potential during the Cs+ ICa2+ immersion was measured to be about 0.1 V vs. Ag/AgCl. (From Ref. 95, with
permission.)

as a monoatomic layer [37,38]. However, limiting packing andlor by redox processes analogous to those observed
densities for monoatomic layers are rather close to those for Be, r- and S2-:
expected on the basis ofthe van der Waals radii suggested
by Pauling [92]. CN- + Pt ---+ Pt - CN+e- (9)

C. Ionic Adsorption and Ion Exchange at
Electrode Surfaces
Polyatomic ions can retain a substantial fraction of their
ionic charge when adsorbed at an electrode surface under
some conditions. For example, a Pt(lll) surface exposed
to an aqueous solution of KCN or KSCN acquires an
ordered layer of chemisorbed CN- or SCN-, as
evidenced by the presence of a substantial packing den-
sity ofK+ counterions [93]. However, the packing density
afK is always less than that of CN or SCN, indicating that
some of the chemisorbed material is neutralized by
protonation:
CN- + H+ + Pt ---+ Pt - CNH
The K + counterions are quantitatively replaced when the
surface is rinsed with an excess of salts such as CsCI or
CaCh [93]. Evidence for the competition between H+
and other ions such as K+ to be the counterion of a
chemisorbed CN - or other anion has been obtained from
Auger spectra recorded after rinsing ("ion exchanging")
the chemisorbed layer as a function of pH [94]. For
example, the Cs+ packing density increased from nil
below pH 2 to about 0.2 Cs+ ions per surface Pt atom at
pH 9, compared with a constant CN packing density of
about 0.7 CN per surface Pt atom (Fig. 3). Evidently, the
proton competes strongly with the alkali metal cations
or alkaline earth cations to interact with the charge of
(8) the chemisorbed anion. It is also apparent that the Ca2+
216
ion experiences spatial limitation at its packing density,
e Ca :::: 0.07 compared with e Ca '" 0.29 [94], due to the
relatively large size of the Ca(H20)~+ ion, which is main-
tained even in vacuum.
AES also serves to explore the competition among
various cations for retention at the Pt(111)
[2J3 x 2J3]R300-CN- ionic adlattice [95]. The results
available to date indicate that cation charge is the
principal factor; for example, La3+ is retained
preferentially to Ca2+ by more than 100-fold and Ca2+ is
in turn favored over Cs+. Among cations of like charge,
the less strongly hydrated cations are preferred.
Quaternary ammonium cations are remarkably
uncompetitive; for example, addition of a lO-fold
excess of (CH3)4N+ to a solution of Cs+ had no
detectable affect on the retention of Cs+ ions by the
Pt/CN- adlattice [95]. That is, the order of cation
preference observed with the Pt/CN- adlattice is
La3+» Ba2+ > Ca2+» Mg2+» K+ > Na+ > Cs+ > NHt
> H+ > Li+ » NRt-
D. Molecular Layers at Electrode Surfaces
Studies of monoatomic adsorbates provide an in-
teresting foundation for exploration of molecular
systems. Use of AES and related electron techniques in
combination with voltammetric studies facilitates study
of the electrochemical reactivity of molecules at elec-
trode surfaces and investigations of the structure and
composition of the near-surface region of electrodes
[5-8]. AES is used primarily to confirm the cleanliness
of the surface and to investigate the stoichiometry,
packing density, and purity of the adsorbed layer,
although also providing clues as to the relative positions
of atoms in the surface layer. Vibrational spectra of the
same surfaces are very useful in deducing the nature of
the adsorbed molecular species and their mode of
bonding to the electrode surface [7,17,96-104]. IR and
far-IR information at moderate resolution (50 cm- I )
and high sensitivity (0.01 monolayer) are obtainable by
HREELS [17]. Mid-IR data at ample resolution (4 cm- I
or better) and moderate sensitivity are obtainable by
use of IR reflection spectroscopy [16] or Raman
spectroscopy [105]. LEED [11] and STM [12-15] are
excellent sources of structural clues.
Types of molecular adsorbates studied to date at elec-
trode surfaces by use of AES include quinones and
hydroquinones, compounds 1-26, the structures ofwhich
are shown below [106-108] (see Appendix); mercaptans,
20, 27-46 [109-111]; alkenoic acids [112], pyridine
derivatives, and related compounds, 47-75 [108,113,114];
alkenes [115], 3-hydroxy-pyrid-2-one, 76 [116];
Hubbard
2,4-dihydroxy pyridine, 77; 2-hydroxy-pyrid-4-one, 78;
4-hydroxy-pyrid-2-one, 79; pyrazine and related
molecules, 80-86 [117]; typical five-membered aromatic
heterocycles, 39, 87, 88 [118,119]; alcohols, 89-102
[120-123]; amino acids and related compounds, 3,
103-109 [124]; and typical nonaqueous solvents, 110-117
[125-128]. A primary objective is to establish the extent
of chemisorption as a function of adsorbate con-
centration, pH, electrode potential, and the nature of
the supporting electrolyte. The next objective might well
be to determine the elemental composition of the
adsorbed layer (adsorption of the entire molecule, or a
fragment?).Vibrational spectra are desirable at this point
to confirm intact adsorption or to help identifY the
adsorbed fragments. In the event ofadsorption primarily
as intact molecules, data from AES can be used to infer
the molecular packing density, which is in turn a source
ofclues as to adsorbate molecular orientation. HREELS
and IR spectra can provide valuable evidence as to the
mode of bonding to the surface, particularly as to which
functionalities are most strongly perturbed by interaction
with the substrate surface. For example, mercaptans tend
to adsorb at noble metal electrodes by dissociative attach-
ment thought the SH moiety, as evidenced by the absence
ofan SH vibration in the adsorbed state. Linear scan vol-
tammetry and coulometry afford important evidence
concerning the stoichiometry and dynamics of the
chemical and electrochemical reactions of adsorbed
species characterized as noted above. Faradaic reactions
of the adsorbed species can alter the vibrational spectra
in instructive ways as well.
Various adsorbates containing a sulfYdryl moiety for
chemisorbability to several metal surfaces and a
hydroquinone moiety for use as an electroactive tag have
proved to be a convenient starting point for AES studies
of single-crystal electrodes [110]. For example,
2,5-dihydroxy-4-methylbenzyl mercaptan (DMBM)
[20, Eq. (10)] is thought to adsorb at Pt(lll) through the
SH group with loss of the H atom to form a "pendant"
HQ moiety, which is reversibly electroactive in the
chemisorbed state [110]:
OH
HO - HO
20
(10)
Auger Spectroscopy of Electrode Surfaces 217

OH 0
(a)

HO

s s -
C\J
I I E
(11) ~ 0 o
<{
All of the more than 20 adsorbed sulfur compounds
studied in this way to date at Pt(111) have proved to be
stable in vacuum, permitting accurate identification,
->-::l
I-
quantification, and characterization [109-111]. Stability Cf)
ofthe adsorbed layer in vacuum is illustrated by the cyclic Z
voltammograms shown in Fig. 4 [110] obtained for the W (b)
0
chemisorbed layer after rinsing away the unabsorbed
DMBM. Solid curve A was obtained before evacuation. I-
The dotted curve in Fig. 4a was obtained after evacuation
Z
W
and characterization of the DMBM layer by use of AES, 0::
LEED, and HREELS. The dotted and solid curves in Fig. 0::
=> 0 o
4a are essentially identical, indicating that the adsorbed U
layer survives evacuation and characterization. Cyclic
voltammetry causes gradual deactivation ofthe reversible
electroactivity of the DMBM layer, probably due to
oxidative/reductive scission of the C-S bond [11]
(compare the solid and dotted curves in Fig. 4b).
To obtain the elemental packing densities from the
Auger signal for that element in a molecular layer, it is -0.2 0.0 0.2 0.4 0.6
necessary to allow for the scattering ofthe Auger electron POTENTIAL, VOLT VS. Ag/AgCI
by atoms situated between the emitting atom and the
detector: Figure 4 Cyclic voltammograms ofa chemisorbed molecular
layer of DMBM, 32, at the Pt(lll) electrode surface. (a) Solid
N
curve, after immersion into DMBM solution, followed by rins-
Ix/I~t =Bx 0 x Lfi L ; (12) ing with supporting electrolyte; dotted curve, immersion into
;=1
DMBM solution and by rinsing with supporting electrolyte,
where Ix and I~t are Auger signals for the element X and followed by I h in ultrahigh vacuum before voltammetry. (b)
the Pt (or other electrode material); B x is the Solid curve, first scan, after immersion into DMBM solution
and rinsing with supporting electrolyte; dotted curve, second
proportionality constant appropriate to a specific
cyclic scan. Experimental conditions: Immersion into 0.7 mM
element (X), Auger electron KE, and electrode material;
DMBM solution in 10 mM trifluoroacetic acid supporting elec-
0 x is the packing density of element X expressed in units trolyte (pH 2) at 0.2 V vs. Ag/AgCI reference; scan rate, 5 mY/so
of atoms per electrode surface atom; fi is the scattering (From Ref.llO, with permission.)
factor (O:s fi :s 1) appropriate to the element X in
location i; and L; is the fraction ofatoms ofelement X situ-
ated in characteristic location i [36]. where Ipt and I~t are the Auger signals from the Pt or other
As a useful test of Eq. (12), there is a procedure for electrode surface at a specific KE in the presence and
obtaining the molecular packing density from the attenu- absence, respectively, of the adsorbed layer; J; is the
ation ofan electrode surface Auger signal in the presence number of nonhydrogenic atoms at a certain location in
ofthe adsorbed molecular layer [113]: the adsorbed molecule; M is the total number of such
atoms per molecule; y is the proportionality factor appro-
IptlI~t = n
M

;=1
(I - J;y0) (13) priate to a particular KE; and 0 is the packing density
expressed in molecules ofadsorbate per electrode surface
218
atom. Estimation of e from the attenuation of the elec-
trode surface Auger signal affords an independent check
ofmolecular packing densities deduced from the elemen-
tal Auger signals, Ix, and packing densities, ex.
The orientation ofan adsorbed molecule with respect
to an electrode surface can be inferred from the measured
packing density in cases where the sizes ofthe "molecular
footprints" corresponding to various possible
orientations are substantially different. The observed
footprint is obtained from the packing density. The
expected footprint can be calculated from the envelope
of the molecule viewed in a given orientation based on
the van der Waals radii [92] of the constituent atoms. For
example, the area of the hydroquinone (HQ) molecule is
54 A2 with the plane parallel to the surface, 29 A2
edgewise and perpendicular to the surface, and 22 A2
with the ring endwise and perpendicular to the surface
(Fig. 5). The molecular area measured by AES at satu-
ration coverage is 57 A2 , which is closest to that expected
for the ring-parallel orientation.Vibrational spectroscopy
indicates dissociative adsorption with loss of both
hydroxyl hydrogens [106], and the results of catalytic
oxidation of adsorbed HQ are also consistent with such
an orientation [128].
VAN DER WAALS RADII
COVALENT RADII
Figure 5 Example ofa molecular unit assumed in theoretical
estimation of molecular packing density. (From Ref. 8, with
permission.)
Hubbard
Numerous pyridine derivatives and related compo-
unds, 47-75, have been studied at Pt(111) electrode
surfaces by use of AES [108,113,114,117]. In neutral or
alkaline solutions, the pyridine moiety bonds to the Pt
surface through the ring nitrogen atom, resulting
in a tilted nearly ring perpendicular orientation; in
this orientation, adsorbed (4-pyridyl)-hydroquinone
(4PHQ), 75 is reversibly electroactive [108]:
OH o
o
HO
+ -
+ 2H + 2e
(14)
However, when adsorbed from strongly acidic solution
4PHQ adopts a ring parallel orientation that is not
reversiblyelectroactive,
o
~C);>-rl' ----7 "._~
eleclroactivity
,
o
(15)
Substitution at the orrho-positions also blocks the ring
nitrogen and results in ring-parallel orientation ofpyridyl
adsorbates [114]:
(16)
A surprising exception to the usual behavior of nitrogen
heteroaromatics is 1,3,5-triazine, 83, which does not
chemisorb to Pt(111) [119].
AES is useful for study of the influence of electrode
potential on the extent of chemisorption and the nature
of the chemisorbed molecular species (Fig. 6). For
example, the behavior of nicotinic acid vs. electrode
potential is typical: The packing density is relatively con-
stant at electrode potentials from -0.4 to +0.4 V but
declines outside that range due to faradaic side reactions
[113] (Fig. 6) such as irreversible oxidative desorption pro-
cesses the details ofwhich are not yet known.
Auger Spectroscopy of Electrode Surfaces 219

N- 0.5 The five-membered aromatic heterocycles, 39, 87, 88,

~
<5 0.4 (a)
also display interesting surface chemical reactions [120].
For example, based on AES data, the oxygen content of
0
E
->-c
0.3 0"
/
/
,n,'O---O--'O-----'O-lJ----O'\
.,
..
chemisorbed furan at pte Ill) is double that expected from
the molecular stoichiometry. Evidently, ring opening
occurs, as evidenced also by HREELS:
~ \I
U5 0.2
I
I
Z I

lLJ
0
©""OzH ~
I

(17)
0.1 ~ N I
(9
Z
y
0.0 The adsorbed layer behaves identically to 3-butenoic
U
~ -0.6 -Q4 -0.2 0.0 0.2 0.4 0.6 0.8 acid, including neutralization by KOH. Pyrrole and
POTENTIAL, VOLTS VI. Ag/AgCI thiophene also undergo some degree ofhydrolysis during
chemisorption from aqueous solution at Pt(lll) [100].
A series of alkenoic acids has been studied at Pt(lll)
[112] :
t\.I
E
u (0) FROM IClI pt
"- 0.5 (b)
0 (<» FROM IptlI pt Packing densities measured by use of AES were surpris-
E
c ingly insensitive to chain length m, each resembling that
0.4
for propenoic acid (0.43 nmollcm z). Evidently, the
>-
I- carboxylate moieties are pendant from the surface rather
(J) 0.3 than bonded directly to the surface. Catalytic
Z
w ~C02H electro-oxidation of the adsorbed alkenoic acids is
Cl 0.2 localized to the point of unsaturation and one adjacent
(9 N
carbon atom, as illustrated by lO-undecanoic acid:
Z pH 3.3, -0.2 v, PtOlI)
~ 0.1
U CH z = CH(CHzhCOZH(ads)
~ + 6HzO --+ HOzC(CHzhCOzH (18)
-6 -5 -4 -3 -2 -I o + 2CO z + l6H+ + l6e-
LOG C (M) The alcohols chemisorb at Pt(l11) to a packing density
of about 0.55 nmollcm z [117]:

m = 1, 2, 3, 4, 8
N
0.6
(0) FROM IClI pt
5 (¢) FROM Ip,lIp, (c)
The C=C bond is preserved in the adsorbed state, as
evidenced by HREELS spectra, and only 3-butene-l-ol
"~ 0.5
..s e 8 ~
¢
S 8

I
0
Q4
>-
~
(j'j Figure 6 Packing densities of chemisorbed nicotinic acid
Z
~
Q3
©
N
(NA), 48, and pyridine (PY), 49, measured by use of AES. (a),
Packing density ofNA vs. electrode potential, (b) packing den-
0.2 pH 7, -O.lV, Pt(III) sity of NA vs. concentration of NA, and (c) packing density of
'"52
U
Z
0.1
PY vs. concentration of PY. Experimental conditions: (a)
I mM NA in 10 mM KF adjusted to pH 7 with HF; potentials
~ vs. Ag/AgCI reference. (b) Electrode potential -0.2; electrolyte
as in (a). (c) Electrode potential, -0.1 V; 10 mM KF adjusted
0.0
-6 -5 -4 -3 -2 -I 0 to pH 7; following adsorption from solution, the electrode was
LOG C (M) rinsed with pure water, evacuated, and examined by AES.
(From Ref. 115, with permission.)
220
has a pendant OH group. The longer chain alkenes evi-
dently engage in intermolecular hydrogen bonding
and lor coordination with the Pt surface. As with the
alkenoic acids, electrocatalytic oxidation of the
chemisorbed alkenols is localized at the point of
unsaturation and the adjacent saturated carbon atom.
The C 4 and smaller saturated alcohols, 89-102,
adsorb at Pt(111) to form significant proportions of
chemisorbed Co. Adsorption of the larger saturated
alcohols takes place primarily at the OH moiety with loss
of the H atom to form the adsorbed alkoxyl derivative
[123]. Electrocatalytic oxidation of the adsorbed alcohol
proceeds primarily to one molecule of CO 2 and the
carboxylic acid containing one fewer carbon atom than
the adsorbate alcohol.
Straight-chain alkenes have been studied at Pt(lll)
electrodes by use of AES as described in Ref. 116:
y = 0, 1, 2, 3, 4, 6, 8
The potential dependence of ethene adsorption from
aqueous solution at Pt(lll) due to competing H
adsorption, hydrogenation, chemisorption, and surface
oxidation processes is an interesting topic in and of itself
[129,130]. The C=C moiety is largely preserved in the
aqueous/chemisorbed state. The aliphatic chain is
pendant and occupies a surface area similar to that of
chemisorbed propene. Electrocatalytic oxidation of the
adsorbed terminal alkenes is localized to the C=C
moiety and two adjacent-saturated carbon atoms:
CH 2 = CHC sH 17 (ads.) + 8H 2 0 -+ C 6 H l3 C0 2 H
+ 3C02 + 22H+ + 22e-
Packing densities measured by use of AES for
L-dopa, 103, indicate surface attachment through the
aromatic ring oriented parallel to the electrode surface
[124]. However, cysteine, 109, adsorbs primarily through
its sulfur atom, whereas alanine, 108, and phenyl
alanine, 105, attach primarily through the amine moiety.
Dopamine, 106, adopts a mixture of adsorbed states,
including a fraction attached through the amine moiety,
giving rise to a reversibly electroactive pendent
cathechol.
Several nonaqueous solvents have been studied by use
of AES at Pt(lll) electrode surfaces [125-127]. Many of
the most useful solvents are strongly chemisorbed at
Pt(111) surfaces, including benzene, 110 [131]; acetone
[132]; pyridine, 48 [129]; dimethylsulfoxide, 112 [129];
sulfolane, 111 [130]; various alcohols, 89-102 [130]; and
dimethylacetamide, 117 [130]. Solvents such as glacial
Hubbard
acetic acid, ethyl acetate, and tetrahydrofuran adsorbed
less strongly [126,131] and may be advantageous in some
situations for that reason.
E. Electrodeposition of Metallic Monolayers
Composition and structure of electrodeposited layers
have been sought in several thousand published studies
during the past hundred years. Direct information has
been accessible recently by use oftechniques such asAES,
LEED, STM, XPS, and grazing angle X-ray diffraction
(XRD), combined with cyclic voltammetry and
chroncoulometry. In particular, AES permits identifi-
cation and quantification ofthe species present at various
stages during electrodeposition. LEED reveals the sym-
metry of the outermost few atomic layers, STM probes
the local structure of the outermost layer [23], and XRD
provides symmetry and structural clues for the surface
and near-surface region.
Electrodeposition of Ag onto iodine-pretreated Pt
single-crystal electrodes illustrates some of the basic
principles [133] (Fig. 7). Electrodeposition of Ag into the
Pt(1ll)(.J7 x J7)R19.l °_1 adlattice occurs in four stages
(peaks 1-4 in Fig. 7): three underpotential processes
(potentials less negative than that of the corresponding
Ag+ lAg half-cell), followed by deposition of "bulk" Ag.
As indicated by the miniature LEED patterns in Fig. 7,
each voltammetric peak gives rise to a new structure.
AES reveals that the iodine layer remains attached to the
outermost layer regardless of the number of Ag layers
deposited. Angle-resolved AES confirms that the iodine
monoatomic layer is the outermost layer of the surface
[133]. The more positive two voltammetric peaks corre-
(19) spond to deposition ofa first full monolayer of Ag atoms,
whereas the third peak completes a second full monolayer
of Ag. AES does not respond linearly to the amount of
Ag deposited beyond the first monoatomic layer due to
the limited escape depth of the 355-eV Au,ger electron
emitted by Ag; that is, AES samples primarily the
outermost atomic layers of Ag regardless ofthe thickness
of the Ag film. The AES and LEED results for Ag depo-
sition onto Pt [31,133-140] have been confirmed and
advanced by a series ofelegant STM studies [15].
Comparison of the LEED/AES/CV (cyclic volt-
ammetry) results for Ag electrodeposition at Pt(ll1) and
Pt(lOO) electrodes illustrate the profound influence of
electrode surface structure on electrochemical reactivity
[134,136].Yoltammetric behavior ofthe two electrode sur-
face planes is very different: The number, location, width,
and area of the voltammetric peaks differ for the two
surfaces. The electrodeposited layers have different
symmetries on the two surfaces (LEED) and different
Auger Spectroscopy of Electrode Surfaces 221

c
.S!
Io
"
I'

"
• I

:~~.~
4'(bulk)
"f-
IOpAl

t- " .. . ::
Z
..
a:: ~-~--~-,.::h~~~~~~~r~
IJJ '

a:: I

::J
u

0.2 03
POTENTIAL, VOLTS
Figure 7 Cyclic voltammograms and LEED patterns after electrodeposition of Ag into the Pt(1ll)(,J7 x ,J7)RI9.l °_1 adlattice.
Experimental conditions: 0.1 mM Ag+ in 1 M HCI04, scan rate, 2 mVis. (From Ref. 138, with permission.)

stoichiometries (AES). These results taken together with
all the others available to date hint at a generally strong
dependence of single-crystal electrode surface structure
and dynamics on crystallographic orientation.
After Refs. 31 and 133-140 appeared, various workers
inquired as to whether studies had been made of Ag
electrodeposition onto Pt in the absence of adsorbed
iodine. In fact, preliminary studies in the absence of
iodine (PtlAg) preceded the PtlIIAg studies, and the
LEED/AES/CV procedures are effective in that case.
However, the electrochemical behavior under those con-
ditions is complex: Ag+ is a rather strong oxidizing agent,
whereas the bare Pt surface is susceptible to oxidation.
The result is that the Pt surface reacts spontaneously with
aqueous Ag+ solutions to form a disordered surface layer
ofPt "oxides"and Ag compounds:
Ag+ + 2Pt + H 20 -+ PtOH + PtAg + H+ (20)
Electrodeposition of Cu onto PtiI ad lattices also is
being studied by use of AES [136]. A monolayer of Cu
with an atop iodine layer is formed in the early stages, as
for electrodeposition of Ag at PtiI. However, subsequent
deposition of Cu forms a series of clusters of Cu, as is
usual in electrodeposition of Cu [136,141,142]. Because
the Cu deposit is not uniformly distributed over the Pt
surface, the Pt electrode Auger signal remains strong
after substantial deposition ofCu, whereas the CuAuger
signal remains weak; that is, the Auger signal for Cu is
controlled by structural/matrix effects. If deposition is
prolonged, the Cu granules become visible under an
optical microscope. Similar results have been reported
for electrodeposition of Cu onto bare Pt [141,142].
Electrodeposition of Pb onto Pt(lll) from aqueous
halide solutions has been studied by use of LEED,
AES, and CV [40,143,144]. Although a fraction of a
monoatomic layer of Pb is stable, higher coverages are
222
unstable at open circuit due to reactions such as
(21)
Quantitation by AES of these unstable deposits is
difficult. The deposition behavior is relatively complex:
for example, 10 or more voltammetric peaks are
observed, corresponding to electrodeposition of about
one monolayer of Pb at Pt(ll1) from an aqueous PbCh
or PbBr2 solutions.
Studies have been reported of the electrodeposition of
Bi, Pb, Tl, and Cu onto Ag(ll1) from aqueous solutions
by use of AES, LEED, and CV [38]. In situations where
the underpotentials (and deposit stabilities) are relatively
small, it is not as straightforward to quantitate the
electrodeposit by use of AES and related methods. AES
studies have also been reported of the underpotential
deposition of Cu on Au [40,145], Ag on Au [146], and
GaAs on Au [47], and of GaAs single-crystal surfaces
[147].
F. Alloy Electrode Surfaces
The Fe-Cr- Ni alloy single crystals reported by Silcock
[148] signaled opportunities for studies of "stainless steel
alloy" single-crystal surfaces in electrochemical sol-
utions [149-155]. Other AES studies have focused on
polycrystalline Fe alloys [156-159], Ni alloys [160-162],
Cr alloys [163], Pt alloys [164-168], Pd [169-171], and Bi
[172].
For example, an Fe-Cr-Ni solid solution consisting
of 70 atm% Fe, 18 atm% Cr, and 12 atm% Ni forms a
face-centered cubic alloy single crystal of composition
similar to that of 300-series stainless steels [149].
Oriented single crystal having the FeCrNi(ll1) and
FeCrNi(IOO) orientations have been prepared [149,153].
Preparation of the surface by Ar+ ion bombardment
(500 eV) and annealing (1000 K) yielded a clean surface
Hubbard
containing slightly more Cr than would be expected from
the bulk composition. C and N impurities were present
at less than 2 atm%.
Exposure of an FeCrNi single-crystal surface to O2
at room temperature rapidly oxidized the surface to a
disordered layer of Fe, Cr, and Ni oxides. Subsequent
heating converted the mixed oxide layer to an ordered
layer of Cr(lll) oxide [149-153]. Similarly, exposure of
the FeCrNi surface to H20 vapor resulted in a mixed
oxide layer that was converted to a Cr(lll) oxide upon
heating to about 1100 K.
Immersion and FeCrNi alloy surfaces into pure liquid
water resulted in extensive oxidation and removal of Ni
and Cr to form a surface film consisting primarily of
amorphous hydrated oxides of Fe. Subsequent heating
to 1100 K converted to the surface layer to an ordered film
of Cr oxide [149].
Immersion and electrolysis of the FeCrNi alloy
surfaces in borate or sulfate electrolytes led to significant
incorporation of anions into the oxide film [152,153].
However, there was no significant participation of per-
chlorate anion in film formation. The Cr(lll) oxides are
much more stable in acidic electrolytes than are the
Cr(lI) oxides, whereas selective dissolution of Fe and
Ni in acidic electrolytes is common. Positive-going
voltammetric scans of the FeCrNi surfaces in aqueous
1 M HCl did not display the usual passivation processes;
current-time noise and hysteresis in the cyclic
voltammogram are observed, which has been associated
with random localized pitting of the passive film [152].
That is, the surface compositions found by use of AES
correlate with the practical behavior of the 300-series
stainless steel surfaces, particularly the dissolution,
pitting, and passivation characteristics.
APPENDIX
(See pages 223-225.)
Auger Spectroscopy of Electrode Surfaces 223

¢::
OH OH OH OH

~ ~qa,. ~~
OH C(CH.3 ~ OH
2 3 4 6 7 8

lH
FxtFH~r~ V'oy~
*
~I <><:.H3c*OH CH
3
¢OH~ ~~ I

H
3
H C
3
CH3 F -OH F OH

OH OH H H OH H
9 10 11 12 13 14 15

OH OH ~ OH OH HS'CH
2
~~hOO
0
~~H
OH
OHHO H I

16 17 18
OH
19
~320
6»~ 21 22

OH 0 H~S 0 o

¢o0~¢o 0
SH
I

OH S03 H 0 o
Q.
23 24 25 26 27

'A' ,~, lv,

,y, ,~, ,y, L~
~ 0
6 ?H /H SH

N<2 S03N.

F F
28 29 30 31 32 33 34

C( 66
SH SH

o
S
((SyCOjl

Vi
35 36 37 38 39 40 41
224 Hubbard

42 43 44 45 46

C~H

~¥ 0 gc~ ¢ 6) HO~~co,H ~co,H

C~ Cot"l
47 48 49 00 51 52 53

C
nY ¥ nyC01i H¥YnyC02H ny H:3 C
H:FYny Ct-\:3
Vcot<Y . g C02 H
g g
~ $ ~ ~ ~

<0>-0 (0 OJ <0)
59 00 61
(0) 0)-<0) (Q,>-<O)
62 63

o H:f C~

(0) (0) (0) (0) 0 N 0 (0) (0)

64 65 66 67

HO:zS COj'i HC>.zq C¥

b-d HO~c¥ HOi' 0 0 c¥

68 ee 70

OH

HO
71 72 73 74
Auger Spectroscopy of Electrode Surfaces 225

OH 0 OH

HO
OH

0:0
OH

Q QC10
N H
~ ~
(N]
N
~J
eN
N

(3H2FO) (24DHP) (2H4PO) (4H2FC)

76 77 78 79 80 81
75

COOH
H

0
N COOH
N~N
0
N 0 N

~ .......N
N ~N) (N:lCOOH
( N J C COOH
;:,.... N""N
0 0
(FRN) (PRR)

82 83 84 85 86 87 88

OH OH
I I
C~OH C~CH.20H CH3CH.2C~ OH C~CH-C~ CH 3 CH 2 CH 2 CH 2 OH CH 3 CHC¥H3
89 90 91 92
93 94

OH

6
H3 C H
f~
CH:3 CHr~-OH CH 3 CH2e-.~- OH C~-OH CH 3 (CH.2 SOH C~(CH2)60H

H H
3
C CH3
95 96 97 98 99 100

OH OH

OH

HOCt-tpH:zCH:fHpH

101
HOCHz;H:zCH:FH2CH:fH2 OH

102

NH2
N~
COji ~~H NH 2
OH
103 104 105
OH OH

~~ C02 H~C02 0 0
Q", ?O

NH 2 °002< '1: H2 H2
benzene sulfolane

106 107 108 109 110 111

0
0 II

/5, • (J
0
H~r/H3 0/
C
.......0
0
~ /CH 3
H C
3
CH 3 CH C=N
3 ....... CH
3 LJ H:f N
.......CH
3
dimethyl acetonitrile p-dio>Cllne dimethyl propylene N,N-dimethyl
sulfOlcide formamide carbonate acetamide
112 113 114 115 116 117
226
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14
Flame-Annealing and Cleaning Technique
Jean Clavilier
CNRS, Meudon, France
ABSTRACT
This chapter is divided into six main sections. In the first
section there is a comparison of the classic concept of
clean surface defined for the metal- gas interface and its
equivalent concept for a metal-electrolyte interface
requiring the necessity to introduce both concepts of
chemically and structurally well-defined surfaces. The
second section is a brief overview of the various
experimental protocols used in the past that failed in the
search for yielding both chemically and structurally
well-defined platinum electrode surfaces. The third sec-
tion is devoted to the flame treatment of platinum
samples. It contains a description of the overall
experimental procedure required for the preparation of
platinum electrodes with chemically and structurally
well-defined surfaces, including the technique of
elaboration ofsingle crystals. This section reports several
aspects of the flame treatment associated with cooling
of the sample in air, such as electrochemical analysis of
the surface species generated or induction of surface
ordering. In the latter case, a clear distinction is made in
the possible use ofthe flame treatment for a simple clean-
ing ofthe surface or for the ordering the surface by raising
the temperature of the sample. In the fourth section
the role of the nature of the composition of the atmos-
phere in contact with the sample is analyzed for
hydrogen-containing atmosphere. This is illustrated in
the cases of Pt(lOO) and platinum surfaces containing
(l00) surface domains such as stepped surfaces with (100)
step sites and Pt(llO). The fifth section is a concluding
remark mentioning some extension of the flame treat-
ment to gold and rhodium and suggesting some open
lines of research, among them the problem of surface
reconstruction or the study of platinum electrodes
with a higher degree ofsurface complexity.
231
I. INTRODUCTION
The introduction of the flame technique for preparing
platinum electrode surfaces has had a profound influence
on surface electrochemistry. For the first time, a
straightforward and highly reproducible method of
investigating structure-sensitive electrochemical pro-
cesses at this electrode material, such as ionic adsorption,
ultrathin-layer formation, and electrocatalysis, was
made available to laboratories unable to gain access to
surface science tools of surface preparation and
characterization.
The study of the effect of surface structure on the
electrosorption behavior of the platinum electrode
started in 1965 with the pioneering work of F. G. Will
[1]. He examined the relationship between hydrogen
adsorption and potential using the three basal
orientations of platinum with the aim of explaining
the origin of the multiple hydrogen adsorption states
observed at polycrystalline platinum electrodes in
terms of intrinsic surface crystalline heterogeneity.
The main difficulty encountered in investigations of
this problem, however, was producing a clean surface
and maintaining its cleanliness during the time of the
experiment.
"Clean" surface in the electrochemical context means
something quite different from its meaning in ultrahigh
vacuum (UHV). The UHV concept of a clean surface
normally corresponds to the topmost layer ofthe material
under investigation (containing exclusively atoms of that
material) in which interaction with the gas phase is pre-
cluded due to the low pressure existing in the vacuum
adjacent to the surface. In an electrochemical system,
232
the situation is radically altered because the topmost layer
is now in contact with the solution and interacts with all
components of the liquid phase. Thus, a definition of a
clean surface in contact with an electrolyte solution is
required. It could be the following: "the atoms of the
topmost layer of the electrode material should interact
exclusively with the nominal components ofthe solution."
In this case, one should refer to a "free" surface in which
solution species are clearly adsorbed at the electrode but
the formation of chemisorption bonds between electro-
lyte species and the surface has not yet taken place. Hence,
there is a"potentiality" for the surface to form chemisorp-
tion bonds subsequently by changing the physico-
chemical conditions.
In most cases, this implies a high degree of purity for
the liquid phase, both of solvent and solute. Beyond this
requirement, the definition above contains another one
related to the cleanliness of the sample surface of the
electrode material before the formation of the interface.
In the case of a material such as platinum (and more
generally platinum metals that possess a high surface
reactivity), clean/free metal surfaces are difficult to
prepare and maintain even in DHV It is therefore more
appropriate to consider in such cases what one may call
a chemically well-defined surface. This could be a free
metal surface or a metal substrate covered with a
well-defined surface compound that protects the
substrate from surface contamination. The only require-
ment is that the surface compound may be readily
removed, leaving behind the metal surface in contact with
the solution.
Despite the fact that platinum has been used and
studied by electrochemists since the very beginning of
electrochemistry, the question of surface structure and
composition characterization was for a long time an
unresolved key problem. It led to a delay in understand-
ing the surface electrochemistry of platinum metals, par-
ticularly in the case of platinum, a material of the
utmost interest for electrochemists, because its catalytic
properties appear in many cases to be structure
sensitive. This structural aspect, although fully appreci-
ated by surface scientists in the early 1960s, was perhaps
less well developed in the electrochemical community
due to the absence of appropriate surface sensitive
probes.
The aim of this chapter is to show how this problem
was eventually solved and to assess the consequences
for electrochemistry of the introduction of the flame-
annealing and cleaning procedure now in use in many
laboratories.
Clavilier
II. REVIEW OF PROTOCOLS USED IN THE
PREPARATION OF PLATINUM
SINGLE-CRYSTAL ELECTRODE SURFACES
Three periods may be distinguished that detail the way
in which the problem of creating a chemically and struc-
turally well-defined Pt(hkl)-solution interface was
achieved.
The first period started with the work of F. G.Will. The
technique used by this author was one commonly applied
to polycrystalline platinum electrodes and colloquially
referred to as electrochemical activation [2] or electro-
chemical cleaning [3,4], It involves the application of
repetitive potential cycles to the electrode ranging from
the formation of a complete oxygen or oxide adlayer to
the onset of hydrogen evolution. All types of platinum
samples with a polycrystalline texture subjected to this
treatment attained similar adsorption properties when
they were examined under equivalent experimental con-
ditions. In other words, they all gave rise to the same
cyclic voltammetric profile when in contact with the same
electrolyte. In Ref. 5, these voltammograms and their
modifications were analyzed in terms of surface
cleanliness and surface impurities. The conclusion of
the work of F. G.Will may be summarized in the following
way:
Whereas the three basal planes ofplatinum were found
to adsorb hydrogen in the same adsorption states, as
found with polycrystalline platinum surfaces, the relative
magnitudes of these states were found to depend on the
surface orientation. Thus, the adsorption state at more
positive potential, predominantly observed with the (100)
electrode was ascribed to hydrogen adsorption at this face
whereas the peak at less positive potential, found pre-
dominantly with the (110) electrode was ascribed to this
particular orientation. A third small adsorption state in
between the two previous ones was ascribed to the (111)
face.
An interesting remark reported in Will's work was
associated with the cumulative effect induced by
repeated cycles of oxidation and reduction. It was found
that for all three orientations, adsorption states
nominally ascribed to the other two orientations would
develop. More specifically, for the (110) and (lll) orien-
tations, minimal differences in the voltammetry after
260 potential cycles were observed. The presence of the
two mains states and the small third one led the author
to conclude that under these conditions, the (111) face
exposes a large fraction of (110) and (100) faces and only
a small contribution of (111). This conclusion is in agree-
ment with the increase of surface roughness reported
by the author as a consequence of the high number of
Flame-Annealing and Cleaning Technique
oxidation and reduction cycles applied to the electrode.
It is interesting to cite the last sentence of Will's article
that acknowledges the need for a new approach to sur-
face electrochemical investigations: "Studies with better
defined crystal planes and under extreme clean con-
ditions are needed...".
It is important to mention here two other articles [6,7]
on the same problem working under the same
experimental conditions as in the previous work, i.e.,
the application to the main single crystal faces of a large
number of electrochemical activation cycles. Because
of the absence of a difference in the voltammograms
recorded with the three cycled faces, both articles con-
cluded that intrinsic surface crystalline heterogeneity
could not explain the multiple adsorption states
observed on polycrystalline platinum. We know now
that this result (in hindsight) was not correct and was
due to the experimental procedure used for surface
cleaning.
The second period of development to reach "extreme
clean conditions" explored by electochemists interested
in surface problems was that commonly used by the
then recent successful approach of surface scientists.
The latter were able to study surface processes on clean
surfaces with new experimental tools based on various
electronic spectroscopies under UHV conditions. The
surface structures and the surface composition were
then under the control of the experimentalist. The idea
was if it was possible to start with a clean surface, it
may not be necessary to use the electrochemical clean-
ing procedure (which was known from Will's work to
cause surface roughening) before checking by vol-
tammetry the hydrogen adsorption capability of a plati-
num electrode surface. Thus, the main problem was to
transfer the clean and well-defined sample from the
UHV chamber to the electrochemical cell while main-
taining the surface conditions. Various groups of elec-
trochemists in the United States started with this task
in the mid-1970s. The coupling of a three-electrode
thin-layer cell (t.l.c.) placed in the main chamber of a
UHV system was proposed and described for the first
time by A. T. Hubbard [8,9]. A complete set of electro-
chemical data appeared later together with low-energy
electron diffraction (LEED) and Auger electron
spectroscopy surface analysis [10,11]. The use of a small
volume of solution in a t.Lc., whose wall area of the cell
is imposed by the crystal face decreases considerably
the risk of surface contamination by solution impurities.
Ershler and Frumkin [12] demonstrated in another con-
text with the purpose of examining the adsorption
properties of bright platinum wires the interest of using
a special cell design using only microliters of electrolyte
233
solution to limit interferences between the main surface
process and electroactive impurities in trace amount.
A more compact t.l.c. was proposed later by the group
of E. Yeager where the reference electrode and the
counterelectrode were made of a single
palladium-hydrogen electrode. In this new con-
figuration, the t.l.c. was placed in an annex chamber
[13,14]. A different system of sample transfer from
UHV to a conventional three-electrode cell via a glove
box was proposed by P. N. Ross [15] as an initial device.
Later it was replaced by an improved version where the
electrochemical cell was in an auxiliary chamber that
could be pumped and back filled with argon [16]. Much
later, the last improvement consisted in adopting a
UHV- t.l.c. configuration where one wall of the cell
was the crystal plane and the other a Pt-ring and Pd-disk
arrangement working as counter and reference
electrodes, respectively [17].
As we remarked previously, the results of Will gen-
erated a renewed interest in platinum surface
electrochemistry. They were at the origin of this new and
general approach that focused the efforts of researchers
on platinum single-crystal investigations in general and
act as a challenge to electrochemists. However, it was
known that clean surface preparation of platinum in
UHV requires a complex and prolonged procedure as
described [11,17]. Hence, platinum was possibly a bold
choice to start with this new technique in the light of sub-
sequent findings regarding the importance of the
experimental difficulties in the interpretation of the
voltammetric results due to the easy contamination of
this surface-reactive material. The existence ofthese diffi-
culties appeared clearly when a sufficient number of
results became available. Despite applying the highest
standards of UHV technique to the Pt(hkl) samples, the
voltammetric results reported for hydrogen coverage on
Pt(ll1) in sulphuric or perchloric acid solutions were con-
flicting and lying in a too broad range of experimental
values. The results obtained with electrodes cycled only
in the hydrogen underpotential deposition (UPD) region
gave very low hydrogen coverage values [13,14], whereas
electrodes subjected to a few number ofcycles in the oxy-
gen adsorption region were found able to reach a
hydrogen coverage close to unity [16] or slightly higher
[11]. Moreover, the voltammetric profiles were found to
show either, respectively, a featureless profile or a fine
structure resembling that reported by Will for this
orientation.
In the previous works, as in the following, the coverage
is defined, respectively, to the atomic surface density of
the crystalline plane of the substrate. The usual way to
define hydrogen coverage on platinum electrodes is
234
obtained by integrating over the time the current of the
hydrogen adsorption states given by voltammetry (QH)
assuming the exchange of one electron per surface site
occupied by one hydrogen atom and from the charge
(Qsat) required for the saturation of the surface in an
amount ofone hydrogen atom per surface platinum atom.
The hydrogen coverage is then defined as the ratio
QH/Qsat. The atomic densities for Pt(l1l) and un-
reconstructed Pt(lOO) and Pt(1I0) are, respectively,
1.516 x 10 15 ,1.313 X 10 15 , and 0.928 x 10 15 atom· cm- 2 ,
which gives Qsat values of 243,210, and 149 J1C . cm- 2,
respectively. These values correspond to a closest
interatomic platinum distance of 0.276 nm.
Referring to Pt(l1l) electrodes directly cycled in the
hydrogen adsorption/desorption range, hydrogen cover-
age reported by the various authors were widely at vari-
ance and equivalent charge as low as 7 J1C . cm- 2 [13]
was measured, whereas the highest charge reported was
96 J1C . cm- 2 corresponding to a coverage of 0.4 [18]. In
the latter, the charges for the two other orientations were
found to fit with those corresponding to the atomic sur-
face densities. In that work reflected high-energy electron
diffraction (RHEED) surface characterizations were
carried out before and after electrochemical potential
cycles. Contrary to LEED, RHEED does not require
UHV conditions but only ordinary high-vacuum con-
ditions. This was an advantage for postelectrochemical
structural analysis that could be performed without use
of an additional surface-cleaning procedure susceptible
to modifY the surface structure. The disadvantage is the
absence of chemical surface characterization. With this
technique the authors have established that after several
cycles ofoxide formation and reduction, the Pt(lll) elec-
trode had acquired both diffraction and voltammetric
characteristics of the (110) surface symmetry, suggesting
a faceting of the initially well-ordered surface. This was
in agreement with the conclusion of Wi I!.
All the Pt( Ill) surfaces prepared and characterized for
these studies by using surface instrumentation could be
considered as structurally well-defined under UHV
However, on the one hand, it was not clear which one of
the surfaces in the cited works could be considered as a
chemically well-defined Pt(lll) surface after their
transfer to the electrochemical cell and the subsequent
recording of the cyclic voltammogram in the hydrogen
adsorption potential range exclusively. This remark was
also valid, whereas not so evident, for the two other basal
orientations that were subjected in each work to
experimental procedures similar to those adopted for
Pt(l1l). On the other hand, it could be stated from the
experimental evidence already available that the electro-
chemical results for Pt(lIl) electrode surfaces reported
Clavilier
after using the electrochemical cleaning procedure of
cycling in the potential range of oxide formation were
likely related to structurally ill-defined (11l) surfaces.
These uncertainties required a novel manner to
approach the whole question. This started the third
period that was proposed in 1980 [19] by using a thermal
route to achieve both structurally and chemically
well-defined platinum electrode surfaces. This route was
open by the flame treatment of platinum single-crystal
oriented samples coupled to quenching with ultrapure
water forming at the crystal face a protecting drop against
atmospheric pollutants. At the beginning, this tech-
nique was strongly criticized for suspected drawbacks
that would have been at the origin of the unusual
voltammograms yielded by the Pt(lll) oriented electrode
subjected to this treatment [20]. This attitude was benefic-
ial to establish firmly the principles on which is grounded
the flame treatment, whose details are reported in Sec.
III. A. 2.
III. FLAME ANNEALING AND CLEANING
TREATMENT
For historic purpose we recall here the few published
works dealing with the effect of a flame treatment on the
electrosorption behavior of polycrystalline platinum
electrodes where it was briefly reported first. Their
authors considered this treatment among other chemical
treatments applied to polycrystalline platinum samples
as a method of activation. Breiter [21] found the same
three cyclic voltammogram profiles for a platinum wire
electrode heated in a rich oxygen- natural gas flame or
chemically activated in hot chromic acid and after an
electrochemical activation. The same result was obtained
with a hydrogen-oxygen flame. Later, a similar exper-
iment was repeated by Warner et a!. [22] with platinum
beads heated in a hydrogen -oxygen flame with identical
conclusion. In 1973, Biegler [23] reported for a platinum
foil electrode heated in a coal gas-oxygen flame a
voltammetric profile significantly different from that
obtained after a classic electrochemical activation
despite applying six potential cycles with oxide
formation and reduction. The result was interpreted in
terms of surface structure modification. In fact there is
no work at that time studying in detail the exact effect of
heating a platinum sample in a flame on its electro-
sorption behavior.
These preliminary results indicate that the treatment
in a carefully controlled flame leads to a reasonably
chemically well-defined platinum surface without any
significant indication of surface contamination.
However, these studies were far away from a specific sur-
Flame-Annealing and Cleaning Technique
face approach from the point of view of surface science
because it could be developed with single-crystal
electrodes.
A. Bead Platinum Single Crystal
1. Crystal Orientation, Cutting, and Polishing
The most suitable configuration for single-crystal metal
for electrochemical studies is certainly the metal bead
formed at the extremity of a wire of the metal by melting
after checking the crystallisation quality of the bead.
Because of the presence of crystalline facets at the bead
surface, it is easy to check the formation of a single
crystal by measuring characteristic angles between these
facets.
It is worth noting that such quasispherical single
crystals may be used as an ideal model for a poly-
crystalline surface because the surface distribution of
crystalline sites obeys the same law whatever the bead
diameter. This is valid as long as the bead generation
occurs under the same conditions. We report later an
example of electrochemical adsorption at these
surfaces.
The crystalline nature ofthe facets is determined from
angle measurements. Thus, the positions of the axes of
the crystal are known. For a determined position of the
crystal, it is then possible to grind it until reaching a
diametral plane in the desired direction. Once the
grinding is achieved, the metal surface obtained is
polished to a mirrorlike finishing.
All these operations may be carried out on the same
experimental device [24]. Briefly described, it consists
of an optical bench with at one extremity a goniometric
head with four calibrated rotations centered at the center
of the bead. At the other extremity, there is a laser light
source. The grinding and polishing machine is attached
to the bench. It has a wheel rotating in a satellite move-
ment in a plane perpendicular to the optical axis of the
system defined by the laser beam. Thus, the laser beam
is used both for the orientation of the crystal by using
the facets ofthe bead as mirrors to determine the position
of the crystal corresponding to the direction of plane
one wants to prepare and to control the evolution of the
quality of polishing. This is achieved thanks to the possi-
bility to escape the wheel apart from the laser beam
whose light is then diffracted and reflected on the surface
under preparation and the emergent light imaged on a
screen.
The final orientation of a surface prepared accord-
ing to this procedure generally does not deviate more
than 3 min of arc off the nominal orientation. This
accuracy in the orientation is much better than usually
235
achieved with classic x-ray diffraction. This is of great
interest when one will perform a systematic study with
a series of stepped surfaces where step density as the
main parameter is strongly dependent on small angle
deviations.
The quasispherical shape of a bead has shown that
diameters in different directions, measured with a profile
projector, equipped with a coordinate table allowing
calibrated translation and rotations have all their
dimensions within I %. This means that the geometric
area ofthe crystalline planes are known with an accuracy
of 2%. Now if we consider surfaces with basal orien-
tations, particularly Pt(l1l), the roughness factor is a
obviously one; otherwise, the surface should be faceted.
This remark is valid for all crystalline faces; however,
faceting may not be so easy to put in evidence as in the
case ofPt(111).
Beyond orientation accuracy, the bead-oriented elec-
trode allows several experimental simplifications. It may
be directly connected to the external electric polarization
device through the metal wire working as a lead; there is
no need for lead welding. The small size of the
hemispherical crystal makes easy the protection of the
plane surface by a drop of water for handling the sample
in air without contamination. Its shape with a perfectly
smooth lateral surface avoids the creeping of the
electrolyte. This property may be then taken advantage
ofto establish the hanging meniscus contact ofthe crystal
face with the solution. This configuration eliminates the
use ofmasking materials to leave free the plane ofinterest
in contact with the solution. Generally, these materials
are a considerable source of surface pollutants, and their
elimination from the experimental protocol was highly
beneficial.
2. Role of the FlameTreatment in Surface
Preparation
After polishing, it is well known that disordering exists in
a region whose depth beneath the surface is several tens
of nanometers thick as a minimum. Moreover, the sur-
face is contaminated by the products used for polishing.
It has been shown that thermal treatments in a flame
under various conditions may be used for examining both
the surface decontamination and the recording of the
perturbed thick layer [25] by decoupling each one of the
two processes on the temperature scale, as will be seen
in Sec. I1I.D.
The principles on which is grounded the flame treat-
ment of platinum samples are the following. First, it has
been seen in the early publications [21-23] that the nature
of gas, either natural gas or hydrogen, has no special
effect; the only condition is the formation of a blue flame
236
when the fuel is a carbon compound. When the tempera-
ture of the platinum is raised there is both an oxidation
and a thermodesorption of all types of impurities and
an oxidation of the metal. If the temperature is main-
tained sufficiently high, the atoms of the metal become
mobile and the disordered zone ofthe crystal may be pro-
gressivelyordered.
During the cooling of the sample in air, because of
the catalytic properties of the metal, the ambient
impurities that contact the platinum surface are
oxidized. The experience proves that the process works
efficiently down to temperature ranging between 200
and 100°C. Below this temperature it becomes critical
for the surface to avoid readsorption of some impurities.
A very simple way for protecting the surface against this
natural tendency is then to put the crystal when hot in
a stream of ultrapure water pouring from a flask. When
the flow is stopped, a drop of water stays attached to
the flat part of the hemispherical sample, allowing its
transfer in air to the electrochemical cell without risk
of contamination.
An additional question is the determination ofthe sur-
face composition at the end of the thermal treatment
applied to each platinum sample and its exact effect on
the final surface structure.
60
20
Figure 1 Cyclic Yoltammogram ofa Pt(lll) oriented electrode recently polished, flame annealed, and cooled in air; solution 0.5 M
H 2 S0 4, sweep rate 50 mV . S-l.
Clavilier
B. Flame 'D'eatment of the Pt(111) and Pt(110)
Electrodes
The effect of a high-temperature flame treatment on a
Pt(lll) oriented electrode in contact with a 0.5 M
sulphuric acid solution [19] or a 0.1 M perchloric acid sol-
ution [26] was reported in 1980. The results were highly
surprising because of the presence on the corresponding
voltammograms ofcomplex adsorption states, with a fine
structure, in an unusual potential range where they were
never observed before with any platinum electrode and
particularly with single crystals previously investigated.
These voltammograms are reported in Figs. 1 and 2,
respectively.
The main characteristics of these unusual adsorption
states are the following:
1. They are extremely more sensitive to the presence of
surface contaminants than those below 0.3 V This is
one reason why they were not observed in previous
work; the other is their sensitivity to surface long
range order.
2. They were observed and stable since the first cycle
after contact with the solution starting the sweep by
decreasing the potential from the open circuit
potential.
3. They show a high degree of reversibility.
E/VevsRHEl
Flame-Annealing and Cleaning Technique
/lpA.cm- 2
Pt<l11)
wo
50
0.1
E!V(vsRHE)
Figure 2 Cyclic voltammogram of a Pt(lll) oriented
electrode; 0.1 M HCI0 4 . All other conditions as in Fig. 1.
4. Taken together with the adsorption states below
0.30 V, the total electric charge is only slightly in
excess over the charge required for the saturation of
the platinum surface atoms by an adsorbed species
transferring one electron per surface platinum atom.
In the sulphuric acid solution this charge was
255 J1.C . cm- 2 out of 243 for a complete layer. The
12 J1.C . cm- 2 in excess could be then ascribed to
the charge necessary to modifY the ionic part of the
double layer subsequent to the change of potential
between the lower potential limit and 0.50 V
5. They were shown to be under the control of
anion-specific adsorption because their potential
range was dependent on the nature of the anion of
the electrolyte and its concentration.
6. In the case ofanion-specific adsorption, their poten-
tial relative to a constant reference electrode is not
affected by a change ofpH [27].
7. In perchloric acid solutions whose anion is con-
sidered as not specifically or weakly adsorbed, all
adsorption states move by 60 mV per pH unit.
1. Effect of Electrochemical Oxidation of Pt(111) on
its Adsorption Behavior
The study ofthe oxidation and reduction ofa Pt(lll) elec-
trode with surface conditions giving rise to the unusual
states was evidently of utmost interest. After recording
the voltammogram as in Fig. I, the electrode was swept
in the positive direction until the beginning of oxygen
evolution. A complete description of the consequences
of an extensive electrochemical adsorption of oxygen
may be seen in Fig. 3. A large oxidation peak appears at
1.425 V, indicating an important inhibition of the
oxidation of this surface relative to the polycrystalline
237
I/f1A.cm- 2
100
b
50
E!V(vsRHE)
Figure 3 Three successive voltammograms of Pt(lll)
showing the first delayed oxidation of the ordered (Ill) surface
and, after reduction, the transformation of the subsequent
adsorption behavior; 0.5 M H2S04, 50 mY . S-I.
surface. After reversing the potential sweep, a complete
voltammogram was recorded in the whole potential
range until a partial oxidation of the surface occurred.
We observe a substantial disappearance of the unusual
adsorption states, whereas below 0.35 V the usual
adsorption behavior of a polycrystalline platinum elec-
trode begins to appear. Subsequently, the second
oxidation of the surface starts at a much lower potential
as for the polycrystalline surface. This result is consistent
with the observation of a restructuring of this face
mentioned in Ref. I and 18. However, it is worth
mentioning that the transformation occurs in one cycle
in contrast to previous results [18] where several cycles
were necessary for detecting this surface modification.
This means that decontamination of the Pt(Ill) surface
proceeds more slowly than the structure change. The con-
clusion is that there was no chance to observe a
voltammetric profile as that in Fig. I starting with a sur-
face partially contaminated and subjected to the electro-
chemical cleaning procedure.
In perchloric acid solution the Pt(lll) electrode struc-
ture formed after the flame treatment resists repeated
oxide formation and reduction until an oxygen coverage
including the totality of the charge under the sharp peak
at 1.065 V (Fig. 2). This behavior compared with that in
238
0.5 M sulphuric acid solution evidenced the combined
role of anion-specific adsorption together with oxygen
adsorption in the restructuring ofthe Pt(lll) surface.This
surface restructuring starts indeed even when cycles of
oxide adsorption are limited to low oxygen coverage in
contrast to the action ofperchloric solutions.
The behavior reported in Fig. I was so considerably
at variance with the then standard adsorption behavior
generally accepted that it was necessary to have
some self-consistent internal ways to the technique for
checking this new experimental approach, allowing a
comparison with previous results.
The first checking was the preparation under the same
conditions of another platinum oriented electrode. It
was Pt(110) subjected to the same flame treatment and
quenching. The voltammogram in 0.5 M sulphuric acid
solution is reported in Fig. 4. The difference of
voltammetric profiles between the two orientations was
quite surprising. The voltammetric profile of Pt(lW) in
contrast to Pt(l1l) was found very close to those reported
previously with a peak at the same potential as in other
works. However, the charge under the curve was
220 pC . cm- 2 compared with 150 pC . cm- 2 obtained
-2
VIJA.em
100
20
o .1 .,5
20 E!V(vsRHEl
100
Figure 4 Cyclic voltammogram of a Pt(lW) oriented elec-
trode recorded in the very first sweeps. All other conditions as
in Fig. I.
Clavilier
with an electrode cycled avoiding the oxygen adsorption
as in Ref. 18. This difference could be then ascribed to a
decrease of the adsorption capability of the surface due
to the presence of impurities in the same way as for
Pt(ll1), whereas the voltammetric profile is not greatly
modified.
With this in mind, it was important to try to reproduce
the voltammograms of Pt( III) reported for surfaces pre-
pared with the vacuum techniques, assuming that surface
contamination resulting of sample transfer was the main
source of discrepancy. Thus, a Pt(l1l) surface giving a
voltammogram as in Fig. I was deliberately con-
taminated. The resulting voltammogram is presented
in Fig. 5, curve a. It shows the same featureless profile
as those recorded after a transfer of an electrode from
UHV to an electrochemical cell and directly cycled in
the low potential range [14,18]. The same sample was then
progressively cleaned from its surface impurities by
applying oxidation-reduction cycles. After 30 cycles in
the whole range ofpotential, a stationary voltammogram
was reached, reported in Fig. 5, curve b. This is typically
the voltammetric profile reported by the various authors
who have applied oxidation-reduction cycles to these
oriented electrodes [11,16,18]. The disappearance of the
unusual adsorption states may be remarked. This exper-
iment (Fig. 5, curve b) compared with that reported in
Fig. 3 confirms that surface decontamination is a much
slower process than the surface structure change
(Fig. 3), both processes being induced by oxidation and
reduction cycles.
I/~A.cm2
100
60 / ",
, I
b I
20 a
0 0.1
20 E/V(vsRHEl
60
100
Figure 5 Cyclic voltammograms of Pt(111). Curve a was
obtained after a deliberate contamination of the surface, curve
b was obtained after 30 cycles ofelectrochemical cleaning. The
dashed curve corresponds to the first excursion in the platinum
oxidation potential range, showing a clear deficit in the sub-
sequent reduction. Other conditions as in Fig. I.
Flame-Annealing and Cleaning Technique 239

The structure of the flame-treated Pt(lll) surface thus

100 II ~A.cm·2 appears as the precursor structure leading to the various
Pt(100) voltammograms previously obtained either after transfer
~C.cm-2 from vacuum or from other preparation techniques. From
(0 0 ) d.. = 212 the above experiment, each voltammogram may be
20
(OH) d.. = 205 explained as a consequence of an irreversible chemical
01-f::L:--~----''---::=:::l-'~--'---'--r---:'': and electrochemical degradation of the structure gener-
1.0
ENrhe ated thermally. A presentation of the various types of
voltammograms yielded by a Pt(lll) surface was
analyzed in Ref. 28.

C. Electrochemical Analysis of the Initial

Surface Content of Air-Cooled Platinum
V~A.cm·2
Samples
Pt(111)

60 ~C.cm-2 It may be expected that after the thermal treatment and

(0 0 ) d.. 95 the cooling step in air of a platinum sample, a certain
(OH) d.. = 240 amount of adsorbed oxygen may be formed at the metal
surface despite the presence of the water drop deposited
when the sample is hot. The question of determining the
amount of oxygen present at the surface was previously
treated [29]. Here a slightly different procedure [29] is
160 V~.cm-2
reported. To carry out the surface analysis of the treated
PI(110) crystal, the sample was put in contact with the solution,
~C.cm-2 forming the hanging meniscus configuration [30] at open
(0 0 ) _ = 195 circuit. Its potential was measured, and generally a value
(0 H)_ =200 between 0.900 and 0.975 V is found. One may remark
40
the existence of a relationship between this potential
and the surface composition of the sample. This relation-
ship has not received sufficient attention until now. It
may be shown by adjusting the surface content in
hydrogen or oxygen of a platinum sample surface that its
open circuit potential may describe the whole range of
potential. The electrode may be then potentiostated at
V~A.cm-2 its open circuit potential, and negligible charge transient
occurs when the circuit is closed. From this potential, a
PI poly sweep may be triggered either in the negative or positive
50
~C.cm-2 direction. Figure 6 reports, for the three basal
(0 0 ) d.. = 233
orientations and the polyoriented surface of a
(OH)d•• = 239
single-crystal bead, the voltammograms recorded in the
first negative-going sweep and the subsequent cycle. All
the first negative-going sweep show a reduction peak
around 0.780 V with a profile that is characteristic of the

Figure 6 Initial voltammograms of the three basal

orientations of platinum and of the polyoriented surface of a
platinum bead recorded after flame cleaning and cooling in air.
They provide an analysis of the surface conditions resulting
from the flame treatment. (QO)des charge values were measured
on the first negative-going sweep from the upper potential down
to nearly 0.5 V, whereas (QH)des values were measured in the
so-called hydrogen underpotential range. Other conditions as
in Fig. I.
240
surface structure. A reduction peak in the same potential
range is present on the stationary voltammogram of a
polycrystalline platinum electrode cycled between 0.050
and 1.400 Vat the surface of which an oxygen - platinum
compound is formed in the upper part of the potential
range. This experiment gives strong evidence that for the
flame-treated samples, an oxygen-platinum surface
compound is thermally formed and exists at the surface
before its exposure to the solution. In the case of the
Pt(100) orientation, its reduction occurs differently from
that of the electrochemical surface oxide, and the latter
is found to lie over a broader potential range, as shown
in Ref. 31.
The electrochemical study of the behavior of the
thermally adsorbed oxygen on pte Ill) in a perchloric acid
solution is particularly interesting for the comparison of
this compound to that equivalently formed in an electro-
chemical process. The positive-going sweep of the
flame-annealed sample is reported in Fig 7; compared
with Fig. 2, curve b, one can see that the sites on which
the oxygen electrochemical adsorption normally occurs
at 1.050 V are substantially blocked. This mean that
nearly no additional amount of a surface oxygenlike
species may be formed electrochemically in this potential
range. The close resemblance of the negative-going
branch ofthese voltammograms in both figures indicates
that the oxygenlike species formed in a thermal process
stays unchanged after a potential excursion to more posi-
tive potentials where normally the electrochemical
reaction of oxygen adsorption occurs. This is evidence
for the stability ofthe thermally adsorbed oxygen in a sol-
ution where the adsorption of the anion is considered
weak. We may postulate that the oxygenlike species
thermally formed and that generated in the peak below
1.120 V play unequivalent roles on the surface [29].
60 IIpA.cm- 2
20
Figure 7 Initial voltammogram of Pt(lll) recorded after
flame cleaning by scanning first the potential in the positive
direction. Same electrochemical conditions as in Fig. 2.
Clavilier
D. Flame Treatment and Its Effect on Surface
Ordering
Very early it was established that a Pt(111) surface yielding
a voltammogram as that in Fig. 5, curve b, could also be
produced by subjecting the well-ordered Pt(111) to a
bombardment of ions ofargon [32] whose effect is the dis-
ruption of the (111) surface order. So these results estab-
lished clearly the relationship between surface
disordering and the impossibility to observe unusual
adsorption states on such surfaces belonging to the (lll)
orientation. Thus, a Pt(1ll) electrode modified by several
cycles of oxidation and reduction was proved to be
restored by the flame-annealing procedure or by a
thermal treatment [28]. In Ref. 28 the authors reported
the temperature ofrestoration ofthe surface for obtaining
the full development of the unusual adsorption states
(Fig. 1), which was found to be around 500°C.
At this point, we know now that the flame treatment
has a double effect: elimination of surface impurities on
the one hand and modification of the surface structure
on the other hand, inducing a unique adsorption behavior
characteristic of the (Ill) atomically flat face. In fact, it
was proved later, first by LEED [33] and after with more
details by STM [34], that atomically flat Pt(lll) surfaces
were achieved after annealing in a gas-oxygen flame. It
was thus interesting to find the experimental conditions
to operate a decoupling of both effects: decontamination
and structure change. The solution to this problem was
found in the different temperatures by which the two pro-
cesses are initiated. Impurities are removed first, and then
by increasing temperature the structure modifications
may be obtained in a separate treatment at higher
temperature. It is worth mentioning that the sequence of
the two processes is quite at the opposite of the effect of
the potential cycling, thus giving the opportunity to fol-
low them separately in contrast to the electrochemical
procedure. This was studied in detail in Ref. 25. Such
an approach gave additional evidence for ascribing
the unusual adsorption states to the existence of
two-dimensional order. This may be observed by comp-
aring the voltammograms of a Pt(1ll) electrode as
received from polishing, with a contamination layer and
a thick perturbed region at its surface, with those resulting
after applying various thermal annealing treatments, a
classic way in metallurgy for the reorganization of sur-
face layers and in UHV surface studies.
Figure 8 shows the voltammogram of the Pt(1ll)
sample whose surface was contaminated by polishing
products (curve 1); then, the latter were removed from
the sample surface by gentle heating around 200°C by
thermal conduction through the platinum wire put in
 Flame-Annealing and Cleaning Technique
Pt(lll)
0,1 0.5
E/V rhe
t subjected to a flame treatment with cooling in air is
Figure 8 Voltammograms ofa Pt(lll) oriented electrode with
surface conditions as the result from polishing, Curve I was
obtained with the sample as received put in contact with the
I'
i
solution, simply rinsed with ultrapure water. Curve 2 was
obtained after flame cleaning without annealing of the
perturbed surface layers, The electrochemical conditions are
the same as in Fig. I.
the flame. It was demonstrated [25] that these conditions
left the surface structure unchanged. Curve 2 in Fig. 8 (see
also curve 1in Fig. 9) shows that the surface is chemically
well defined with a voltammetric profile corresponding
to a polycrystalline surface. The second step ofthe exper-
iment consisted in an increase of the temperature of the
treatment and ofthe time the sample was maintained hot.
The temperature was first chosen between 500 and 600°C
for two short periods of a few seconds. The two corre-
sponding voltammograms were recorded and reported
in Fig. 9 (curves 2 and 3). Then, a new flame treatment
was carried out for 10 s between 1300 and 1400°e.
The voltammogram obtained corresponds to curve 4.
An additional annealing in this temperature range for
15 min ensures the final quality of the crystal face. Its
voltammogram is that reported in Fig. 1. Figures 1and 8
clearly show the progressive restructuring of the region
below the surface that was disordered by the mechanical
polishing. The two adsorption states characteristic of
the polycrystalline surface at 0.110 and 0.260 V were
vanishing, whereas the unusual states were growing until
the two first disappeared, providing us the elements for
241
defining an electrochemical criterium and providing in-
formation on the quality of the Pt(1ll) orientation under
investigation. On the oxygen adsorption side of the
voltammogram, one may observe the progressive
inhibition ofthis adsorption reaction. This is a clear indi-
cation that oxygen adsorption in this solution is easier at
surface defect sites than at sites belonging to (111) ordered
surface domains. This remark provides a second
criterium for an estimate of the presence of surface
defects on such (111) surfaces.
IV. FLAME TREATMENTAND ROLE OF THE
COOLING ATMOSPHERE
A. Pt(100) Electrode
This surface is treated separately because of its great var-
iety ofinterconvertible voltammetric profiles in sulphuric
acid solutions, suggesting a surface structure mobility
under electrochemical conditions [35].
In Fig. 6 the voltammogram of a Pt(100) electrode
reported. Early it was observed that the voltammetric
profile was dependent on the amount of thermal oxygen
adsorbed during the cooling step of the (100) oriented
sample [29]. This amount was controlled by the nature
of the gas saturating the water used for quenching. It
was minimum when hydrogen was used for water
saturation. The consequence was the growth of a major
adsorption state at 0.365 V not observed with activated
polycrystalline platinum where all the state are observed
at lower potentials.
Motoo and Furuya [36] systematically carried out the
cooling step in a hydrogen atmosphere. Whereas with
Pt(111) this mode ofsurface preparation does not produce
any significant difference on the voltammetric profile
comparing with its cooling in air, in the case of Pt(100)
there is a drastic difference between the two ways used
for cooling. This remark can be generalized to all surfaces
containing (100) surface domains because it will be seen
with stepped surfaces in Sec. IVe. Moreover, the interest
ofthe hydrogen cooling is it offers the possibility to apply
the flame treatment to some oxidizable metals such as
rhodium.
Several experimental ways for performing hydrogen
cooling have been experienced [25,36,37]. The device
used by the author is briefly described that combines the
hydrogen gas-phase treatment to the water protection of
the surface.
A hydrogen line and an argon line are connected to the
inlet of two bubblers containing ultrapure water. The
two outputs merge in a single line where the proportion
between the two gases in the mixture may be roughly
242
Figure 9 Four voltammograms corresponding to four steps in the ordering of the polished Pt(lll) surface by applying successive
flame-annealing treatments with cooling in air. Curve I corresponds to the same flame-cleaning treatment as for curve 2 in Fig. 8. Elec-
trochemical conditions as in Fig. 1.
adjusted by controlling each flow in the bubblers. The gas
mixture is introduced at the lower part of an
Erlenmayer-shaped vessel filled with ultrapure water
whose surface is continuously renewed by the bubbling.
Above the liquid, a gas chamber is formed open to the
atmosphere through a narrow and sufficiently long neck.
After the crystal is heated in the flame, it may be intro-
duced into the chamber filled with the gas mixture and
then dipped into the water and removed covered with a
protective drop for its transfer to the electrochemical cell.
An interesting advantage of the device is the possibility
to maintain the platinum crystal hot (dark red to orange)
at the outlet of the vessel chamber by the catalytic
oxidation of hydrogen when the gas mixture comes in
contact with air. This is particularly convenient in the case
of rhodium. The use of argon is strongly recommended
both for safety and for its high density in a system whose
upper part is open to air to leave a free access of the
sample into the atmosphere contained in the vessel.
Figure 10 shows three voltammograms of a Pt(100)
oriented electrode at different steps of the flame
treatment. All the curves were obtained after cooling in
air. The first one was recorded at the end ofpolishing after
the surface was made free from impurities. Its profile is
that of a polycrystalline surface (curve I in Fig. 10) as it
Clavilier
was found for Pt(lll). Curve 2 was obtained after few
seconds of flame annealing around 400°C. It shows a
large increase of the adsorption states above 0.2 V to the
expense of the state at 0.110 V The third voltammogram
(curve 3) was recorded after 30 min of flame annealing
between 1300 and 1400°C. We may observe that the
major state is at 0.365 V This is slightly different than
the curve in Fig. 6. The difference is due to the fact
that the voltammogram of Fig. 10 was obtained with a
new electrode and used for the first time for this
experiment, whereas in Fig. 6 the electrode was used for
many experiments previously. This difference is due to
an effect of the degradation of the surface quality of the
sample.
After the recording of curve 3, the crystal was flame
heated until red and cooled in the stream ofH2 + A gases
using the device previously described and then trans-
ferred covered with a drop ofultrapure water to the elec-
trochemical cell. The new voltammogram is given in
Fig. 11 (full line). The remarkable transformation is the
quasidisappearance of the state at 0.265 V to the advan-
tage of that at higher potential. Simultaneously we
may remark a continuous lowering of the voltammetric
current between 0.1 and 0.2 V since the beginning of the
overall flame treatment.
 Flame-Annealing and Cleaning Technique
t Pt1100l
100
50
.~. 0.1 .=~-.~
E/VevsRHEl
Figure 10 Three voltammograms showing the ordering of a
polished Pt(lOO) electrode surface after the surface was
subjected to flame cleaning (curve I) and to two additional flame
annealing treatments (curves 2 and 3) with cooling in air.
Electrochemical conditions as in Fig. l.
It was reported in Ref. 38 that a transformation similar
to the last one could be achieved, the sulphuric acid
solution, by applying to the Pt(lOO) electrode a specific
electrochemical program of polarization. It consists of
subjecting the electrode to polarization cycles for
I
typically 30 s between 0.05 and 1.0 Vat a sweep of the
1 order of 100 V . S-l. This program was applied to this
new hydrogen-cooled electrode after recording the curve
full line in Fig. 11. The resulting voltammogram corre-
sponds to the dashed line in the same figure showing a
slight increase of the state at 0.365 V and a complete
disappearance of the state at 0.265 V.
This polarization program is particularly useful as
a substitute to the hydrogen-cooling procedure after
the surface was disordered by cycles of adsorption
T
1
t
243
N
E
u
b
200 -i. a
-<:
100
EjVevsRHEl
Figure 11 Two voltammograms of the Pt(100) electrode.
Curve a was obtained after flame treatment and cooling in
H 2 +A atmosphere of the Pt(lOO) sample having yielded curve
3 in Fig. 10. Curve b was reached from curve a after applying
the fast cycling program (see text). Same electrochemical
conditions as in Fig. 10.
and desorption of oxygen at high coverage. The
voltammogram of a Pt(lOO) electrode perturbed in this
way is reported in Fig. 12 for two upper potential scan
limits showing that by avoiding the adsorption of oxygen,
the reversibility of hydrogen UPD is fully achieved. After
applying to this perturbed surface the fast-sweep
program, a voltammogram similar to those in Fig. 11 is
restored. This is a marked difference with the Pt(lll)
orientation for which there is no known electrochemical
way for restoring, after an electrochemical desordering,
a voltammogram similar to that yielded by the flame
treatment.
An ex situ topographyofaPt(lOO) surface correspond-
ing to the three types ofvoltammograms reported in Figs.
10 (curve 3), 11, and 12 has been carried out by STM [39].
Wide atomically flat domains were observed with the
conditions corresponding to Fig. 11, whereas a dense
array of monoatomic steps in two perpendicular direct-
244 Clavilier

potential range. In this respect, it is easy to demonstrate

that the process is strictly controlled by the nature of the
solution, the sweep rate, and the precise limits of the
potential sweep.

B. Pt(110) Electrode
A preliminary result is given in Fig. 6 showing the first
voltammetric cycle after the flame treatment and cooling
in air. The characteristic behavior of this orientation
cooled in air is a progressive change of the voltammetric
profile with repeated cycling in a sulphuric acid solution
avoiding the potential range of oxygen adsorption. A
stabilized profile is reached after nearly 10 cycles. This
transformation, occurring under clean conditions, is
characterized by the appearance of a fine structure. It
consists in the splitting of the main adsorption state at
20 0.125 V into two sharp peaks at 0.112 and 0.135 V, respect-
ively (Fig.B, solid line). This transformation is essentially
o a redistribution of the total electric charge between the
EN (rhe)
adsorption states below 0.3 V with a substantial increase
of the peak intensities [41] to the expanse of the low state
between 0.2 and 0.3 V. The transformation occurs with
a constant total charge. There is no available structural
study of this transformation. Sun [42] showed that once

Figure 12 Voltammetric profile of the pte 100) electrode after

six scans in the whole potential range presented in the upper part
ofthe figure. The lower curve shows the effect ofthe upper limit
of the scan on the reversibility of the adsorption/desorption
process in the hydrogen UPD region. Same electrochemical
conditions as in Fig. 10. 100 '\
,:',
,, ,
,I

,I ,,
I

ions is characteristic of voltammograms as in Fig. 10

, .
(curve 3) or in Fig. 6. It is important to remark that after 0
0.5 E!V(vsRHEl
the (100) electrode was subjected to several experimental
runs and flame treated again, the wide flat domains start
to be populated by monoatomic and almost square mesas
and lacunas. This is a topography also observed in the
case ofthe Au(100) face [40]. Finally, the topography Cor-
responding to the voltammogram in Fig. 12 shows a
fragmentation of the surface domains with fOrmation of
nanodomains with monoatomic, Or biatomic height
formed on the topmost layer. This organization of the
perturbed surface layer may explain the ease with which
Figure 13 Voltammogram of flame-annealed Pt(llO) cooled
a voltammogram as in Fig. 11 is recovered by an electro- in air showing the treatment characteristic splitting of the main
chemical procedure. The mechanism of this surface adsorption state on cycling (compare with Fig. 4). The dashed
modification may be found in the lateral mobility of the curve was recorded after a deliberate contamination ofthe same
surface platinum atoms activated by the combination of sample by adsorbing iodine at partial coverage. Electrochemical
the relaxed adsorption effects at the two limits of the conditions as in Fig. 1.
Flame-Annealing and Cleaning Technique
~
E
u
<i:L
---
200 -
1.3
E/V(vsRHE)
Figure 14 Voltammogram of the Pt(llO) electrode flame
annealed and cooled in the H 2 +A atmosphere (solid line). The
dashed line was recorded after a single excursion in the oxygen
adsorption/desorption region. Electrochemical conditions as
in Fig. 13.
the transformation was achieved, there was a consider-
able loss of electrocatalytic activity of the Pt(1lO) elec-
trode for the oxidation of formic acid and for methanol.
The effect of the flame treatment with cooling in a
H 2 + A atmosphere was investigated [43] with special
attention to contamination effects that seem very often
underestimated with this orientation. The resulting
voltammogram, reported in Fig. 14, shows a single
narrow adsorption state at 0.125 V that persists despite
cycling out of the oxygen adsorption range in contrast
with the previous case. The voltammetric charge below
OJ V is the same as for the air-cooled sample, i.e.,
215 flC . cm- 2 . Structural data are missing, accounting
for the effect of the cooling atmosphere on the
voltammetric profile of this orientation. However, the
profile as a consequence of cycling in the oxygen
adsorption/desorption potential range changes to that
resembling the initial one for the air-cooled sample
(dashed line in Fig. 14). This suggests that a higher degree
of surface order is achieved after the cooling in a
hydrogen atmosphere than in air.
The details in the peak shape discussed in this section
correspond to subtle differences that may escape the
observation for two main reasons: a misalignment of
the crystal face or the presence of a small amount of sur-
face contaminants. Regarding the latter effect, it is
important to stress that the presence of surface con-
taminants has only a dramatic effect on the fine structure
discussed previously, whereas the general shape is
maintained. An example is reported in Fig. 13 (dashed
245
curve); in this case the contaminant is iodine at low
coverage. This effect affects essentially the electric charge
measured on the voltammogram below 0.3 V that
decreases with increasing surface contamination. Too
low experimental values (typically below 190 flC . cm- 2
in 0.5 M H 2 S0 4 ) for this charge should be considered as
a possible sign of contamination, and its detection then
becomes necessary. Surface contamination may be then
distinguished from other effects such as reconstruction
by a study of the balance of the charges for the formation
and reduction of the oxygen adlayer, avoiding any trace
ofoxygen evolution by using an adequate upper potential
limit. The ratio ofthe two charges measured, respectively,
during oxygen adsorption and the subsequent desorption
should be found very close to unity for a clean surface.
The value of the ratio increases with the amount of con-
taminant, whereas the voltammetric profile for the for-
mation of the oxygen adlayer appears to be less sharp
[43]. This is not an innocuous surface control. Its use
requires new flame treatments until the source of con-
tamination is detected and eliminated.
A recent analysis of the components of the
voltammetric charge below 0.3 V by using the CO dis-
placement method has shown that only 150 flC . cm- 2
of the voltammetric charge could be ascribed to an
adsorbed hydrogen-like species. The remaining part of
the charge could be due to an adsorbed species anodically
formed at the surface in this low potential range. This
result was established for sulphuric and perchloric acid
solutions [44,45] in contact with the Pt(llO) electrode.
C. Example for a Choice of Cooling
Atmosphere Composition: Stepped
Surfaces
The example presented here is a consequence ofthe effect
on the voltammetric profile ofa Pt(100) electrode of the
nature of the atmosphere to which the oriented sample
was exposed during its cooling subsequent to the flame
treatment. We consider in this section platinum surfaces
that are cut a few degrees off the (111) basal orientation
in the direction of a [001] pole. Such surfaces may be
ideally represented as stepped surfaces containing (100)
step sites and (111) terrace sites. Each terrace is then
separated from the next one by a monoatomic step.These
oriented surfaces may be denoted using the following
Miller indices (n + 1, n -1, n -1) where n is the number
of atomic rows of the terraces. An alternative notation
describes the surface in terms of terrace and step with
the two types of constitutive sites at the atomic level:
n(1ll) x (100), where n has the same meaning as in the
Miller formalism.
246
From the study of the three basal orientations, we
determined characteristic adsorption states specific of
the orientation in a given electrolyte. In 0.5 M HzS04,
for the Pt(1lO) electrode, a main narrow state is observed
at 0.125 V, whereas for Pt(WO) two other narrow states
are present at 0.265 and 0.365 V Finally, the Pt(lll) elec-
trode is characterized by its unusual state spreading from
0.3 to 0.5 V associated to a broad flat voltammetric cur-
rent below 0.3 V without any localized contribution at
the characteristic peak potentials for the two other
orientations.
If we apply the flame-annealing procedure with
cooling in air to Pt(n + 1, n -1, n -1) oriented samples
with terraces containing more than three atomic rows,
an anomalous distribution of the adsorption states is
observed with the presence of an adsorption state at
0.115 Vand a smaller one at 0.26 V A result of this type
is reported in Fig. 15 for the Pt(544) electrode, otherwise
noted 9(111) x (100). This notation means thatthe surface
is composed of (111) terraces of nine rows of atoms wide
separated by monoatomic steps with the (l00)
orientation. After reduction of thermally adsorbed oxy-
gen (dashed curve in Fig. 15), the adsorption state distri-
bution is clearly in contradiction with the step-terrace
notation because of the presence of the state at 0.115 V
characteristic of (110) sites, whereas the state at 0.26 V
characteristic of (l00) sites is poorly developed. The way
to eliminate this conflicting behavior consists of
I/pA.cm- 2
Pt(544)
100
50
or-to-;----i~~~;=:::::::E=::=±~/ :;-.
---.."
/~- EjVevsRHE)
J
Figure 15 Two successive voltammograms of flame-treated
Pt(544) with cooling in air. Dashed curve is the first
voltammogram obtained after the electrode was put in contact
with the solution at the upper potential limit. Solid line corre-
sponds to the subsequent potential scan. Electrochemical
conditions as in Fig. 1.
Clavilier
N
I
E
u
80 <i:I..
::::::
Pt(544)
20
oH-;::;----~---+----+--==~~~--:;-"r
---------------------,~
E/VevsRHE)
Figure 16 Voltammograms of the Pt(544) electrode after
flame treatment and cooling in H 2 +A atmosphere. Same
conventions and same electrochemical conditions as in Fig. 15.
performing the cooling step ofthe treatment in an Hz + A
atmosphere. In this case, in addition to the usual and
unusual states for the Pt(lll) ordered surface domains, a
single sharp peak at 0.265 V is then well developed, as
seen in Fig. 16, indicative of the contribution of the (100)
sites [46]. The charge under the peak is found in quantitat-
ive agreement with the stepped surface model [46].
Correlatively it may remarked a considerable decrease
of the reduction current in the first positive-going sweep
(Fig. 16, dashed curve) as a consequence of the cooling
conditions, leading to a substantial decrease of the
thermally adsorbed oxygen on this surface.
v. CONCLUDING REMARKS
I presented here some characteristic applications of the
flame-annealing technique in the case of the platinum
electrode. However, this technique was also applied suc-
cessfully to gold single-crystal electrodes.With this metal
it was found particularly useful for the approach of the
general problem of gold single-crystal reconstruction
under electrochemical conditions [47]. This interesting
point with this metal is the absence of formation of an
r
Flame-Annealing and Cleaning Technique
oxygen adlayer during the cooling step in air leading
spontaneously to a free metal surface when put in contact
with the solution at open circuit. In contrast, it was
thought initially that the flame treatment was not suitable
for rhodium because ofthe ease with which a thick oxide
layer is formed at the surface [48]. In this case the
difficulty was overcome by using the cooling in the
mixture of hydrogen and argon gases [49].
The unusual results obtained by the flame technique
were confirmed later to be characteristic ofwell-ordered
Pt(lll) surfaces by independent experimental ways: by
DHV coupled to voltammetry [17], by the technique of
replacement of adsorbed iodine by carbon monoxide
[50], and by in situ STM [34].
The main finding of the flame treatment was the dis-
covery of highly reversible unusual adsorption states on
the Pt(lll) electrode whose existence was demonstrated
to be related to the existence of the two-dimensional
long-range order of the crystal face. The replacement of
the species involved in the unusual states by a neutral
and strongly chemisorbed species like carbon monoxide
was shown to give rise to a reduction current [44,51]. The
charge evolved in this process was found the same as the
voltammetric charge measured for these states. It was
then concluded that the formation of the unusual states
was the result of an anodic surface reaction. The most
important and intriguing conclusion is then relative to
the effect of a surface disordering, inducing a decrease
of the unusual states to the advantage ofusual states in a
lower potential range, particularly in the potential range
of the Pt(1W) electrode. This transformation of the
voltammogram occurs with a constant total charge below
0.7 V Because the same anodic surface reaction was
detected on the Pt(IlO) in the usual range of hydrogen
adsorption [44], it may be inferred that the
transformation of the voltammetric profile subsequent
to disordering with formation of (110) sites results in the
negative shift of the species formed in the anodic surface
reaction from the unusual to the usual potential range.
This process was suggested intuitively by Ross [52] by
observing the redistribution of the charge from the
unusual to the usual potential range for a series of stepped
surfaces and as for a Pt(lll) electrode with various
degrees of disordering. Experiments using the carbon
monoxide for probing the adsorbed species have given
strong evidence to the interpretation proposed by Ross
for the effect of disordering on the voltammetry and
charge distribution of the Pt(111) oriented electrode
subjected to surface perturbation. The consequence is
that the nature ofthe charge components in the hydrogen
UPD region of a polycrystalline platinum electrode has
to be reexamined.
247
It is now quite evident that the introduction of the
flame-annealing and cleaning technique has contributed
considerably and will continue to modifY our concepts
of surface electrochemistry, particularly for platinum
metals. For instance, an interesting open question is rela-
tive to the induction of surface reconstruction of these
metals under the effect of a modulation of the conditions
ofthe flame treatment [53] or by comparing with alterna-
tive surface preparation techniques. However, in every
case, the electrochemical response of the system should
be taken as a guide for detection ofsurface contamination
by using very simple criteria, because contamination is
the first source to suspect when discrepancies between
results appear.
ACKNOWLEDGMENTS
I am grateful to Professor Gary Attard for many com-
ments and to Dr. M. Petit for help in the preparation of
the manuscript.
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6. VS Bagotzky,Yu B Vassiliev, II Pyshnograeva, Electrochim
Acta 16:2141,1971.
7. H Angerstein-Kozlowska, WBA Sharp, BE Conway. In:
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8. AT Hubbard, Crit Rev Anal Chern 3:201,1973.
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15
Interfacial Chemistry of Palladium Electrodes
Manuel P. Soriaga,Youn-Geun Kim, and Jose E. Soto
Texas A&M University, College Station, Texas
ABSTRACT
Recent investigations on the surface electrochemical
properties of polycrystalline and single-crystal Pd elec-
trodes have uncovered unique phenomena that serve to
further establish the remarkably rich interfacial chemis-
try of this metal. Such chemistry may have its origins
in the anomalously weak intermetallic palladium-
palladium bond, a circumstance that is expected not
only to enhance lateral surface mobilities but also to
facilitate the disruption of substrate~substrate bonds
and/or the formation of substrate-adsorbate bonds.
The present chapter is intended to showcase studies that
help advance the knowledge base on the interfacial elec-
trochemistry of palladium. The discussion is centered
on three interrelated subjects: electrode-surface
coordination/ organometallic chemistry, adsorbate-
activated electron- transfer sites, and adsorbate-induced
substrate reactions. The methodology adopted in these
studies rests on a combination ofelectrochemistry, in situ
scanning tunneling microscopy, and ultrahigh vacuum
surface spectroscopy.
I. INTRODUCTION
The ability ofpalladium to catalyze a wide variety of het-
erogeneous reactions is well documented [Ia]. The
propensity of this metal to absorb unusually large
amounts of hydrogen is also widely known [lb]. In elec-
trocatalysis, palladium has not found use as extensively
as platinum even if it has been shown to be a suitable cata-
1yst in more than a few reactions. Recent investigations
on the surface electrochemical properties of palladium
249
have uncovered unique phenomena that serve to further
establish the remarkably rich interfacial chemistry of this
material. Such chemistry may have its origins in the
anomalously weak inter metallic palladium-palladium
bond: The dissociation enthalpy ~Hdiss of the diato-
mic Ni 2 species is 203 kJ mol- 1 and that of Pt2 is
357 kJ mol-I; whereas the normal trend would locate
~Hdiss for Pd 2 between these two extremes, the observed
value is actually only 100 kJ mol~1 [Ic]. The same diver-
gent trend extends to bulk properties, such as the cohesive
energy (enthalpy of atomization) where the values
decrease in the order Pt (564 kJ mol-I) > Ni (428
kJ mol-I) > Pd (376 kJ mol-I) [Id]. Such anomaly is
expected not only to enhance lateral surface mobilities
but more importantly to facilitate the disruption of
substrate-substrate bonds and/or the formation of
substrate- adsorbate bonds.
The intent ofthe present chapter is to provide a concise
anthology ofstudies that help expand the archives on the
interfacial electrochemistry (EC) of palladium. The
discussion revolves around the following interrelated
subjects on which our research efforts are concentrated
electrode-surface coordination/organometallic chem-
istry, adsorbate-activated electron-transfer sites, and
adsorbate-induced substrate reactions. Work from other
laboratories exist [2], although the emphases may be quite
different from those presented in this chapter.
Unfortunately, due to severe space restrictions, only
selected investigations from our (own and collaborative)
laboratories can be included in this brief compilation;
for the other studies, the reader is directed to the current
literature.
250
A. Experimental Approach
The invention of the scanning tunneling microscope
(STM) [3] and the developmental work [4] that ensued
to adapt the technique to EC have led to dramatic
advances in electrochemical surface science and the elev-
ation of EC-STM as the premier experimental tool. By
itself, however, EC-STM is unable to unravel all the
nuances of complex heterogeneous processes. It is, for
example, not able to provide other critical information
such as adsorption enthalpies, surface composition, and
adsorbate electronic structure. Complementary surface
spectroscopic techniques would always be necessary if a
more detailed understanding ofelectrocatalytic reaction
were the objective. A strategy that combines EC-STM
with ultrahigh vacuum (UHV) surface analytical
methods appears most suitable because it bridges the
gaps inherent in the separate approaches [5]; it is this
approach that has been adopted in our studies. Included
in the arsenal of UHV techniques [1,6] are low-energy
electron diffraction (LEED) for surface crystallography,
Auger electron spectroscopy (AES) for elemental
analysis, x-ray photoelectron spectroscopy (XPS) for
elemental analysis and chemical valency determina-
tions, high-resolution electron energy loss spectro-
scopy (HREELS) and Fourier transform infrared
reflection-absorption spectroscopy (FT-IRAS) for
vibrational studies and bond-strength information, and
temperature-programmed desorption mass spectro-
metry for thermal reaction chemistry and adsorption
enthalpy measurements. The virtues and protocols of
EC-STM [4] and UHV-EC [7] are well extolled and are
not further belabored here.
II. DISCOURSE
A. Surface Coordination/Organometallic
Chemistry
We have long subscribed to the view that "if there is a
choice among explanations in chemistry, one must select
the explanation which permits a connection between the
structure at hand and some discrete molecule" [8]. Along
these lines, we have embraced as a goal the description
of spontaneous surface-solution interactions in terms of
classic concepts of coordination and organometallic
chemistry [9]. An axiom in this approach is that a
commonality exists between an interfacial structure and
a discrete molecule; that is, surface compounds can be
modeled after known molecular or cluster complexes
[10]. Sucha commonality provides a chemical foundation
on which the correlation between the structure, com-
position, and reactivity at the electrode surface can be
Soriaga et al.
Homogeneous Coordination Chemistry:
M54 + 4L < >- M1.4 + 45
Electrode Surfaces:
5 5 5 5 L L L L
4L
~
+ 45
UM
S: SolventlElectrolyte
>
Figure 1 Analogous reactions in homogeneous and
electrode-surface coordination chemistry.
established [10]. As an example, the chemisorption pro-
cess can be regarded as a complex formation reaction that
transpires at the electrode surface; its driving force, in
the absence of extreme applied potentials, is expected to
depend on the chemical properties of both the adsorbate
(ligand) and the substrate (metal center) in an environ-
ment that includes the solvent and supporting electrolyte.
As rendered in Fig. 1, the electrode is initially covered
by (weakly) coordinating electrolyte and/or solvent
molecules; hence, chemical interactions between
solution-phase reagents and the electrode surface involve
displacement reactions very similar to those in homo-
geneous systems. Specific examples [10] of the latter are
the water/halide ligand substitution reaction:
Pd(H20)~+ + 4X- ---+ Pdxf + 4H 20 (1)
or the halide/halide exchange reaction:
(2)
where X =Cl-, Br- or 1-.
To showcase the close analogy between electrode-
surface (heterogeneous) and homogeneous coordination
chemistry, the present section describes the interaction
of well-defined Pd(100), Pd(1lO), and Pd(111) single-
crystal electrode surfaces with chloro, bromo, and iodo
ligands in aqueous solutions. The section is concluded
with preliminary results on the interaction of a substi-
tuted diphenolic compound on Pd(lOO) as a harbinger
of future investigations on the organometallic chemistry
of Pd electrode surfaces.
1. Noncompetitive Surface Coordination
The chemisorption of iodine from dilute aqueous iodide
solution onto well-defined Pd(hkl) surfaces has been
described previously [11]. In summary, I(';q) undergoes
oxidative chemisorption to form stable and well-ordered
adlattices ofzerovalent iodine atoms. Adlattice structures
that spontaneously form at potentials within the
Interfacial Chemistry of Palladium Electrodes 251

Figure 4 LEED patterns for Pd(llO)-pseudohexagonal-I.

8nm X 8nm Parallel studies on the interaction of aqueous chloride

and bromide anions with Pd(hkl) surfaces [15] indicate
Figure 2 In situ STM image of Pd(1ll)-(.J3 x .J3)R300-I similar trends: In the double-layer potential region, both
adlattice. halides are oxidatively chemisorbed to form well-ordered
adlattices. For example, on Pd(111), (.J3 x .J3)R30°
double-layer region are Pd(l1l)-(.J3 x .J3)R300-1 (Fig. structures are formed, as with iodine (Fig. 2). But differ-
2), Pd(l00)-c(2 x 2)-1 (Fig. 3), and Pd(llO)-(pseudo- ences do exist, as on Pd(100), where noncentered (2 x 2)
hexagonal)-I (Fig. 4). The chemisorption of iodine onto adlattices are generated (Fig. 5). It is not understood
Pd(hkl) from aqueous iodide has been represented by why Cl and Br coverages are only half that of the I cover-
the following: age at Pd(IOO), when the structures (coverages) for all
three halogens are identical at Pd(111). It has been
H~q) + I~lq) + Pd(lll) -+ observed, however, that higher coverages of CI and Br
(3)
Pd(1ll)-(.J3 x .J3)R300-1 + 1/2H 2(g) can be obtained at more positive potentials, although
such changes are accompanied by metal oxidation to
form PdX2 salt films [2].
H~q) + I(;;q) + Pd(100) -+
(4) As in the case ofiodide, the chemisorption reactions of
Pd(100)-c(2 x 2)-1 + 1/2H 2(g) the lighter halides may be described by the foil owing:

H~q) + X(;;q) + Pd(1ll) -+

(5)
Pd(1ll )-(.J3 x .J3)R30° -X + 1/2H 2(g)

H~q) + X(;;q) + Pd(100) -+

(6)
Pd(l00)-(2 x 2)-X + 1/2H 2(g)

where X == CI and Br.

o 1.0 2.0 3.0nm

Figure 3 In situ STM image ofPd(lOO)-c(2 x 2)-1 adlattice. Figure 5 Pd(lOO)-(2 x 2)-X structure.
252 Soriaga et aI.

Pd(111) Pd(111 H"3xv3)R30"·1

,
1 fTIMCI-! 1 m.".! *1fT1Msr
,.

1 mMBr~

• X 1 mMCI-

Figure 6 LEED patterns for Pd(lll) after sequential exposure to I mM NaX (X ""Cl-, Br-, or I~).

2. Substitution (Displacement) Reactions

Pd(100)
Figures 6 and 7 summarize, by way ofLEED patterns and .1mMCI-
AES spectra, the changes that take place when a Pd(jzkl)
electrode surface pretreated with an ordered monolayer r~-"'-
Pd(100)-(2x2)-CI
of one halogen is exposed to a dilute aqueous solution of
another halide. The data provide evidence that regardless LU f1mMBr-
of the electrode-surface crystallographic orientation, :!2
the heavier halide displaces the lighter halogen initially
present on the surface; the displacement occurs
-
UJ
Z
"0
Pd(100)-(2x2)-Br

spontaneously, irreversibly, and quantitatively; and the

substitution reaction leads to the same ordered adlattices
obtained under noncompetitive chemisorption con-
ditions. These observations are consistent with estimates Pd(100)-c(2x2)-1
obtained from temperature-programmed desorption
experiments [11,12]: l1H(ads)(I) ~ 65 kcal mol- 1 ,l1H(ads)
(Rr) ~ 50 kcal mol- 1,andl1H(ads)(Cl) ~ 35 kcalmol- 1. o 100 200 300 400 500 600
Equations (1) to (4) imply that the chemisorption of Kinetic Energy/eV
the subject halides involves an oxidation-reduction
reaction. The substitution reaction would therefore also Figure 7 AES spectra for a Pd(lOO) electrode after sequential
be expected to be a redox process that transfers an elec- exposure to I mM NaCl, NaBr, and Nal.
r Interfacial Chemistry of Palladium Electrodes
tron from the incoming (adsorbing) halide to the
outgoing (desorbing), halogen. In chemical equation
form, these reactions may be written as
Br(;;q) + Pd( III )-(.j3 x .j3)30° -Cl ---c>
(7a)
Pd(l11)-(.j3 x .j3)R300-Br + Cl(;;q)
Cl(;;q) + Pd(l1 1)-(.j3 x .j3)R300-Br---c>
(7b)
No Reaction
I(;;q) + Pd( III )-(.j3 x .j3)R30°- Br ---c>
(8a)
Pd(l1 1)-(.j3 x .j3)R300-1 + Br(;;q)
Br(;;q) + Pd(l1 1)-(.j3 x .j3)R30o-I---c>
(8b)
No Reaction
Br(;;q) + Pd(l00)-(2 x 2)-Cl ---c>
(9a)
Pd(l00)-(2 x 2)-Br + Cl(;;d)
Cl(;;q) + Pd(l00)-(2 x 2)-Br ---c> No Reaction (9b)
I(;;q), + Pd(l00)-(2 x 2)-Br ---c>
(lOa)
Pd(l00)-c(2 x 2)-1 + Br(;;d)
Br(;;q) +Pd(l00)-c(2 x 2)-1 ---c> No Reaction (lOb)
It must be realized that Eq. (lOa) involves not only the
complete displacement of the preadsorbed bromine but
also an additional adsorption of iodine. This is because
the (initial) coverage of Br (0 Br == r Br/r Pd, where r is
the surface packing density in mol cm -2) is only 0.25,
whereas the (final) coverage of I is 0.5.
3. Competitive Surface Coordination
In this phase of the study, the halide-free Pd(hkl)
electrodes were exposed to solutions that contained
equal concentrations of two or three halides; the
combinations used were Clr;;q/Br(;;q), Br(~q/I(;;q)' and
Cl(;;q/Br(;;'q/I(;;q). In essence, the halides were allowed
to compete, at identical solution-phase activities, for
chemisorption sites. The results, summarized in Fig. 8
and 9 in terms of LEED patterns and AES data, show
that only Pd(l1l)-(.j3 x .j3)R300-1 is formed from a
solution containing 1 mM each of Cl-, Be, and 1-. It
was also found that exposure of Pd(lll) in a mixture
of Cl- and Be resulted in the formation of only a
Pd(l1l)-(.j3 x .j3)R300-Br adlattice.
253
Based on the aforementioned results, the competi-
tive chemisorption reactions involving the three subject
halides at Pd(hkl) single-crystal electrodes can be rep-
resented as
H+ + Br- + Cl- + Pd(lll) ---+
(ll)
Pd(l1 1)-(.j3 x .j3)R300-Br + 1/2H 2(g) + Cl-
H+ + 1- + Br- + Pd(lll) ---c>
(l2)
Pd(l11)-(.j3 x .j3)R300-1 + 1/2H 2(g) + Br-
H+ + Br- + Cl- + Pd(lOO) ---c>
(l3)
Pd(l00)-(2 x 2)-Br + 1/2H2(g) + Cl-
H+ + 1- + Br- + Pd(lOO) ---c>
(l4)
Pd(l00)-c(2 x 2)-1 + 1/2H 2(g) + Br-
The data just summarized serve to illustrate the
contention that the interaction of the subject halides
with Pd electrode surfaces closely follows the homo-
geneous coordination chemistry of halo-Pd complexes
[9]. That is, the strength of surface coordination
decreases in the order 1- > Br- > Cl-; this is in con-
formity with the fact that for the homogeneous-phase
reaction [Eq. (1)], the overall complex-formation
constants f3 are 1.6 x 10 12 for Cl-, 1.3 x 10 16 for Be,
and 7.9 x 10 24 for 1- [9c].
Equations (3) to (6) state that the chemisorption ofthe
halides occurs oxidatively to yield a layer of zerovalent
halogen atoms; this reaction may be considered [lOa] as
the surface analog of oxidative addition [9]. In the latter,
such as in the reaction of HCl with coordinatively unsatu-
rated complexes [9], the valence of the metal center is
increased. At surfaces, where the metal needs to maintain
its zerovalency, it is the adsorbate that instead undergoes
oxidation. Reductive desorption, the reverse of reactions
(3) to (6), would serve as the heterogeneous equiva-
lent [lOa] of reductive elimination [9]. For reversibly
electroactive ligands, the spontaneity of chemisorption
(the facility of the heterogeneous Red(ads) *+ OX(aq)
process) is simply a manifestation ofthe ease ofthe homo-
geneous Red(aq) *+ OX(aq) reaction [lOa]; this may help
explain why, on Pd(lOO), 0 1 is higher than 0 Br or 0 0
[lOa].
4. Molecular Adsorption
Studies conducted in the mid-1980s [13] on the chemi-
sorption of aromatic compounds at smooth poly-
crystalline platinum electrodes suggested the formation
of monolayers in which the molecules are immobilized
254
Figure 8 LEED patterns for a Pd(lOO) electrode after exposure to dilute aqueous solutions that contained binary and ternary
mixtures ofNaX(X""Cl-, Br-, or 1-).
on the surface at specific nonrandom orientations; the
nonrandomness of the orientations imply the specificity
of substrate-adsorbate chemical bonds. The particular
orientation adopted was found to be primarily a function
of the adsorbate molecular structure, although other
factors, such coadsorbed anions, temperature, and con-
centration, were also found to exert influences. For
example, from absolute surface coverage measurements,
it was shown that hydroquinone (HzQ) adopts a flat (~6)
orientation when adsorbed from dilute (:s 0.1 mM)
solutions; in view of experiments that indicated
oxidative [HzQ(aq) +* BQ(ads)(BQ :=benzoquinone)]
chemisorption, the surface complex in this orientation
was assumed to be very similar to the well-known Pt - BQ
organometallic complex (Fig. 10) [14a]. At much high-
Soriaga et al.
er concentrations (:::::1 mM), a higher coverage was
obtained that suggested a vertical (2,3-~z) orientation;
o-benzyne organometallic cluster complexes (Fig. 11)
[14b,c] served as the analogues for this particular ad-
sorbate orientation. Subsequent experiments with
grazing-incidence IRAS [lOb] confirmed the initial con-
jecture of vertically oriented HQ species. Later radio-
tracer measurements [15] also yielded higher HzQ
coverages when adsorbed from higher concentrations,
in agreement with theTLE data. Coverage measurements
by AES of the potassium salt of hydroquinone sulfonate
(HSQ) [16] on Pt(lll) likewise corroborated theTLE res-
ults. However, later work based primarily on HREELS
indicated that, at least On Pt(ll1) exposed to DHY,
nonsulfonated diphenols are chemisorbed in essentially
Interfacial Chemistry of Palladium Electrodes 255

o==< \\ /
I )=0
Pt
Pd
Ph 3 P
/ \ PPh
3

- Figure 10 Organometallic complex [14a] as a model for

benzoquinone chemisorbed parallel to the platinum surface.

!
J!3
"2 mMCI-
:::;)
1 mMBr-
..c
~

:-
C'Cl 1 mMI-

~
.. taken of HQS chemisorbed on Pd(lOO) from 0.1- and
100-mM solutions; in both experiments, the pretreated
surface was rinsed with HQS-free supporting electrolyte
w Ipd(111)1 before the HREELS measurements. The results are
;g,
-
w
Z
'1:l 1mMci
shown in Fig. 12. Although other experiments (e.g., AES,
XPS, EC-STM, and/or in situ FT-IRAS) may be needed
for a more definitive conclusion, the overall increase in
peak intensities indicate a higher HQS coverage when
adsorbed from 100-mM solution: The increased coverage
is possible only if the molecule adopts a more compact
(vertical) orientation. That the increased coverage may
be due to the formation of an edge-oriented (C-H
activated) species is evidenced by the increase in O-H
peak intensity, because the O-H stretch is more com-
pletely perpendicular to the surface; the decrease in
C-H peak intensity, due to scission of C-H bonds; and
the emergence ofa C-Pd peak that arises from the forma-
tion ofC-Pd bonds.

o 100 200 300 400 500 600

Kinetic Energy/eV

Figure 9 AES spectra for a Pd(lll) electrode after exposure to

I mM NaCI (bottom) and to a ternary solution of I mM each
ofNaCI, NaBr, and NaI (top). H H

H H C,j:2<rCI
CI...... / .... CI ...... \ ""CI
I , CI CI

only the flat orientation [17].

In view ofthe possibilities that the nonsulfonated com-
pounds might just be pumped away in UHY, whereas
the salt of the sulfonated diphenol would remain on the
3
(CO) t -'-'-

~...............
""\:/
(CO)3
t(CO)3

Pt ___'H c'-5-
CI....\ ......CI .... / ...... CI
C1

surface and the 100 surface may be more reactive than

the 111 plane towards C-H activation (a precursor to Figure 11 Organometallic clusters [14b,c] as models for
vertically oriented adsorption), HREEL spectra were hydroquinone 2,3-edge-adsorbed on Pt.
256 Soriaga et al.

Hydroquinonesulfonate (HQS) on Pd(lOO) protonation reactions, the BQ-reduction reaction

sequence at pH 4 was concluded to be e- H+ H+ e-
- - 0.1 roM HQS
[18d,n].
lOOroMHQS
\ u(PdC) It was first suggested more than a decade ago that
V\ I "CS) 0.1 roM CF 3COOH
at least on smooth polycrystalline Pt, the reported
\t " riCH)
variations in the electrode kinetics of the BQ/H2Q
\/\..../\ jl
I\, ri\ u(8=O)
reaction may arise from the strong dependence of the
\J j \.
electron-transfer rate on the composition ofthe electrode
i \ \J(CC)
surface [19]. For example, the presence of unreactive
\J(CH)
J!J
c u(a-I) chemisorption-immobilized diphenol-derived species
./'\\
g
U
...._~ .. .
~'--''''''''--~ ~ led to a rate-vs.-pH plot that displayed a minimum at
pH 4. However, on surfaces pretreated with iodine,
u(CH) quasi reversibility was observed at all pH values studied.
This work was recently extended by us to other noble-
metal electrodes to ascertain whether the adsorbate-
dependent alterations in BQ/H 2Q electron-transfer
500 !(Xl() 1500 2000 2500 3000 3500 4000
kinetics is a general phenomenon or is unique only to Pt
surfaces [20].
Wavenumbers/cm- 1
Table I shows dEvalues for Pd, Au, Ir, Pt, and Rh elec-
trodes in a I-M Na2S04 solution, phosphate buffered at
Figure 12 HREEL spectrum of the potassium salt of pH 4, that contained I mM H 2Q. As can be seen, the
hydroquinone sulfonate (HQS) chemisorbed on Pd(100) from BQ/H 2Q reaction rate attheiodine-free electrode surface
two different concentrations. decreases in the order Au > Rh > Pd > Pt > Ir. It should
be noted that except for Au, an I-free surface actually con-
tains a layer of H 2Q-derived species, as illustrated in the
EC-STM image in Fig. 13 for an iodine-free Pd(lll)
B. Adsorbate-Activated Electron-'lransfer surface immersed in O.OI-mM H 2Q solution. Iodine
Sites pretreatment results in a dramatic increase in the reaction
The electrochemical kinetics of the BQ/H 2Q redox rates at Ir, Pt, Rh, and Pd electrodes. In contrast, a minus-
couple in aqueous solutions has been the subject of cule rate retardation is caused by I treatment of the Au
numerous investigations [18]. The mechanism that surface.
appears to have gained wide acceptance [18a] provides The influence ofadsorbates other than iodine was also
for a rate that varies with solution pH: In strongly acid investigated. Figure 14 shows thin-layer cyclic volt-
media, reduction of BQ occurs in an alternating ammograms for I mM H 2Q at pH 4 at Ir electrodes that
sequence of protonation (H+) and electron-transfer (e-)
steps; at higher pH, the reaction sequence is reversed.
Table 1 Thin-Layer Electrode Kinetic Parameters of the
For a variety of quinones, a minimum in the overall rate
BQ/H 2 Q Redox Couple at Noble-Metal Electrodes Before and
was found to occur at pH 4, presumably the transition After Pretreatment with Iodine
between the two different mechanisms.
Electrode !J.E(mV)

Rh 35
I-coated Rh 15
Pd 50
I-coated Pd 25
Ir 100
I-coated Ir 25
Later experiments showed that the kinetics of BQ Pt 75
reduction was pH independent; hence, another mechan- I-coated Pt 25
ism was suggested in which a direct two-electron transfer Au 10
step was considered to be rate limiting; the sequence pro- I-coated Au 15
posed was e- e- H+ H+ [18c,g]. In a more recent !J.E values, corrected for ohmic drop, were measured in 1 mM H 2Q in
analysis, based on a theory that assumed equilibrium 1 M Na2S04 buffered at pH 4.
Interfacial Chemistry of Palladium Electrodes 257

a dramatic rate enhancement was noted at the S-coated

Figure 13 In situ STM image ofPd(lll) electrode immersed in
a 0.01 mM hydroquinone solution; the scanned area was
5.5 x 5.5 nm.
were either completely oxided, contained sulfur, or had
BQ on the surface at monolayer coverages. The data show
complete rate retardation at the oxided surface
(kO ~ 10-9 cm S-I) and moderate retardation at the
BQ-pretreated electrode (kO ~ 10- 6 cm S-I). However,
surface, kO:::::10- 3 cm s-l; this was unexpected because
chemisorbed sulfur has long been thought to poison
essentially all surface reactions.
To ascertain ifthe rate enhancement by adsorbed I (or
S) is due primarily to site-blocking effects (prevention of
organic adsorption) or if other influences (electronic
effects) playa major role, kinetic measurements were
obtained as a function of fractional surface coverage
(8 == r /r m, where r m is the surface packing density for a
full monolayer). A simple blocking mechanism would be
manifested by a monotonic increase in f..E as 8s (or ( 1) is
decreased because, as already demonstrated elsewhere
[23,24], the sites left vacant by iodine or sulfur are occu-
pied by chemisorbed BQ. The results, in terms of a
f..E-vs.-8 s plot, is shown in Fig. 15 for S on Ir; similar
results were obtained for Ion Pt, Pd, Ir, and Rh. It is evi-
dent from the data that mechanisms other than simple site
blocking are operative in these two cases because
quasi-Nernstian behavior is already manifested even at
fractional coverages as low as 0.1. It is not known at this
time what these other factors are. Because the BQ/H2Q
reaction at an electrode covered with surface oxide or
with diphenol-derived intermediates is slow, the case
may be made that the quasireversibility observed when
8s (or 8r) ~ 0.1 is due to preferential electron transfer at
sites activated by adsorbed S (or I). This site-selective
redox process is schematically illustrated in Fig. 16.

0.40
15

10
pH 4
\ Fully Oxided
pH 4
\ Electrode
0.30
5
\
\

0
)
~<l
c(
~ , 0.20
-5

-10
\
\
T
Oxide-Coated Ir Full Coverage S
(NoSQ)

~
0.10
-15

-20
-0.1 -0.0 0.1
f

0.2
----S-Coated Ir

0.3 0.4 0.5 0.6

-0>-------<\
0.00 L...~~.L......~~..L-~~--'--~~--'--~~--'-_~-J
-0.1 0.1 0.3 0.5 0.7 0.9 1.1
EN vs. Ag/AgCI Fractional Sulfur Coverage

Figure 14 Thin-layer voltammetric curves at pretreated Ir in Figure 15 tlE-vs.-8 s plots for Ir in I mM H 2Q in pH

I mM H 2Q in I M Na2S04 buffered at pH 4. Solid line full 4-buffered I M Na2S04. The solid line interconnects the data
monolayer ofsulfur; dashed line surface oxides; dotted line, full points and does not represent any theoretical curve. All other
monolayer of H2O. experimental conditions as in Fig. l.
258
H H H H
o o HO
Figure 16 Schematic illustrations of the BQ/H 2 Q redox reaction at a Pt-metal electrode. Top: Surface with a monolayer of BQ.
Middle: Surface with a monolayerofS (or I). Bottom: Surface with coadsorbed organic and S (or I).
Despite the numerous issues that remain to be resolved
on this subject, such as the sizes of the S or I domains in
the presence of coadsorbed organic and the electronic
structure of the adsorbate-activated sites, one aspect
appears to have been established by the data presented:
It will be necessary to specifY the structure and compo-
sition ofthe electrode surface whenever electron- transfer
kinetic parameters are reported.
c. Adsorbate-Induced Substrate Reactions
In an earlier study [21] with polycrystalline Pd electrodes
in halide-free acid solutions, it was discovered that a
Pd~sfto-Pd{~) anodic dissolution reaction was induced
when a layer of iodine atoms was present on the surface.
The rate of dissolution varied directly with the fractional
coverage ofthe chemisorbed iodine, which suggested that
only those Pd sites covered with iodine are activated
toward dissolution. In the absence of the iodine adlayer,
no corrosion transpired; only a passive surface-oxide
layer was formed. XPS experiments showed that iodine
was not removed from the surface even after prolonged
Pd dissolution. This type of corrosion runs counter to
the conventional view that catalyzed dissolution occurs
only in the presence of bulk quantities of corrosive
electrolyte, such as Cl-, in solution [22].
In subsequent related studies [23], it was also found
that a clean and ordered Pd(lll) surface, previously
roughened by several electrochemical oxidation-
reduction cycles (aRC), can be regenerated simply by
exposure, even at ambient temperatures and in the
Soriaga et al.
OH
H H H H
O"'-~O
b O~- :.:.:.- 0
H H H H
absence of applied potentials, of the damaged surface
to an aqueous solution of 1- anions. The immer-
sion spontaneously yielded an ordered Pd(lll)-
CJ3 x y'3)R30° -I adlattice, reductive desorption of
which generated a pristine Pd(lll) single-crystal surface.
Later work demonstrated that the adsorbed-
iodine-catalyzed dissolution process can also be used to
regenerate an ordered Pd(lll) surface from one that had
been roughened by multiple aRC [23c]. Evidently, the
dissolution of Pd atoms at the disordered sites occurred
more readily than those at the ordered domains; as a con-
sequence, extended dissolution eventually converged
toward an interface consisting exclusively of the (more
stable) low-index planes.
These unique iodine-catalyzed reactions of Pd elec-
trode surfaces were recently studied in greater detail; the
results from such studies are the subject of the present
section.
Figure 17 shows photographs of LEED patterns when
Pd(lll) and Pd(lOO) single-crystal electrode surfaces,
previously disordered by multiple aRC, are immersed
in pH IO-buffered I-M Na2S04 solution containing
1 mM KI. The absence of distinct integral-index LEED
spots for the surfaces subjected to aRC indicated that
they had been rendered disordered. However, immersion
ofthe aRC-roughened electrodes in aqueous KI resulted
in the spontaneous formation of well-ordered iodine
adlattices, as evidenced by the sharp LEED patterns
for the regenerated Pd(1ll)-(y'3 x J3)R300-1 and
Pd(lOO)-c(2 x 2)-1 interfaces, these LEED spots are
as sharp as those obtained from UHV-prepared
Interfacial Chemistry of Palladium Electrodes 259

Disordered Pd(100) Disordered Pd(111) in direct contact with four Pd atoms. The formation of
interfacial clustered structures, facilitated by the unusual
mobility of the interfacial Pd atoms, is most probably the
driving force in the spontaneous disorder-to-order rec-
onstruction brought about by iodine chemisorption. If
the surface is roughened more extensively, such as by
Ar+-ion bombardment, the reordering is not immediate-
ly accomplished: Multiple cycles of iodine adsorption-
desorption, at potentials within the double-layer region,

l Dilute KI
""i
Dilute K1l are required [25]. Evidently, a kinetic effect accompanies
the iodine-chemisorption-induced reordering, an effect
that becomes more pronounced for extensively
0

."
0
C') roughened Pd surfaces.
--...
Q,

0
a:
M
-.,.
x
The chemisorbed-iodine-catalyzed dissolution of Pd
was investigated by LEED [26] and EC-STM [27] on
~ C')
single-crystal electrodes to determine whether or not
Ii:)
~
X
,....
,.... changes in the surface morphology accompanied the
'!: ,....
:c
0..
corrosion. Figure 18 shows the current-potential curve

l Reductive
Desorption
Reductive
Desorption
l Pd(111 H·J3x..J3)R300-1
. '

400
LEED

Pd(100) Pd(111)

N
200 STM-EC
Figure 17 LEED patterns for aRC-disordered Pd(lll) and 'E (Atomic Resolution) ~i
Pd(lOO) electrodes after exposure to I mM KI in pH lO-buffered u

-
<{
Na2S04 solution followed by reductive desorption of iodine. ::::l..
100
single-crystal surfaces. Reductive desorption of the STM-EC
iodine, at potentials just before the hydrogen evolution
50 (Layer-by-Iayer Resolution)

region (HER), yielded well-ordered, I-free Pd(lll), and ~./

Pd(lOO) electrode surfaces, as shown by the distinct
a
(l x 1) LEED patterns in the botton pictures of Fig. 17.
For Pd(llO), a well-ordered Pd(llO)-(pseudohexagonal)-1
-50
adlattice (Fig. 4) is also formed upon immersion of the
disordered Pd(110) surface to dilute KI. However, the -100
Pd(111)
potential at which the surface iodine is reductively
desorbed from this plane is well within the HER; hence, a 05 1.0 1.5
almost certainly due to hydrogen absorption, a E/V vs. RHE
reconstructed I-free Pd( 110) surface is generated [24].
The LEED, AES, and EC-STM data all indicate that Figure 18 Cyclic voltammograms of clean (solid curve) and
the real-space Pd-I adlattice structures are such that one I-coated (dashed curve) Pd(lll) in 0.05 M H 2S0 4. The arrows
iodine atom is in intimate contact with several Pd surface indicate the potentials at which the LEED and STM-EC data
atoms; for example, in Pd(100)-c(2 x 2)-1, one I atom is were taken.
260 Soriaga et a1.

Pd(100)-c(2x2)-1 solution process is suggested. The LEED results,

however, were unable to discern whether the corrosion
transpires at steps or via place exchange between the I
and Pd atoms at terraces. For this type of information,
in situ STM experiments had to be carried out.
The initial EC-STM work [27a] was done at potentials
at the foot ofthe anodic dissolution peak (cr., Fig. 18); that
is, in contrast to the high dissolution rates used in the

l
UHV-EC studies, the earlier EC-STM measurements
were carried out only at minimal dissolution rates. Figure
20 shows typical EC-STM images of Pd(lll)-I before
30.ML ML

1
and after I-catalyzed dissolution. In this experiment, a
Etch 30-
Etch
scratch on the surface was made to serve as a marker
(M) to ensure that the STM scans are taken in the same
area of the surface. The top photograph was obtained
before dissolution; the step, monatomic, and diatomic
in height that was to be monitored during the dissolution

Figure 19 LEED patterns for Pd(11l)-(V'3 x V'3)R300-1 and

Pd(100)-c(2 x 2)-1 adlattices before and after anodic dissolution Step
of approximately 30 monolayers (ML) ofPd surface atoms.

for a clean and an iodine-coated Pd(lll) facet, formed on

a single-crystal bead, in 0.05 M H 2S04. The exceedingly
large anodic peak at about 1.2 V represents the
Pd~sfto-Pd~~) anodic stripping that occurs only when
interfacial iodine is present. It is important to mention
that if the potential is held just below 1.2 V, the current,
as expected from a material-limited dissolution process,
does not decay but remains constant. At potentials
beyond the dissolution peak, the iodine is oxidatively
desorbed as 103 ions; the vacated sites are then oxidized
to form a passive oxide film. Evidently, the role of iodine
is to prevent the formation of the passive oxide film. The
potentials at which the LEED and EC-STM measure-
ments were performed are indicated in Fig. 18.
Figure 19 shows photographs of LEED patterns for
Pd(1ll)-(.J3 x .J3)R300-I and Pd(l00)-c(2 x 2)-1 before
and after removal of about 30 monolayers of Pd surface
atoms. In this experiment, the potential was held close
to but not past the anodic dissolution peak (Fig. 18) [26];
that is, the corrosion was carried out at a fairly high rate.
The LEED data clearly show that the postcorrosion Figure 20 STM-EC images of a Pd(1ll)-(V'3 x V'3)R300-1
I-coated Pd surfaces remained as well ordered as they facet on a single-crystal bead at various stages of adsor-
were before the dissolution reaction; a layer-by-layer dis- bate-catalyzed dissolution. M, marker; S, step.
..,.....

Interfacial Chemistry of Palladium Electrodes 261

process is marked S. The middle photograph was taken I on lon-Bombarded Pd(111)

after 10 min of (mild) oxidative dissolution at 0.9 V In
this image, it can be seen that the step has moved toward
the marker and an enlarged smooth terrace has been for-
med. The bottom image was obtained after another
10 min of additional dissolution. It is more evident here
that not only has the step advanced further toward the
marker but that the area ofthe atomically smooth terrace
has also become much larger. The medium-resolution
STM images in Fig. 20 clearly demonstrate that under
conditions of mild dissolution, the reaction takes place
at the steps and one layer at a time.
The STM results show that dissolution of Pd atoms
occurs selectively at step (disordered) sites provided the
impetus for an additional study to ascertain whether or 20-ML
not the anodic dissolution process is able to regenerate
an ordered Pd(lll) surface from one that had been Etch
severely roughened such as by Ar+-ion bombardment.
The results, in terms of LEED patterns, are summarized
in Fig. 21 [27b]. The LEED pattern that results when
the ion-bombarded Pd(111) surface is exposed to aque-
ous iodide is shown in the top photograph; the
(,J3 x ,J3)R30° LEED spots are not discernible, which
signifies that simple chemisorption of iodine does
not reorder the extensively damaged selvedge. The
iodine-coated but disordered Pd(lll) was then placed in
0.05 M H 2 S04 followed by anodic dissolution for
preselected durations; the amount ofanodically stripped
Pd was determined from the measured charge using
Faraday's law. The middle picture shows the LEED pat-
tern obtained after the equivalent of 20 monolayers had
been dissolved; at this stage, the (,J3 x ,J3)R30° LEED I 40-ML Etch
spots have become discernible. The bottom picture shows
the LEED pattern obtained after an additional 20 layers
t I Desorption
are dissolved and the iodine adlattice is reductively
desorbed; the appearance of a distinct Pd(lll)-(1 xl)
LEED pattern provides evidence for the reestablishment
ofa well-ordered surface.
The I(ads)-catalyzed-dissolution reordering reaction is
unique because it occurs in the absence ofbulk corrosive
reagent and only if a chemisorbed layer of iodine is
present. This process may be viewed similarly to digital
etching [28] under electrochemical conditions [29] except
that bulk material is not needed to replenish the adsorbed
iodine that activates the surface and the dissolution pro-
cess does not cease even after the atomically smooth sur-
face has been regenerated. Pd(111 )
Although the data in Fig. 19 show unaltered LEED
patterns for the corroded Pd(lOO)-c(2 x 2)-1, EC-STM Figure 21 LEED patterns of ion-bombarded Pd(111) after
experiments uncovered extraordinary features in the dis- exposure to NaI, after dissolution of 20 layers of Pd, and after
solution process [27a]. Figure 22 shows EC-STM images removal of an additional 20 layers of Pd and reductive
taken at selected intervals at a potential where the desorption of iodine.
262
o 40 80nm
Figure 22 STM-EC images of Pd(100)-c(2 x 2)-1 obtained
(A) 5, (B) 6, and (C) 7 min oflow-current dissolution in 0.05 M
H 2 S0 4 . T, terrace.
corrosion rate is rather low. Causal inspection of the
images shows that Pd(l00)-c(2 x 2)-1 behaves similarly
to Pd(1ll)-(.j3 x .j3)R30o-I. For example, as with the
Pd(lll) surface, atomically flat terraces with monatomic
Soriaga et al.
o Ion the uppe< terrace Pd" uppe< terra"
o I on the lowe< terr"e 0 Pd at lowe' terr"e
Figure 23 Schematic model of a stepped Pd(100)-c(2 x 2)-1
surface to illustrate anisotropic dissolution.
steps were observed; dissolution, likewise, transpired
layer-by-layer at step edges because corrosion via pit
formation at the terraces (T) was not observed.
On closer inspection, however, it can be seen that the
dissolution occurred anisotropically. For example, the
"narrowing" (and subsequent disappearance) of the T 1,
T 2, and T 3 terraces took place almost entirely along the
[OOI]-directed step, with only minimal (if at all) in the
direction perpendicular to it. This type ofanisotropic dis-
solution has been reported for sulfur-modified Ni(lOO)
in acid sulfate solutions [30] and appears to be also oper-
ative in the corrosion ofCu(lOO) in Cl- media [31].
The phenomenon of anisotropic dissolution has been
explained [27a] in terms of the schematic model in Fig.
23 that depicts a Pd(l00)-c(2 x 2)-1 adlayer with
monatomic step edges. From simple coordination-
number considerations, itcan be argued that the Pd atoms
A and B on the upper-left corner of the top terrace are
the most reactive toward anodic dissolution. Removal of
atom A (as in the case of dissolution along the
Interfacial Chemistry of Palladium Electrodes 263

A {100}-directed step edge) easily permits the iodine atom

to slide down from a fourfold (hollow) site at the upper
terrace onto another hollow site (H) at the lower terrace.
On the other hand, iodine descent onto site H cannot be
accomplished upon removal ofatom B (dissolution along
the orthogonal {01O} direction) because of steric hin-
drance by atom A. In this scenario, the ease by which
iodine descends from a high-symmetry site from the
upper to lower terrace is the major driving force in aniso-
tropic dissolution [27a].
Of the three low-index planes studied, the 110 surface
was the most reactive [27a]. Anodic dissolution, even
for short durations, led to deterioration of the
Pd( 110)-( pseudohexagonal)-I LEED patterns (Fig. 24A);
B evidently, the surface, even if still covered with iodine,
had become disordered. This was verified by EC-STM
experiments that showed the formation of randomly
located pits immediately upon initiation of anodic dis-
solution, even at very low currents rna]. After only a few
minutes into the dissolution reaction, the population of
the pits increased significantly. Extended dissolution led
to the following changes in the STM images (Fig. 24B):
the pits became larger, the pit shapes transformed from
circular to rectangular with edges that run parallel to
the {1l0} and {100} directions, the rectangular terraces
were elongated toward the {l00} direction, and
rectangular pits formed at the bottom of the (upper) pits.
o 100 200 300 400 500 The preferential elongation of the rectangular pits is
nm diagnostic of anisotropic dissolution. The anisotropy
has been rationalized in terms of the schematic model
c shown in Fig. 24C of a Pd(110) surface that contains a
rectangular pit two atomic layers in depth. It can be seen
from the model that the step edge along the {110} direc-
tion is constituted by the 111 plane (triangle), whereas
the step edge in the {100} direction consists of the 100
plane (rectangle). The observation that the rectangular
pits are elongated along the {100} direction suggests that
the 111 step is preferentially (albeit slightly) corroded over
the 100 edge. Such preferential dissolution is consistent
with the current-potential data [27a] which show that
the onset of Pd(lOO)-I corrosion is at a potential slightly
more positive than that ofPd(ll1)-1 dissolution.
The propagation of pit corrosion on the upper terrace
and inside the rectangular pits obviously causes the
progressive deterioration ofthe Pd(llO)-l surface. The for-
Figure 24 Pd(lIO)-I. (A) LEED pattern after IO-ML etch (cf., mation of these pits is due to the dissolution ofPd atoms
Fig. 4) (B) EC-STM after 4 min dissolution (C) model of a on the 110 terrace plane after place exchange with the
rectangular pit; the steps are represented by the triangle (Ill adsorbed iodine. In view of the aggressive reactivity of
plane) and rectangular (100 plane). the Pd(llO)-I surface relative to Pd(lll)-1 and Pd(lOO)-I
[27a], it may just be that pit corrosion on Pd(110)-1
terraces cannot be eliminated, even at very low dissol-
ution rates.
264 Soriaga et aI.

Pd(111 )-('J3x..J3)R300-1 Pd(111 )-(..J3x..J3)R300-1

0 2.5 5,0 7.5

0 5.0 10
nm
0.05 MH 2 S04 0.05 MH2 S04

t 1.1 V (RHE)
5 Minutes
0.75 V (RHE)
10 Minutes t
8.0 7.5

6.0
5.0
1.0V (RHE)
3 Minutes
4.0
~
2.5
2.0

0 0
0 2.0 4.0 6.0 B.O 0 2.5 5.0 7.5
nm nm

Figure 25 Atomic-resolution EC-STM images of the Pd(1ll)-(~3 x ~3)R300-1 adlattice as the potential, initially within the
double-layer region, is made more positive and then reverted to its original value.

The question remains as to how the dissolution
transpires at more positive potentials (at much higher
reaction rates) for the Pd(lll) and Pd(lOO) surfaces. To
support the higher corrosion rates, place exchange
between iodine and palladium could occur on a terrace
site to expose a Pd atom and enable its dissolution. Evi-
dence for this, even at low current densities, has already
been described above for Pd(llO); in this particular case,
pit formation also occurred on the lower terraces, which
led to extensive disorder within the interfacial layers. If,
on the other two low-index planes, pit formation occurs,
one must reconcile the result with the fact that the LEED
experiments indicated unroughened surfaces even after
corrosion at high rates. An overalliayer-by-layer dissol-
ution can still occur if the more facile step-selective
mechanism is immediately triggered after a pit is formed;
in such a sequence of events, the pits will become larger
in width but remain constant in depth.
In this part of the work [32], the applied potential
chosen was that which provided the highest possible cur-
rent densities without deterioration of the EC-STM
images; this potential is shown in Fig. 18. Figure 25
displays a sequence of structural transformations, as
conveyed by atomic-resolution EC-STM images, of
the Pd(1ll)-(~3 x ~3)R300-I adlattice as the potential,
initially within the double-layer region, is made more
positive and then reverted to its original value.
Two important features are to be noted in the image
obtained after 5 min at l.l V: the erstwhile smooth
terrace has become strewn with small-size pits, the widths
ofwhich are equivalent to 2-5 iodine atoms, and the sec-
tion profile of the pits indicate step heights of about
0.23 nm, a value indicative of a Pd-atom, not an I-atom,
vacancy. These two features point to an I1Pd
place-exchange process in which underlying Pd atoms
are segregated to the outermost layer before their dis-
Interfacial Chemistry of Palladium Electrodes
solution. The facts that the pits are not deeper than one
Pd-atomic step; for extended corrosion times, the lateral
size ofthe pits become larger but the depth remains con-
stant; and the (.)3 x .)3)R30° structure of the adlattice
at the bottom of the pit is identical to that on the upper
terrace all point to a layer-by-layer dissolution process
subsequent to the place-exchange reaction. Such a mech-
anism is not unexpected because pit formation exposes
defects that enable the kinetically favored step-selective
mechanism to proliferate. It is quite interesting to note
that at 1.1 V, pit formation does not occur randomly but
appears to follow a hexagonal pattern. The reason for
such preferential I1Pd place-exchange sites is presently
not understood.
When the potential was lowered to 1.0 V, two changes
take place: the population of terrace pits decreases and
the sizes of the pits are reduced to the equivalent of no
more than two iodine atoms. Section-profile measure-
ments of the pits continue to indicate an atomic-step
height characteristic of palladium, not iodine. Evidently,
the extent of 1-Pd place exchange depen ds on the applied
potential (reaction rate): The incidence of place-
exchange-induced monatomic pits increases as the dis-
solution rate (applied potential) is increased.
Within minutes after the applied potential is returned
to its original (double-layer region) value, the terraces
become free of pits and revert back to their original
well-ordered Pd(111)-(.) x .)3)R300-1 structures. A
decrease in electrode potential thus induces a reverse
place-exchange process in which all embedded iodine
atoms are transported back to the uppermost layer;
implicit in this reaction is the redeposition of Pd onto
the pits before place exchange. The structural
"relaxation" toward pit-free atomically smooth terraces
when the anodic stripping reaction is halted may explain
why distinct LEED patterns were retained even after
prolonged dissolution at high rates (Fig. 19): When the
electrode is emersed, the applied positive potential
is disrupted. Apparently, such disruption leads to a
Faradaic discharge that, in turn, results in the dis-
order-to-order "relaxation." The reverse place-exchange
process is almost certainly due to the fact that in the lower
oxidation states, iodine can accommodate only one
covalent bond [lOa,b]; that is, to maintain monovalency,
the top Pd atom must trade places with the bottom iodine
atom.
III. CONCLUSION
The "palladium anomaly' is one of those breakdowns in
periodic trends that to the non practitioner of theoretical
inorganic chemistry can be expediently swept under
265
the electron-repulsions and/or relativistic-effects rug.
Whereas theaujbau and related rules [9a] are readily sat-
isfied for the first-row transition-metal atoms, d-orbital
electron-electron repulsions in the later elements of the
lower transition series lead to an increase in the energy
gap between the nd and (n + l)s orbitals [31]. As a con-
sequence, the valence electrons in these metals are forced
into the lower energy d orbitals. Hence, although the
valence-shell electronic configuration for an Ni atom is
3d8 4s 2 , that for an isolated Pd atom is 4d lo 5so. In the case
of Pt, relativistic effects narrow the nd/ (n + l)s energy
gap such that the electronic configuration for atomic Pt
is 5d 9 6s 1 [32]. These effects are carried over, albeit to
a lesser extent, into the bulk where to maintain stable
metal- metal bonds, (n + l)s-orbital contributions are
required; without such contributions, there would only
be dlO_dlo (electron-electron) repulsions. Given the
absence of (n + l)s electrons in atomic Pd, it should be
no surprise that the Pd-Pd bonds in the bulk metal are
unusually weak.
Regardless of the detailed explanation, the fact
remains that the palladium anomaly does exist, and, as
the above discourse has illustrated, it can playa critical
role in the interfacial structural and chemical properties
of palladium electrodes.
ACKNOWLEDGMENTS
The cases discussed in this chapter have resulted from the
studies of several coworkers: I B. Abreu, R. I Barriga,
G. M. Berry, E. Binamira-Soriaga, M. E. Bothwell, B.
G. Bravo, G. I Cali, I E. Harris, I-I Jeng, E. A. Lafferty,
I R. McBride, M. R. Marrero, T. Mebrahtu, S. L.
Miche1haugh, S. Mukerjee, I F. Rodriguez, S. A. Salinas,
and W F. Temesghen. Our research has also benefitted
from collaborations with the laboratories of A. I Bard
(DW Suggs), K. Itaya (K. Sashikata), and I L. Stickney.
Financial support has been provided by the National
Science Foundation, the Robert A. Welch Foundation,
the Dow Chemical Company, and the Energy Resources
Program of Texas A&M University.
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16
Electrochemical Double-Layer Modeling Under Ultrahigh
Vacuum Conditions
G. Pirug and H. P. Bonzel
Institutjiir Grenzfliichenjorschung und Vakuumphysik, Forschungszentrum Jiilich GmbH, Jiilich, Germany
ABSTRACT
The simulation ofthe electrochemical double layer under
ultrahigh vacuum (UHV) conditions allows the
characterization of the chemical interaction between
electrode surface and electrolyte constituents. The elec-
tron work function measured for an adsorbate covered
metal in UHV is considered to be equivalent to the elec-
trochemical potential for the same adsorbate-electrode
pair in solution. This common potential scale represents
an important link between UHV studies and
electrochemistry. The potential range accessible by the
investigation of substrates with different work functions
can be expanded by the coadsorption of electronegative
and electropositive species, such as halogens or alkali
metals, which induce large work function changes. The
adsorption of anions or cations from electrolytes,
achieved in UHV at low temperature, is of particular
interest. Solvation processes and surface reactions, which
result from the electrostatic interaction between the
partially ionically adsorbed species and coadsorbed
H 20, the most frequently used solvent, can be studied by
applying surface sensitive techniques. A variety of
methods have been developed that allow the investigation
ofthe surface structure and chemical composition.
I. INTRODUCTION
Numerous different experimental approaches are being
used to study the physical and chemical processes within
an electrochemical cell. Recent research concentrates in
particular on the region of the electrochemical double
layer in the immediate vicinity of the electrodes. The gen-
269
eral consensus seems to be that a complete understanding
of the double-layer physics and chemistry can only be
gained by combining the information obtained by all
possible approaches. Depending on the environmental
requirements of the experimental techniques, one dis-
tinguishes "in situ" and "ex situ" and ultrahigh vacuum
(UHV) model experiments, which are also called
"non-situ" experiments [1]. Of course, the most realistic
case is the in situ investigation where electrode,
electrolyte, and applied electrochemical potential are
present and where the investigative technique is directly
applicable. The number of techniques suitable for the
study ofsolid -liquid interfaces is unfortunately relatively
small, such that other experimental approaches have
been developed over the years. The ex situ technique
involves the removal of the electrode under particular
conditions ("emersion"), and the subsequent application
of a surface diagnostic tool outside the electrolyte. It has
been demonstrated by such emersion experiments that
the electrochemical double layer, which is shown
schematically in Fig. 1, appears to stay intact after
removal from the bulk electrolyte, thus allowing an ex situ
characterization by spectroscopies, such as photo-
electron spectroscopy or low-energy electron diffraction,
which are only feasible under vacuum [2-4].
Finally, there is a third possibility to study model elec-
trochemical preparations outside the electrochemical
cell, namely under vacuum conditions, without applied
electrochemical potential. These experiments have the
advantage that the full arsenal of surface analytical
techniques, of which some exclusively function under
270 Pi rug and Bonze)

Metal and electrode potential are aligned at the potential E k of

(a)
plane the normal hydrogen electrode (NHE). Although some
~::---'--'-J
controversy exists concerning the exact value of Ek, it
can be localized at 4.6 eY, with an uncertainty of ± 0.2 eV
[1]. Figure 2 summarizes data for some systems studied
so far. These findings represent an important link
between in situ and non-situ UHVmodel experiments [1].
............... Solvated Under these precautions, results obtained under UHV
anions conditions can be transferred to the electrochemical case
to get a better understanding of basic processes in the
immediate vicinity of the electrode.
Nevertheless, UHV model experiments entail con-
siderable simplifications, because an electrochemical cell
Specifically
represents a rather complex system that is not readily
, .,..~~~~.,y.+--adsorbed simulated under UHV conditions. Controlled by an
anions externally applied electrical potential, the overall proper-
ties of an electrochemical cell depend on the material of
the two electrodes and the nature of the specific electro-
lyte dissolved in a particular solvent. Here the structure
Inner Outer
Helmholtz plane
and composition of the double layer in front of the elec-
trodes are of particular importance and therefore of
(b) special interest. Figure la shows schematically the distri-
bution of the solvent molecules and electrolyte anions
(j)m
\
near a positively charged electrode surface [2,3]. The
metal I\ electrolyte accumulated charge associated with specifically
1\ adsorbed and solvated ions results in a substantial poten-
(j)2 - - --- - - r J,_ -- tial drop, as shown in Fig. Ib. The distribution of these
(j), L---""oH-v'-~--- x extra charges is not only determined by electrostatic
forces but also influenced by the chemical interaction
between the electrode surface and the electrolyte ions.
Specific adsorption of ions induces the polarization of
Figure 1 (a) Model of the electrochemical double layer,
featuring solvated cations and anions near the anode surface;
a specifically adsorbed anion is also shown. (b) Potential distri-
bution across the double layer without (--) and with (- - -)
specific adsorption. (From Ref. 3.)

<I> / eV ...l..._--,_LL-F==J.-...,...L...L.....l_.....l.,
vacuum conditions, can be used for the study of the
"model double layer"consisting oftypical ions and frozen
electrolyte. Low temperature is required to keep the elec-
trolyte on the surface of the electrode material. The fea-
tures of low temperature and missing electrochemical
potential put this experiment in to the class ofan idealized
"model experiment," also called non-situ [1], meaning
that it is neither an in situ nor ex situ electrochemical
study. For this case ofexperiments, it has been shown con-
vincingly that one of the most important quantities in
the electrochemical cell, namely the electrode potential, Figure 2 The analogy between UHV model experiment and
is related to the work function measured for the electrode electrochemistry, illustrated by the comparison of the electro-
surface under UHV conditions.The relationship between chemical potential and the work function scales. (Adapted from
the two scales is illustrated in Fig. 2. The work function Refs. 1,9, and completed by data for Au(lll) from Refs. 4 and 18.)
UHY Conditions for Double-Layer Modeling 271

charge in the electrode surface, giving rise to a local mini- requisite for a better understanding of electrochemical
mum in the potential at the inner Helmholtz plane. phenomena. The fundamental aspects of the interaction
Specific adsorption is assumed to be analogous to of H 20 with solid surfaces have been recently reviewed
chemisorption, which is usually the subject of UHV [14]. But H 2 0 especially represents an example where
model experiments. the transferability of UHV data to solution chemistry is
The UHV model experiments [1,5-11] simulate an by no means straightforward. Although electrochemistry
electrochemical double layer by the adsorption ofelectro- takes place mostly under atmospheric pressure at room
lyte constituents on single-crystal surfaces, such as Ag, temperature, where H 20 is present in its liquid phase,
Au, Cu, Ni, Pt, or Ru, closely related to materials com- UHV studies are restricted to lower temperatures of
monly used in electrochemistry. These species can be typically less than 150 K where the vapor pressure of
adsorbed separately, sequentially, or simultaneously. The H 2 0 is low enough to get stable (frozen) H 20 layers [12].
main difference between the adsorbed layers produced The substrate-dependent interaction strength can be
under UHV conditions and the real double layers in elec- illustrated by the corresponding thermal desorption
trochemical cells is the absence of an externally applied spectra of H 20, shown in Fig. 3. This method finds its
electric field that allows a variation of the surface charge counterpart in cyclic voltammetry, which is frequently
[12]. This surface charge induces specific or unspecific applied in electrochemistry for the investigation of the
adsorption of electrolyte ions and charge polarization adsorbed states on electrode surfaces. Whereas in cyclic
and molecular ordering within the double layer. However, voltammetry the desorption is induced by a charge vari-
the charging of the electrode surface is not only induced ation and monitored by the resulting current flowing
by an applied potential but also by a chemical charge through the cell, thermal desorption spectroscopy (TDS)
transfer between electrode and electrolyte species. The
latter effect occurs also in the modeled double layer and
can be investigated in UHVadsorption experiments.
Furthermore, the influence of electric fields on the eH20 =lmL
adsorption of electrolyte species can be modeled by the
adsorption of electropositive or electronegative species, :J
such as alkali metals or halogen atoms [5-10,13]. These «
species adsorb ionically on metal or semiconductor H/Cu(110)
surfaces, resulting in the formation of a dipole layer that
W
t-
e
leads to substantial work function changes (increase or «
a:::
decrease). According to Fig. 2, these work function
z Cs/Cu(110)
changes are analogous to the charging of the electrode d
by an externally applied potential. Although certain
objections concerning the transferability of these data
--o..
0
t-
0::: Br IAg{nO)
exist [12], important information, difficult to obtain
otherwise, can be gained by using the common potential
0
(f) c
scale for interpreting UHV model experiments. For w
0
example, well-established spectroscopies or imaging I
techniques can be used to study the chemical reactivity 0
N clean Ag(110)
between the constituents of electrolyte and electrode I b
surface. Besides the chemical composition, structural
effects can also be investigated. This refers not only to
the adsorbed phase but also to the electrode surface
clean Cu(110)
whose chemical state or surface structure may be altered
upon the adsorption of electrochemically relevant
a
specIes.
100 200 300
II. H 2 0 ADSORPTION
TEMPERATURE/K
H 20, the most frequently used solvent, plays a major role Figure 3 Thermal desorption spectra (TDS) for H 20
in electrochemistry. Therefore, a profound knowledge of interacting with Ag(llO) and Cu(llO) surfaces and coadsorbed
its adsorption properties seems to be a mandatory pre- H, Cs, and Br. (From Ref. 9.)
272
data are obtained by measuring the desorbing H 20 mol-
ecules mass spectroscopically upon heating the substrate
with a linear temperature ramp. Different states can be
distinguished whose peak temperatures allow the deter-
mination of the activation energies for desorption. The
most weakly bound H 20 molecules, desorbing first at
about 150 K, correspond to the sublimation from con-
densed icelike layers. On substrates such as Ag(llO) (Fig.
3b), which do not exhibit additional desorption peaks,
the chemisorbed layer cannot be distinguished from the
condensed phase. The chemisorption strength is obvi-
ously comparable with the lateral interaction due to H
bonding within the H20 layer. Other metals, e.g. Cu(llO)
(Fig. 3a), interact more strongly with H 20, leading to
desorption peaks at higher temperatures. These peaks
can be related to molecular H20 layers in contact with
the surface. The weak chemical interaction of H20 with
metal surfaces, which is comparable with the H bonding
strength, favors the formation of ice clusters even in the
submonolayer regime. Because of the low energy barrier
for surface diffusion, H20 monomers can be observed
only at very low temperature, as has been shown on
Cu(lOO) and Pd(lOO) at 10 K [15]. The coadsorption of
H, Cs, or Br leads to a stronger chemisorption of H 20,
giving rise to higher desorption peak temperatures (Fig.
3c-e). Under these conditions, even recombinative
desorption from dissociation fragments, such as OH
and H, has to be taken into account. as is discussed in
more detail below.
H bonding and the small surface corrugation are
responsible for the formation of ordered H 20 layers.
These surface structures were mostly studied by low-
energy electron diffraction (LEED), but also methods
that probe the local bonding configuration, such as
electron-stimulated desorption ion angular distribution
(ESDIAD) [16] or x-ray photoelectron diffraction (XPD)
[17], contributed to the proposed structure models.
Especially hexagonal surfaces, such as Au(lll) [18],
Pt(lll) [19,20], or Ru(OOI) [16,21], are well suited for the
formation of two-dimensional icelike structures. On
these substrates, ordered .J3 x .J3R30° structures are
observed. These structures do not simply consist of one
layer but are formed by two hexagonal layers, one in con-
tact with the metal surface and the second H bonded on
top. A schematic diagram of a perfect bilayer structure
on a hexagonal substrate is shown in Fig. 4. These bilayer
structures closely resemble the structure of crystalline
°
ice [22]. The next nearest distances within the same
layer of about 4.69 A (Ru), 4.8 A (Pt), and 4.98 A (Au)
are very close to the corresponding value for ice of about
4.52 A. The local arrangement within such a structure
has been determined by quantitative LEED [21], whereas
Pirog and Bonzel
~
:~:~r I
secondt
layer
•
Figure 4 Schematic diagram of a perfect H20 bilayer on a
hexagonal surface. (From Ref. 16.)
the direction of free O-H bonds could be determined
by an ESDIAD pattern [16]. Vibrational spectroscopy
(infrared reflection-absorption spectroscopy [IRAS] [23]
and high-resolution electron energy loss spectroscopy
[HREELS] [17,24,25]) has been used to study the molecu-
lar structure with special emphasis on different kinds of
H bonding. Stretch frequencies for H-bonded OH groups
within the H20 layer and for those directed toward the
surface at the rims of ordered bilayer islands could be
clearly distinguished. Although the former are character-
ized by a broad vibrational feature near 3400 cm- 1, the
latter give rise to a relatively sharp mode at frequencies
below 3200 cm -I. Also free (non-H bonded) OH groups
could be detected at higher frequencies above
3600 cm- I . The most direct proof for the formation ofa
bilayer on a Pt(lll) surface has recently been obtained
by scanning tunneling microscopy (STM), as shown in
Fig. 5a [20]. The molecular ice structure is characterized
by hexagons that correspond to the unit cell ofthe bilayer
schematically shown in Fig. 5b.
The electrochemically most relevant quantity derived
from UHV measurements is the work function change
due to the adsorbate-induced surface dipole layer. Chemi-
cal interaction between the substrate and the adsorbate is
associated with a redistribution ofcharge. Depending on
the type of chemical bonding, a redistribution or
polarization of charge occurs for ionic, covalent, or even
van derWaals bonding, respectively. Also, the orientation
of permanent dipole moments of adsorbed species con-
tributes to work function changes. For molecular H 20,
=
which has a large dipole moment of (l D 10- 18 esu.cm)
1.6 D, one generally observes a work function decrease
during adsorption.The latter is consistent with a preferred
UHV Conditions for Double-Layer Modeling 273

2.4
Pt (111) + K + H2O
T= 110K
2.0

1.6
~
$
<l
lJJ 1.2
C)
z
«
I
u
z 0.8
0
i=
u
z:;)
LL
::.::
a::
0
~ 0

-0.4

0
-0.8
0 1 2 3 4 5

Pt o • II
H2O EXPOSURE (10-6 mbar· 5)

Figure 6 Work function change for H 20 adsorption on a

clean and K covered Pt(lll) surface at 110 K. (From Ref. 26.)

of about 0.8 D. Ab initio total-energy calculations for a

b work function change and dipole moment becomes ques-
Figure 5 (a) STM image (28A x 28 A) of an H20 bilayer on
Pt(lll) with a solid drawn hexagon indicating one hexagonal
molecular ice ring as schematically shown in b. (From Ref. 20.)
average orientation of the permanent dipole moment of
the H20 molecule, where the H atoms are pointing toward
the vacuum, whereas the chemical bonding to the
substrate surface takes place via the a lone pair orbital.
As an example, the work function change for H20 adsorp-
tion on a Pt(111) surface is shown in Fig. 6 [26]. The linear
decrease for small H 20 coverages yields a dipole moment
single H 20 molecule adsorbed on a Pt 1a-cluster with (111)
symmetry showed that not only the orientation ofthe per-
manentdipolemoment but also the polarization ofcharge
due to the chemical interaction between the metal atoms
and the a atom contributes to the adsorption-induced
overall dipole moment and thus to the work function
change [27]. On the other hand, the correlation between
tionable for the cases of bilayer and three-dimensional
cluster formation. The dipole moment can no longer be
associated with a single molecular species or a definite
charge transfer at the interface.
In summary, the UHV results for H20 adsorption on
clean metal surfaces cannot directly be transferred to
the situation in electrochemical cells. Under UHV con-
ditions, the necessary low adsorption temperature
reduces the mobility of H 20 molecules, such that H20
cannot be studied in its liquid state. Nevertheless, some
fundamental results can be obtained with implications
for electrochemistry. The weak chemical interaction with
the substrate results in a small but not negligible potential
corrugation that allows the nucleation of ordered mol-
274 Pirog and Bonzel

ecular HzO layers. H bonding within these layers is 0.6 r-------,----~----~----.

responsible for the formation of bilayers and possibly
three-dimensional clusters. The physical properties of 0.6
b ".,-"",;
--- ---
~'
these adsorption structures resemble more closely those ,,"
ofcrystalline ice than ofliquid Hzo.
0.4

0.2
III. COADSORPTION OF IONIC SPECIES AND /
/
H2 0 I
0.0 l.-o==:;.._....... ..J..- .L-_---.l

The main difference between liquid-solid systems in o -100 -200 -300

electrochemistry and gas -solid interfaces in UHV is the Potential versus Onset of
Hydrogen Adsorption (mV)
lack ofelectrode potential control for the latter. Although
the work function corresponds to the electrode potential
(compare Fig. 2), it cannotbe varied as simply as the exter- Figure 7 H coverage as a function of (a) the electrochemical
potential vs. the onset of hydrogen electrosorption in 0.3 M
nally applied potential in an electrochemical cell. This
HF and (b) work function change upon adsorption on Pt(11l).
difficulty can be partly circumvented by coadsorbing (From Ref. 28.)
ionic species, such as halogens or alkali metals. The
adsorption of these electronegative or electropositive
species causes a coverage-dependent work function
increase or decrease, respectively. Hence, the adsorption functions, such as Cu(11O) [29] or even at steps on a
of HzO can be performed in UHVon a high or low work stepped Pt(lll) [30], indicate that hydrogen can also act
function surface, analogous to the anodic or cathodic as an oxidizing-agent.
regime in electrochemistry. Beyond the molecular H+ ions, whose concentration is given by the actual pH
adsorption, also chemical reactions, such as the dis- value, are always present in solutions, even in neutral Hzo.
sociation of HzO or ion hydration processes expected These protons in solution can be hydrated, an effect that
under these conditions, can be studied. is also measurable under UHV conditions. The influence
ofthe work function on the hydration ofprotons has been
demonstrated by comparing Pt(lll) and CuCllO) [31].
A. Hydration of Protons The work function of the HzO-covered Cu(llO) surface
is with 3.7 eV, much smaller than the corresponding value
The correlation between work function change (UHV of about 4.9 eV for the H 2 0-covered Pt(111) surface, as
model experiment) and electrostatic potential can be dis-
cussed for the simple process of hydrogen adsorption on
a Pt(111) surface. Figure 7 compares directly the work o
function decrease vs. increasing H coverage for Hz
adsorption on Pt(111) (Fig. 7b) to the electrosorption of
H expressed as coverage vs applied electrode potential
~2
1 f-
4.9
)
4.8 ., !:
in OJ M HF solution (Fig. 7a) [28]. Although the two
curves are not identical, they describe the same trend.
Increasing H coverage results in a work function
decrease, similar to H electrosorption upon lowering of
the potential in solution. The differences between the
-
c:
.23
u

-
§4
.:0::
"L
I"", , . ":--
5.9

SHE 1 atmH2
,u.J... Hads
~.;'
Co ''0,"
Cu(110)
f
05
two curves may result from interaction of electrosorbed 3: pte 111)
H with water or other components in the electrochemical 6
double layer that are not present in the UHV counterpart. 7
The monotonic H-induced work function decrease
indicates at least partially positively charged adsorbed Figure 8 Work function for clean and H2 0 monolayer
H. Hence, hydrogen can be considered as a reducing covered Pt( III) and Cu(ll 0) surfaces related to the absolute elec-
agent under these conditions. But this is not a general trochemical potentials of a standard hydrogen electrode (SHE)
property of adsorbed hydrogen. Work function increases in equilibrium with I atm H2 , neutral water (pH 7), and
observed for the adsorption on surfaces with lower work adsorbed Hads ' (From Ref. 32.)
UHV Conditions for Double-Layer Modeling
shown in Fig. 8 in comparison with the work function of
the standard hydrogen electrode (SHE), which has been
set to 4.8 eV [32]. In addition, the corresponding absolute
electrode potentials for equilibrium with adsorbed H
and a neutral H 20 solution (pH 7) are indicated, which
relate more closely to the DHV and electrochemical
situation, respectively. In the language of electro-
chemistry, the H 20 covered surfaces of Pt(lll) and
Cu(llO) resemble the more anodic and cathodic potential
regions, respectively.
Consistent with the foregoing, it has been found that
coadsorbed H can be oxidized and hydrated to H30+ on
an H20 covered Pt(lll) surface but not on H 20 covered
Cu(llO) [31]. Wagner and Moylan [28] identified the for-
mation of H 30+ ions upon H 2/H 20 coadsorption on
Pt(lll) using HREELS. The HREELS spectra presented
in Fig. 9, obtained after adsorption of H on an H 20
precovered surface and a subsequent anneal to 150 K,
exhibit a peak at 1150 cm- I . This peak can be un-
ambiguously assigned to the symmetric bend vibration
of a pyramidal H30+ species. The necessary anneal to
150 K indicates that the formation of H30+ is an acti-
Loss Energy (1/c~
400 1200 2000 2800 3600
o 100 200 300 400
Loss Energy (mV)
Figure 9 HREELS spectra at 90 K of 0.9 monolayer H 2 0
with and without 80% saturation H2 predose: (a) 1.4 L H20,
90 K; (b) 1.4 L H20, flashed to 150 K; (c) 10 L H 2+1.4 L H 20,
90 K; (d) 10 L H 2 + 1.4 L H 2 0, flashed to 150 K. (From Ref. 28.)
275
vated process, which may be responsible for the drop in
electrochemical kinetics below 160 K reported pre-
viously for the H 2 evolution in frozen HCI0 4 . 5.5 H 20
by Frese and Stimming [33]. By comparison, H30+ for-
mation could not be observed on an H20 covered Cu(llO)
surface [31]. Because ofthe low work function in this case,
there is no tendency for the metal to abstract an electron
from the adsorbed H. Instead one observes a work func-
tion increase for H adsorption of Cu(llO) [29]. Rather
than forming the oxidized hydronium species, a forma-
tion of hydride seems to be more likely, as expected in
the cathodic potential range.
B. Coadsorption of Electronegative Species
One other example illustrating the analogy between the
DHV work function and the electrochemical potential
is the adsorption ofBr~ ions on Ag(llO) [9,13]. To simulate
a situation of high anodic potential under DHV con-
ditions, different amounts of Br have been adsorbed,
together with H 20 up to one monolayer. As shown in Fig.
10, the work function increases monotonically with
increasing bromine coverage 8 Br . Analogous data for
the corresponding potential drop in front of a charged
electrode, attributed to only adsorbed Br- ions, cannot
directly be measured. However, in situ capacity measure-
ments for solutions with different Be concentrations
allow the determination of the adsorbed Br- charge O'Br
that induces, partly compensated by excess charges in
the diffuse layer, a certain potential drop, such as shown
in Fig. 10, for varying electrode charges 0'. The corre-
sponding data result in straight lines, which can be
extrapolated to values, where the adsorbed Be charge
O'Br is equal to the electrode charge 0' (black dots). In this
d
way it has been demonstrated that the potential drop
within an electrochemical double layer agrees reasonably
well with the work function changes observed in DHV
for adsorbed Br on Ag(llO) surfaces. Similar results were
c obtained also for Cl- on Ag(llO) surfaces [9].
C. Coadsorption of Electropositive Species
The adsorption of alkali metals, the electropositive
b counterpart of halogens, on metal substrates has also
been intensely studied to simulate the cathodic charging
of electrodes in DHV adsorption experiments, as
a reviewed recently [11]. Alkali metals reduce the work
500 function in a characteristic way. An example is shown in
Fig. 11 for Na and K adsorption on a Pt(lll) surface [26].
A linear decrease at low coverage is followed by a some-
what shallow minimum until almost the alkali metal bulk
value is reached for monolayer coverages. The coverage
dependence is generally well understood and has been
276 Pirug and Bonzel

-2
Electrode Charge 6sr( lJ.C em )
o 20 40 60 o Pt (111) + No
.Pt(111)+K
~
-e- 800
<J
C1I
o UHV
01 • in situ
c
o
..c
U
g 600
·z
u
C I
:J
U. I

.:x.
~

~ 400 -SOL...----'---..L----'O---O...L---'-S-----'6
O.1 0.2 .3 .4 O. 0.
COVERAGE 8

Figure 11 Work function change for Na and K adsorption on

Pt(lll). (From Ref. 26.)
200

The large work function change is the outstanding

o 0.2 0.4
Bromine Coverage aSr(MU
Figure 10 Comparison of the work function changes due to
the adsorption of one monolayer of coadsorbed Br and H 20
on Ag(llO), as determined in UHVand the electrostatic poten-
tial drop in the electrochemical double layer as derived from
capacity measurements in solution with varying Br- concen-
tration and electrode charge (J at conditions ofzero diffuse layer
charge as a function of the Br- coverage, expressed as a
fractional surface coverage 8 Br and electrode charge (JBr,
respectively. (From Ref. 9.)
theoretically described, although different views exist
concerning the amount of charge transfer between the
substrate and the alkali atom [34~36]. The linear decrease
at low coverage results from a more or less ionically
property ofalkali metal adsorption. The linear range, i.e.,
the ionic part, is of particular importance for the simu-
lation of charged electrodes. A characteristic quantity
for the strength ofthe induced electrostatic field is the cor-
responding initial dipole moment, /lo, which can be cal-
culated from the slope of the linear portion of the work
function change. The Helmholtz equation describes the
work function change ~<1> for an ionically adsorbed
species with an elementary charge e and a surface density
Na:
The dipole moment
/l = 2de
includes the image charge contribution separated by a
distance 2d. Hence, the initial dipole moment /lo is given
by
1 d~<1>1
/lo = 2ne dNa N,,-.O

chemisorbed species, although the charge transfer from

the alkali metal is not complete. The increasing lateral The initial dipole moment /lo can be expressed in the
interaction with increasing coverage leads to a more met- common unit ofD [1 D = 10- 18 esu em] according to
allic overlayer. The slope of the work function change
decreases. Finally, after passing the minimum, a work /lo
d~<1>1
= 5.31 x 10 14 d
function similar to that ofthe bulk alkali metal is reached. Na INa->O
UHV Conditions for Double-Layer Modeling 277

Table 1 Survey of H 20/Alkali Metal Coadsorption Data for Pt(lll) and Ru(OOl)

avo H20 dipole Alkali dipole

System 0 crit ~<I>ma, (eV) moment J1 (D) moment J1AM (D)

Na/Ru(OOI) 0.05 ~O.l -0.2 6.0

K/Ru(OOl) 0.05 0.5 -0.4 13.8
Cs/Ru(OOI) 0.08 ,=,,0.9 -0.9 21.5
Na/Pt(lll) 0.10 ::::1.2 -0.53 7.1
K/Pt(lll) 0.10 2.0 -1.l4 15.0
Source: From Ref. 26.

with A<D in Vand N a in cm-2. Table 1 summarizes some of 531 eY. The saturation coverage of these species
dipole moments for different alkali metals and substrates increases with the amount ofpreadsorbed K. On the basis
[26]. of the observed binding energy, it can be concluded that
As an example of the coadsorption of H 20 and alkali H 20 adsorbs dissociatively, leaving OH on the surface.
metals, data for the Pt(lll) + K system are summarized. The identification of the OH species is also supported by
Generally speaking, such systems have been studied by UPS [37] and HREELS [17] results. No molecular H20
applying several UHV techniques, such as X-ray can be detected on these surfaces at room temperature.
photoelectron spectroscopy (XPS), UV photoelectron Now the interesting question about the origin of the
spectroscopy (UPS), work function measurements, and initial work function increase at low temperature remains
vibrational spectroscopies (HREELS and IRAS), illus- to be answered; this increase has been observed below
trating also how different methods complement each the critical K coverage, i.e., in a range, where at room tem-
other [17,26,37,38]. perature no effect of added H 20 is observed at all. All
The most significant influence of coadsorbed alkali applied spectroscopies, such as XPS, UPS [37], HREELS
metal on H 20 adsorption is revealed by the work function
data, such as shown for the system K/H20 in Fig. 6 at a
low temperature ofllO K. H 20 induces the typical work 1.2 ....---------,•. ...-----------,
function decrease for the K-free surface and an initial
work function increase for K-covered surfaces. With Pt(111) + K + H2 0, T=320 K
increasing H 20 exposure, eventually a maximum is
reached whose height is proportional to the K coverage.
'G
<3
1.0 ~
8 K =0.141
At still higher water exposures, the work function
decreases again. A different behavior is recorded at room
lJJ
(!) r
temperature, for which data are summarized in Fig. 12. z 0.8
Here the work function increases with water exposures.
«
:c
This effect can only be observed for K coverages u
8K = 0.138
exceeding a critical coverage of about 0.1 monolayer.
Whereas the slope of this initial linear increase is inde-
pendent of the K coverage, the saturation value increases
z 0.6
0 r
I-
with the amount of preadsorbed K. u 0.4 8 K = 0.129
An interpretation of the work function data for room
z
::J
temperature adsorption can be reached by applying elec- l.1...
tron spectroscopies. XPS allows the determination of ~ 0.2 8 K = 0.105
the chemical composition of the adsorbate layer. In cr:
addition, quantitative information about the relative 0
3: 0 8 K = 0.033
amounts of adsorbed K and H20 can be gained by the
intensities of the K2p and Ols core levels, respectively. 0 1 2
Different species can be distinguished by different elec-
tron binding energies. Ols spectra for H20 exposure at H2O EXPOSURE (10- 6 mbar· 5)
room temperature are shown in Fig. 13. Above the critical
Figure 12 Work function changes as a function of H 20
K coverage, an Ols peak is observed at a binding energy exposure on K precovered Pt(lll) at 320 K. (From Ref. 26.)
278 Pirug and Bonzel

0(15) Pt(111) + K + H20 Pt (111) + Hp

nw =1253.6 eV T=305 K
T=110K
6K=Q35 3380
1630 I
c, /\ sH,O
'-" .50'/ ' - - 0,74
N(E) 1630 3430
I I
'50~0,52

I
a. .100 ~0,22
.... 2.0)( 10-4 Po' 5
I
535 530 .250 ~0.15
EB(eV)
I
Figure 13 XPS 01s spectra for H 20 adsorption on K .500 ~ 0,07
precovered Pt( Ill) at 305 K. (From Ref. 37.)
500 1000 1500 3000 3500 4000

Energy Loss (em'1)

[17], and IRAS [38], showed unambiguously that

reversibly adsorbed molecular H20 is responsible for this
positive work function change at low temperature. The blr- pt (111) + K + Hp
8 K = 0.06
corresponding HREEL spectra, shown in Fig. 14, differ 1535
characteristically from those for H20 adsorbed on a
335
I I T = 110 K
.250
K-free surface. The vibrational modes have been ident- "'- !L .250 anneal
~5 5pO
ified by comparing data for H 20 and D 20 as presented 10303
in Table 2. The results are that H20 adsorbs predomi- 1635
3395
nantly at K-affected sites and that ice clustering is no ic I I
SH,O
longer observed at low H 20 coverages, indicated by the
absence of the 0-0 translational mode at 240 em-I.
::J
.50 J\.- 0.22

The most significant changes occur in the frequency

3325
ranges of the librational modes (300-500 em-I) and the I
O-H stretch frequency (3200-3620 em-I), respectively. X100J'-- 0.15
The librational modes are better resolved in the presence
ofK. Sharp peaks at 330 and 445-480 em-I, whoserela- 32253620
tive intensities vary with the H 20 coverage, have been I I
.250~
0.07
identified by comparison with the corresponding D 20
data (Table 2) as the "rocking" (R y ) and "wagging" (R,
frustrated rotation, respectively. Two bonding con- no H2 O
figurations, such as shown in Fig. 15, have been proposed
on the basis of symmetry selection rules for dipole 1000 2000 3000 4000
scattering. The rocking and wagging modes are Energy Loss (em'1)
alternatively the only HREELS-active vibrations for
H 20 with a molecular plane perpendicular or inclined Figure 14 HREEL spectra for H 2 0 adsorption on (a) a clean
to the substrate surface, respectively. Consistently, two Pt(ll1) and (b) a K precovered Pt(ll1) surface at 110 K. (From
peaks at 3620 and 3225 cm- I were observed in the Ref. 17.)
DHV Conditions for Double-Layer Modeling 279

(a) K (b) K a-0 +0.8

N
x:
:>. •
H20/Cs/Ag (1101
C +0.6
e Alkali - 0.01
'"0E
::0:
'"
"0
0
Co +o.~ H20/KI PI (111)
lh ~ ,

.!:! KO~
~ ~

+0.2
Figure 15 Schematic models for possible local structures for
molecularlycoadsorbed H 20 and KonPt(111) below the critical Alkali Ion Radius (AI
K coverage for H 20 dissociation (a) for small and (b) slightly
higher H 20 coverage. (From Ref. 17.)
0
0.5 1.0

O-H stretch region for OH ligands pointing toward the
vacuum and the substrate surface, respectively. For both
bonding configurations, the dipole moment of the H 2 0
molecules is directed toward the surface, a fact that
explain the observed work function increase. Most
recently, this system has also been studied by IRAS [38].
Within the frequency range of this technique, which is
restricted to values above llOO cm- 1 , the results agree
reasonably well with the HREELS data.
The phenomenon of a critical alkali metal coverage,
below which H 2 0 adsorbs only molecularly, has not only
been observed for K but also for other alkali metals, such
as Li, Na, and Cs and on different substrates. Table 3 [11]
lists all systems studied so far to our knowledge. The
reorientation capability, such as deduced from the initial
•
15
N. Q~HH
H2OINa/Ag(110)
• L1g~
-0.2 H20/li/Ag(110 I
".H2 O/A9(l10)
~
-O.~
Figure 16 Initial dipole moments and proposed orientations
for molecular H 20 on clean alkali covered Ag(110) and for K
covered Pt(lll) surfaces. (From Refs. 8 and 11.)
dipole moment of adsorbed molecular H 2 0, seems to be
related to the size ofthe alkali ion. This behavior, shown
in Fig. 16, has been explained by a continuous change of
the orientation of the permanent H 2 0 dipole, directed
toward the vacuum in the case ofclean Ag(110) or toward
the surface under the influence of coadsorbed Cs [8].

Table 2 Vibrational Frequencies of H 20 and D20 Adsorbed on Clean and K-doped Pt(lll)
Frequency (em-I)

H 2O D 20 Mode assignment

Clean Surface
240 240 Frustrated translation of H 20, 0-0 stretch in solid ice
560 Pt-OH 2 stretch, (frustrated z-translation)
695 510-580 Frustrated rotation
1630 1195 H-O-H symmetric bending ("scissors")
3430 2560 O-H stretch, due to H bonding
3680(w) 2700(w) O-H stretch, due to free -OH groups
With K coadsorption. K coverage: 0.06
110 110 Pt- K stretch
330 260 Frustrated rotation (R" "rocking"), low coverage, supports model Fig. 15a
485 375 Frustrated rotation (Ry "wagging"), higher coverage, supports model Fig. 15b
1525 1525 Impurity CO (stretch)
1590-1630 1200 Symmetric bending
3225 2350 O-H stretch, with hydrogen bonding to Pt, only at very low H 20 coverage
3395 2550 0 -H stretch, H bridge bonding to H 20, only at high coverage
3620 2685 0-H stretch, due to free -OH groups, only at very low coverage
Source: From Ref. 17.
280 Pirog and Bonzel

Table 3 Summary of H 20/Alkali Metal Coadsorption Systems

H 2O
dissociation Critical alkali metal
System product coverage 0 c Applied technique Reference

Li/Ru(OOI) OH 0.05 TDS, AES, LEED, ESDIAD [48,49]

Na/Ru(OOI) OH 0.25 TDS, AES, LEED, ESDIAD [49,50,5IJ
Na/Ru(OOI) OH,O 0.05 11<1>, AES, UPS, XPS [26,39J
K/Ru(OOI) OH,O 0.05 11<1>, TDS, AES, XPS, [26,39,52J
HREELS
Cs/Ru(OOl) OH,O 0.08 11<1>, AES, UPS, XPS, [26,39]
K/Ni(lll) OH 0.14 11<1> TDS, ARUPS [53]
Na/Pt(111) OH 0.10 11<1>, AES, UPS, XPS [26]
K/Pt(111) OH 0.10 11<1>, TDS, AES, UPS, XPS [26,27,37,54]
Na/Cu(llO) ? 11<1>,TDS, UPS [55]
Cs/Cu(llO) OH,O <0.22 11<1>, TDS, AES, XPS [56]
Cs/Cu(llO) ? 0.10 11<1>, TDS, HREELS [9,55,57,58]
Li/Cu(111) ? 11<1>,TDS [7]
Na/Cu(lll) OH 0.46 UPS [59,60]
Li/Ag(llO) ? 11<1>, TDS [7,8]
Na/Ag(llO) ? 11<1> [8]
Cs/Ag(llO) ? (> 0.16) 11<1>, TDS [6,8]
K/Ag(lll) OH 0 TPS, AES, UPS, XPS [61]
Source: From Ref 11.

The data for K on Pt(lll), also shown in Fig. 16, fit well
into this picture [11]. The general idea, that the
reorientation capability depends on the ionic radius of
the coadsorbed alkali metal, is supported also by the
findings for Na, K, and Cs covered Ru(OO!) surfaces [39].
The proposed model has been directly proven by the
vibrational data for K covered Pt(111) [17,38] and earlier
for Na on Ru(OOI) by ESDIAD [16]. Finally, ab initio cal-
culations for a PtlO cluster with hexagonal symmetry
reveal that the orientational change of coadsorbed H 20
is driven by the electrostatic interaction with the partially
ionic K species [27]. Unfortunately, this calculation did
not prove the existance ofa critical alkali metal coverage
for the dissociation of adsorbed H2O.
The important aspect of the onset of H20 dis-
sociation above a critical coverage of the coadsorbed
alkali metal may be qualitatively understood in terms
of electrochemistry. If the lowering of the work function
corresponds in this case also to a lower electrode
potential that favors the reduction of water to
chemisorbed hydrogen, the following argument is
thinkable. Because a critical electrochemical potential
is needed for this reaction, it follows that the dis-
sociation of H20 on Pt(lll) in UHV, for example,
requires a certain minimum work function that may
be achieved by adsorbing a finite amount of alkali
metal. A quantitative verification of this argument is
difficult because the "work function" is a
macroscopically measured quantity, whereas the local
electrostatic potential near an adsorbed alkali species,
which may be driving the H20 dissociation, is
unaccessable to the experiment.
In summary, the discussion of H20-alkali metal
coadsorption shows that the electrostatic interaction
between these species may lead to a reorientation of
the H 20 molecules in the field of ionically coadsorbed
K. Hence, one can conclude that the presence of charges
at surfaces overcomes the lateral interaction between
the H20 molecules, such that the UHV situation
becomes more comparable with the electrochemical
case. Below a critical coverage, the electrostatic field of
the adsorbed alkali metal is shielded by the permanent
dipole of coadsorbed H 20 monomers, whereas above
the critical alkali metal coverage, the surface potential
is reduced to the extent that H20 dissociation becomes
energetically favorable. Hence, ranges of (local) electro-
static potential for the existance of molecular and dis-
sociated H20 can in principle be defined for UHV
model experiments, although their actual values remain
unknown.
UHV Conditions for Double-Layer Modeling
IV. ADSORPTION OF ELECTROLYTE SPECIES
The next logical extension of the UHV approach in
simulating the electrochemical double layer is an investi-
gation ofthe interaction between ionic species in the elec-
trolyte and the metal surface. The aim of these
experiments is to model specific adsorption of cations
and/or anions and their possible hydration by
coadsorbed H 2O. A first example for a nonspecifically
adsorbed cation in UHV is the formation of H 30+ upon
coadsorbing H2 and H 20 on Pt(lll), as discussed above
[28]. Because of its importance in electrochemistry, the
adsorption of perchlorates and bisulfates as typical an-
ions has also been studied by surface sensitive probes in
UHV [1,18,40,41]. Perchlorate ions are known for their
tendency to adsorb nonspecifically. Metals with low work
functions should favor this trend. Therefore, Stuve et al.
[40,41] have chosen a Ag(1lO) surface, which exhibits a
relatively small work function, 4.3 eV, to study the adsorp-
tion ofperchloric acid and the reaction ofthe adsorption
products with coadsorbed H 2O. The influence ofthe sur-
face potential on these reactions has been tested by Pirug
and Bonzel [18], performing similar UHVexperiments
on Au(lll), which has a substantially larger work
function, 5.3 eV, for the clean surface.
The results for the Ag(1lO) substrate are presented
first. Liquid perchloric acid can not be admitted directly
to the substrate surface under UHV conditions. Instead,
the vapor pressure above the liquid, composed to mini-
mize the partial pressure of water vapor, is leaked via a
valve into the UHV chamber. Nearly anhydrous per-
chloric acid vapor is obtained from a mixture ofone part
70 wt% perchloric and one to three parts 96.6 wt%
sulfuric acid, which retains the residual H 20 from simul-
taneous evaporation [40]. In the following we distinguish
between perchlorate, Cl0 4 , and perchloric acid, HCl0 4 ,
assuming that the latter is completely anhydrous. Per-
chloric acid condenses on a Ag(110) surface at substrate
temperatures of about 110 K. Thermal desorption
spectroscopy shows that the condensed phase desorbs at
about 150 K, leaving molecular perchloric acid on the
surface, which deprotonates to adsorbed perchlorate
Cl0 4 at temperatures above 150 K, with simultaneous
H 2 desorption [40]. The resulting adsorbed perchlorate
layer has been characterized further by surface sensitive
methods, such as LEED, ESDIAD, and HREELS
[1,40,41]. Structural information can be gained from
LEED and ESDIAD results [40]. The observation of a
e(2 x 2) LEED pattern indicates a periodically ordered
layer for perchlorate with a coverage of 0.5. The local
bonding configuration has been determined by electron
stimulated desorption of 0- ions, which occurs into two
281
1660 A (b)
"~'-....-I \:.
33
2000 3000 4000
Energy loss I cm- 1
Figure 17 HREEL spectra for CL0 4 (0 = 0.1) adsorbed at
100 K on Ag(IlO) (a) before and (b) after coadsorbing H 20
(0 = 0.5) and a subsequent anneal to 170 K to remove H 20
multilayers. (From Ref. 1.)
angular lobes ofintensity tilted with respect to the surface
normal. These two lobes are aligned in the [001] and
[110] azimuths for coverages of 0.1 and 0.5, respectively
[40]. Obviously, the adsorbed perchlorate changes its
orientation on going from lower to higher coverage.
These findings should be interpreted in terms of the
corresponding HREELS spectra, shown in Fig. 17 [1,41].
The observed losses for adsorbed perchlorate at a cover-
age of 0.1 can be identified by comparison with IR data
for metal perchlorates and ClOi solutions [42].The ClOi
ion exhibits pyramidal symmetry and belongs, in its fully
hydrated state, to the Td symmetry group, which in
principal cannot be preserved upon adsorption. Instead,
a symmetry lower than C 3v should be observed for the
twofold symmetric substrate surface, consistent with the
loss features in Fig.17a. As suggested by the CI-O stretch
frequency of 1220 cm- 1 , it has been concluded that the
perchlorate is adsorbed in a tridentate configuration,
possibly still partially hydrated. This tridentate bonding
configuration is maintained independent of coverage,
which has been varied between 0.1 and 0.5. The different
alignments of the lobes in the ESDIAD pattern can now
be explained by perchlorate in two different local bonding
configurations, illustrated in Fig. 18.
The addition of H 20 to a preadsorbed perchlorate
layer with a coverage of 0.1 causes a shift of the CI-O
stretch frequency from 1230 to 1090 cm- 1 (Fig. 17b). By
analogy, an increase from 1100-1119 to 1218-1234 cm- 1
has been observed by in situ IR data for a Pt(111) electrode
in HCI0 4 solution at a potential between 575 and
 ,
282
0+
[110]
L [001]
r 40
[001]
[110]
[110] a Figure 19 Relative 0 Is intensities vs. temperature for mixed
L [110]
0+
.-v
b been studied on Au(l1I) [18,44], whose work function,
Figure 18 Model for tridentate adsorption ofCI0 4 onAg(IlO)
(a) e = 0.1 and (b) e = 0.5. (From Ref. 41.)
1100 mV vs. the NHE [43]. This blue shift has been inter-
preted as being due to specific adsorption of perchlorate
anions via the lone pair 0 orbitals, which are antibonding
with respect to the CI-O bond. Decreasing the elec-
tronic charge in the 0 lone pair orbitals upon chemisorp-
tion results in a stronger Cl-O bond, leading to an
increased Cl-O stretch frequency. Hence, it has been
concluded for Ag(llO) surfaces, that chemisorbed per-
chlorate can be hydrated by H 20 adsorption under
DHV conditions. A reasonable hydration number of
about three to four has been estimated on the basis of
complementary TDS data, showing also that the
hydration water is more strongly bound than H 20 on the
clean Ag(1lO) surface [41]. It is worthwhile to note that
the hydration of chemisorbed perchlorate could not be
observed at a higher coverage of 0.5, at least not at low
temperatures of about 100 K. In agreement with this
observation, a Born-Haber cycle showed that perchlor-
Pirug and Bonzel
100
80
~
;>..
.~
60
______ 0
_1.5
- A - 2.4
'"
~
B - . - 3.0
~
...... 20 _8.0
~13.0
---fr- ~
0
100 150 200 250
T[K]
HzO/HCl04 layers on Au(lll) for various molecule ratios
nH,olnHclo,. (From Ref. 44.)
ate hydration is thermodynamically possible on Ag(1lO)
and more likely in the lower than in the higher coverage
regime [41].
The probability ofspecific adsorption ofanions should
increase in the anodic potential range, i.e., at higher work
function. Correspondingly, one can expect that the
solvation of specifically adsorbed species is less likely on
subtrates with higher work functions than that ofAg(IIO).
In this context, the coadsorption of HCl0 4 and H20 has
5.3 eY, exceeds that of Ag(1lO) by 1 eY, thereby emulating
the anodic potential regime in electrochemistry.
A preliminary XPS study showed that perchlorate
species can be hydrated by coadsorbed H 20 even on
Au(lll). Although the adsorbed species could not be
clearly identified, due to the limited resolution ofthe elec-
tron spectrometer, it has been found at substrate tempera-
tures of about 80 K, that sequential adsorption results
in separate layers of HCl0 4 and H 2O. Depending on the
adsorption sequence, these layers can be mixed by a
postanneal at elevated temperature. This mixing is most
complete ifone first adsorbs H 20 and then HCl0 4 . When
covered by the HCl0 4 layer, the H 20 is prevented from
desorbing before its penetration into the HCl0 4 layer.
This intermixing of the two species seems to be an acti-
vated process, starting at temperatures slightly above the
H 20 desorption temperature of 150 K. The stability of
the hydration-H 20 is increased, as indicated by an
increased desorption temperature ranging from 220 to
150 K, depending on the solvation number, as shown in
Fig. 19. The maximum solvation number has been esti-
mated at about eight [44].
DHV Conditions for Double-Layer Modeling 283

A more detailed picture ofthe coadsorption ofHCI0 4
and H 20 on Au(lll) is obtainable by vibrational
spectroscopy using HREELS [18]. At 128 K, HCI0 4
adsorbs molecularly, as shown by spectrum a in Fig. 20.
A comparison with tabulated vibrational frequencies for
solid, liquid, and gaseous HCI0 4 [45] leads to the con-
clusion that HCI0 4 is adsorbed in C s symmetry, because
all eight HREELS active modes are observed (Table 4).
Only the vibration of the molecule as a whole against the
substrate, expected at low frequency due to the large mol-
ecular weight of 100 amu, could not be resolved from
the tail of the elastically reflected beam. It is interesting
to note that the molecularly adsorbed HCI0 4 formed an
ordered surface layer in the monolayer regime, as
evidenced by a.j3 x .j3R30° LEED pattern; a structure
model for this layer is currently not available.
The coadsorption of H 20 and HCI0 4 at 128 K results
in a gradual removal ofthe molecular vibrational features.
Instead, new peaks occur, as shown in Fig. 20b, which
could be related to perchlorate species. A subsequent
anneal to 173 K results in a complete loss of the
vibrational modes for molecular HCI0 4 . Finally, only
three peaks remain after heating to 223 K. The number
and frequency values of these losses suggest that under
these conditions, perchlorate has formed that is
chemisorbed in C 3v symmetry, with a characteristic
CI-O stretch frequencyofl205 cm- 1[42]. However, the
appearance of additional peaks in the temperature
regime between 153 and 213 K indicates the presence of
a second species, characterized by a reduced CI-O
stretch frequency of 1115 cm -I, which is expected for
hydrated Cl0 4 [43]. This result supports the earlier XPS
results mentioned above. The effect of coadsorbed H20
on molecularly adsorbed HCI0 4 is twofold:
H20-induced dissociation of molecularly adsorbed
HCI0 4 occurs at low H20 coverage followed by a gradual
solvation of the resulting perchlorate CI0 4 to an extent
that depends on the stoichiometry of coadsorbed H20
and CI0 4 species.
The composition of the mixed layer depends on the
adsorption sequence and the stoichiometry of the
coadsorbed species. HREEL spectra taken for the
reversed adsorption sequence, i.e., H20 exposure
followed by HCI0 4 , are shown in Fig. 21. Initially, HCI0 4
coadsorbs dissociatively under the formation of
chemisorbed and hydrated perchlorate CI0 4 , as deduced

100,000

-§
en

o
50,000
o c) T = 173 K

b) +H,o

o 0
m ;e
:
~ r~,~: 0 ~
. .~0
Ul
~ 'A,': ;g
.,. \ : . T = 128 K
" , t. !
\j ~ i\./
(.
o 1000
'-...1

2000 3000
-
------------
O........-,----,.------r---""T""--"""T'"----.---r----,.---"""T""----.....I
4000
a) 0.55 ML HCIO,

·1
Energy Loss (em )

Figure 20 HREEL spectra for HCI04 on Au(lll), after coadsorption of H 2 0 at 128 K and after a subsequent anneal to 173, 203, and
274 K with partial and total coverages chosen to be in the submonolayer regime. (From Ref. 18.)
284
..
25,000
20,000
(/) 15,000
.-
c
::J
o d)T=183K
()
10,000
5000
o 1000
Energy Loss (cm-
Figure 21 HREEL spectra forcoadsorbed HCI0 4 on Au(lll) precovered with H 20 at 133 Kand after a subsequent anneal to 183,203,
and 223 K with partial and total coverages chosen to be in the submonolayer regime. (From Ref. 18.)
from the appearance of the characteristic CI-O stretch
frequencies at 1185 and 1115 cm- l , respectively.
Additional HCI04 exposure changes the observed loss
structure significantly, which can be explained by the for-
mation of oxonium perchlorate (or perchloric acid
monohydrate) (H 30+ClO;j). The loss peaks observed in
Fig. 21 c and d, can be assigned to the vibrational modes
of H 30+ and CIOi, in agreement with tabulated data
for oxonium perchlorate composed of hydronium H 30+
and unsolvated perchlorate CIOi [46]. Oxonium per-
chlorate is known as a solid protonic conductor and has
been characterized by various techniques, such as x-ray
diffraction, JR, inelastic neutron scattering (INS), and
Raman spectroscopy [46]. By analogy to crystalline
structures reported for bulk oxonium perchlorate, we
observed an ordered LEED pattern that could be indexed
as a elI21)structure, also known as an oblique
(J3 x J'J) structure. A similar pattern has been
observed by Funtikov et al. [47] in in situ STM studies of
bisulfate adsorption on Pt(ll1) after preparation under
Pirug and Bonze)
f) T =223 K
e) T = 203 K
c) + 2 doses HCIO,
T= 121 K
b) + 1 dose HCIO,
T= 121 K
2000 3000 4000
1
)
electrochemical conditions in sulfuric acid media. For
Au(lll), the coverage and the stoichiometryofthe mixed
H 30+ /CIOilayer has been determined by XPS. Consist-
ent with the oxonium perchlorate hypothesis, the
H 3 0+ /CIOi ratio is near one with a molecular coverage
of ~O.2 [18].This surface structure may be compared with
the crystallographic structure of oxonium perchlorate.
Two crystal structures have been reported, namely
monoclinic and orthorhombic, with a phase transition
at252 K [46]. His interesting to notethatthelow tempera-
ture monoclinic phase exhibits a layered structure that
may favor the two-dimensional ordering observed by
LEED under the UHVadsorption conditions.
V. SUMMARY
The basics of UHV experiments modeling the
electrode-electrolyte situation in electrochemistry have
been described in detail. The central part are specially
prepared adsorbed layers on metal surfaces, aimed at
UHV Conditions for Double-Layer Modeling 285

Table 4 Assignment of Fundamental Vibrations of Gaseous, Liquid, Solid [Infrared Vibrational

Frequencies (cm- 1)] [45] and Adsorbed [18] Hydrogen Perchlorate (HCI0 4 , C s Symmetry)
HCI0 4 , C s symmetry Gaseous Liquid Solid Adsorbed

A'modes
v (O-H stretch) 3560 3275 3260 3325
Vas (CI0 3 stretch) 1326 1315 1315 1330
b (O-H bend.) 1200 1245 1245 1260
VS (CI0 3 stretch) 1050 1041 1033 1045
Vs (CI-OH stretch) 725 743 760,740 760
bas (CI0 3 deform.) 563 571 566 590
bs (CI0 3 deform.) 519 ? ? 460
p (in-plane CI0 3 rock.) 403 ? 371,346 350
A" modes:
Vas (CI0 3 stretch) 1263 ? 1283 Inactive
bas (CI0 3 deform.) 579 582 585 Inactive
p (out-of-plane CI0 3 rocking) 430 440 428 Inactive
r (CI0 3 torsion) 312 480 478 Inactive

simulating the composItIon of the double layer in
electrode-electrolyte solutions, and their complete com-
positional and structural investigation. A large variety
of surface diagnostic techniques is applied to character-
ize such layers at different coverages, compositions, and
temperatures. Important information on a molecular
level can be gained on the behavior ofsuch layers, in par-
ticular on the interaction between ionic solutes,
preadsorbed ionic species, and solvate molecules, such
as H 2O. In principle, the results are useful for a better
understanding of basic processes within the double layer
of an electrochemical cell. It is still a great challenge to
find a clear relationship between the UHVexperiment
derived results and corresponding data from electro-
chemical experiments. The equivalence between the elec-
trochemical potential and the work function measured
in UHV should be used in a comparison for reference
purposes. Local and long-range order of solvents and
electrolyte ions can be studied in both cases and can be
compared. Ionically adsorbed species, such as alkali
metals, are convenient additives to simulate the extra
charge in the electrochemical double layer. The dipole
orientation ofcoadsorbed solvent molecules in the elec-
trostatic field of these ionically adsorbed species can be
determined by different methods, such as work function
measurements, ESDIAD, or vibrational spectroscopies
(lRAS and HREELS). In addition, ordered surface
structures have been observed for adsorbed solvents,
electrolyte ions, and mixtures of both by LEED.
In particular, surface reactions, such as the
decomposition of electrolyte constituents and their sub-
sequent solvation, can be studied well by the UHV model
experiment. In this context it has been shown that the
analogy between the electrochemical potential and the
work function of the adsorbate system represents an
important link between observations in electrochemical
cells and in UHY. Examples ofthe validity ofthis analogy
are the alkali-metal-induced decomposition of H20 at
low work function, the work function controlled balance
between H adsorption and its hydration to H 30+ species,
the hydration of perchlorate, and the formation of
oxonium perchlorate. A direct identification of these
species by applying various spectroscopies should lead
to a better understanding of chemical processes on elec-
trode surfaces and in electrochemical cells.
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1995.
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1987.
4. UW Hamm, 0 Kramer, RS Zhai, OM Kolb. J Electroanal
Chern 414:85-89, 1996.
5. JK Sass.Vacuum 33:741-751, 1983.
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7. JK Sass, K Bange, R Dohl, E Piltz, R Unwin. Ber
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17
Modeling of the Electrochemical Double-Layer in Ultrahigh
Vacuum: Adsorption of Sulfuric Acid Species on Pt(111)
Yoshitaka Shingaya and Masatoki Ito
Keio University, Yokohama, Japan
ABSTRACT
The structure of sulfuric acid species adsorbed on a
Pt(lll) electrode has been successfully determined by
using the ultrahigh vacuum modeling tactics. An elec-
trode potential change induces an interconversion
between a bisulfate anion-hydronium cation co-
adsorbate and a sulfuric acid molecule. The solvation
structure of the adsorbed ions indicates that single
hydration water molecules per bisulfate anion-
hydronium cation pair stabilizes the ion pair. The water
molecules in the overlayers are subjected to a preferential
orientation that is induced by the presence of the
adsorbed anions in the first layer. These microscopic
informations about the structure ofan adsorbed electro-
lyte anion and water as a solvent would be indispensable
to a true molecular level understanding of the electro-
chemical double layers and chemical reactions at the elec-
trode surfaces.
I. INTRODUCTION
There has been tremendous progress in the field of
interfacial electrochemistry due to development of a
number of new surface-sensitive techniques. Since the
use of a single-crystal electrode was developed by
Clavilier et al. [1], atomic level studies on single-crystal
electrodes have opened up a window revealing structural
aspects of a metal-electrolyte interface, such as surface
reconstruction of top layer atoms, electrolyte anion
adsorption, and underpotential deposition of metals.
287
An important question being asked in electrochemis-
try is how the water molecules are arranged at charged
aqueous interfaces. Despite extensive studies, direct
measurements of the adsorption or ordering of water
molecules at an electrode are quite sparse, because huge
amounts ofwater outside the double layers interfered with
the measurement of adspecies on metal surfaces. On the
other hand, a large number of surface science studies on
water adsorption on well-defined single-crystal surfaces
under UHV conditions have been conducted using tech-
niques such as infrared (IR) [2], Raman [3], low-energy
electron diffraction (LEED) [4], high-resolution electron
energy loss spectroscopy [5], and ESDIAD [6]. Con-
sequently, the search for closer links between in situ elec-
trochemistry and ultrahigh vacuum (UHV) surface
science has become an imperative issue for exploration.
Ever since Bange et al. [7] presented the basic idea of
UHV-electrochemical modeling, many surface science
approaches to water adsorption on metal electrode
surfaces have been conductedVillegas et al. [8] examined
the hydration effects of work functions by introducing
water into an UHV chamber. Toney et al. [9] reported a
voltage-dependent water density profile perpendicular
to a silver(111) electrode surface.
An "immersed gap" is often used to define the differ-
ence between the UHV and electrochemical situation,
but the molecular level interpretation of immersed gap
still remains unclear. To develop a microscopic view of
an immersed gap, it is necessary to clarifY the micro-
scopic definition of an electrochemical potential. An
electrode potential is mostly controlled by the individual
288
electric double-layer structure, and inversely, such an
interfacial structure is induced by the electrode potential.
Therefore, it is important to elucidate the connection of
an electrode potential with a precise double-layer struc-
ture on the surface because a relationship exists between
the electrode potential and the double-layer structure.
The adsorption behavior of sulfate or bisulfate on a
Pt(111) electrode has been studied widely by in situ
infrared reflection-absorption spectroscopy (IRAS).
Kunimatsu et al. [10,11] observed two absorption bands
at 1200 and 1100 em-I for adsorbate on polycrystalline
platinum electrode. They attributed these bands to
adsorbed bisulfate and sulfate, respectively. In the Pt(111)
case, only a single band at 1200 cm- 1 was observed, and
Faguy et al. assigned the band to S03 asymmetric
stretching mode ofbisulfate adsorbed on pteIll) via three
oxygen atoms. Nart et al. [12] concluded that adsorbate
on Pt(1l1) is a sulfate that coordinated via three oxygens
presenting a C 3v symmetry. Recently, Faguy et al. [13,14]
proposed that the adsorbed species is not adequately
described as either sulfate or bisulfate; the spectra are
more consistent with an adsorbed H 30+ -SO~- ion pair.
As stated above, there are various explanations about
adsorbate on Pt(111) electrode in sulfuric acid solution.
In this chapter, UHV modeling experiments of
adsorbate on a pte 111) electrode in sulfuric acid solution
were described. To examine the UHV modeling and to
study the relationship between an electrode potential
with a controlled double-layer structure in UHY,
coadsorption ofwater and S03 gases at low temperatures
on a Pt(l1l) surface was studied by IRAS.
II. EXPERIMENTAL
An in situ IRAS cell was attached to an FTS-45RD
Fourier transform infrared spectrometer (Bio-Rad) with
a liquid nitrogen-cooled MCT detector with 4 em -I res-
olution. Two types of measurements were performed.
Using the stepwise method, the electrode potential was
changed from 50 mV [standard hydrogen electrode
(SHE)] stepwise to a more positive potential. The second
method used was subtractively normalized interfacial
Fourier transform infrared spectroscopy (SNIFTIRS).
The signals originating from the solution phase were
mostly canceled out by subtracting the spectra at a
reference potential. The reference electrode was
Hg/Hg2S04/0.5 M H2S04, but the potentials were
quoted vs. the SHE.
The measurements of double-layer modeling on
Pt(111) under UHV condition were carried out in a
chamber with a system-2000 Fourier transform in-
frared spectrometer (Perkin Elmer) with a liquid
Shingaya and Ito
nitrogen-cooled MCT detector and 8 em-I resolution.
After conventional cleaning of Pt(111), H20 and S03
gases were sequentially introduced on Pt(ll1) at 110 K
by a pulse doser. The amount of H 20 and S03 gases were
controlled by the pulse duration, the number of shots,
and the vapor pressure in the gas line. Mainly, a 2-ms
pulse duration and a vapor pressure of 2 Torr were
used. The coverages estimated by thermal desorption
spectroscopy (TDS) were quite reproducible: Doering
and Maday'S "bilayer" structure [6] was used to refer to
the coverages of H2O. The exposure ofone shot in the pre-
sent study corresponded to a coverage of 0.2 ML. The
amount of 3 ML H20 was preadsorbed on Pt(111) at
110 K, followed by a subsequent dose of S03 (variable
amounts) at the same temperature. To simulate a
double-layer structure at a particular electrode potential,
the sample was annealed at 190 K (lower temperature
annealing) and 260 K (higher temperature annealing)
and cooled to 110 K. Thermal desorption of water was
examined to reveal the amounts of water derived from a
bisulfate anion (HSO,,n and a hydronium cation (H30+)
on the surface. An AQA-100-R(ANELVA) quadrupole
mass spectrometer was used in the TDS measurements.
Solutions were prepared using Milli-Q water
(18.3 MO, Millipore) and high-purity sulfuric acid sol-
utions (Ultrapure, Cica-Merk). In UHVmodeling, sulfur
trioxide (Wako Ind.) and sulfuric acid fuming were used
to introduce sulfur trioxide gas.
III. RESULTS AN D DISCUSSIONS
A. In Situ IRAS Measurement of Sulfuric Acid
Species Adsorbed on a Pt(111) Electrode
in 0.5 M H 2 S0 4 Solution
Figure la shows typical examples ofSNIFTIRS results for
the lower frequency region down to 850 em-I. Two
absorption bands in the wide potential range of
500-1050 mV were definitely present. At 500 mY, a
strong absorption with a broad band width was observed
at 1231 em-I. The band showed a large frequency shift to
1252 em-I at 650 mY, whereas the lower frequency band
at 950 em-I remained unchanged. On the other hand,
at 800 mY, the higher frequency band at 1270 em-I
became sharp and strong, whereas the lower one at
949 em-I showed no substantial change except for a
lower frequency shift. The frequency shifts for these two
absorption bands are plotted as a function of electrode
potential in more detail in Fig. Ib. The slope for the shifts
demonstrates a clear discontinuity at 750 mY Also, the
halfwidth of the higher frequency band changes remark-
ably at the same potential of 750 mY Notably, the poten-
 UHV Modeling Use in Sulfuric Acid Species 289

tia1 of 750 mV coincides with that where the abnormal

1050 peak starts to develop in the CV curve ofPt(lll) in 0.5 M
H2S04 solution.
To understand the relationship between electrode
900 potential and electric double-layer structure, an elec-
trode potential change induced by electrode reactions in
an adsorbate layer in a 0.5-M sulfuric acid solution was
examined as a function of time as shown in Fig. 2a.
Initially, the electrode potential was set at 50 mV where

I
800 no anion adsorption occurs. The potentiostat electronic
circuit was then opened. The electrode potential
increased gradually and then grew rapidly after 20 s.
950 Finally, it converged at 950 mV Figure 2b presents
'E 0.005
CI:
<I
synchronous time-resolved IRAS results of which the
measured potentials are indicated in the curve in Fig.
650 2a. At 400 mY, a S-O stretching absorption started to
r appear (b) and then develop (c to d). At the time off and
g, the band at 1270 cm- 1 became sharp. Figures 2, a and
i b, can be explained as follows. At 50 mY, atomic
I
hydrogen, H 20, and H 30+ molecules are forced toward
i
I
500
E/mV
the Pt(lll) electrode. On open circuit, atomic hydrogen
and water molecules (mainly H30+) desorb from the
V5.SHE surface, resulting in an electrode potential increase
(around 300-400 mY). The bisulfate anion then starts to
1400 1300 1200 1100 1000 900
be adsorbed (coadsorption of H 30+ with HS04""). This
(a) Wavenumbers fem -1 increases the electrode potential remarkably to
f 500-700 mV
I 952 1290 Thus, in situ IRAS under a potentiostatic condition in

I
I

1
950
•
1280
Fig. 1 were completely reproduced in the present results
of Fig. 2b under an open-circuit condition. The fact that
almost identical IRAS were observed under both
potentiostatic and open-circuit conditions means that
i 1270
the electrode potential also undergoes electrode

t
!I
E
0
948
l!?
reactions and changes spontaneously with the
double-layer structure. To shed light on the relationship
between the electrode potential and the double-layer
1 Ql 1260
.c structure, it is important to reveal actual double-layer
i E
~ 946 structures at each electrode potential in more detai1.
f
I
J
>
Ql

III
~
1250
One possible method is to simulate a surface structure
that is comparable with actual double-layer structures
under UHV conditions.
944
1240
B. Coadsorption of H 2 0 and S03 as a UHV
Model for a Double-Layer Structure on
942 +----,----+-----,---....----+-1230
Pt(111) in H 2 S04 Solution
250 500 750 1000 1250 1500
(b) E/mV vs. SHE
1. Thermal Desorption of Water on Pt(111)
f
1
Figure 1 (a) In situ IRAS in the lower frequency region down A hexagonal ice1ike bilayer structure was formed by
to 850 cm- 1 on Pt(lll) in a 0.5-M H 2 S0 4 acid solution as a func- a controlled dose of water on Pt(111) at 110 K.
tion ofelectrode potential. (b) The frequency shifts at 1250 and Subsequently, S03 gas was introduced onto the H20
950 cm- 1 as a function ofelectrode potential preadsorbed Pt(111) at the same temperature. The water
290 Shingaya and Ito

coverages were evaluated by TDS. Figure 3 shows a

typical TDS result after the sequential dosages of
H 20 (3 ML) and S03 gases on Pt(lll) at 110 K. It is
well known that water on a bare pte Ill) surface is
UJ desorbed at temperatures lower than 180 K [15] (Fig.
I
(/) 3a). Actually, the excess water that did not react with
~ 600 S03 on Pt(1l1) was desorbed at lower temperatures
> from the surface (Fig. 3b). After cooling the sample,
E
the new desorption signal was clearly observed as
shown in Fig. 3c. The coadsorbates of HS04 and
H 30+ obtained from H ZO+S0 3 were stable until they
reached temperatures of ~190 K. Signals associated
with the further thermal desorption started to appear
o 30 60 90
(a) tis

164

M/e = 18
9 (a)

56

e p-
'c
a:::
..... ::s
a:
<l ...
..c:i
~
~
d 'iii
c::
$
.E 170

b 189

a
(e) x10

1400 1300 1200

(b) Wavenumbers I em" 120 200 300

Figure 2 (a) Time response ofelectrode potential ofPt(1l1) in T (K)

a 0.5-M H 2S0 4 solution under an open-circuit condition. (b)
Time response of in situ IRAS of bisulfate adsorbed on Pt(lll)
in a 0.5-M H2S0 4 solution under an open-circuit condition.
IRAS measured at points a-g (0.25, 0.40, 0.63, 0.73, 0.84, 0.86
and 0.88 vs. SHE), respectively are shown in (a).
Figure 3 (a) TDS result from a l-ML H20 of bilayer ice on
Pt(111). (b) TDS result from a coadsorbate of3 ML H 20 + S03
on Pt(1l1). (e) TDS result with a further temperature increase
after b.
f
!
UHV Modeling Use in Sulfuric Acid Species 291

at ~ 190 K. With the temperature increase, the following 2. IRAS of Model Double-Layer Structures on Pt(111)
reaction (1) evolved on Pt(1ll) to form a sulfuric acid
molecule and water, the water being desorbed from Figures 4 and 5 show the IRAS ofbisulfate adsorption on
the surface: Pt(111) at 1.0- and 2.0-ML coverages, respectively. The
lower IRAS spectrum in Fig. 4 was obtained by a
(1) sequential adsorption of 3 ML H20 and S03 gases on
Pt(111) at 110 K followed by annealing at 190 K. The
t Thus, a broad peak around 200 K is a result of
desorption of water involved in reaction (1).
spectrum showed three absorption bands at 1233, 1051,
and 953 em-I. The coverage of an adsorbed anion was
Therefore, the annealing temperatures of 190 K (a
saturated (1.0 ML) because no desorption signal from
lower temperature anneal just before the water
bilayer water on a bare Pt(lll) was observed. Previous
desorption) and 260 K (a higher temperature anneal
vibrational spectroscopic studies ofsulfuric acid solution
after the water desorption) were chosen to simulate
[16] showed that a bisulfate anion (HSO;n shows three
actual double-layer structures. A second desorption
signal of water at 325 K (not shown in the figure) was
also found, and the higher temperature peak around

r 325 K is due to the desorption of water associated with

the decomposition of a sulfuric acid molecule to S03
(ad).

f,
1273

(b)

~ :
-
a:
a:
<I
: 190 K
Pt(111)

-I
a:
a:
<I 0005
1276

(a)
1233
953I;K
P1(111 )
1500 1400 1300 1200 1100 1000 900 800 700
1500 1400 1300 1200 1100 1000 900 800 700
Wavenumbers I cm- 1
Wavenumbers I cm- 1
Figure 5 IRAS ofmodel double layers on Pt(lll) under UHV
Figure 4 IRAS ofmodel double layers on Pt(lll) under UHV conditions. To create overlayer adspecies on the surfaces, doses
conditions. After the sequential doses of 3 ML H 2 0 + S03 on two times larger than those in Fig. 4 were introduced at 110 K
Pt(lll) at 110 K, the coadsorbate of hydrated HSO; + H30+ and the coadsorbate ofhydrated HSO; + H30+ pairs on Pt(lll)
pairs on Pt(lll) was annealed at 190 K (a) and 260 K (b). was annealed at 190 K (a) and 260 K (b).
292 Shingaya and Ito

IR active bands arising from S-O stretching in the

infrared spectrum, ~1050 (vsso,), ~900 (VS-OH), and (a) (b)
~ 1200 (vasso l } ) cm -1. Figure 5 shows the results in which
the S03 gas exposure was increased to coverages of
1.0-2.0 ML. Not only chemisorbed bisulfate on Pt(111)
in Fig. 4 but also overlayer bisulfate species are included
in the spectra. Therefore, the bands at 1057 and 895 cm- I
in Fig. 5a are assigned to S-O stretching absorptions of
the overlayer bisulfate species. Figure 6, a-d, presents vSO asymmetric VS03
four normal vibrations of a bisulfate anion together with (1305 cm- 1 ) (1254 cm-1 )
the observed frequencies in the increased exposure run,
1.0-2.0 ML. The bands at 1057 and 895 cm- I were
(c)
assigned to be symmetric, VS03 (c) and VS-OH (d),
respectively. It was difficult to observe the other bands
for higher frequencies, vso (a) and asymmetric VS03 (b)
vibrations because of the band overlapping at
1200-1300 cm -I. The values in the parenthesis are those
from Ref. 17.
However, the adsorption ofa bisulfate anion on Pt(1ll)
symmetric V503 V5-0H
is expected to produce remarkable changes in the 1057 cm- 1 895cm- 1
frequencies. Furthermore, the local geometry of the
adsorption site must be considered when determining
the symmetry of the adsorbed bisulfate on Pt(1l1). On
(e) (f)
the other hand, the adsorbate symmetry of the bisulfate
anion can be deduced from an analysis of the number of
observed S-O stretching bands in the spectral range.
Two bands were detected in this study, and the VSO (a)
and asymmetric VS03 (b) vibrations were eliminated from
the above consideration. Thus, the two adsorption bands,
1233 and 953 cm- I in a spectrum of Fig. 4a, were antisymmetric v 5=0 symmetric V 5=0

X..,'
assignable to S-O stretching vibrations of a bisulfate 1364 cm- 1 1181 cm- 1
anion adsorbed on Pt(1l1): one, symmetric VS03 (Fig. 6c),
and the other, VS-OH (Fig. 6d). This means that the
bisulfate anion on Pt(111) takes the conformation in (9)
which the pseudomolecular C 3 axis is perpendicular to (h)
'" !~i<!.
the Pt(1l1) surface. It is noted that the higher frequency
shift of symmetric VS03 vibration, 1051 ~ 1233 cm- I , was : '.:':
observed upon adsorption ofa bisulfate anion on Pt(1l1).
This suggests that the bisulfate anion is adsorbed on
Pt(l1l) through three oxygen atoms.On the other hand, antisymmetric V 5-0H symmetric V 5-0H
the frequency shift for the symmetric VS-OH band
1055 cm- 1 992cm- 1
(895~953 cm- I ) was at an ordinary degree (~50 cm- I ).
The upper spectrum (b) in Fig. 4 also revealed three
absorption bands, 1276, 1043, and 941 cm- I , which are Figure 6 Normal vibrations concerned with S-O stretching
assigned to S-O stretching vibrations of a sulfuric acid ofHSO" (a-d) and H 2 S04 (e-h). The frequencies of overlayer
molecule adsorbed on Pt(1l1) as in the following adspecies obtained from the increased exposure run of HSO"
explanations. The amounts of H20 and S03 sources were + H 30+ (1.0-2.0 ML) are given together with their assignments.
the same as those for the lower spectrum (a), but the cover- The values in the parenthesis are those from Ref. 17.
age of the adspecies on Pt(l1l) was unsaturated (less than
1 ML). Figure 5b shows the spectra from increased
exposures of H 20 and S03 sources (2 ML amount), and
the other absorption bands appeared at 1364, 1181, 1055,
UHV Modeling Use in Sulfuric Acid Species 293

and992 cm- 1 as shown in Fig.6, e-h.Thosefourbandscan

reasonably be assigned to the four normal vibrations of a
neutral sulfuric acid molecule because the frequencies
coincided well with those of the previous study [18]. The •
previous study also shows that two are symmetric,
1181 cm- 1 (vso, Fig. 6f) and 992 cm- I (VS-OH, Fig. 6h), •
and the other two are antisymmetric, 1364 cm- 1 (vs=o,
Fig. 7e) and 1055 cm-I(vs-OH, Fig 6g). As described •
above, the antisymmetric modes are not likely to be active
due to the dipole selection rule. Ifwe assume that a sulfuric
acid molecule adsorbs on Pt(ll1) through two oxygen
atomsthathaveadouble-bondedcharacterwithamolecu-
lar C2 axis perpendicular to the surface as shown in the
inset, the latter two absorptions cannot be observed in
the IRAS spectrum because ofthe surface selection rule.
Alternatively, the former two absorptions give rise to large
absorptions, because the dipole moment changes associ-
ated with S-O stretching become perpendicular to the
surface. Therefore, the three absorption bands in the
spectrum in Fig. 4b can definitely be assigned as follows:
The sharp and strong absorption band at 1276 cm- I is
assigned to a symmetric Vs=o vibration (Fig. 6f), whereas
the weak band at 941 cm- 1 is assigned to a symmetric
VS-OH vibration (Fig. 6h). The band at 1043 em-I, which
was located at 1055 em-I in increased exposure measure-
ments as a strong absorption band ofthe overlayer sulfuric Figure 7 (a) Pt(lll) (./3 x ./7) LEED pattern of adsorbed
bisulfate. The electron beam energy was 96 eV (b) Pt(lll)
acid molecules, is assigned to an antisymmetric VS-OH
(./3 x ./3)R30° LEED pattern of adsorbd sulfuric acid
vibration (Fig. 6g). Furthermore, the higher frequency molecules. The electron beam energy was 95 eV
shiftsofS=O stretching(1l81---+1276 cm-I)indicatesthat
the molecule is adsorbed on Pt(111) through two
double-bonded oxygens. On the contrary, the band at domain sizes of the bisulfate adlayer (three domains).
941 cm- I revealed a lower frequency shift upon adsorp- The existence of such small domain explains the broad
tion (992---+941 em-I). UHV IRAS bandwidth at 1233 em-I. A similar
The anion adsorbed on a Pt(lll) electrode was not a (.j3 x .)7) structure was observed in in situ scanning
sulfate but a bisulfate. Both UHV and in situ IRAS tunneling microscopy (STM) studies ofbisulfate adsorp-
measurements on Pt(l1 1) with O 2 and 02S04 showed fre- tion on Pt(lll) in sulfuric acid solution by Funtikov et al.
quency shifts and intensity attenuation of the band at [19,20]. They found that the domain sizes in the STM
1230 em-I. Ifthe adsorbate was a sulfate, the shift would image were extremely small. In contrast, the LEEO pat-
not occur. According to ab initio molecular orbital tern obtained by annealing at 260 K was sharp and was
calculations, it was indicated that S03 symmetric a (.j3 x .)3 )R30° structure. The clear noninteger spots
stretching mode couples with SOH bending mode but that were derived from much better ordering are
not with SOD bending mode. The difference in frequency suggestive of the fact the domain size of the H 2S0 4
and intensity ofthe band arose from the fact. adlayer is relatively large. The sharp IRAS bands
observed at 1277 and 1276 em-I, in in situ and UHV
3. LEED Observation of Model Double-Layer studies, respectively, can reasonably be explained by
Structures on Pt(111) the existence of a well-ordered H2S04 adlayer with
In this study, LEEO and IRAS were observed wide domains. It is ascertained that HS04 and
simultaneously. The LEEO images obtained by H2S04 adsorbed on Pt(lll) forms (.j3 x .)7) and
annealing at 170 and 260 K are shown in Fig. 7, a and b, (.)3 x .j3)R30° structure, respectively, by using LEEO
respectively. The LEEO pattern at 170 K showed a observations of UHV model surfaces. The periodical
(.)3 x .j7) structure, although the spots were rather structure model of adsorbed HS0 4 and H 2S0 4 in real
diffuse. The diffuse spots come from remarkably small space is shown in Fig. 8, a and b.
294
(b)
Figure 8 Structure model of adsorbed bisulfate (a) and
sulfuric acid molecule (b) in real space. Filled circles indicate
hydronium cation.
C. Comparisons of CV, TDS, IRAS, and LEED
Results
It is now possible to compare the results of in situ IRAS
(Figs. 1 and 2) with those ofUHVmodel spectra (Figs. 4
and 5). The direct comparisons are shown in Fig. 9. The
frequencies, 1231 (broad) and 951 cm- 1 , obtained from
0.5 M H2S04 solution at 500 mV in Fig. 9a (also in Fig.
la) agreed perfectly with those, 1233 and 952 cm- 1, in a
UHV model spectrum from a lower temperature
annealing in Fig. 9b (also in Fig. 4a). Also, the frequencies,
Shingaya and Ito
(b) 190 K
I 0.005 1276
1400 1200 1000 1400 1200 1000
Figure 9 Comparisons of UHV IRAS with in situ (solution)
IRAS; a and c are the spectra for in situ IRAS at the electrode
potentials of 500 and 900 mY, respectively (see Fig. la, band
d) are the spectra for UHV modeling at the annealing tempera-
tures of 190 and 260 K, respectively (see Fig. 4).
1277 (sharp) and 949 cm- 1, obtained from H 2S04
solution at 900 mV in Fig. 9c were close to those, 1276
and 941 cm- 1, in the spectrum from the higher tempera-
ture annealing in Fig. 9d (also in Fig. 4b) respectively.
Whole spectral features, intensities, bandwidths, and
frequencies in Figs. 9, (a) and (b), and 9, (c) and (d),
remarkably resembled each other. Thus, the following
important conclusion was deduced: The spectra ob-
tained from a more negative potential than 750 mV were
ascribed to a bisulfate anion and those from a more posi-
tive potential than 750 mV to a neutral sulfuric acid mol-
ecule based on these results. This indicates that a proton
transfer reaction occurs on a Pt(lll) electrode at 750 mY
Therefore, it is concluded that hydrated bisulfate anions
and H3 0+ cations form the (~3 x ~7) structure between
500 and 750 mV with the molecular C 3 axis normal to
Pt(lll); however, the proton transfer reaction (1) begins
at 750 mY Neutral sulfuric acid molecules that were
r URV Modeling Use in Sulfuric Acid Species
stabilized by such a process dominate on the surface with
a molecular C 2 axis perpendicular to Pt(ll1) with
double-bonded oxygens attached to the surface at
750-1100 mY.
There have been a number ofdiscussions aboutthe ori-
gin of the peak at 750 mV in CV for Pt(lll) in 0.5 M
H 2S04solution. This present study revealed that a proton
transfer reaction from HSOi +H 30+ to H2S04+H20
proceeded on a model double-layer surface of
coadsorbates of HSOi +H 30+ under UHVat "'200 K
and the same proton transfer reaction progressed on a
Pt(lll) electrode in 0.5 M H 2S0 4 solution at 750 mY.
Note that the interconversion proceeded as a result of a
desorption or an adsorption (postdose ofwater at 110 K)
of excess hydration water on the surface. Large amounts
of the hydration water [at least several molecules per
HSOi +H 30+ pair on Pt(ll1)] were needed to stabilize
the HSOi and H 30+ phase, and inversely, a decrease in
the hydration water on Pt(ll1) gave rise to a H 2S04 mol-
ecule. The inconsistency of the CJ3 x J3)R30° structure
(UHVsurface) seeninexsituLEED [21]vs. theJ3 x J7)
structure (solution surface) observed in in situ STM
[19,20] can now be rationalized: Sufficient hydration
water surrounding HSOi +H30+ ion pairs on in situ
Pt(lll) at 500-750 mV served to stabilize the (J3 x J7)
structure, whereas the elimination of the water from a
UHV surface at temperatures of'"200 K forced a change
in the structure to (J3 x J3)R30°.
D. Structure of a Hydronium Cation on Pt(111)
The UHV model structure ofH 30+ and H 20 on Pt(ll1)
could be simulated by a sequential adsorption of
hydrogen and water gases on Pt(ll1) at 110 K. The IRAS
ofH 30+ on Pt(lll) at 110 Kare shown in Fig. Was a func-
tion of H 30+ coverage. To produce a H 30+ species on
the surface, 1 L (a), 3 L (b), and 6 L (c) of hydrogen were
introduced on Pt(ll1) at 110 K where atomic hydrogens
were created on the surface. Then 2 ML of water were
adsorbed onto the H-covered Pt(ll1) at 110 K, and an
excessive hydration water adlayer was made to flash by
heating to 155 K, thereby leaving H30+ on the surface.
The broad band at 1150 cm- 1 is assignable to a sym-
metric bending vibration ofan H30+ adsorbed on Pt(lll).
The frequency of the band agreed well with the
well-known results ofH 30+ in both crystalline hydrates
[22-24] and aqueous strong acid solutions [25] and the
previous HREELS results as reported by Wagner and
Moylan [26]. An asymmetric vibration of the H 30+,
which should appear at a higher frequency than that of
the bH,O scissoring vibration, however, was not observed
in the ~pectrum. The absorptions at 3430 and 1633 cm- I
295
3430
1633
a:
........
a:
<l
1632
3412
I 0.001
1632
4000 3000 2000 1500 1000
Wavenumbers I em- 1
Figure 10 IRAS ofhydrated H 3 0+ adsorbed on Pt(lll) at liO
K. To yield H30+ on the surface (a) 1 L, (b) 3 L, and (c) 7 L of
hydrogen gas were admitted into Pt(lll) at 110 K.
are attributable to VOH stretching and to bH,O scissoring
vibrations of coadsorbed water, respectively. The fre-
quencies of the bands are close to the previous results of
a bilayer-like H20 [27] on Pt(lll). The weak shoulder
absorption at a lower frequency side than 3430 cm- 1 in
the spectrum 9c could be the symmetric VOH stretching
ofH 3 0+ on the surface.
The band at 1150 cm- I shifted to 850 cm- I when
deuterated water (D20) was used. The band at 850 cm- I
was tentatively assigned to a symmetric bending of the
D 30+ species on the surface. The frequency (850 cm- I )
is also in agreement with the previous HREELS results
[28]. The absence of an asymmetric bending absorption
of H 30+ on Pt(ll1) in the spectrum suggests that the
H 3 0+ has C 3v symmetry with the molecular C 3 rotation
axis perpendicular to the surface. The coverage of
H 30+ in Fig. IOc was saturated because the intensity of
the symmetric bending remained constant after a
further increase in hydrogen exposure. The band started
to disappear during annealing at temperatures higher
than 155 K.
296
E. Coadsorption of HaO+ and HS0 4 on Pt(111)
H 30+ and HS0 4 on Pt(lll) in 0.5 M H2S04 solution are
coadsorbed in the potential range of 500-750 mY, and
the conversion of H30+ and HS0 4 to an H2S04 mol-
ecule proceeds at potentials more positive than 750 mV
as previously described. The double-layer structures in
the solution was simulated on Pt(ll1) under UHV con-
ditions. Figure 11 shows the IRAS of a coadsorbed layer
of hydrated HS0 4 and H 30+, which possibly represents
a model double layer on Pt(111) at 110 K. To yield the
coadsorbed layer, 3 ML of an H 20 bilayer was formed
on Pt(lll), and S03 gas was subsequently introduced onto
the H 20 covered Pt(11) at 110 K. The coadsorption
adlayer was then annealed by increasing the temperature
to 190 K. To form a stable hydrated HS0 4 and H30+
(a)
1224
(e)
M 1705
1039
Io.005 1273
4000 3000 2000 1500
Wavenumbers / cm- 1
Figure 11 IRAS of hydrated HS0 4 and H 30+ adsorbed on
Pt(lll) : (a) 110 K, (b) 138 K, (c) 151 K, (d) 162 K, (e) 186 K,
and (f) 260 K.
Shingaya and Ito
adlayeron the surface, a further 2 ML ofwater was added
while the temperature was lowered to 110 K. Figure 11,
a-f shows the IRAS of the hydrated HS0 4 and H 30+
on pte 111) before (a) and after heating the sample stepwise
to 138 (b), 151 (c), 162 (d), 186 (e), and 260 (f) K, respectively.
The bands at 3395 (VOH) and 1652 cm- 1 (JH 20) can be
assigned to the icelike water that was adsorbed on the
coadsorbed layer. The frequencies are roughly similar to
those of water on bare PtOll), as shown in Fig. 11. With
the temperature increase, the intensity of the band was
reduced because of the desorption of water from the
adlayers. The intensity of the band of HS0 4. however,
remained unchanged in the spectrum e.
As described before, a broad absorption at 1705 cm- 1
in the spectrum e is assignable to an asymmetric bending
vibration of an H 30+ on the surface from the frequency
[23,29,30]. In contrast, the band ofthe symmetric bending
vibration ofH 30+, which was found in Fig.lOc together
with the bands of hydration water, was not observed from
the coadsorbed layer. The fact that the symmetric bend-
ing vibration was missing while the asymmetric one
appeared in the IRAS of the coadsorbed layer indicates
that the molecular C 3 axis of the adsorbed H 30+ was
parallel to the surface. The measurement of TDS showed
that an appreciable amount of hydration water remained
on the surface even at a temperature ofl86 K. Therefore,
the absence of the bands of the hydration water in the
spectrum e indicates that the hydration water molecules
were adsorbed in a molecular plane parallel to the
surface. The spectrum fshows the result ofthe conversion
of H3 0+ and HS0 4 to a neutral sulfuric acid molecule
as described previously. Figure 12 represents a schematic
model of HS0 4 and H 30+ on Pt(lll). We described
earlier, that H 30+ adsorbs preferentially with the mol-
ecular C 3 axis perpendicular to the surface. When the
H 30+ ions are coadsorbed with HS0 4, however, the
molecular C 3 axis of the H 30+ becomes parallel to the
1000
Figure 12 A schematic diagram of HSO; and H30+ on
Pt(lll).
UHV Modeling Use in Sulfuric Acid Species 297

surface. The orientation ofboth ions on the surface favors

157
the viewpoint of hydrogen bonding. Furthermore, the 192
H 30+ played an important role in the reduction of a
coulomb repulsive force between HS0 4 molecules on
the surface. The crystal structure of solid oxonium
hydrogensulfate (H30)(HS04) (or hydronium bisulfate) (a)
have been reported [31,32]. In oxonium hydrogensulfate,
the HS0 4 tetrahedra form infinite hydrogen bonded 157
chains that are linked by H 30+ ions to form layer c
·2
structure. The structure of hydrogen bonded HS0 4 and :::I
.c
H30+ on Pt(lll) is similar to that in oxonium ~
hydrogensuifate. A hydration water is also drawn in the .z-
°Vi
c:
diagram. The hydration water is necessary to stabilize !!!
the HS0 4-H 30+ ion pair on Pt(lll). The hydration of oS (b)

the ion pair is mentioned in the next section.

The in situ IRAS of H30+ on a Pt(lll) electrode in a
153
0.5-M Na2S04 or a O.l-M Hel solution was successfully
observed. The symmetric bending vibration of H 30+
was observed at around 1200 cm -I in hydrogen potential
regions where electrolyte anions were absent on the (e)

surface. Thus, the molecular orientations of H 30+ on

the Pt(lll) electrode observed from in situ IRAS were
reproduced in the present UHV model double-layer 120 190 120 260
structures. (A) T (K) T (K)

10.----------------------,
F. Coordination Number of Water onto HS0 4
on Pt(111) as a Function of HS0 4 coverage ~ 8
(I)

When both H 3 0+ and HS0 4 coexist on Pt (Ill) and both ..c

E
ions are coordinated (or hydrated) by water molecules, ::J
c:: 6 a
it is important to determine the coordination number of c::
0
water onto the ions as a function of HS0 4 coverage ~ 4
(B HSO; or BH ] 0+ ). To evaluate the coordinaton number -g,
ofwater molecules per ion, the absolute quantity ofwater .c::

molecules on the surface must be known. To observe the 2

absolute amount of water, TDS measurements of I-ML
bilayer ofwater on Pt(lll) were performed. A well-known
hexagonal structure [33] was used to define 1-ML ofwater
as BH20 = 2/3. All peak areas in Figure 13 were
normalized by the I-ML bilayer ofwater amount.
Next, the absolute coverage of HS0 4 on the surface
should be determined. Regarding the saturation coverage
of HS0 4 on Pt(lll), we must rely on the results from a
radiotracer [34] and in situ STM [19,20}. Actually, the
results from those studies gave the same conclusion that
the saturation coverage ofHS0 4 on Pt(lll) is 0.2. Figure
13, a-c, shows theTDS results for water desorption that
is associated with a temperature increase to 190 K. The
coadsorption layers (H30+ + HS0 4) with three different
coverages were formed on Pt(lll) (S03 amounts were
controlled). The coverage was largest in Fig. l3c. During
the annealing process, the H30+ + HS0 4 coadsorption
O+------,----,----,--------r-----l
o 0.04 0.08 0.12 0.16 0.20
(8) HS04 coverage
Figure 13 (A) TDS results of excess water as a function of
HSO" coverage. The coverages ofHSO" were changed by S03
exposure amounts (a-c). TDS results of water associated with
the conversion of HSO" to H2S04 (d-f). (B) The hydration
number per HSO" on Pt(111) as a function of8 Hso,.
layer on Pt(lll) was completed. The larger desorption
peak on the lower temperature side in Fig. 13, a-c was
due to overlayer water molecules that were not consumed
in the reaction 2 H 20 + S03 ---+ HS0 4 + H 30+. The
smaller one on the higher temperature side, however,
298
was due to water molecules that were adsorbed on the Pt
(lll) surface. The fact that the peak areas in Fig. 13, a-c,
at the higher temperature peaks, in others word, the water
coverages (BH,o) occupying the Pt(lll) surface site, were
reduced in this order, means that the coverage of the
HSOi + H 30+ coadsorbed species on the Pt surface
increased in the same order.
Thus, we can deduce the coverage ofHSOi on the sur-
face from the peak area in Fig. 13, a-c. From the peak
area, the coverage of HSOi was determined to be
0.064(0.2 x (1-0.68»,0.15(0.2 x (1-0.27», and 0.18 (0.2 x
(1-0.10», respectively. The saturation coverage ofHSO;
is assumed to be 0.2 as mentioned in this section.
The temperature was lowered again to 110 K after the
TDS measurement (a-c). Figure 13, d-f, shows theTDS
results that are associated with a further temperature
increase to 260 K. The TDS signals are ascribed to the
desorption of water mainly from the form, HS0 4 (ad) +
H30+ (ad) + (H20)n, on the Pt(lll) surface, where HSO;
and H30+ were coordinated with (H 20)w The amounts
of water desorption from each surface were normalized
relative to the absolute H 2 0 values. However, the
dehydration from ion pairs on the surfaces caused a
proton transfer and a subsequent H 2 0 evolution during
a temperature rise. We mentioned a conversion reaction,
i.e., HS0 4(ad) + H 30+(ad) --+ H 2 S0 4 (ad) + H 2 0 (to be
desorbed), in both UHVand in situ environments in the
earlier section. The results in Fig. 13, d-f, include the
latter component of water desorption that should be
removed from the present consideration. This is a simple
correction because the conversion water number equals
that of HSO; on the surface.
The water coordination number per HSO; molecule
was then evaluated from theTDS results and plotted out
as a function of HSOi coverage as shown in Fig. 13b.
From the curve, it was determined that the number of
water molecules was reduced exponentially with an
increase in BHSO 4-. The result also indicated that both
HSOi and H 30+ on Pt(lll) are always hydrated, the
coordination number being 1 to 8 per HSOi. Recent ab
initio molecular orbital calculations of the hydrated
sulfuric acid molecule [35], H 2 S0 4 (H 2 0)n (n = 1-8)
showed that the hydrated stable structures were found
up to n = 1-6, whereas n 0:: 7, OH dissociation started to
occur, giving H30+ + HS0 4.Therefore, we can conclude
that the ample hydration water molecules should be
necessary to stabilize HSOi (and also H 30+) on Pt(lll).
Sass and colleagues [36, 37] reported that the hydration
number increased with the decrease in adsorbed oxygen
on Cu(llO) or Ru(llO). The smaller an island of adsorbed
oxygen becomes, the larger is the hydration number per
oxygen atom. Similar considerations are possible in the
Shingaya and Ito
present result between the hydration number and BHSO4-'
When an island, which is composed of HS0 4 + H30+
on the surface, is surrounded by water molecules, the
number of the water molecules is closely connected with
the size of the island. When the size of an island is small
(i.e., low HSOi coverage), larger numbers of water mol-
ecules can fit on the periphery of an island. This is the
reason why the hydration number per anion increased
with a decrease in HSOi coverage.
G. Potential Drop atthe HS04"/H 3 0+ Adlayers
It is important to understand the relationship between an
electrode potential and an electrochemical double-layer
structure. It has been a central subject of the UHV
modeling studies since an early stage of the development
of the modeling method. Bange et al. [7] showed directed
relevance between electrode potential and work function
in UHVas a function of anion coverage for the Br/H20
system on Ag(1IO). In this case, the coverage of Br and
H 20 at the first layer controls the electrostatic potential
drop across the inner layer. It was shown that water mol-
ecules in the overlayers also contribute to the potential
drop. They proposed that overlayer water molecules
assume a preferential orientation, induced by the
presence of the adsorbed bromide in the first layer.
Then, how does the HSOi 1H30+ adlayer contribute
to the potential drop? To inquire into this question, IRAS
ofHSOi in UHV was compared with in situ lRAS under
active potential. In in situ IRAS, the absorption band of
HS0 4 started to appear at 400 mY, and the intensity of
the band increased as with the positive potential change.
The band of adsorbed HSOi showed remarkably large
frequency shift upon the potential change between
400-750 mV (130 cm- 1 IV). Therefore, the shift of the
band center frequency gives an important clue to answer
the question whether HS0 4/H 30+ contributes to the
potential drop. Figure 14 shows IRAS ofHSOi adsorbed
on Pt(lll) in UHVas a function of HSOi coverage. After
forming HS0 4 adlayers on Pt(lll), about I-ML water
was added on the surface to saturate the first layer. The
HSOi coverage is (a) 0.32, (b) 0.63 and (c) 0.90 ML, which
was estimated by TDS of water. The spectra show that
band center frequencies for the various HS0 4 coverage
are almost the same. The shift 00 cm -I can be explained
by a dipole-dipole coupling. This suggests that the cover-
age change of HSOi 1H30+ does not contribute to the
large frequency shift and also to the potential drop created
on Pt(lll) electrode. Then, what is the origin of the band
shift in the in situ IRAS during the electrode potential
change? One of the candidates is the electric field effect
UHV Modeling Use in Sulfuric Acid Species
(b)
1233
(e)
1234
1500 1400 1300 1200 1100 1000 900 800 700
Wavenumbers I em- 1
Figure 14 IRAS of HSO.:! adsorbed on Pt(lll) under UHV
conditions as a function of HSO.:! coverage.
derived from overlayer water on top of the HS0 4/H 30+
adlayer. Figure 11 shows IRAS of about 1-ML HS0 4 and
2-ML overlayer water adsorbed on Pt(ll1) in UHV. The
S03 symmetric stretching band of HS0 4 at 1232 cm- I
in Fig. 11 (a) shifted down to 1211 cm- I in (c), associated
with slight annealing temperature increase. The further
increase in annealing temperature started to desorb the
overlayer water. With the desorption of the overlayer
water, the band of HS0 4 increased in frequency up to
1235 cm- I . The frequency shift can be explained as
follows. The initial overlayer with 2-ML water at 110 K
would form a disordered structure with relatively random
orientation. After an annealing, the overlayer water
would form a preferential structure in terms of the
hydrogen bonding to the adsorbed HS0 4. Because the
preferential orientation of the water dipole should pro-
duce the potential drop [38], the lower frequency shift
would occur by the change of the potential drop. Then,
the frequency recovered to a higher value by elimination
ofthe overlayer water. These results indicate that the large
frequency shift (24 cm -I of adsorbed HS0 4 arise from
299
structural change of the overlayers, especially from the
change of the electric field associated with the overlayer
water. Of course, other cation and anion distribution at
an overlayer would contribute to the potential drop in
the same manner.
IV. SUMMARY
H20, H 30+, HS0 4, and H 2S04 molecules on a Pt (111)
surface were investigated by means of Cv, LEED, TDS,
and in situ and UHV IRAS. The potential-dependent
electric double layers on Pt(lll) in H 2S0 4 solution were
successfully simulated by the gas-phase adsorption of
H 20 and S03 under UHV conditions.
Model structures on Pt(lll) under UHVobtained from
surfaces after annealing at 190 and 260 K agreed well with
the structures from surfaces at negative (500-750 mY)
and positive (750-1100 mY) electrode potentials, respec-
tively. A sulfuric acid molecule on a Pt(lll) observed at
750-1100 mV was reproduced by dehydration from the
coadsorption ofH 30+ and HS0 4 at 200-300 K
The hydrated H 30+ molecules have C 3v symmetry and
are adsorbed on Pt(111) with the molecular C 3 axis per-
pendicular to the surface, whereas the H 30+ coadsorbed
with HS0 4 changed molecular orientation on Pt(111)
with the C 3 axis parallel to the surface.
When an HS0 4 + H30+ ion pair island was sur-
rounded by water molecules on Pt(ll1), the number of
the coordination water molecules per HS0 4 and the ion
pair island size are related.
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18
Adsorbate Bonding and Reactivity in Electrochemistry:
Some Vibrational Spectroscopic Links to Surface Science
and Interfacial Chemistry
Michael J. Weaver and Shouzhong Zou
Purdue University, Jtest Lafayette. Indiana
ABSTRACT
Some current issues and recent progress in utilizing
infrared and especially Raman spectroscopies for the in
situ vibrational characterization ofadsorbates at electro-
chemical and related interfaces are outlined and illus-
trated by means of examples culled chiefly from our
laboratory. The primary factors responsible for the
differences in experimental strategies pursued for
metal-solution interfaces compared with surfaces in
gaseous and ultrahigh vacuum (UHV) environments
are discussed, and the virtues of infrared reflection-
absorption spectroscopy (IRAS) and surface- enhanced
Raman scattering (SERS) for scrutinizing the first
interfacial type are assessed. The influences of the elec-
trochemical double layer on chemisorbate vibrational
properties at ordered metal-solution interfaces as
gleaned by in situ IRAS data in comparison with anal-
ogous interfaces in UHVare described, and briefly illus-
trated for carbon monoxide and nitric oxide on
low-index Ir and Pt surfaces. The broad-based import-
ance of the surface potential in controlling chemisorbate
properties on metal surfaces is quantatively examined.
The burgeoning prospects for using SERS as a versatile
and uniquely sensitive vibrational probe of chemically
significant, especially transition-metal, interfaces in
both electrochemical and gas-phase environments are
delineated. Illustrative examples include elucidating aro-
matic chemisorbate bonding and the reactive nature of
surface oxides.
301
I. INTRODUCTION: EVOLUTION OF
ELEC·rROCHEMICAL VIBRATIONAL
STRATEGIES
Our understanding of adsorptive chemistry in electro-
chemical systems, as for metal interfaces in gas-phase
and ultrahigh vacuum (DRV) environments and related
moieties such as metal clusters and colloids, has been
influenced greatly in recent years by the development of
various in situ vibrational spectroscopies. The sensitivity
of molecular vibrations to surface coordination, inter-
molecular interactions, and molecular structure and sym-
metry makes such methods of paramount importance in
interfacial chemistry. Given the diverse nature of
metal-based interfaces and especially the challenges
imposed by the presence of the solution phase in electro-
chemical systems, the vibrational strategies used for the
latter have been somewhat different to those commonly
used in DRV surface science. In particular, electron
energy loss spectroscopy (EELS) provides a powerful tool
for vibrational characterization at metal- DRV inter-
faces yet is entirely inapplicable to metal surfaces in higher
gas pressures or solution-phase environments. On the
other hand, with suitable modifications, photon-based
vibrational spectroscopies can be used at such interfaces.
Infrared reflection-absorption spectroscopy (lRAS), in
particular, has found widespread applications to
metal-solution and metal- DRV systems. Although the
solution phase usually strongly absorbs infrared radi-
302
ation, as first demonstrated by Bewick and Pons [1],
remarkably sensitive infrared spectra for adsorbed species
can nonetheless be obtained by using thin-layer electro-
chemical cells in conjunction with potential-difference
(PDIR) tactics [2]. As outlined elsewhere in this volume
[3], for adsorbates whose presence can be controlled by
electrooxidation!electroreduction or from potential-
dependent adsorption! desorption, such PDIR strategies
can yieldvaluable information for reactive and stable elec-
trochemical systems.
Similarly to IRAS at metal- UHV interfaces, the
availability of sensitive (and inexpensive) Fourier trans-
form infrared spectrometers has led to an increasingly
widespread use of infrared methods for the vibrational
characterization of electrochemical adsorbates. The
emergence of reliable and straightforward non-UHV
means of preparing ordered single-crystal surfaces,
especially using flame-annealing tactics [4], along with
the ability to characterize the atomic!molecular spatial
structures at moncrystalline metal electrodes, especially
by means of scanning tunneling microscopy (STM) and
surface x-ray scattering [5-7], provide a strong incentive
to undertake detailed in situ IRAS studies [2,3]. Indeed,
IRAS-based vibrational information coupled with other
detailed microscopic structural data has played an
important part in the emergence of the coherent disci-
pline of "in situ electrochemical surface science" within
the last decade or so [8,9]. Of particular fundamental
interest in this context are electrochemical adsorbate
systems, most notably (but not exclusively!) carbon
monoxide on monocrystalline Pt-group electrodes, for
which similar vibrational information can also be
obtained by IRAS at analogous metal-UHV interfaces
[2]. As outlined further below, such links between mol-
ecular adsorbate properties in structurally well-defined
electrochemical and UHV environments serve as an
important avenue for unifYing these traditionally discon-
nected segments of surface science [2,9].
Another more recently developed in situ vibrational
technique applicable to monocrystalline metal-solution
interfaces [10] and surfaces in UHV (and gaseous)
environments [11] is infrared-visible sum frequency gen-
eration (SFG). Whereas the electrochemical SFG tech-
nique has several limitations, including solution
absorption of the incident infrared light and photo-
chemical damage from the visible pulse laser, the
intrinsic surface selectivity of SFG offers opportunities
for the vibrational characterization of electrochemical
interfaces, especially at single-crystal metals.
Although these approaches, especially IRAS, consti-
tute valuable in situ vibrational methods in electro-
chemical and UHVlgas-phase surface science, they
Weaver and Zou
have inherent limitations for the broad-based
characterization of adsorbates, resulting particularly
from sensitivity restrictions, surface selection rules,
and the inaccessibility of low-frequency vibrational
modes. Even before the advent ofelectrochemical IRAS,
Raman spectroscopy had garnered considerable atten-
tion for in situ surface vibrational characterization. Nor-
mal Raman scattering is usually sufficiently weak to
preclude vibrational analysis at most planar interfaces.
However, the discovery and realization of the
surface-enhanced Raman (SER) effect in the mid-late
1970s attracted widespread interest [12], primarily
because the magnitude of the scattering enhancement
results in readily detectable Raman signals even for
low adsorbate coverages. (The effective increases in the
Raman scattering cross-sections, or "surface enhance-
ment factors," SEF, are typically ca. 106 - fold on
electrochemically roughened silver, gold, and copper
[12].) This high degree of intrinsic surface selectivity
typically swamps the bulk-phase contributions even in
liquids, enabling sensitive surface vibrational spectra to
readily be obtained for submonolayers at electrochemi-
cal interfaces without the need for spectral-difference
tactics. Despite an early emphasis on examining
pyridine and related molecules, chiefly from the stand-
point of exploring enhancement mechanisms, it is
unassailably true that SERS is applicable to a wide var-
iety of adsorbates, including inorganic and complex
organic systems.
The recognition that the SER effect was limited in
practice to roughened surfaces of the "coinage" metals
copper, silver, and gold, however, dampened the interest
of the UHV surface-science community. This relative
indifference was undoubtedly also encouraged by the
concurrent emergence of EELS and IRAS for UHV-
based systems in the late 1970s. Unlike SERS, these
vibrational techniques are applicable to the ordered
monocrystalline metal surfaces of primary interest in
UHV surface science, even though the feasibility ofusing
unenhanced Raman spectroscopy for such systems was
demonstrated shortly afterwards by Campion and co-
workers [13]. The markedly greater interest shown, by
comparison, by the electrochemical community in SERS
was probably due in part to the near-exclusive usage (at
the time) of polycrystalline metal electrodes, along with
the availability of a straightforward preparation of
SERS-active surfaces by means of controlled-potential
oxidation-reduction cycles [12].
Since that time, SERS has found broad-based
applications, particularly for silver interfacial and
colloidal systems in analytical chemistry, although the
technique has a rather more chequered history in funda-
Vibrational Spectroscopic Links
mental surface chemistry. On the one hand, its remark-
able sensitivity, wide wavenumber ranges, and liberal
selection rules endow SERS with unique attributes for
in situ surface vibrational characterization, especially in
challenging ambient environments. Indeed, the breadth
and types of vibrational modes accessible with Raman
spectroscopy compare very favorably with EELS, with
the crucial advantage that, unlike the latter technique,
the former approach is applicable to surfaces in
liquid-phase and ambient gas-pressure environments
and in UHY. On the other hand, the apparent restriction
of the SERS effect to primarily a few "free-electron"
metals along with the required presence of (often
ill-defined) surface roughness has relegated the strategy
in the opinion of some to the status of odd curiosity, the
results from which are to be viewed with suspicion, rather
than constituting a surface vibrational technique of abid-
ing fundamental value.
Attention in our laboratory has long been focused on
SERS on gold substrates [14], encouraged by its desirable
electrochemical properties, including a resistance to
oxidation and a wide polarizable potential window even
in aqueous media. Of particular interest to us have been
strategies to broaden the applicability of SERS to other
surface materials. Although roughened transition-metal
surfaces have been predicted to yield SERS on electro-
magnetic grounds, albeit more weakly than for the
coinage metals [15], the occasional earlier experimental
reports of such phenomena have by and large not led to
useful chemical applications (vide infra). Given the practi-
cal and fundamental significance of transition metals,
the demonstration in 1986 and 1987 that SERS could
readily be extended to Pt-group surfaces [16] and metal
oxides [17] by electrodeposition as overlayers on gold
was of particular importance to us. A limitation of the
procedure at that time to electrochemical systems was
that the influence of the underlying gold substrate on the
adsorptive chemistry via the presence of residual
"pinhole" sites was typically evident in the vibrational
spectroscopy of chemisorbates on the ultrathin films
(::; 3-5 monolayers) necessary to retain near-optimal
SERS. This complication, however, turned out to be
much less ofan impediment to the utilization of the tech-
nique in gas-phase environments, especially at the
elevated temperatures of particular catalytic relevance,
because gold displays near-negligible adsorptive proper-
ties under these conditions [18]. Indeed, the applicability
of SERS as a sensitive in situ vibrational technique for
transition-metal catalysts even under ambient-pressure
flow-reactor conditions has spawned a number of
applications in our laboratory along these lines (vide
infra).
303
Several other factors emerging only recently, however,
are conspiring to encourage a renewed and (we hope) a
more broad-based interest in exploiting SERS as a
chemically versatile and uniquely sensitive vibrational
probe of adsorbates at surfaces in electrochemical and
gaseous environments. A key stimulus lies in the substan-
tial improvements in the analytical sensitivity of Raman
spectroscopy brought about primarily by the advent of
notch filter/single-grating spectrometer arrangements
and high-efficiency charge-coupled device detectors
[19,20]. Indeed, McCreery and coworkers [20] have been
able to detect Raman spectra for adsorbates at
carbon-aqueous interfaces in the apparent absence of
electromagnetic surface enhancement. As shown
recently by Tian et aJ. [21], by using such instrumentation
along with confocal optics, it is now feasible to obtain
Raman spectra for diverse adsorbates at transition
metal-solution interfaces in the presence of only mild
surface enhancements, say SEF '"30-100.
We have found that near-uniform overlayers of
Pt-group transition metals on mildly roughened gold
can be formed by constant-current electrodeposition
[22,23]. Their essentially pinhole-free characteristics
even for ultrathin films (down to ca. 2-3 monolayers) pro-
vide near-optimal SERS characteristics yet free of the
spectral (and chemical) interferences from the underlying
substrate that limited our earlier efforts along these lines
(vide supra). Although the SEF values, as expected, are
attenuated progressively as the overlayer thickness
increases, chemisorbate Raman spectra are nonetheless
readily measurable even on relatively thick (5-10 nm)
transition-metal films [23], demonstrating the practical
value of this strategy (vide infra). While still under initial
development, as outlined below such tactics, especially
when the overlayer film strategies are coupled with
improved Raman instrumentation, can offer uniquely
sensitive vibrational information for a widening range of
interfacial systems.
Overall, then, the vibrational strategies developed
for in situ electrochemical systems, including SERS
and IRAS, are becoming capable of examining
metal-adsorbate systems that are increasing chemically
broad-based and encompassing the structurally
"well-defined" single-crystal surfaces studied previously
only in UHV environments. Furthermore, the need
to meet the challenges imposed by solution-phase
interferences in electrochemical systems has yielded
experimental strategies that can also provide valuable
means of acquiring surface vibrational information in
other technologically relevant environments, such as
ambient-pressure gaseous systems. As a consequence,
vibrational spectroscopic explorations of in situ electro-
304
chemical surfaces are now acquiring stronger ties both to
fundamental issues of adsorbate structure and bonding
at metal- UHV interfaces and interfacial chemistry in
other catalytically relevant systems.
The chief aim of this article is to sketch some of the
physical and/or chemical insights that can be extracted
by exploring the vibrational properties of electrochemi-
cal systems with these twin objectives in mind. We con-
sider recent examples, taken chiefly from our laboratory,
ofIRAS- and SERS-based investigations of in situ elec-
trochemical interfaces along with those involving related
metal- UHV and ambient gaseous systems. The dis-
cussion is selective, biased, and far from comprehensive
(or even detailed), the intention being to illustrate some
elements in which vibrational spectral studies may aid
the evolution ofsurface electrochemistry into a discipline
having greater microscopic-level significance to
interfacial chemistry as a whole.
II. INFLUENCE OF INTERFACIAL SOLVENT,
SURFACE POTENTIAL, AND CHARGE ON
CHEMISORBATE INFRARED PROPERTIES
As already mentioned, the emergence of reliable means
of preparing monocrystalline metal electrodes, primar-
ily using labo ratory flame-annealing tactics [3,4] coupled
with in situ IRAS measurements, have recently enabled
adsorbate vibrational properties to be scrutinized in
detail at such ordered electrochemical interfaces [2,3,9].
Ofparticular interest are chemisorbed carbon monoxide
and nitric oxide, both in view of the sensitivity of their
intramolecular vibrations to the chemical and electro-
static environments and the detailed information also
attainable (and available) for these adsorbates at corre-
sponding UHV-based interfaces. Comparisons with the
latter data provide intriguing opportunities for assessing
the influence of the so-called electrochemical "double
layer," encompassing the interfacial solvent and electro-
static (electronic and ionic) charge, on the chemisorbate
vibrational properties. A number of concerted examin-
ations along these lines have been undertaken during
the present decade [2,9,24,25]. We now briefly consider
some findings along these lines obtained in our labora-
tory by means of both low-temperature UHV-based
IRAS measurements involving sequential additions of
solvent and ionic/electronic charge [25] and in situ elec-
trochemical lRAS [1,5]. The former "UHV electrochemi-
cal modeling" tactics, pioneered by Sass and coworkers
[26], enable the synergetic effects of the additional com-
ponents present in electrode-solution interfaces to be
explored in incremental fashion, thereby aiding interpret-
ation ofthe in situ electrochemical IRAS data [25].
Weaver and Zou
We summarize first some salient findings for an
illustrative pair of such electrochemical systems exam-
ined by IRAS, carbon monoxide on Pt(1l1) and Ir(111).
The former has been reviewed recently in some detail
[2,25], so that the remarks here are correspondingly brief.
The Pt(1l1)/CO system has been examined in the
presence ofa number ofsolvents, both at in situ interfaces
[27,28] and in UHV [25,29-31], and has also been the sub-
ject of a detailed combined in situ STM/IRAS examin-
ation of the potential-dependent saturated CO adlayers
[32,33]. Interestingly, the in situ electrochemical IRAS
data for CO on Pt(lll) show two marked differences to
the corresponding vibrational behavior on clean Pt(lll)
in UHY. First, the C-O stretching (vco) frequencies for
both atop and bridging CO are 30-50 cm- 1 lower in the
former environment [27,28]. Second, although the atop
binding site is energetically preferred for the latter,
multi fold CO coordination is more prevalent in the for-
mer case [27]. The latter difference is indicated from
UHV electrochemical-modeling experiments to be due
predominantly to solvent coadsorption, arising from
more favorable CO~solvent dipolar interactions for the
multifold vs. atop chemisorbate [30]. The former dissimi-
larity has been shown to arise from differences in the sur-
face potential drop developed across the CO adlayer
within the electrochemical and solvent/charge-free
UHVenvironments [27,29,31].
Again, the UHV electrochemical-modeling tactics
provide an insightful molecular-level picture of these
effects, showing how the dipolar solvent and the solvated
ionic charge contribute importantly to alterations in the
surface potential and hence the Vco frequency, .1Vco [31].
The dependence of the former quantity on the interfacial
composition, involving sequential dosing of solvent
and/or ionic charge, is evaluated from changes in the
work function .1<1>. Although <1> measurements are now
somewhat unfashionable in UHV surface science, they
yield crucial fundamental insight into interfacial
electrostatics and provide the required link between sur-
face potentials in UHV-based and in situ electrochemical
systems [25]. The .1vco -.1<1> dependences, well known
from in situ IRAS (and SERS) studies in interfacial elec-
trochemistry (the so-called Stark-tuning effect), arise
from alterations in the C-O force constant induced by
the varying local electrostatic field, together with surface
charge-induced changes in the metal-CO chemisorbate
bonding [34]. Interestingly, the .1vco - .1<1> plots for atop
CO on Pt(lll) are found to be approximately coincident
for both in situ and UHV-based model electrochemical
interfaces in a variety ofsolvents, emphasizing the central
role of the surface potential in influencing chemisorbate
vibrational properties. This point for saturated CO
Vibrational Spectroscopic Links 305

parameters, specifically the band frequency, integrated

• CO
2100
--e-- KICOJD20
-e- KICO/MeOH
• absorbance, and bandshapes, to be explored in detail [35].
The Veo frequencies increase markedly towards higher
"'0'" KICO/ACN Beo due chiefly to enhanced dynamic dipole coupling,
- '\iL • KICO/ACETONE
. ·0· . KICO/NH3 and again display near-coincident values at a given cover-

-
...
'S 2080
--...- In-Situ (aqueous) age in the electrochemical and DRVenvironments once
the differences in surface potentials are taken into
account. Significantly. the observed marked double-layer
~ effects on the latter two vibrational parameters can be
/.'/lI. accounted for quantitatively in terms ofsolvent dielectric
screening and dipole-coupling effects.
2060 As an example, Fig. 2 compares the integrated Veo
? ..... band absorbance, Ai, evaluated in the coadsorbate-free
./,: DRV and aqueous electrochemical environments
. '//'0
(triangles and circles, respectively), plotted against the
. 1./ fractional CO coverage [35]. The markedly curvilinear
'"
so
.u 2040 . / ..
/6- Ai - Beo plot seen in DRV [36], attributable chiefly to
:>
'i1 Beo-dependent dipole coupling, contrasts the more lin-
ear behavior obtained for the electrochemical system.

2020

0.2-r-----------------.
4 5 6
o
WORK FUNCTION (eV)

Figure 1 Infrared Veo band frequency for atop coordinated

CO in saturated adlayers on Pt(lll) in UHV in the presence of 4-

.'
/
the multilayer solvents (as indicated in the inset) and at varying /
K+ coverages. plotted against the surface work-function. Filled '1
circles are from corresponding in situ data for Pt(lll) in aqueous
0.1 M HCl04. (Adapted from Ref. 31.) /
I •
I
•
adlayers on Pt(lll) is illustrated in Fig. 1 (taken from Ref.
31). The open symbols were obtained by dosing multilayer
solvents along with K atoms (so to yield K+ plus elec- J::"I
I
I

"
I

•
. •

I
tronic charge) on Pt(lll)/CO in DRY, whereas the filled 0.05 I
circles refer to the corresponding in situ aqueous electro- I
I
chemical system [31]. A reasonable concordance between
each ofthe Veo - <l> plots is evident.We further discuss this A•
issue below. I
f
The Ir(lll)/CO aqueous electrochemical system, o4--...,....-...,-...,....-...,-...,....-...,-...,....-...,-...,....-...,-...,....-...,-...,....-...,-""T""""""'\
recently examined in detail [35], is also of particular fun- o 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
damental interest because the infrared spectra display
only a single Veo band located at 2020-2075 cm- I on
CO Coverage
Ir(lll) over the full range of CO coverages, Beo , both in
Figure 2 Integrated absorbance of atop Veo band for CO
DRV in the absence of coadsorbate [36] and in aqueous
dosed on h(lll) as afunction ofthe CO coverage, Beo , obtained
electrochemical environments [35], indicative of exclus- in UHV (from Ref. 36) (triangles) and in aqueous 0.1 M HCl0 4
ive atop (or near atop) surface coordination. This unusual at 0.4 V vs. SHE (circles). Dashed and solid traces are corre-
behavioral simplicity enables the influence ofthe electro- sponding predictions from a theoretical dipole-coupling
chemical double layer on the fundamental vibrational analysis. (Adapted from Ref. 35.)
306
The former Ai - Beo curve shape, commonly seen in
UHY, arises from the effect upon the band absorbance
from increases in oscillator density towards higher Beo
being offset by increasing dielectric screening by
neighboring chemisorbate dipoles [36,37]. The smaller
Ai - Beo slope at low coverages observed in the electro-
chemical case is consistent with the occurrence of
dielectric screening of the chemisorbate dipoles by
coadsorbed solvent molecules. Although the electro-
chemical Ai - Beo slopes still decrease towards higher
coverages, the Beo-dependent nonlinearity is markedly
smaller than in UHV because the degree of dielectric
screening induced by coadsorbed water is not greatly dif-
ferent to that from surrounding chemisorbate molecules
[35]. Also included in Fig. 2 are calculated Ai - Beo plots
for the UHV-based and aqueous electrochemical systems
(dashed and solid traces, respectively), obtained from a
numerical dipole-coupling analysis [ef, Ref. 33]. The
acceptable fit to the experimental data in both cases
supports the essential validity of dipole-coupling models
in accounting for coadsorbate screening effects in this
case. Indeed, the smaller degree of nonlinear Ai - Beo
behavior commonly observed for CO at electrochemical
interfaces as compared with the corresponding
solvent-free UHV systems [e.g., Refs. 27,38] is probably
due chiefly to solvent dielectric screening [also see Ref.
30].
Substantial differences in the Beo-dependent band-
widths, ~Vl/2, are also evident on Ir(lll) in the electro-
chemical solvent-free UHV environments, in that the
former values increase to a greater extent towards lower
coverages [35]. These differences, however, are due pri-
marily to changes in the stochastic line broadening
associated with local CO--CO interactions rather than
to the effects of solvent-induced inhomogeneous
broadening. Nevertheless, the ~Vl/2 values for com-
pressed (i.e., high-Bco) adlayers in the electrochemical
environment approach the values, ca. 5-7 cm- 1,
observed in UHY, suggesting that the Lorentzian
lineshapes obtained under these conditions are affected
by only a small or moderate extent by second-layer
solvation [35]. A related detailed study of coverage-
dependent infrared absorbances and bandwidths within
intermixed CO/NO adlayers on Ir(lll) in aqueous sol-
ution also yielded approximate concordance with the
predictions of dipole-coupling models [39]. In this case,
the vibrational behavior of both coadsorbates can be
followed (via the Veo and VNO infrared bands), an
interesting complication being the occurrence of sub-
stantial "intensity transfer" from the lower to higher fre-
quency band partners, also arising from dynamic dipole
coupling [39,40].
Weaver and Zou
The physical effects of the solvent or other
coadsorbates in the simple Ir(lll)/CO system, i.e., in the
absence of coadsorbate-induced site switching or mul-
tiple CO coordination geometries, therefore appear to
be relatively well understood. More generally, these and
other detailed IRAS studies of chemisorbed CO and
NO at analogous well-defined UHV-based and electro-
chemical interfaces give us considerable confidence
that the observed vibrational properties in the latter,
more complex, environment cannot only be related
straightforwardly to the observed behavior of the for-
mer chemically simpler systems, but also can be under-
stood in terms of fundamental physical models of
intermolecular interactions [6].
We have already noted the importance of the surface
potential in influencing the chemisorbate vibrational
frequencies. The relationship between the properties of
CO and NO adlayers on metals in electrochemical and
UHV environments in this context is now illustrated
further. Table 1 summarizes data for CO and NO
vibrational frequencies on low-index iridium and plati-
num surfaces in aqueous electrochemical (0.1 M HCI0 4)
and solvent- /charge-free environments. The systems were
selected chiefly in view of the essentially single-site
chemisorbate binding [except for Pt(lll)/CO] deduced
from the vibrational spectra, together with the known
occurrence ofpurely molecular (as opposed to partly dis-
sociative) NO adsorption. Listed for each electrochemi-
cal system in Table 1 are the IRAS Veo and VNO values,
labeled Vee, for known (mostly saturated) coverages at a
given electrode potential, E (vs. SHE), together with the
corresponding frequency-potential ("Stark-tuning")
slopes, dveo/dE and dVNO/dE. Given in adjacent
right-hand columns are the corresponding Veo and VNO
values obtained on the same surface in UHV, termed
Vuhv, along with the work functions of the clean metal
surface, <1>, and the changes, ~<1>, brought about by CO
or NO chemisorption to the appropriate coverage (see
the footnotes toTable 1for appropriate references).
Alongside each Vuhv value is listed a corresponding Vee
frequency, labeled vee(extrap). The latter values are
obtained from the experimental Vee and dvee/dE values
by extrapolation to a higher electrode potential equiv-
alent to the work function, <1>ad( = <1> + ~<1», for the
corresponding chemisorbate-containing metal-UHV
interface. This procedure, of course, requires a knowl-
edge of the relationship between the surface potentials
measured on the electrochemical and vacuum scales. We
have addressed this point previously for various systems
[e.g., 24,25,31,35] by means of the following relation [55]:
E = <1>/e - E k (1)
Vibrational Spectroscopic Links 307

Tablet Comparison ofPotential-Dependent Intramolecular CO and NO Stretching Frequencies at Corresponding Electrochemical

and UHY Interfaces
E Vee b dvecidE e cI>/ ~cI> d Vuhv e vee(extrap) f
System Coverage a
Yvs. SHE (em-I) (cm-1 y- 1) (eY) (em-I) (em-I)

Gaseous CO (214W (l2)h

Gaseous NO (l877)g (8)h
Ir(lll)/CO 0.7 0.4 20761 25 5.7/0.l5 e 2092 g 2090
0.1 0.4 20W 50 5.7 2050 2050
Ir(lll)/NO sat 0.6 1847i 60 5.7/~O.l1 1860' c::::; 1865
Ir(100)/CO 0.65 0.2 2046 k 30 5.6/~0.2k 2071' 2070
Ir(lIO)/CO 1.0 0.35 20671 25 5.5/0.21 2086' 2082
Pt(lll)/CO 0.65 0.35 2073 ffi 30 5.9/0.1 u 2104 v 2100
Pt(lll)/NO sat 0.6 1686n 62 5.9/- O.l5 w 1714w 1712
Pt(100)/CO 0.85 0.3 2060°·' 35 5.7/0.4' 2097 Y 2098
Pt(lOO)/NO sat 0.6 1630P 42 5.7/-0.l aa 1641' 1640
~O.l5 0.6 1580 100 5.7 1605 1610

a Coverage values referenced to metal atomic density; "sat" is saturated adlayer ofuncertain coverage.
b Chemisorbate stretching frequency, measured at electrode potential, E, noted alongside, in aqueous 0.1 M RCI0 4, extracted from literature source
noted.
C Stretching frequency-potential ("Stark-tuning") slope, from literature noted for Vee values.
d Work function ofclean surface in URY/work-function change induced by CO or NO adsorption, to coverage indicated, extracted (or estimated) from
data quoted in references listed.
e Chemisorbate stretching frequency evaluated in URYat coverage indicated (mostly at 300 K), from literature source noted.

f Chemisorbate stretching frequency evaluated at coverage indicated in electrochemical environment, but extrapolated to surface potential correspond-
ing to that for URY system by using Eq. (I).
g Stretching frequency for gaseous CO or NO, obtained from Ref. 41 (also see Ref. 34).
h Gas-phase Stark-tuning slopes for CO and NO, estimated as in Ref. 42.
iRef.35.
iRef.39.
k Ref. 41
I Refs 35,42.
m Refs. 32,44.

n Refs. 45, 46.

o Ref. 44.
p Ref. 47.
q Ref. 36.

'Ref. 48.
s Ref. 49.
'Ref. 50.
u Refs. 27, 29.

v Refs. 29, 31.

wRef.46.
x Ref. 51.
YRef.52.
z Ref. 51
aa Ref. 54.

where E and <DIe are the corresponding "surface
potentials" measured vs. a reference electrode and
vacuum, respectively, and Ek is the corresponding
"absolute potential" (vs. vacuum) of the reference
electrode. The precise value of Ek for the SHE (or any
other reference electrode) remains somewhat uncertain,
estimates clustered around 4.45 and 4.85 V being de-
duced by various means [56]. For the present purpose,
we have selected an Ek value of4,8 V, partly from the con-
sistency thereby achieved between the electrochemical
and UHV-based vibrational data [46]. (The same proce-
dure was also used in generating Fig. 1 above [31],) The
vee(extrap) values listed in Table 1were therefore obtained
by extrapolated the Vee values up to an electrode potential
equivalent to the <Dad value on this basis to which the Vuhv
value refers.
308
The corresponding vee(extrap) and Vuhv frequencies for
each of the eight metal-CO and metal-NO interfaces
inTable I are seen to be in very good agreement, uniformly
within 5-10 em -I ofeach other. This degree of concord-
ance is comparable with the uncertainties associated with
the frequency-potential extrapolations, the coverage
values in the electrochemical vs. the UHY environments,
and especially the <1>ad estimates for the latter systems.
(Note that the Vee - E-extrapolations required for the
NO data are shorter than for CO because the former
adsorbate is stable towards aqueous electrooxidation
even at electrode potentials approaching the high values,
ca. I Y vs. SHE, to which the UHY-based data refer.)
The close concordance between the corresponding Vuhv
and vee(extrap) values for NO is also particularly signifi-
cant in view of the high (40-100 em -I y- I ) observed
dVNo/dE values. This marked sensitivity of the VNO fre-
quency to the electrostatic chemisorbed environment
renders NO in some respects a more optimal choice for
exploring such surface potential/field effects than Co.
Although most data in Table I refer to saturated adlayers,
reflecting the reliability of coverage control (and
determination) under these conditions, a pair of systems,
for Ir(lll)/CO and Pt(100)/NO, are included also at low
coverages. Significantly, a good concordance between
the Vuhv and vee(extrap) values is again seen under these
latter conditions. Furthermore, comparable findings are
obtained for NO and CO adlayers on other Pt-group
monocrystalline surfaces, including rhodium and pal-
ladium [45]. The dvco/dE and especially the dVNo/dE
values included in Table I are also worthy offurther com-
ment. In particular, the high (40-100 em -I y- I ) values
evident for the latter are seen to be much (5 to 15-fold)
larger than the estimate (8 em -1 y- I ) for isolated (i.e.,
gas-phase) NO. The corresponding dvco/dE values for
chemisorbed CO are also larger than for gas-phase CO,
but only by two- to five-fold. These differences, especially
for NO, illustrate clearly the important role played by
potential-dependent metal-chemisorbate bonding in
the adsorbate vibrational properties [34,42,45].
What are the overall implications of such findings?
Most obviously, they emphasize further that double-layer
effects upon molecular chemisorbate bonding can be
understood most straightforwardly in terms of the com-
bined influence of the solvent and charge upon the
interfacial electrostatic field. In more detailed double-
layer models, of course, it is useful to consider also local
fields in the vicinity of the chemisorbate molecules and
the occurrence of discrete ionic size (and diffuse-layer)
effects [57]. Indeed, the latter effects become evident when
examining Vee - E dependencies in nonaqueous solvents
with different cations [28,57]. As already mentioned, the
Weaver and Zou
separable influences wrought by the dipolar solvent itself
along with the solvated charges are most clearly seen from
UHY-based electrochemical modeling experiments,
although these have been undertaken systematically so
far only for Pt(lll)/CO [31]. Although numerous details
remain to be elucidated, however, the findings demon-
strate clearly the intrinsically close ties between the struc-
ture and bonding of these simple chemisorbates on
ordered surfaces in ambient electrochemical and UHY
environments.
III. CHARACTERISTICS OF RAMAN
COMPARED WITH INFRARED
SPECTROSCOPIES AT
ELECTROCHEMICAL AND RELATED
INTERFACES
The preceding section utilized in situ vibrational spectra
obtained exclusively by IRAS, prompted by a desire to
obtain quantitative spectral information at atomically
ordered electrochemical interfaces for comparison with
UHY-based data. The sensitivities of the infrared
absorbance and bandshape, as well as band frequencies,
to the electrostatic and chemical environment are key
attributes of IRAS for such purposes. Although SFG
may also be used along these lines, the more
straightforward interpretation afforded to the infrared
absorbance parameters will remain a major advantage.
By its very nature, the flavor ofvibrational information
attainable from SERS is distinctly different to IRAS. Most
obviously, the former technique is limited usually to poly-
crystalline samples, so that the vibrational subtleties
associated with the presence ofuniform specific adsorb-
ate bonding and environmental interactions are largely
lost to SERS. The sensitivity of Raman scattering
intensities to coupling with specific electronic (include
adsorbate-metal) transitions, together with the lack of
strict "bond-directional" surface selection rules [58,59],
often render SER band intensities less quantitatively
informative. The relationships between SER band
intensities and adsorbate coverage are also rather more
tenuous than in IRAS, partly because different nanoscale
(and even micron-scale) surface regions can yield dis-
similar enhancement factors due to local variations
in the substrate morphology. Additionally, SERS bands
are often broader than in corresponding IRAS data
[60], probably arising from a differing extent of
inhomogeneous band broadening associated with dispar-
ate binding-site geometries and surface microstructures.
On the other hand, several combined factors enable
SERS to yield remarkably rich vibrational spectra, most
notably for large polyatomic organic adsorbates. The
Vibrational Spectroscopic Links
wide wavenumber ranges that are readily measurable
with Raman spectroscopy encompass the low-frequency
region, say < 1000 cm ~ I, which is largely inaccessible
to IRAS and SFG. Like EELS, SERS exhibits
intrinsically high sensitivity in this region, enabling
metal-adsorbate and intramolecular modes to be
accessed. The nature of the bond polarizability-based
selection rules for SERS (and surface Raman in general)
[58,59] also favors the spectral detection ofa much larger
fraction of the adsorbate normal modes than in usually
feasible with IRAS and SFG. In particular, vibrational
modes for molecules (or functional groups) oriented
parallel, as well as tilted or normal, to the metal surface
are commonly observable in SERS. (Specific examples
are considered below.) This characteristic of SERS is
shared to some extent by EELS, even though the latter
vibrational strategy is inherently limited to UHV
environments. As in bulk-phase Raman scattering, the
occurrence of resonance enhancement combined with
SERS provides additional sensitivity in observing
vibrational modes coupled to the electronic transition(s).
Furthermore, in many cases SERS modes can be detected
that are Raman-forbidden in the bulk phase, resulting
from the lowering in molecular symmetry upon adsorp-
tion and/or to the presence ofthe steep interfacial electric
field gradient [58].
The large magnitude of the SER effect, yielding
typically enhancement factors of several powers of ten
(or higher [61]), of course plays a crucial role in
determining the sphere of applicability of the technique.
Besides enabling vibrational spectra to be obtained in
electrochemical environments largely without the need
for bulk-phase background subtraction, SERS is readily
applicable to interfaces transferred between ambient
environments, such as liquid and gaseous phases.
Although IRAS also offers some applicability along these
lines, spectral subtraction tactics are usually mandatory
to recover infrared signals for adsorbates at planar elec-
trochemical interfaces. The remarkable intrinsic surface
selectivity of SERS, however, carries a price. Unlike con-
ventional IRAS, there are an array ofinteresting, yet often
perplexing and obfuscating, questions concerned with
the relations between the physical/chemical conditions
of the substrate and the SERS intensities. These issues
are intertwined with the continuing debate on the funda-
mental physical mechanisms (electromagnetic, chemical
resonance, etc.) that are responsible for SERS [62]. The
tactics used to prepare SERS-active substrates are many
and varied and have recently included deposition of met-
allic particles of (partly) known morphology [63].
However, electrochemical deposition and, particularly,
the use of sequential oxidation-reduction cycles remains
309
the most potent, straightforward, and therefore com-
monly employed tactic. As already mentioned, current
substrate preparation issues include the use of thin-film
deposition and other overlayer strategies to extend the
range of interfacial materials to which SERS can be
applied. We consider this important topic below.
Somewhat analogously, there is interest in achieving
some degree of surface enhancement with IRAS.
Whereas IRAS by itselfofcourse often exhibits sufficient
sensitivity to detect adsorbed species even when the
infrared absorption cross-sections in the interfacial and
bulk-phase states are comparable, the presence of some
surface enhancement would be beneficial, especially in
electrochemical environments where solution inter-
ferences are problematical. Significantly, there is
evidence that some metal films, especially silver and
gold, can yield moderate (say 10- to 30-fold) surface
enhancements in the IRAS signals [64]. This applies both
to external reflection and attenuated internal reflection
geometries [64]. The surface enhancements are seem-
ingly triggered partly by excitation oflocalized plasmons
within mesoscopic metal particles in a formally similar
fashion to SERS electromagnetic enhancements [64].
Although therefore requiring some degree of surface
roughness, the phenomenon is apparently also operative
with some monocrystalline metal films [65]. An inevi-
table complication, also evident in SERS, concerns the
likely presence of additional "chemical" enhancement
arising from chemisorbate-surface interactions,
although the latter should not necessarily require surface
roughness. From a practical perspective, surface-
enhanced IRAS (SEIRAS) offers important oppor-
tunities for examining the vibrational properties of
adsorbed solvent (and other species for which bulk sol-
ution interferences are problematic) and time-resolved
monitoring of surface electrochemical processes [64].
On the other hand, the very existence ofinfrared "surface
enhancement," at least that associated with particular
substrate morphologies, yields essentially the same com-
plications in interpreting band intensities and other
quantitative spectral parameters that can beset SERS,
without providing the degree of "chemical richness" that
characterizes the latter in situ method. Consequently,
conventional IRAS will probably remain the vibrational
technique ofchoice in "electrochemical surface science,"
although SEIRAS offers some analytical advantages that
are shared to some extent with SERS.
The overall character of SERS emanating from the
above considerations is that ofa surface vibrational tech-
nique that, despite continuing uncertainties in its precise
physical nature and requirement of particular substrate
structural moieties, can yield vibrational information
310
for in situ ambient systems that is both uniquely detailed
and applicable not only to a remarkably wide swath of
adsorbate systems, but also to a broader range of
substrates than hitherto. In our opinion, however, the
strategy remains decidedly underutilized, at least in fun-
damental surface chemistry. Nonetheless, we believe that
SERS is now (as oflate 1998) finally poised to become a
surface vibrational technique having a genuinely
broad-based impact in ambient-based interfacial chem-
istry, especially for characterizing reactive (catalytic)
systems. In the following section, we outline more
specifically some recent findings involving surface
Raman spectroscopy that appear to portend significant
future applications along these lines.
IV. SERS ON TRANSITION-METAL SURFACES
Although most SER studies continue to be concerned
with adsorptive chemistry on the coinage metal surfaces,
one of the hoped-for consequences of the current new
generation of more sensitive spectrometers is the oppor-
tunity to examine SERS, or possibly even surface
unenhanced Raman spectra, for adsorbates on other
substrates. We have already mentioned the impressive
recent work of McCreery and coworkers [20], who have
demonstrated that rich Raman spectra could be obtained
for large organic adsorbates on carbon electrodes in the
absence of electromagnetic surface enhancements, even
though resonance effects appear to be operative. As noted
above, particularly desirable substrates from a catalytic
and adsorptive chemistry standpoint are transition
metals. The manner and extent to which transition-metal
surfaces may yield measurable Raman spectra in electro-
chemical in addition to gaseous environments has been
the subject of sporadic earlier experimental reports [e.g.,
66-69]. Although the measurements themselves are in
some cases impressive, the restriction of most studies to
the doyen molecule of SERS, pyridine (or related
systems), makes it difficult to judge the broad-based
chemical viability of such tactics. As already mentioned,
recently Tian and coworkers [21,70-73] reported more
systematically instances of measurable Raman spectra
for adsorbates on several transition-metal surfaces in
aqueous media. Following Ref. 69, in most cases the
surfaces were prepared by extensive roughening pro-
cedures to yield surfaces having very high roughness
factors (RF ~10-300). After such pretreatment, Pt
surfaces yield estimated surface enhancement factors
(calculated on the basis of the "real" microscopic surface
area) that are still significant, typically 10-100 [22].
Detection of vibrational signals for chemisorbates such
as CO, thiocyanate, and atomic hydrogen, which are weak
Weaver and Zou
to moderate Raman scatterers, and the excellent scatterer
pyridine, were found to be feasible by using a notch-
filter/single-stage spectrometer coupled with a confocal
microscope [21,73]. (The last component provides
improved detection of electrochemical adsorbates in the
face of solution-phase Raman scattering). These studies
provide an important testament to the value of
new-generation high-sensitivity spectrometers. However,
the extreme degree of surface roughening (yielding
geometrically and structurally ill-defined surfaces)
necessary to incur measurable Raman signals, at least
for nonoptimal adsorbate scatters, constitutes a draw-
back of the strategy for fundamental electrochemical
studies.
As outlined in the Introduction, we have long been
intrigued by the prospects for extending SERS to surfaces
beyond the coinage metals, particularly encompassing
transition metals given their central importance in both
adsorptive and catalytic chemistry [16,17]. The formation
ofthin Pt-group metal films, chiefly by electrodeposition
onto gold, has proved to yield transition-metal surfaces
displaying near-optimal SERS properties, prompting
applications in our laboratory to characterizing molecu-
lar adsorption and reactivity in both electrochemical
and ambient gas-phase environments [e.g., 16,18,74-78].
As already noted, the recent improvements in
electrodeposition procedures for Pt-group transition
metals, yielding essentially uniform pinhole-free
transition-metal films, even down to two to three
monolayers [22,23], now provide us with surfaces devoid
ofchemical or spectral interferences from the underlying
substrate yet displaying enhancement factors that
approach those for unmodified gold. Furthermore, the
films are relatively smooth, having roughness factors no
greater than ca. 2 [23]. These types of transition-metal
surfaces therefore appear to be extremely well suited for
expanding applications ofSERS in a broad-based fashion
to catalytically significant systems. We first describe
briefly their Raman properties as a function ofoverlayer
film thickness, followed by some illustrative recent
examples from our laboratory of their application for
examining adsorptive and catalytic surface chemistry in
electrochemical and ambient gas-phase environments.
Figure 3 illustrates the dependence of the Raman
intensity I (filled circles) for a suitable model
chemisorbate, carbon monoxide, on a SERS-active gold
substrate as a function of increasing thickness, d, of
an electrodeposited palladium film, evaluated in
monolayers, ML. The data, taken from Ref. 23, refer to
the C-O stretching band at ca. 1960 cm- 1 with 647 nm
excitation, although similar I-d behavior is obtained for
the metal-CO stretch at 370 cm -I. (The open circles
Vibrational Spectroscopic Links 311

ladium overlayer films (up to 200 ML) on gold show that

-+-Raman the log I-d attenuation in the SER signals becomes pro-
1 --<3-- Continuum gressively milder with increasing d, so that I becomes
virtually d independent for d:::: 50 ML. This result is
clearly inconsistent with EM predictions, assuming that
the enhancement is due to the underlying gold substrate.
0.8 Furthermore, similar Rh overlayers deposited on either

....~
•• "smooth" (polished) gold or even glassy carbon neverthe-
·tii •• less yield detectable Raman signals for CO (and other
=
Q,I
•
••• chemisorbates), which increase with d so to yield
C
~
0.6
&III
intensities comparable to those on roughened gold for
thickoverlayers (say, 50-100 ML) [81]. These results indi-
Q,I III
......
~ III
".
.. ... cate that a component of the SER effect is arising from
the transition-metal overlayer as well as from the
~
......
'i
~ 0.4 .....
o ........ .......(")
roughened Au substrate, with enhancement factors from
the former being of the order of 10 3 [81]. Although only
-. -"-..() preliminary (and more may be evident by the time this
volume is published), the findings point towards the
0.2 notion that transition metals themselves yield SERS to
an extent that offers true practical utility, even though
the enhancement factors are apparently substantially (say
102 to 10 3 -fold) smaller than on coinage metals.
Such enhancements for electrodeposited transition-
o metal films are undoubtedly related to the earlier reports
o 10 20 30 40
ofweaker transition-metal SERS byTian et al. (vide supra).
Pd Film Thickness We emphasize again that a key practical factor respon-
(equivalent monolayers) sible for the new-found feasibility of exploiting SERS on
such transition metals, as well as coinage-metal surfaces,
Figure 3 Integrated intensity of C-O stretching SERS band lies in the greatly improved sensitivity of new-generation
atca.1960 cm- 1 (filled circles) for CO chemisorbed on Pd over- Raman spectrometers, especially using longer excitation
layer on gold plotted against film thickness (in monolayers).
wavelengths. At this point, however, the near-optimal
Excitation wavelength was 647 nm. Open circles are corre-
SERS obtained for ultrathin (few ML) transition-metal
sponding intensities of the "continuum background" (see text).
(Ad.lpted from Ref. 23.) overlayers on roughened gold makes this strategy particu-
larly attractive to us, largely because the enhancement
factors then approach the near-optimal levels (SEF "-'10 5
refer to the so-called continuum-background signal to 10 6 - fold) characteristic ofcoinage metals. Under these
measured at comparable wavelengths.) The SER signal conditions then, surface Raman spectra can readily be
is seen to be attenuated progressively as the Raman obtained for a variety of adsorbates on transition metals,
chromophore is increasingly separated from the including weak scatterers (and/or vibrational bands),
SERS-active substrate. This I-d dependence is qualitat- even when using less-sensitive Raman instrumentation!
ively consistent with the conventional electromagnetic It is already apparent, however, that the opportunity to
(EM) theory of SERS, although the anticipated relation- engender SERS on a growing selection of largely
ship is sensitive to both the size and shape of the Au "smooth" electrodeposited transition-metal surfaces will
roughness features [79]. Interestingly, the I-d plot in Fig. offer considerable opportunities for harnessing the tech-
3 is not greatly different in form from those obtained with nique for the concerted exploration of reactive/catalytic
thioalkyl films [80], suggesting that the transition-metal surface chemistry in the relatively near future. Some
overlayer acts largely as a "spacer" rather than exerting recent applications along these lines are outlined below.
an additional electronic (or electromagnetic) influence One question which is germane to the general issue of
on the adsorbate SERS. transition-metal SERS, yet remains incompletely under-
Very recent evidence, however, indicates that the stood even for the more "traditional" coinage-metal
actual situation is rather more interesting [81]. First, surfaces, concerns the relative importance of EM vs.
experiments conducted with thicker rhodium and pal- "chemical" contributions to the observed surface
312 Weaver and Zou

enhancement factors. An instructive recent overview is

available [62]. The latter enhancement components,
which includes adsorbate-metal (or metal-adsorbate)
charge transfer (CT) and resonance transitions within 885
the adsorbate electronic manifold should be inherently
970 I 795
adsorbate specific, in contrast to the EM contribution
[62]. One complication that has tended to obfuscate this 1445
1245
1040 1 I
distinction, however, is that the "intrinsic" Raman
scattering cross-sections for adsorbates can vary widely, 1350
1
1140 I
I
not only because of the properties of the isolated
molecules, but also because of "static" (chemical
bonding) interactions between the adsorbate and the
metal surface, along with the occurrence of surface
selection rules. The latter two factors are known to affect
the intensity of infrared adsorbate transitions, often by
ca. lO-fold or so, and the effects can be of comparable
magnitude for Raman scattering. Consequently, the
experimental separation between EM and the various
types of "chemical" enhancements is usually far from
straightforward, even with the availability of detailed
Raman intensities (for known adsorbate coverages) as a
function of the excitation wavelength and electrode
potential. Some distinctions for most systems therefore
remain suggestive rather than clearcut, although a recent
impressive exception (for an organic adsorbate on 1400 1200 1000 800 600 400 200
monocrystalline copper in UHV) has been described
[62]. Raman Shift (em-I)

Figure 4 SER spectra for C 6 H 6 adsorbed on rhodium and

V. ILLUSTRATIVE APPLICATIONS OF SERS TO palladium films (both ca. 5 monolayers) on gold substrate at
ADSORPTIVE AND REACTIVE SURFACE 0.05 V vs. SHE in ca. 10 mM benzene + 0.5 M H 2 S0 4 .
CHEMISTRY (Adapted from Ref. 22.)

We now briefly consider two specific applications of

SERS as a vibrational probe at metal interfaces in ambi-
ent (electrochemical or gaseous) environments, studied
recently in our laboratory, to illustrate the degree of
chemical diversity and detail that can readily be obtained
for either stable or reactive adsorbate systems by this
means.
The first illustration utilizes "pinhole-free"
transition-metal overlayers on gold, specifically for
exploring the chemisorption of aromatic molecules on
Pt-group metals in aqueous solution [22], as exemplified
by benzene. Figure 4 shows typical SER spectra obtained
for C6H6 adsorbed on rhodium and palladium thin films
from near-saturated solutions of benzene in aqueous
0.5 M H 2 S04 [22]. The wavenumber region shown in Fig.
4, 200-1500 cm- 1, encompasses most of the aromatic
ring normal modes. These modes, including some that
are Raman forbidden in the bulk phase, are readily
discernable in the SER spectra. Detailed band
assignments were made primarily on the basis of the
observed frequencies combined with the measured HID
isotopic shifts [22]. The spectral features also enable the
deduction of an essentially flat adsorbate orientation,
chiefly by comparison of the relative band intensities for
modes in different symmetry groups with surface
selection-rule predictions [22]. (It is noteworthy that the
SER features include several ring vibrations that therefore
occur parallel to the metal surface, but nonetheless yield
readily observable bands due to the applicability of
polarizability based, rather than the "transition-dipole,"
selection rules familiar in IRAS.) Furthermore, compari-
sons with EELS vibrational spectra obtained for benzene
on Rh and Pd surfaces in UHVare instructive. The shifts
seen for some bands in the SER spectra, such as the
marked redshifts in the VI (symmetric ring breathing)
mode, ca. 110 and 40-60 cm- I , and the blueshifts in the
1
Vll (C-H out-of-plane) mode, 120 and 30 cm- on Rh
and Pd, respectively, are closely similar to those observed
in EELS [82] and are diagnostic ofthe changes in adsorb-
Vibrational Spectroscopic Links 313

ate bonding wrought by surface anchoring involving the

ring n electrons.The vibrational information content con- time (s)
tained within such corresponding SER and EEL spectra
are therefore comparable and self-consistent. In contrast,
corresponding IRAS data for chemisorbed benzene in
UHY, which exhibit only a single band (C-H
out-of-plane bend) [83], reflect graphically the important
differences in surface selection rules.
A key difference, however, between SERS and EELS is
the ability of the former technique to attain a level of
vibrational detail for in situ metal-solution and other
ambient interfaces, whereas the latter technique is limited
strictly to UHV environments. Furthermore, such SER
spectra can be required both rapidly (within ca. 0.1-1 s)
and in real-time sequences by means of multichannel
Raman instrumentation, especially in conjunction with
.c
.
the new generation of high-throughput spectrometers. l-

This latter property offers important opportunities for

e
.......
the kinetic exploration of reactive adsorbates, especially
for individual surface processes (including elementary
steps) of significance to heterogeneous catalysis.
Indeed, the second specific example now considered
provides an illustration of the value of such rapid SER
spectral acquisition for exploring catalytically relevant
surface kinetics. We have explored the roles of surface
oxides formed on rhodium and palladium during the
catalytic oxidation ofgaseous methanol by O 2 at elevated
temperatures and near-ambient pressures [76,77]. The
acquisition of simultaneous (or parallel) SER spectra
along with mass spectrometric analysis of the gas-phase
products enable the relationships between the surface BOO 400
speciation and the overall catalytic kinetics and mechan-
ism to be explored in uniquely direct fashion [76]. Exten-
Raman Shift (cm- 1)
sive surface oxidation of both rhodium and palladium
Figure 5 Transient SER spectra showing the time-dependent
is seen to occur above 300°C or so, as gleaned from
reduction of a surface Rh 2 0 3 film upon sudden exposure to
characteristic SERS metal-oxygen vibrations around 110 Torr of methanol at 350°C. (Adapted from Ref. 76.)
500-650 cm- I . However, while Pd oxide formation is
seen to markedly inhibit methanol oxidation, the more
facile catalysis observed on Rh, yielding CO 2 and water
in the presence of excess O 2, is largely unaffected by the at the times indicated (0.5-4.7 s) after the pulsed-flow
presence ofsurface Rh 20 3 [76]. The reasons for this latter addition of 110 Torr of methanol. The observed rapid
behavioral difference were explored further by means of CH 3 OH-induced removal ofthe oxide evident from these
transient SERS measurements, monitoring the kinetics spectra, combined with similar kinetic data obtained over
of rhodium oxide removal upon sudden exposure to a a range of temperatures and methanol pressures, enable
gas stream containing methanol [76]. rate laws to be established. This analysis suggests that the
An example of time-dependent SER spectra for sur- rate-determining step involves the decomposition of the
face Rh 20 3 reduction obtained under these conditions, oxide lattice driven by rapid scavenging of the ensuing
taken from Ref. 76, is shown in Fig. 5. The bottom adsorbed oxygen by chemisorbed methanol fragments
spectrum, consisting of a pair of Rh-O bands at [76]. Interestingly, the rates of this process, while
5101560 cm -I that are diagnostic ofsurface Rh 20 3, refers substantially slower than those corresponding to the most
to a surface heated in 02-rich methanol and then adjusted facile production of CO 2 and water, are sufficiently rapid
to 350°C in argon. The upper three spectra were obtained to earmark the oxide as a reactive species rather than
314
merely a catalytic poison [76]. In complete contrast, the
oxide formed under similar conditions on palladium
was found to be entirely unreactive towards methanol,
which along with corresponding catalytic rate data clearly
labels this species as a catalytic poison [77]. A further
reason for the more sluggish methanol oxidation kinetics
observed on Pd compared with Rh was evident from the
more discernable presence of adsorbed methanol
fragments on the latter surface as seen from the SERS
vibrational fingerprints [77]. An ensuing study ofsurface
rhodium oxide reduction kinetics by CO and H 2, again
using transient SERS under ambient-pressure flow-
reactor conditions, demonstrates the sensitivity ofthe rate
law and hence the likely surface reaction mechanism to
the nature of the gas-phase reductant [78].
The value of SERS for probing surface oxide
formation, along with the widespread importance of such
species in metal-ambient chemistry, suggests manifold
other applications. For example. we have recently been
exploring the occurrence ofoxygen adsorption and oxide
film formation on copper in aqueous media and
ambient gaseous environments, taking advantage of the
intrinsic SERS activity of this metal [84,85]. The
potential-dependent formation of a "bulklike" CU20
phase film was identified at higher pH values under
controlled electrochemical conditions. This process is
distinct from the more unexpected occurrence ofoxygen
adsorption discerned over wide potential ranges in acidic
media [84]. The electrochemical production of Cu 20
(and other species) on copper could also readily be linked
to the surface state in gaseous oxygen, which can also be
controlled readily by solution rinsing [85]. This system
provides a simple example ofthe abilityofSERS to readily
link metal surface chemistry in ambient solution and
gaseous environments; copper is of burgeoning techno-
logical interest as an interconnect material in
microelectronic devices, as well as in catalytic chemistry.
More generally, the ability to monitor the reactivity of
selected adsorbed species even at ambient (or even
higher) gas pressures constitutes another valuable, if
heretofore underutilized, property of SERS. The new
generation of Raman instrumentation should also enable
rapid real-time surface kinetic and structural data to be
obtained for a wide range ofadsorbate vibrational modes
on timescales, say 10-100 ms, commensurate with the
rapid turnover frequencies (10-100 s-I) of central rel-
evance to practical heterogeneous catalysis. The ability
to evaluate in such rapid molecularly specific fashion
the reactivity and identity ofadsorbed species in challeng-
ing technologically relevant, gaseous, or liquid-phase
environments offer substantial opportunities in hetero-
geneous catalysis research.
Weaver and Zou
VI. CONCLUSIONS: OVERALL PROSPECTS
The experimental challenges provided by the presence of
the solution phase in electrochemical systems are primar-
ily responsible for the somewhat different development
of surface vibrational methods in electrochemistry as
compared with more traditional UHV-based metal
interfacial science. Nevertheless, the widespread applica-
bility and fundamental value ofvibrational spectroscopy
in electrochemical surface science and catalysis has been
made feasible primarily by the exploitation oftwo distinct
properties in achieving the desired detection of
interfacial species in the face of otherwise-dominant
liquid-phase interferences. First, the unique degree of
control of the interfacial composition and chemical
properties in electrochemical systems afforded by the
electrode potential form the usual basis by which IRAS
can be used as a versatile in situ vibrational technique.
This potential-difference spectral strategy is noteworthy
in the more general context ofvibrational spectroscopies
in surface science in that the technique is applicable to
solution-phase conditions that encompass those desired
for practical catalytic and fundamental adsorptive
electrochemistry. As such, it entirely circumvents the
"pressure-gap" problem that separates the conditions
characterizing "practical" catalysis at metal- gas inter-
faces and the UHV conditions (at ca. 10 10 to 10 12 -fold
lower pressure) usually desired for fundamental adsorb-
ate characterization using vibrational and other
methods. Furthermore, the substantial progress made
recently in understanding molecular chemisorption at
monocrystalline metal-solution interfaces by means of
in situ IRAS is forging an intriguing link between the
adsorptive properties of such ordered metal surfaces in
electrochemical and UHV environments. The increasing
utilization oflRAS [86] and SFG [11] for the vibrational
characterization ofmetal surfaces at higher gas pressures
should provide another means of interconnecting chemi-
cal properties of these inherently related systems.
The second distinctive tactic providing, in more
intrinsically surface-sensitive fashion, the detection of
adsorbate vibrational signals is based on the phen-
omenon of SERS. In contrast to IRAS, however,
SERS-based vibrational approaches have so far remained
the near-exclusive purview of electrochemical systems.
This preoccupation is understandable given the avail-
ability of powerful additional vibrational methods,
especially EELS, in UHV-based systems together with
the inapplicability of SERS to the ordered metal surfaces
used extensively in UHY. However, the recent dramatic
improvements in the sensitivity of Raman instrumen-
tation (especially at longer wavelengths) coupled with
Vibrational Spectroscopic Links
the realization of improved SERS-based strategies for
achieving surface sensitivity and selectivity, especially
for transition metals and other catalytically important
materials, offers much for the future. Although its practi-
cal restriction to polycrystalline and/or film materials
makes SERS a technique of primary interest in "applied"
surface science, the feasibility of providing in uniquely
sensitive and rapid fashion rich vibrational spectra for
diverse surface-adsorbate-liquid/gaseous combinations
constitues an enticing prospect.
In addition to SERS, in some circumstances IRAS has
also proven valuable for examining transient surface
phenomena. Besides strategies along these lines
harnessing SEIRAS, mentioned above [64], also note-
worthy are time-resolved IRAS studies involving CO
migration on single-crystal metal electrodes [87]. There
are good reasons, therefore, to expect that IRAS and
SERS will contribute substantially to our developing
appreciation of fundamental kinetic along with struc-
tural phenomena in electrochemical systems.
Overall, then, it is anticipated that the vibrational
characterization of related metal interfaces in variable-
(including ambient-) pressure gas-phase and electro-
chemical and UHVenvironments will facilitate increas-
ingly the ongoing development of a more unified
understanding ofinterfacial science. That such interdisci-
plinary efforts naturally encompass both "practical
chemical" and structurally "well-defined" interfacial
systems would also appear to bode well for the future.
ACKNOWLEDGMENTS
Several other recent group members-Chris Williams,
Ignacio Villegas, Cathy Tang, and Harry Chan-
contributed industriously to the research described
herein. The collaboration with Prof. Christos Takoudis
on applying SERS to surface chemistry at metal- gas
interfaces is also acknowledged. Support has been pro-
vided by grants from the Analytical and Surface Chemis-
try and Chemical and Transport Systems Divisions of
the National Science Foundation.
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19
Sum and Difference Frequency Generation at Electrode
Surfaces
AbderrahmaneTadjeddine and Alain Le Rille
CNRS, Orsay, France
ABSTRACT
This chapter presents and discusses the investigation of
vibrational and electronic properties ofthe electrochemi-
cal interface by using nonlinear optical techniques of
visible-infrared sum (SFG) and difference (DFG) fre-
quency generation. We first introduce the theoretical
approach that describes principles of SFG/DFG
spectroscopy and of the calculations of second-order
susceptibilities of the interface. The resonant sus-
ceptibility of the adsorbate is discussed, and the
nonresonant contribution is correlated to the electronic
properties of the substrate. In particular, the contri-
butions of the intraband and interband electronic
transitions are explicitly determined and compared with
experimental results obtained on platinum, silver, and
gold electrodes. We compare the SFG and DFG tech-
niques and suggest to use both techniques for a better
quantitative analysis of the experimental data. We then
discuss the experimental requirements for SFG/DFG
and experimental setup and procedures developed at
the authors' laboratory to study the electrochemical
interface. Selected results that we cover are the
vibrational behavior of H-Pt(hkl) system, both in the
underpotential and overpotential regime; adsorption of
CN- on Au(hkl) electrode (using DFG); electrode sur-
face electronic properties; and potential of zero charge
measurements. Finally, the adsorption geometry of
pyridine on Au(l11) is studied by DFG in the 900- to
1150-cm- 1 spectral range.
317
I. INTRODUCTION
The knowledge ofthe interface structure and its potential
dependence is essential in interfacial electrochemistry
and electrocatalysis. However, the complexity ofthe elec-
trochemical systems and the molecular nonspecificity
of electrochemical techniques call for the use of
surface-sensitive techniques for in situ (mainly optical
techniques and near-field microscopy) and ex situ pro-
bing of the structure and of the chemical composition of
the electrochemical interface. However, linear optical
techniques suffer from the undesired contribution from
the bulk, the interface contribution to the overall signal
being several orders of magnitude weaker than that of
the bulk electrolyte. It is then necessary to use modulation
or difference techniques to extract the surface signal by
assuming that the electrode is released at a particular
potential, taken as reference.
On the other hand, second-order nonlinear optical
processes, such as second harmonic (SHG) and sum
(SFG) and difference (DFG) frequency generation, are
forbidden under the electric-dipole approximation in a
bulk of a medium with inversion symmetry. SHG, SFG,
and DFG are then generated only at the surface of such
media where the symmetry is broken and appear to
be highly surface specific for interfaces between
centrosymmetric media [1]. As a result, submonolayer
of adsorbed species can be readily detected for all inter-
faces accessible by light, including the electrochemical
interface. These techniques have inherently high spectral,
318
temporal, and spatial resolution and constitute a non-
destructive remote sensor of surfaces and interfaces.
SHG is presented elsewhere [2] and is not discussed
here. The incapability of SHG to probe the surface
vibrational structure can be overcome by using the
infrared (lR) visible SFG and DFG techniques, as dem-
onstrated at the electrochemical interface in 1990 for
SFG [3] and in 1997 [4] for DFG. The development of
high-power IR lasers, tunable in a wide spectral range,
is stimulating an intense research activity on the elec-
tronic and vibrational properties of various interface
using SFG and DFG techniques.
In this chapter, we show, through some selected
examples, what kind of information is brought by these
techniques to the investigation of the electrochemical
interface. The theoretical modeling of the interface
nonlinear optical response is presented in Sec. II. In this
section we present the principles ofSFG/DFG and their
generation at the electrochemical interface; the calcu-
lations of the interface second-order susceptibility are
then developed, with special attention being paid to the
contribution of the intraband and the interband elec-
tronic transitions of the metal electrode to the
nonresonant signal. Effects of the interference between
the resonant and the nonresonant component on the
SFG and the DFG signal will be analyzed and compared
with the experimental data. Finally, some questions
arising in fitting the SFG and DFG data are discussed.
Section III deals with the experimental techniques and
procedure and the description ofthe experimental setups
developed in our laboratory for the investigation of
the electrochemical interface by SFG and DFG.
-----_. ---------
Vvisible
-----
.~...
..........,.
VSFG=Vvis+ VIR
..
.........
~.
-- ~ ...
9
Figure 1 Scheme of the energy level diagram for SFG and DFG.
Tadjeddine and Le Rille
Experimental examples are discussed in Sec. IVWe have
restricted ourselves to the application of SFD/DFG in
spectroscopy, even if these techniques are also efficient
for dynamics studies. The first results relies to the study
by SFG of the adsorption of hydrogen on platinum in
acidic solution. Resonance structures of the absolute
SFG spectra allow for the identification of the adsor-
bed species and of the sites of adsorption in the
underpotential (UPD) and in the overpotential
depositions (OPD). The advantage ofusing DFG is illus-
trated by the study of CN- on gold electrode, and the
capability ofthe technique to probe the electronic surface
properties of the electrode is demonstrated on silver in
contact with CN- species. Finally, the large tunability of
the free electron laser in the IR has been recently used
to investigate the gold-pyridine system, and some new
results are presented. We conclude this contribution by
an outlook on the interest and the development of the
investigation of the electrochemical interface by
nonlinear optical techniques.
II. THEORETICAL APPROACH
A. Equations of SFG/DFG
1. Principles of SFG and DFG Spectroscopy
By nonlinear optical coupling via the second-order
susceptibility, two interacting laser beams of frequency
WI and W2 (WI> W2) can create two new waves at
the sum (WSFG = WI + W2) and the difference
(WDFG = WI - W2) frequency. SFG and DFG belong to
second-order nonlinear optical processes (Fig. 1), which
Vvisible
VDFG=Vvis- VIR
SFG/DFG at Electrode Surfaces 319

z
DFG reflexion of
e visible
earn
Electrolyte

SRJ

o x

Electrode

Figure 2 Geometry ofthe incident and reflected beams in a coplanar configuration.

are forbidden in the bulk of centrosymmetric media
(within the dipolar approximation) and generated only
at the interface, where the symmetry is broken.
Moreover, SFD/DFG signals are enhanced if one of
the four waves is in resonance with either a vibrational
or an electronic level. One usually chooses one wave (at
a fixed frequency, WI) in the visible range and the other
in the IR (at variable frequency W2) to excite adsorbate
vibrational level. So these nonlinear optical techniques
become an effective and versatile vibrational probes
of the interface between centrosymmetric media such
as the electrochemical solution and the usual material
electrode [1-5].
2. SFG and DFG at the Electrochemical Interface:
Geometric Consideration
We discuss the case ofa boundary between the electrolyte
and the electrode. The electrode surface is located at the
xOy plane, its normal being along the Oz axis, directed
to the electrolyte (Fig. 2). There is no wave, but there are
reflected and incident waves in the electrolyte.
The involved electrical fields E a (rx = 1,2, or 3) are given
by
The wave vector is given by Eq. (2), where c is the
celerity oflight in the vacuum, U a is the unit vector in the
direction of the wave vector k, nr(w a) and ni(w a), are,
respectively, the real and the imaginary part of the
refractive index of the electrolyte at the frequency W a :
(2)
The phase cPa of the wave at the frequency W ais obtained
from
(3)
We assume a coplanar configuration where all the
waves have the same plane of incidence zOx (Fig. 2). In
this configuration, the angle of incidence of the beam rx
is 8a (8 1 and 82 are positive on the left-hand side and
8SFG and 8DFG in the right-hand side direction).
Both incident waves are p-polarized, with the electric
field along the x-axis:
(4)
3. Generation of SFG and DFG at the
Electrochemical Interface
The source of SFG and DFG is the nonlinear
polarization generated at the interface, given by

where r is the position vector, t the time, and W a and k a the (5)
frequency and the wave vector of the wave rx, respectively.
320 Tadjeddine and Le Rille

The projection of the complex polarization on the j-axis

WSFG WI
(j, k, and I are x, y, or z) is given by Eq. (6) were the n,(wSFG)--' USFGy = n, (WI)-
c C
subscript asterisk skirls for complex conjugate and the W1
electric fields are taken above the surface for the adsorb- . Uly + n,(w2)~' U2y = 0
C
ate and below the surface for the substrate. (9)
WOFG WI
n,(wOFG)--' UDFGy = n, ( w d -
c c
W1
. Uly - n,(w2)~' U2y = 0
c

n,(WSFG) . WSFG . sin(8 sFG ) = n,(wd . WI

. sin(8d + n,(w2) . W2 . sin(8 2)
n,(wDFG) . WDFG . sin(8 DF G) = n,(wd . Wj
~NLS ""' (0) - -
. sin(8d - n r (w2) . W2 . sin(8 2)
Pj (WI - W2) = L...J Xk- . Elk' E21'
k.l
(10)

= L Xk 2
)(WI, w2, WI - W2) Neglecting the dispersion of water in the visible and
k.1 near IR leads to
o EO i ((k 1 -k2)·r-(Wl-w2)·t)
. E lk' 21' e . (8 ) WI' sin (8d + W2 . sin(82)
sm SFG = ----'------'---------'-------'-
(6) WI +W2
(II)
. (8 ) WI' sin (8\) - W2 . sin(8 2 )
sm DFG =
WI - W2

4. Conditions of Phase Matching at the Interface In the case of SFG, Eq. 10 always has a solution:
The phase-matching condition between the waves and
WI . sin(8d + W2 . Sin(82)!2::::: 1
the nonlinear polarization results in Eqs. (7), which have (12)
to be true for every time t and for every position r on the I Wl +W2

surface: the angle of emission of the SFG referred to Oz being

given by

· (WI' sin(8 1)
8 SFG = A rc sm
+ W2 . Sin(82)) (13)
WI +W2

On the contrary, DFG may have no solution in some

cases [8] because Eq. 11 has a solution only if

WI . sin(8d - W2 . Sin(82)/2::::: I
(14)
I WI -W2

Figure 3 shows the calculated map of the DFG-allowed

and the DFG-forbidden domains of incidence angle as
(7) a function of the IR wavelength A2 ,for a constant visible
wavelength Al = 532 nm (which is the wavelength of the
The frequencies should then satisfY the following con- doubled YAG laser). It shows that the DFG-allowed
dition: domain extension increases with the IR wavelength. It is
worth noting that the less appropriate configuration is
WSFG =W\ + W2 (8) the contrapropagating one [6,7], whereas the more appro-
WOFG =WI - W2 priate is the collinear one [4]. This reason has brought us
to design the best optical geometry of the setup, with an
By choosing r either along the y- or the x-axis, Eqs. (7) angle of incidence of 65° for the infrared beam and 55°
lead to Eqs. (9) and (10), indicating that SFG and DFG for the visible one, obtained by using a prismatic window
are generated in the plane of incidence. (made of BaF2 or CaF2), to ensure the good angle of
SFG/DFG at Electrode Surfaces 321

A, and Tare the overlapping in space and time visible

80
and IR pulse energy, the irradiated area of the sample,
Q)
(.)
60 and the overlapping pulse duration, respectively. The
C
Q)
second-order equivalent surface susceptibility, X(2), is
"0
'(3 deduced from the component of the second-order sur-
c
'0 face susceptibility, x;~l, by [10-12]
Q)
0> (2 ) " (2)
c
<tl
X = L...J ajkl . Xjkl (17)
eJ jkl
~ 20

"0 The coefficients ajkl are real [12] and depend on 87 and on
:* ·40
the optical properties of the medium (electrolyte or
'"o
"0 .60 metal) where the nonlinear polarization is created.
Because the signal is proportional the Ix(2)1 2 , it is of
80
interest to build up a model ofthe second-order nonlinear
-80 -60 -40 so
-20 20 40 60
susceptibility of the system. The effective surface
infrared angle of incidence n nonlinear susceptibility can be split into two parts:
Figure 3 Forbidden DFG configuration in a coplanar con- X(2) = X~) + x~k (18)
figuration (filled areas) for different infrared wavelengths (1, 3,
5, and 10 J-lm). Our setup configuration is indicated by a point. In Eg. (18) X~) stands for the IR-frequency dependent res-
onant contribution of the adsorbate vibrational level
and x~k accounts for the contribution of the interface
impinging on the sample. The angle of emission of the
that does not change significantly with the IR wave
DFG referred to Oz is given by
number. In the case ofIR-vis SFG or DFG spectroscopy
. (WI' sin(e j ) - W2 . Sin(e2)) of molecules adsorbed on the electrode, the electrode will
8DFG = Arc sm (15) contribute solely to the nonresonant background,
WI -W2
whereas the detected resonances come from the
One should emphasize that the difference frequency adsorbate. The microscopic description of the nonlinear
lays below the frequency of the visible beam and the response presented below further analyzes the interpret-
DFG signal is obscured by the fluorescence signal pro- ation and the processing of the nonlinear optical
duced by the interaction of the visible laser beam with spectroscopic data.
the sample. Moreover, the required collinear configur-
ation makes filtering ofthe DFG photons from the visible 2. Resonant Susceptibility of the Adsorbate
beam more difficult. These severe experimental con- The orientation of the admolecules in the adsorbed layer
straints explain why the DFG technique is hardly used. is controlled by the molecule-surface interactions and
We have tackled this problem both by defining the appro- the dipolar interaction with the static interfacial electric
priate configuration and by using a suitable experimental field. This molecular ordering is favorable to the
setup [4,8]. electric-dipole contribution to the nonlinear response.
A quantum mechanical description of the molecular
B. Calculation of the Second-Order second-order dipolar polarizability, in the case ofvisible
Susceptibilities and IR pump beams, is presented in [13].
1. SFG and DFG Signal
Assuming that only the ground state population p~O) is
occupied, the resonant second-order susceptibility X~)
The number S ofdetected SFG (DFG) photons, recorded
generated by the adsorbate is given by [l]
as a function of the IR beam frequency, is given by [9]
e3 . p(O)
2 2 (2) ( ) _ g
ILl' L2' L3' i )1 'VI . V2
(16)
XRjkl WI +W2 - ~
Soc A.T
. (X Ijkl + X2jkl +X3jkl + X4jkl + XSjkl +X6jkl)
where L; account for the beam polarization and the (19)
Fresnel factors, which describe the modification of the
beam propagation in the interfacial region. x<2) is the where W2 = + WIR for SFG and -WIr for DFG, h is the
second-order equivalent surface susceptibility. VI, V2, Planck's constant, e the electron charge, and jkl the
322 Tadjeddine and Le Rille

projections ofthe susceptibility tensor along x, y, or z. The On the other hand, the DFG is resonant for
various elements of the right-hand side of Eq. (19) are W[R = -W2 = -w ng or -w mg [third and fifth terms of
given in Eq. (20), (r a ) being the dipolar matrix elements: Eq. (20)], leading to

(22)

Hence, the surface susceptibilities can be written as

two Lorentz oscillators:

l(2)(WSFG) ~ f3SFG .
(WIR - w vg + I . C g)
(23)
.. (w _ ""
~
(rj)gm' (rk)mn' (r;)ng
X41}k ) - L (
n.m W + wng + I.' r ng )(WI + wmg + I.' r mg ) XS(2)(WDFG)
(WIR -
f3DFG .
w vg - I, r vg )
where the "oscillator strengths" f3SFG and f3DFG are real
and account for the Raman cross-section ofthe adsorbed
species. The SFG (respectively DFG) process can be then
understood as a combination of an IR absorption
(respectively stimulated emission) and a Raman
anti-Stokes (respectively Stokes) process, as skeched in
Fig. 4. As a consequence, a mode has to be both IR and
(20) Raman active for being SFG or DFG active. In the first
approximation, the activity of an admolecule can be
If only one excited vibrational level (labeled v) is inferred from the IR and Raman activities of the isolated
involved, the SFG is resonant for WIR = W2 = w ng or molecule. However, these properties can be strongly
W[R = W2 = W mg , and only the first and the sixth terms modified in the adsorbed phase as a result of the chemi-
of Eq. (20) are resonant, leading to sorption and ofthe loss ofmolecular symmetry. Textbook
examples of such effects are the IR activity gained by the
S(2) e 3 . p~O) . (rk)gv
stretching vibration of CO or O 2 when these molecules
Xijk (WSFG)~ h2 .
(
WIR - w vg + I,. r vg ) are adsorbed on metallic surfaces as a result of a

.
L( n
(ri)gn . (rj)nv
(WSFG - w ng
(ravn . (rj)ng
+ i· r ng ) + (WI + w ng + i· r ng )
)
dynamical charge transfer [14,15]. A recent example is
the detection of a SFG signal of K-doped C60 adsorbed
on Ag( Ill) in a UHV environment. The centrosymmetry
(21) of C60 prevents the vibrations of the free molecule to be

I'

=1 ~ ~~
0lJ 0lJ
CQro OM
vibrlfu1al
level (v)
~R T ~R I
IR Rrrm
!JCUXi Rrrm IR
SFG ctBllii01 a1i-8cka3
level (g)
Scka3 enissicn
oro
Figure 4 Scheme of the energy level diagram for SFG, infrared absorption, Raman anti-Stokes diffusion, Raman Stokes diffusion,
infrared emission, and DFG.
SFG/DFG at Electrode Surfaces 323

simultaneously Raman and IR active, thus forbidding In the case of SFG, Petukhov proposes the following
any SFG activity. However, the interaction of C 60 with a expreSSlOn:
silver substrate induces a dynamical dipolar activity lead-
ing to the observed SFG activity ofthe Ag 2 Raman active (25)
mode [16,17].
In the case of corrugated surfaces, one can obtain an
ii is the bulk electron density and Xa, Xb, and Xd the normal,
enhancement of the nonlinear response due to the
the tangential surface, and the bulk susceptibility, given,
inhomogeneity ofthe interfacial electric field [18,19]. This
respectively, by
phenomenon can be related to the electromagnetic
enhancement effect observed in surface-enhanced
Raman scattering [20].
It is noteworthy [Eq. (23)] that second-order surface
SFG and DFG susceptibilities are basically different,
because they are both imaginary at the resonance but with
an opposite sign. The phase opposition between SFG
and DFG is used later in the quantitative processing of
the experimental data.

3. Nonresonant Susceptibility Contribution of the

Metal

The polarization of the metal is more intricate to
calculate. One usually separates the dielectric constant
of a metal into two parts, coming from the intraband
and the interband electronic transitions (Fig. 5) [21].
Following the same approach, we can split up the
second-order polarization of the substrate into the con-
tributions of the free and the bound electrons:
P(w3 )metaj = pew 3)intra + pew 3).mter
(a) Free Electron Metal Contribution.
The nonlinear response ofthe conduction electrons ofthe
metal electrode has been calculated for SHG [21] and for
SFG [8], using ajellium model for the free electron metal.
bound
electrons
. ( J£J - sin 2(e l ) . j £2 - sin 2(e 2) + sin (ej) . sin (e 2 ))
(28)
The parameter a of Eq. (28) is the only one sensitive to
the static electric field across the interface, and the elec-
trode potential. As for SHG, Xa can be expressed as a func-
tion of the static electric field Ede across the interface
and the rational electrode potential (Ede - E pze ):
(24)
Xa = X(3)(O, WI, w2)Ede ex X(3)(0, WI, W2)( Vde - Vpze )
(29)
For a free electron-like metal described by a Drude
model, the dielectric constant is given by Eq. (30) where
r is equal to 1 (visible beam), 2 (IR one), or 3 (SFG or
D FG one) and w p is the plasma frequency ofthe free elec-
tron gas (around 10 17 Hz, 100 times higher than IR and
visible frequencies w r ).

(30)

Using Eq. (30), the intraband contribution to the

free electrons
second-order susceptibility becomes

Ir 1
Fenni
..
,..
X
(2)intra _ 4· £3 . ii (sin(el)' sin(e2) . sin(e3)
- W 2 ,w2'
j 2
4
Energy
sin(ej) + sin(e 2) sin (e 3 ))
·a (Wj,W2 ) + 2 + --2-
Figure 5 Scheme of the density of electronic levels of noble
metal. (31)
324
It is worth noting that X(2)intra is real and potential
dependent. The metal electrode intraband contribution
to the second-order nonlinear effect can then be
expressed as
X(2)intra = rx . (Vdc - V pzc ) + b (32)
where rx and b are real.
(b) Interband Transition Metal Contribution.
The above-describedjellium model neglects the coupling
of the optical beams to the bound electrons of the
substrate. It is therefore restricted to noble metal
substrates and low optical frequencies that enable only
electronic excitations near the Fermi level, involving elec-
tronic orbitals of s symmetry. However, the contribution
of the d-electrons will dominate if the optical frequencies
lie in the interband transition range.
There is no available modeling of the second-order
susceptibility generated by the interband transitions.
However, in linear optics, the interband transitions are
accounted for by a sum of Lorentzian oscillators [22].
We have extended this model to the second-order
nonlinear susceptibility, in accordance with Shen's
equations [1]. In doing so, the interband contribution
can be expanded into several Lorentzian lines of fre-
quency (J)eg, of damping reg, and oscillator strength Pe
(note that the oscillator strength Pc of the transition
between the levels e and g is proportional to the density
ofjoint states):
(33)
Among these oscillators, one (labeled eo) may become
resonant, with the visible wave
(34)
Its contribution is then dominant and one can neglect all
the other oscillators in the calculation of the
susceptibility:
(35)
The interband susceptibility is then given by Eq. (36),
where 'Y is a real number independent of the electrode
potential:
l2)inter 0::::; i . }' (36)
The magnitude of the interband susceptibility is
enhanced when the visible wave lies in the interband
transition. Notice the fundamental difference between
Tadjeddine and Le Rille
the real contribution of the free electrons and the
imaginary contribution of interband transition to the
second-order nonlinear susceptibility.
C. Comparison Between SFG and DFG
1. Interference Between the Resonant and the
Nonresonant SFG (DFG) Signal
In the present section, we apply the above theoretical
approach to various metals, our attention being focused
on the nonresonant term and its interference with the
resonant adsorbate contribution. The interface
second-order susceptibility is then given by
Il2)12=lx~)12+IX~kI2 + 2· IX~I . Ix~kl' cos(cp) (37)
The shape of the SFG (DFG) signal and the
magnitude ofthe resonance structure are strongly depen-
dent on the magnitude of the interference term [last term
of Eq. (37)]. Figure 6 displays the evolution of the SFG
and DFG spectra with the phase cp of the nonresonant
signal, assumed of the same intensity. In the case of a
destructive interference (cp = +90 for SFG and 0
cp = -90 for DFG), the resonance peak is completely
0
hidden, which prevents any quantitative data analysis,
whereas for a constructive interference (cp = -90 for 0
SFG and cp = +90 for DFG) the resonance peak is
0
enhanced, leading to an easier quantitative analysis of
the adsorbate vibrational properties. It is therefore of
great importance to improve our knowledge of the elec-
tronic properties of the metal substrate to predict the
effect of the interference between the nonresonant
substrate and the resonant adsorbate contribution.
2. Evaluation of the Interband Transitions from
Linear Optical Properties
We can deduce the interband transitions of the noble
metals from the linear optical properties. The Drude
theory gives the dielectric constant with free electron
gas with only two parameters (the plasma frequency,
vp 0::::; 10 15 Hz, and the relaxation time, (r 0::::; 10- 13 s):
(J)2
IPrude = 1_ P (38)
2 . (J)
(J) +Z'-
r
Following a standard procedure in linear optics [21], the
interband contribution to the linear dielectric constant
is obtained as a difference between the experimental
values of the dielectric constant and the calculated
intraband contribution:
(39)
SFG/DFG at Electrode Surfaces 325

nonnlSonant phase:
8 - ~- O· for SFG and 180· for DFG
- 90· for both SFG and DFG
-h 180· for SFG and O· for DFG
-S- 270· for both SFG and DFG

·10 -5 o 5 10
(cr-(J' 0)/Llcr

Figure 6 Simulated interference between a nonresonant signal and a resonant signal ofthe same magnitude for different phase ofthe
nonresonant (0°,90°, 180°, and 270°), in the case of SFG and DFG.

This interband contribution to the imaginary part of 3. Cyanide on Platinum

the dielectric constant (£2) brings very interesting in- Platinum has no interband transition in the visible range
formation about the joint density of states Pu/(w) for and the nonresonant term is real, because it comes only
vertical transition between bands u and I [Eq. (40)] from the adsorbate and the intraband transitions con-
and the density of states neE) of the interband tributions:
tmnsition [Eq. (41)] from a bound to the Fermi level
EF [21,23]: (2)inter // (2)intra....... (2) _ (2) + (2) '" (2) + (2)intra
XNR "XNR ~ X - XR XNR -XR XNR
(42)
(40) As a consequence, the resonant term is purely
imaginary both in SFG and in DFG and cannot interfere
with the real nonresonant term. Therefore, the SFG and
where Eo is a function of the matrix elements associ-
the DFG spectra should be similar. This is clearly demon-
ated to the transitions.
strated in 8, which shows the SFG and DFG spectra of
CN- on Pt, recorded at -0.95 V (SCE). Moreover, fit of
Pu/(w) = - -23 . JEF dE· neE) (41) both spectra to Eqs. (16) and (18) gives almost the same
(2· n) EF--!i·w value of 180 for the nonresonant phase angle (Table 1).
0

This way, we can deduce the density of bound level
that participates to an interband transition and evaluate
the magnitude of the interband contribution to the
nonresonant second-order nonlinear susceptibility
(which can interfere with the resonant one). We shall
illustrate the interference effect by three examples: the
adsorption of CN- on silver, gold, and platinum
substrate, where the interband transitions lie above,
within, and below the spectral visible range, res-
pectively.
4. Cyanide on Silver
The plot (Fig. 7) of the density of joint states for silver
clearly shows that there is no interband transition in the
visible spectral range. As a consequence, the nonresonant
silver signal comes solely from the free electrons. The sil-
ver nonlinear behavior should be relatively close to that
of platinum, as shown in the experimental SFG and
DFG spectra (Fig. 8) recorded for a polycrystaline silver
electrode in contact with a solution of cyanide, at
-1.2 V/SCE (Fig. 9), and in Table 1.
326 Tadjeddine and Le Rille

Table 1 Parameters ofthe Fit ofSFG and DFG Spectra (Ratio Nonresonant on Resonant and Phase Angle ofthe Nonresonant) for
Pt(lOO) Electrode at E= -0.95 V vs. Saturated Calomel Electrode, Ag Electrode at E= -1.2 V vs. Saturated Calomel Electrode,
and Au(lOO) Electrode at E = -0.8 V vs. Ag!AgCI in Contact with an Aqueous Electrolyte Consisting of 0.1 M NaCI0 4 and 0.025 M
KCN
Spectroscopy SFG DFG

Metal Ratio nonresonant! Phase angle ofthe Ratio nonresonant! Phase angle ofthe
electrode resonant nonresonant C) resonant nonresonant C)

Pt 0.286 174 0.303 174

Ag 0.256 III 0.465 139
Au 1.648 112 0.562 69

1.5

g;
+
~
61- -
9
•••• Au
PI

1.0

,A
f~ I' I
J
•I ,
lO.5
1lI I ,
I
•
~ .. rn

,,
I,
I, •,
:...... -
0.0
'~
..
2 4 6 B
energy (eV)

Figure 7 Calculated interband transitions of platinum, gold, and silver.

2.0
ic 0 CN"/Pt(100)
Therefore, SFG and DFG are very similar, and SFG is :> 1.5
the best and simpler. We will show that monitoring the
.e~ -0.95V/calomel
iii 1.0
nonresonant contribution ofthe silver substrate can bring c
0>
'iii
insights on the surface electronic properties of the 120 0.5
electrode, such as the determination of the potential of
0.0
zero charge (PZC).
2.0
~
c
:> 1.5
5. Cyanide on Gold
e
~
The case of gold is very different because the interband iii 1.0
c
transition lies in the visible range. Figure 7 shows that ,~
0.5
the doubled-YAG, the DFG, and especially the SFG fre- l2rn
quencies are in the interband transition spectral range.
As a consequence, there is a dominant contribution of 2000 2050 2100 2150
., 2200 2250

the interband transition to the nonresonant gold signal, Infrared wavenumber (em )

given by
Figure 8 DFG (circles, top) and SFG (circles, bottom) spectra
(2)inter"
XNR
(2)intra ----"
/ / XNR ----..' X
(2) _
-
• (2)
XR
+ XNR
(2) ~ (2) + (2)inter
~XR XNR
ofPt(IOO) electrode (continuous line: results of the fits) in con-
tact with an aqueous electrolyte consisting of 0.1 M NaCl04
(43) and 0.025 M KCN at E = -0.95 VlSCE.
SFG/DFG at Electrode Surfaces 327

lil
2.0

eN-lAg
...."
c
1.2
1.0
0.8
'2 1.5 €
"~ -1.2V/calomel .!. 0.8
11

€
e
.!.
1.0 .c
.2'
(!l
0.4
0.2
u.
(/)
Cii 0.0
c: CN-/Au(100)
'~ 0.5 0.4
-O.85V/calomel
fe
c 0.0 I--....u.........._~=- ---'r=c; ~ 0.3

€"
.!. 0.2
iii
2.0 c
0.1
'"
'ilI
!20 0.0
2000 2050 2100 2150 2200 2250 2300
.,
infrared wavenumber (em )

Figure 10 DFG (circles, top) and SFG (circles, bottom)

spectra of Au(IOO) electrode (continuous line: results ofthe fits)
in contact with an aqueous electrolyte consisting of 0.1 M
0.0 ""-..J....L-L...J.....L...J.....JL....L....L...L-l-L-L...L...L-l-L-L....L...&-L............l...JL....L...........J NaCl0 4 and 0.025 M KCN at E = -0.85 VlSCE.
1950 2000 2200 2250

For the modeling of experimental data close to a

Figure 9 DFG (circles, top) and SFG (circles, bottom) spectra vibrational resonance, one usually separates the
of Ag electrode (continuous line: results of the fits) in contact second-order susceptibility into the resonant one, which
with an aqueous electrolyte consisting of 0.1 M NaCl0 4 and varies with the IR wave number, and the nonresonant
0.025 M KCN at E = -1.2 VI SCE. one, which does not [Eq. (18)] [24].
One assumes a Lorentzian shape for the resonant
term, with a homogeneous broadening of the vibrational
Because the nonresonant signal is imaginary,
resonances:
according to Eq. (36), it interferes with the adsorbate
resonant signal, which becomes imaginary at the (2) -
XR -
L m··a·
J J
(44)
resonance, with a phase angle <[Jr of -90 for SFG 0
.
J
WIR - Wi + i . t: . ri
and +90 for DFG [see Eq. (23)]. However, the inter-
0

ference pattern should be different for SFG and DFG, In Eq. (44), ai, Wi, and ri are real and positive and stand
depending on the sign of the interband term, i.e., of for the oscillator strength, the resonance frequency, and
the phase angle <[JNR of the nonresonant susceptibility. the halfwidth at half maximum, respectively. t: = +1 for
This is clearly demonstrated by the experimental SFG SFG and t: = -1 for DFG, as stated previously, and
and DFG spectra recorded for CN-/Au(100) at mi = + 1 or -1 depending on whether the adsorbate
-0.8 VlAg/Agel, presented in Fig. 10. The interference dipole projection of the jth resonance along the surface
between the resonant and the nonresonant term is con- normal is positive or negative [25]. The nonresonant part
structive for DFG and destructive for SFG, with a of the susceptibility comes essentially from the metal
phase angle <[JNR close to 90° (Table 1). It is experimen- substrate. We can model it by Eq. 45 where the real part
tally possible to monitor the relative magnitude of the aCE) depends on the electrode potential E, whereas the
nonresonant signal by switching from SFG to DFG. imaginary part b does not. The nonresonant term is dras-
In the case of gold substrate, the ratio of the intensities tically depending on the nature of the substrate material.
of the nonresonant signal to the resonant one is
reduced (Table 1), making DFG a more suitable probe x~k = C . e i·'P = a (E) + i . b (45)
of the vibrational properties of adsorbate on gold, as
we have shown recently [4]. 2. Lifting the Fit Degeneracy by Combining SFG and
DFG for One Resonant and a Nonresonant [8]
D. Modeling the SFG/DFG Spectra We address in this section DFG as a SFG complementary
spectroscopy for a quantitative data analysis. Actually,
1. Model of the Second-Order Susceptibility Eqs. 16 and 18 have two mathematical solutions, among
328 Tadjeddine and Le Rille

which only one has a physical meaning. Let the two electronic properties of the metal when the frequency is
solutions to be tuned from WSFG to WOFG and the detected nonresonant
signal should be the same for SFG and DFG. In par-
X(2) = CO' ei.cp + ao . ticular, the phase angle of the nonresonant signal should
WIR - Wo + I . £ . r 0
be constant upon switching from SFG to DFG.Therefore,
(46)
(2)1 = c' . e i·cp' + a o the constancy of the phase angle can be addressed as the
X o WIR - WIo + I. . £. r'0 pertinent parameter for seeking after the physical sol-
ution of the fit.
(with Co, ao, Wo, r o, Co' a o'wo,
r o positive real numbers,
and £ = +1 for SFG and £ = -1 for DFG). These two sol- X~~(WSFG) = X~k(WOFG)
utions are exactly the same ifand only ifEq. (47) is verified (50)
for all frequencies w. => CPSFG ~ CPOFG
This procedure has been tested for platinum where no
(47) particular feature in the electronic properties is expected
in the visible spectral range. The nonresonant signal is
This condition leads to two mathematical solutions that
therefore the same for SFG and DFG and the physical
have identical parameters (w o= Wo, r o = r o, C' = C)
solution of the fit must lead to the same phase angle of
except the oscillator strength [Eq. (48)] and the phase of
the nonresonant signal for SFG and for DFG. Table 2 pre-
the nonresonant [defined by Eq. (49)].
sents the results ofthe fit of SFG and D FG signal for cyan-

ao = Ja6 + 4 . £ . C . ao . r 0 . sin cp + 4 . C2 . r6
ide ion adsorbed on platinum 100, in KCN (25 mM),
and NaCI0 4 (100 mM) electrolyte at -0.95 VlSCE.
(48) These data show that only one set of adjustment (number
2 for SFG and number I for DFG) leads to the same angle
, ao . cos cp of phase for the nonresonant contribution, cP = 173 o.
cos cp = , We have then shown clearly that combined investi-
ao
gation ofthe interface by SFG and DFG leads to a unique
. -(ao·sincp+2·£·ro) set offitting parameters and therefore allows for an unam-
SIn cp' = I (49)
ao biguous quantitative analysis of the experimental data.
, 2·£·C·ro
tan cp = - tan cp - - - - -
ao . cos cp
III. EXPERIMENTAL
However, the two models are not equivalent and only
A. Required Lasers for Nonlinear
one has a physical meaning, the other being a nonsense.
Spectroscopy of Surfaces
It is then a major task to discriminate between the physi-
cal and the nonsense solution to give a correct expla- Nonlinear optical process is enhanced by using short
nation of the experimental data. laser pulses that enable high peak intensity on the sample
We show below that the comparison between SFG and with low heating. The thermal response ofthe surface will
DFG data for the same system in the same conditions also influence the maximum of the nonlinear signal. A
should bring the solution in the case of substrate with no short pulse duration At enhances the nonlinear signal
interband transition in the investigated spectral range. [Eq. (16)]; however, a resolution of a few wave numbers
In this case, there is no significant modification of the (Aa ~ 1 cm- I) sets the optimum pulse length in the

Table 2 Parameters ofthe Fit of SFG and DFG Spectra for Pt(lOO) Electrode at E = -0.95 V vs. Saturated Calomel Electrode
SFG DFG

Fit no. 1 Fit no. 2 Fit no. I Fit no. 2

Nonresonant module: C (arb. units) 0.3056 0.3056 0.296 0.296

Nonresonant position: qJ CO) 155 174 174 -144
Resonance position: roo (em-I) 2069 2069 2070 2070
FWHM: 2.ro (em-I) 28 28 32 32
Oscillator strength: ao (arb. units) 16 15 16 19
SFG/DFG at Electrode Surfaces
picosecond range, in accordance with Heisenberg's
relation [Eq. (51)]:
!1E·/1t ~ Fi
I (51)
E = 2rrFi . c . a => /1t > - - - -
- 2rr . c . !1a
Focusing the beams also increases the nonlinear
signal, but one should care about damaging the sample.
The thermal heating of the surface will limit the maxi-
mum achievable focusing. Commercial nanosecond or
picosecond Nd : YAG lasers with an output power of
a few hundred mWare suitable for the generation of the
visible wave at fixed frequency WI.
However, the development of a tunable IR laser
providing the wave at W2 with the adequate peak power
is still a challenging step for performing SFG/DFG
spectroscopy. As stated in the early development stage of
SFG spectroscopy [6], only free electron lasers can pro-
vide the adequate picosecond IR beam tunable over the
broad spectral range of the molecular vibrations that
spans from 2.5 (4000 cm- I ) to few hundred microns
(10 cm- I ).
However, its cost and its heavy handling make free
electron laser still ofexceptional use; since the beginning
[6,26,27], benchtop lasers were used for SFG/DFG
spectroscopy. Although the first benchtop systems
offered limited tunability in the near IR around 3 /lm,
advances in laser technology mean that cost-effective sol-
utions become available for the 2.5- to 10-/lm domain.
This range should be further extended to ~20 /lm
stemming from the availability of adequate nonlinear
crystals for parametric conversion [28]. This spectral
domain from 2.5 to 20 /lm covers the most relevant
spectral range of the molecular vibrations. Tunable IR
lasers for SFG spectroscopy are usually obtained by fre-
quency conversion of near-IR or visible picosecond laser
pulses. Down-frequency conversion is achieved either
e- EEL mirror
beem
dump IllSer
belllll
enerey
llIle1y;ine
slit
5m
Figure 11 Layout of the free electron laser CLIO.
329
by stimulated Raman scattering in gas or by frequency
mixing oftwo synchronous beams in a nonlinear crystal.
All these setups use a primary beam tunable in the visible
or near IR that is generated by either a dye laser or a
parametric generator.
B. The Setup Used for SFG/DFG at LURE
The Laboratoire pour l'Utilisation du Rayonnement
Electromagnetique (LURE) at Orsay, France is equipped
with operational SFG setups, attached to the free electron
laser (FEL) "CLIO" (Centre de Lasers Infrarouge
d' Orsay) [29]. The IR beam delivered either by the free
electron laser or an optical parametric oscillator
(OPO)-based benchtop laser is mixed with the visible
wave generated by an additional benchtop synchronized
laser.
1. Free Electron Laser CLIO
Making use of accelerated electron packets propagating
in vacuum through the periodic magnetic field of an
undulator, the free electron laser technology gives access
to all the electromagnetic spectrum up to the Uv, an
upper limit fixed by the lack of cavity mirrors for shorter
wavelengths. Figure 11 presents the principle of CLIO
[30,31].
2. Benchtop Nd:YAG-Pumped Visible Laser
A commercial picosecond Nd:YAG laser has been
synchronized with the temporal structure of the CLIO
pulses and frequency doubled to produce the synchron-
ized visible beam for SFG/DFG. Details of the
synchronization can be found in [32].
3. Benchtop OPO Laser
Tunable benchtop laser requires a nonlinear crystal
pumped by one beam at fixed frequency wp (Fig. 12).
The pump wave produces two new waves at lower fre-
quency W s and Wi, by second-order optical processes in
330 Tadjeddine and Le Rille

infrared tunabla laser

Figure 12 Scheme ofan OPO-based benchtop IR laser.

the nonlinear crystal: wp = Wi + W s ' The parametric gen-
eration is dependent on the geometric configuration, as
in an optical parametric amplifier. In an o PO, one of
the two beams (called "signal", at vs ) is recycled in a laser
cavity. The second one (called "idler", at Vi) is used as a
tunable wave. The reduction of the number of conversion
steps allows higher overall conversion efficiencies,
whereas the use of a limited number of optical com-
ponents improves the device reliability and the cost
effectiveness.
Peremans et al. [33] recently developed a picosecond
OPO-based IR laser, which uses a commercial
picosecond NdYAG laser to pump an AgGaS2 crystal.
This device generates nearly Fourier transform limited
"idler" pulses with a bandwidth of 1.8 em-I and a
duration of 11 ps, in a spectral range spanning from
2.5,um (4000 em-I) to 10 11m (1000 em-I). The beam
power (single pulse energy) at 3, 5, and 10 11m is 40
(25 ,ul), 30 (18 ,ul), and 3 mW (2 ,ul), respectively.
Pumping the OPO above saturation ensures good bunch
to buneh energy stability of better than 3% rms variation
(at 5 11m), a characteristic relevant to the performances
of SFG. The OPO configuration also limits the degra-
dation of the faces of the nonlinear crystal, an effect
intrinsic to AgGaS2. Using the more resistant LiNb03
crystal upgrades the power performance to 300 mW near
3 ,urn; all other characteristics, except spectral agility
limited from 2.5 to 4.6 ,urn, remain the same.
In this device, the same NdYAG laser is used to pump
the tunable IR generator and to produce the visible beam
for SFG/DFG. This leads to similar duration (11 ps) and
ensures a natural synchronization ofthe two color pulses.
These characteristics have been taken into account in
Table 3 for the comparison ofthe performances of differ-
ent laser sources used in SFG spectroscopy. In addition
to a broad tunability, the OPO configuration appears to
provide the best figures with respect to the sensitivity
and the resolution. Table 3 shows that in the 2.5 - to IO-Ilm
spectral range, benchtop OPO is competitive to free elec-
tron laser, whereas at longer wavelengths, the latter tech-
nology remains an unique solution. We note, however,
that free electron lasers are able to achieve high temporal
resolution for time-resolved spectroscopy at the expense
of the spectroscopic performances [33,34].
c. Signal Detection
1. Detection
Figure 13 shows a conventional SFG detection setup. The
IR and visible beams impinge on the sample surface with
incidence angles of 65 and 55°, respectively. The
second-order signal from the sample surface is detected

Table 3 Infrared Laser Sources used for SFG Spectroscopy (Not Exhaustive)
OPOLiNb0 3 OPOAgGaS2 FELCLIO

Typical average power 70mW 30mW IW

Macropulses frequency, Hz 25 25 25
Macropulses duration, IlS I I 10
Micropulses frequency, MHz 62.5 62.5 62.5
Micropulses duration, ps 11 11 0.4-5
Typical micropulses energy, fiJ 25 25 60
Typical peak power, MW 2 1.7 60
Spectral range, fim 2-4.5 4-10 3-50
Relative spectral width, o/., 0.1 0.1 0.4
Spectral peak power
(effective power), MW/cm- 1 8
SFG/DFG at Electrode Surfaces
spectra
melers
ko_ _-+-.. 1 infrared
T quency using a grating monochromator equipped with a
fillers
1 signal
·'III'f---+--+
r1reference
Figure 13 Layout ofthe detection setup for SFG spectroscopy.
Filters, Raman filter; dielectric plate, BaF2 , ZnS reference
sample.
using a photomultiplier after spatial and spectral filtering
through a holographic filter and a monochromator. The
low noise of a photomultiplier guarantees a sensitive
detection of the weak nonlinear signal generated at the
interface. In the experimental spectra presented in the
present chapter, each data point is averaged over 50 laser
bunches corresponding to an acquisition time of 2 s.
The scan step was set at 1 cm -1 .
2. Normalization
The SFG or DFG yield of the sample is normalized to a
simultaneously acquired reference signal to compensate
for the spectral dependence ofthe IR beam intensity [35].
Figure 13 describes the principle of this reference line
where the weak reflections of the pump beams on a
dielectric plate (such as BaF2) are mixed in a bulk sample
with nonlinear activity. We found polycrystalline ZnSe
or ZnS samples as bulk references very convenient to
use because these noncentrosymmetric but isotropic
materials exhibit no angular dependency of their bulk
nonlinear signal. The reference signal is detected simi-
larly to that ofthe sample. Comparing the sample and ref-
erence signals in real time eliminates the noise sources
331
resulting from the beam power fluctuations, from the
beam disynchronization, and from the frequency depen-
dence of the IR beam power.
3. IR Wavelength Measurement
When using the free electron laser CLIO, the detection
system includes real-time monitoring ofthe IR beam fre-
pyroelectric detector array [32]. With the OPO, there is
no need of such a measurement, because the OPO laser
is calibrated beforehand.
D. Spectroelectrochemical Cell
An IR beam is readily absorbed by a few hundred micron
thick aqueous layer, even in the IR transparency window
of the water around 5 .urn [36]. This requires the design
of a spectroelectrochemical cell with an electrolyte thin
film (Fig. 14).
The cell is equipped with a 60° prismatic window to
prevent the strong refraction of the electrolyte and to
ensure a high angle of incidence of the laser beams on
the sample. In our case, the angle of incidence was set at
65° for the IR and 55° for the visible beam, close to the
optimum SFG/DFG yield [37].
The material window must be chemically inert and
optically transparent at the IR and visible wavelengths
and free of nonlinear second-order activity. CaF2 and
BaF2 windows satisfY these requirements up to 9.5 and
11 ,urn, respectively.
The spectroelectrochemical cell was made of KelF
equipped with a Teflon port for the electrolyte filling and
argon bubbling. The counter electrode was a large-area
platinum wire. The reference electrode was a SCE [4] or
Ag/AgCl electrode in saturated KCl solution connected
to the cell via a salt bridge between the cell and the refer-
ence electrode.
Electrolyte solution was made from high-grade purity
reactants and pure water of a resistivity of 18 MQ . cm- 1
deaerated by a continuous argon flux.
Working electrodes were single and polycrystaline
discs of 6 mm diameter and 2 mm thickness, cut from
high purity single crystal rod. They are mechanically
polished to a mirrorlike finish and chemically cleaned in
high purity reactants and pure water. Platinum and gold
samples are flame annealed for 10 min, cooled in air,
and quenched in an argon-saturated high purity water
droplet to prevent further contamination during the
transfer to the electrochemical cell.
Electrodes are immersed and polarized for 15 min at
negative potential, near the hydrogen evolution onset.
Then the sample is pressed lightly against the cell window
332
_--1m A /--11--;
counter working reference
electrode electrode electrode
Figure 14 Layout of a thin film electrolyte spectro-
electrochemical cell.
to minimize the IR beam absorption in the electrolyte
during the measurements. Spectra were recorded at
stepwise increasing potentials. Each spectrum is
acquired in 15 min [4].
IV. EXPERIMENTAL RESULTS
A. SFG Vibrational Study of H- Pt Interface
Hydrogen is involved as reactant or product in numerous
surface catalyzed reactions. In electrochemistry, the
hydrogen evolution reaction (HER) is of fundamental
interest with regard to the development of efficient and
environmentally benign technologies for energy conver-
sion and storage [38]. Nichols and Bewick [39] presented
the first spectroscopic identification by IR spectroscopy
ofelectrochemically deposited hydrogen. The absorption
band was found at 2100 cm- I for all investigated elec-
trode materials: polycrystalline platinum, rhodium,
iridium, and Pt(lll), indicating a terminal adsorption
site. Ogasawara and Ito [40] recently showed IR spectra
of Pt single crystal of various orientations. All the
H-Pt(hkl) bands were found in the 1990- to 2090-cm- 1
spectral range, confirming the on-top adsorption site of
hydrogen. They were only observed at low underpotential
where the authors also expected hydrogen adsorption
on defects. Furthermore, for Pt(lll), the H- Pt band was
only detected when the surface was incompletely
oriented, suggesting that this band and the one previ-
Tadjeddine and Le Rille
ously observed by Nichols and Bewick for the same
crystallographic orientation corresponds to hydrogen
adsorbed on defects.
SFG offers the possibility of recording absolute
vibrational spectra without the need to make reference
to a particular potential. This advantage also allows pro-
bing of the interface at overpotential where the
perturbation of the electrolyte by the release of H 2
hampers the performance ofdifferential IR and Raman
spectroscopies. Moreover, the power ofthe IR beam pro-
vided by CLIO-FEL gives the SFG spectrometer enough
sensitivity to record the vibrational signature of the
hydride interface in the electrochemical environment
[9,35,37,41-43].
1. UPD of Han Pt
The potential-evolved SFG spectra of H - pte lll),
H-Pt(lOO), H-Pt(llO), and H-Pt in 0.1 M H2S04 sol-
ution are shown in Fig. 15 [42]. Detailed analysis of the
data can be found in [37] and [42]. The internal structure
of the underpotential resonances can be resolved into
two surface orientation dependent resonances. Their
peak positions are (1890 em-I, 1970 em-I) for Pt(lOO),
1900 cm- I , 1980 cm- 1 for Pt(110), and (1945 em-I,
2020 cm -I) for Pt(l1l), respectively. The intensity of these
resonances increases regularly as the potential is lowered,
except for Pt(llO), where a sudden intensity increase
occurs near the HER onset potential. Only H-Pt
vibrations can account for the observed SFG resonances.
At underpotential, the frequency range of the H - Pt(hkl)
SFG resonance (1800-2100 em-I) indicates that the
UPD hydrogen occupies a terminal adsorption site.They
are broad and shifted to lower wave numbers in compari-
son with the terminal H - Pt IR band detected at
2100 em-I in metallic hydride complexes [44] or on plati-
num aggregates [45] in the gas phase. This shift and
broadening is a consequence of the hydrogen bonding
between the adsorbed hydrogen and the water molecules
of the electrolyte. This interaction between the hydride
interface and the electrolyte double layer may explain
the different adsorption behavior of hydrogen in electro-
chemical and ultra-high vacuum environment. In the
latter case, its coordination on all metals is always found
multifold [46].
2. GPD Hydrogen on Platinum
The SFG resonances associated with the UPD hydrogen
arenot perturbed by the new hydrogen adspecies showing
up in the overpotential range, as seen in Fig. 16 [41]. This
indicates that the UPD hydrogen remains on the surface
at potential negative of the HER onset and that the OPD
hydrogen is either coadsorbed with the UPD hydrogen
SFG/DFG at Electrode Surfaces 333

B: Pl(110) 1980 em-1

1900em-1 I
1765 em- 1 I "
:1'1.., .' ••
.
.......~ ....:
~'
.,."
"- ", 2050 em- 1
~.~. .-.',; ~.:
.~ ~":-
,. " -......
.. •• : ••: •• a•• a.
.
CJ
.-....'''' 'tI'.~"
~"r,., ..... .
'. \
1.1..
I/) fo
...
"'y,,: ..\.I.,...~......... .:........J

1600 1800 2000 2200 1600 1800 2000 2200

Wavenumber (cm- 1) Wavenumber (cm- 1)
D: poly. Pt 1990 em-1
1205Ocm -l
1nOcm-1 I , '"
, " ,!'
I ,.... ........
.. . , ...... .... ."

~.:,." 1·:'· ,.roo-

h 'oo •• ...
.
.t/a . . .
t .. ,..

.v. \..:..
,~ .. / . '"
..,: ,: ....
.... : ...
\

t ..
.. . '"
::' I . '.'., ~......... :.. w":"
,.' ,
.... .. ...... ..,
::::-.,.
U)
.
.. : ... ll'
.,.",
i ' .. ,.
¥
.... " .. "...
.. •

..
.1

.,.. ~ ..... "-

oo ••

..
....
.' .!..~'. ;'~J.".: ... ir"" ........ ,"y'" ....L ...... ~.

~I •• .., • •
- w.AJ', ... .,y· • .",. ....., .....
1I:' ........
b
'.". .~ .. to \ ....... ,... tJ . . . ~, . . . . . '- _co.~ .".':11 • • • •

• • af .''1 •• '''.''''',_ •• ~ ... _ ...... ~

1600 1800 2000 2200 1600 1800 2000

Wavenumber (cm- 1) Wavenumber (cm-1)

Figure 15 Potential-evolved SFG spectra ofPt(lOO), Pt(llO), Pt(lll), and a polycrystalline platinum surface in 0.1 M H 2 S0 4 electro-
Iyte (the curves are offset along they axis for clarity). (A) Pt(lOO): 0.7 (a); 0.55 (b); 0.3 (c); 0.15 (d); 0.0 (e); -0.08 (f) V (vs. RHE). (B)Pt(ilO):
0.65 (a); 0.5 (b); 0.35 (c); 0.2 (d); 0.05 (e); -0.1 (f) V (vs. RHE). (C) Pt(lll): 0.5 (a); 0.35 (b); 0.2 (c); 0.05 (d); -0.05 (e); -0.1 (g) V (vs. RHE).
(D) Polycrystalline Pt: 0.55 (a); 0.45 (b); 0.35 (c); 0.25 (d); 0.15 (e); 0.05 (f); -0.05 (g); -0.15 (h) V (vs. RHE). From Ref. 35.

or its coverage remains low such that it may not signifi-
cantly affect the UPD hydrogen. These spectroscopic
observations are consistent with the electrochemical res-
ults. The frequency of the SFG resonance at 1770 em-I
that appears at overpotential on all the samples lies out
of the conventional spectral ranges of the vibrations
of multifold (500-1300 em-I) and onefold (1800-
2200 em-I) coordinated hydrogen-metal bound. It
is, however, close to the H - Pt vibration in hydride
complexes of the form of H 2 Pt-R (1735 em-I) [44],
suggesting a dihydride adsorption configuration. These
species are still detected in methanol-containing
solution, indicating that the adsorbed CO poison does
not block the HER.
3. Contribution of Adsorbed Hydrogen to the
Unusual Adsorption State on Pt(111) Electrode
The origin ofthe unusual adsorption states on Pt(111) that
take place over a range of 0.2 Vabove 0.3 V (RHE) and
are positively shifted when the acid concentration is
decreased is subject to an intensive investigation. Two pro-
cesses were proposed to explain the origin of these states:
adsorption-desorption of specifically adsorbed
hydrogen sulfate anions [47] and adsorption-desorp-
tion of hydrogen controlled by the anion
adsorption-desorption [48]. Recent independent inves-
tigations using iodine [49] and CO [50] replacement
method and STM observation [51] are consistent with
the first process that assigns the high potential features
334
\ ~ poly·pt
1600 1800 2000 2200
Wavenumber (cm- 1)
Figure 16 H - Pt(hkl) SFG spectra at overpotential
(-0.1 VlNHE) [42].
of Pt(111) voltammetry to the adsorption of anions. On
the other hand, one should also elucidate the role of
coadsoibed H30+ species that have been evoked to
explain STM images observed on Au(111) [52] andPt(lll)
[51] in sulfuric acid solution. A possible contribution of
hydrogen to the high potential energy adsorption states
on Pt(lll) was inferred from the fit of the SFG spectra of
this orientation, following the procedure described in
[53]. Calculations have been performed assuming either
a parallel or an antiparallel orientation of the over-
potential resonance against the underpotential
resonances. Figure 17 shows the results of the best fit,
obtained when the overpotential resonance is taken
antiparallel to the underpotential ones. Both
assumptions lead to a significant value of the hydrogen
coverage value at 0.35 V, attesting some contribution of
hydrogen to the unusual adsorption states of Pt(111) in
sulfuric acid electrolyte. However, the magnitude of the
hydrogen coverage of 0.1 to 0.2 at 0.5 V is within the accu-
racy of the SFG spectra. This result has then to be
supported by more experimental investigations of the
vibrational properties of this interface. It would be of
great interest to perform SFG measurements of H - Pt
and (H) SO; Pt, in the same conditions, to access simul-
taneously to the spectroscopic signature and the adsorp-
tion behavior of both species.
Tadjeddine and Le Rille
P1(111)
_-22 ..... b
8
1600 1700 1800 1900 2000 2100 2200 2300
Wavenumber (cm- 1)
Figure 17 Fits to Eqs. (18) and (44) of the SFG spectra of
Pt(llI) [35].
B. DFG Vibrational StUdy of Au-eN Interface
The adsorption ofpseudohalide anions on noble metals is
closely related to fundamental stages of metal etching
and dissolution processes and has been investigated using
electrochemistry and other in situ and ex situ surface
techniques. However, IR and Raman spectroscopic
studies ofCN- on gold substrate were made only on poly-
crystalline electrodes [54,55]. A major limitation for IR
studies on single crystal is the lower IR dipole moment
of CN stretch compared with CO and the need ofa refer-
ence potential. DFG provides a mean to overcome this
limitation, as shown in Sec. II. Absolute vibrational
spectra recorded over a large potential range for Au(111),
Au(lOO), and Au(llO) have allowed us to study the
adsorption behavior of CN- on these surfaces and to
bring basic insights into the interfacial properties and
the surface-adsorbate interactions [4].
Figure 18 shows the potential-evolved DFG spectra of
Au(1lO)(a), Au(lOO)(b), and Au(111) (c) electrode, in con-
tact with an aqueous electrolyte consisting of NaCI0 4
0.1 M and KCN 0.025 M, along with their fits to Eq.
(46). Each spectrum is adjusted with only one
potential-position dependent resonance, indicating the
presence of only one absorption band localized within
the CN- stretching spectral range. Although the disap-
SFG/DFG at Electrode Surfaces 335

IAU(110) I peek 28

• r 40

1
8
a L -1.35V/SCE

~~~
J~
20
.21'~
.. :J
C!l •
u.€
o~
..
=-

I
a r.-
•• ~
• •"

•
.b
••

•
•
. . . .1.05V/SCE

• ·0.55V/SCE

.... ·0.05V1SCE
.~
g -20
"C

~
i3
-40

-60

IAu(100) I . . . n. UW4 • .,. _ b .1.15V1SCE -8Oxl0 -3

:±::~::-,~~
b

k- ~
"0"4. alP V.... 1.__ - - - -o.95V1SCE
-o.05V/SCE

IAu(111) I --t.1t'RW!I ""' -nour • •• - -o.85V1SCE

t" xL .... A -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0

A
e ;JIb . . . . potential (ViSCE)
b 1- -o.75V1SCE

~~~
l;!lK!

~~
o ~
.....1""
•• At ·.lII.IlI'--..
..... .... • . -o.65V1SCE
Figure 19 Cyclic voltammogram of Au(lIO), Au(IOO), and
Au(lll) electrode in contact with an aqueous electrolyte consist-
I '" I ra:-:"!1IIf~~ r,t;! 1FM -o.15V1SCE ing of 0.1 M NaCl0 4 and 0.025 M KCN, from -1.35 V/SCE to
2000 2100 2200 2300 o V/SCE recorded, at 20 mV/s, after 10 cycles.
-1
infrared wavenumber (em )

Figure 18 Potential-evolved DFG spectra (circles) of (a)

Au(100), -1.05 Von Au(100) and -0.85 Von Au(lll).
Au(lIO), (b) Au(IOO), and (c) Au(lll) electrode (continuous line: Note that Au(CN)2- has a symmetry inversion and is
results ofthe fits) in contact with an aqueous electrolyte consist- not SFG or DFG active. These results reveal some marked
ingofO.1 M NaCI0 4 and 0.025 M KCN at different potentials. differences in the process of CN- adsorption on the dif-
ferent surface orientations of gold single crystal
electrodes. This behavior is confirmed in Fig. 19, where
pearance of the resonance upon oxidation of the the voltammograms recorded after 10 cycles exhibit sev-
adsorbed CN- layer is completed at the same potential eral orientation-dependent anodic features, summarized
for the three investigated orientations, the potential at on Table 4, along with previous results of Thurgood et al.
which the adsorption starts depends on the electrode sur- [56] on gold polycristalline electrode. There is a good
face orientation: CN- adsorption starts at -1.35 Von agreement between these measurements, except for

Table 4 Labels and Positions of Oxidation Peaks of Gold Electrode in Contact with an Aqueous Electrolyte
Consisting of KOH 100 mM + KCN 100 mM [56] and of Au(lIO), Au(IOO), and Au(lll) Electrodes in Contact
with an Aqueous Electrolyte Consisting ofNaCI0 4 100 mM + KCN 25 mM [12]
Results of Thurgood et al. [56] Results of Au(hkl) [12]

Au(poly) Au(llO) Au(IOO) Au(lll)

Peak Subpeak (V/SCE) (V/SCE) (V/SCE) (ViSCE)

-1.05 -1.01 -1.05

la -0.81 -0.86 -0.88
Ib -0.62 -0.57
Ie -0.51 I -0.25 -0.44 -0.37 -0.27
2 2a +0.01 -0.04 -0.07 -0.03
2b +0.14
3 +0.39
336 Tadjeddine and Le Rille

peaks labeled 2 and 3 that lie above the potential region

• ..
oo~
a
investigated in the present work. The substructure ofpeak
1 (labeled la, Ib, and Ie) are absent on Au(lW) and poly-
crystalline sample. On Au(lOO) and Au(l11), the first
anodic peak la starts at -1.05 v/SCE and -0.85 V, res-
'I: I
• • ••I •• •• •• ItI I I

pectively; these potentials are identified as the onset of

..• a
2140
CN- adsorption on Au(lOO) and Au(lll), from the DFG b
2130
spectra of Fig. 18.
The decrease of the resonant DFG signal at anodic -~

E 2120
.!:!.
potential coincides with the positive peak Ie of the g'" 2110
voltammogram (Fig. 18) and should be assigned to the '"
c:
0
~ 2100
oxidation of the adsorbed CN- layer to Au(CN)2' as
proposed by Kunimatsu et al. [55]. Au(CN)2' has been 2090
detected in the solution by Fourier transform IR spectra 2080
for potential more positive than -0.6 V/SCE. 100

1. On-Top Adsorption of CN-Ions on Au(hkl) ~ 80

The full width at half maximum (FWHM) of the DFG

resonance is plotted in curve a of Fig. 20. The most
striking and unexpected result is the invariability of the
FWHM resonance width with either the electrode poten-
tialor the surface orientation. Its constant and weak value
of 17 cm- 1 can be explained by an homogeneous
broadening mechanism indicative of a same single
adsorption site of CN-.
The DFG resonance peak frequency (curve b of Fig.
20) obeys a quadratic potential dependence, increasing
from 2090 cm- 1 at -1.3 V to 2130 cm- 1 at 0 V A simi-
lar potential dependence has been observed for CN-
on Pt single crystals [57], although this system appears
more complicated. The potential dependence of the
DFG resonance frequency (Stark effect) is the same for
all the investigated surface orientation, which implies
that CN- is tightly bound to the gold surface and experi-
ences only the electric field of the surface atom on which
it is adsorbed. Because of the very different surface sym-
metry of the investigated orientations considered here,
only an adsorption on an on-top site can account for
this behavior, as previously shown for polycrystalline
gold electrode [55]. In the same way, recent IR and
STM works suggest an on-top adsorption for CN- on
Pt(11l) [58].
2. Energetics of CN- Adsorption on Au(hkl)
We have already noticed that the adsorption onset
depends on the electrode surface orientation. These
observations are clearly evidenced on curve c of Fig. 20,
where we have plotted the potential dependence of the
integrated DFG resonance intensity normalized to its
maximum value, for each crystal orientation. CN-
adsorption starts at -1.35 V on Au(lW), -1.05 V on
Au(lOO), and -0.85 V on Au(l11). This observation
'~" 60
i
.!:!
"iii 40
E
0
c: 20
0
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
electrode potential (V/SeE)
Figure 20 Potential dependence of the FWHM, the fre-
quency of the peak, and the integrated peak of the DFG
resonance of Au(llO) (squares), Au(IOO) (circles), and Au(lll)
(triangles) electrodes in contact with an aqueous electrolyte
consisting of 0.1 M NaCI0 4 and 0.025 M KCN. All these data
are the results of the fits ofthe DFG spectra.
indicates that the electrode-adsorbate interactions are
stronger on the more open 110 surface and decrease on
the more dense surface. This follows the trend of the
PZC in CN--free solution, where the most positive PZC
is found for the III and the most negative for the 1I0 sur-
face orientation [59].
Following the theoretical analysis by Trasatti [60], one
can get some insights on the mechanism and the
energetics of CN- adsorption from the position of the
onset adsorption potential relative to the PZC ofeach sur-
face orientation, in CN- free solution [M"(hkl)]. The
larger (more negative) ~E(hkl), the stronger the
metal-ion interaction. Quantitative results are given in
Table 5. ~E(hkl) values indicate a strong adsorption bond
energy of CN- on gold electrode comparable with the
bond energy of iodine [59,61]. They demonstrate also
that the CN- -Au interaction is stronger on the
less-dense 110 face. This is likely due to the weaker
adsorbate-adsorbate repulsion attendant the more open
face.
SFG/DFG at Electrode Surfaces 337

Table 5 Potentials of Zero Charge Without CN- Measured by Electrochemical Methods [60], Potentials
of Cyanide Adsorption Measured by SFG [4], and their Differences for Au(llO), Au(lOO), and Au(lll)
Electrodes in Contact with an Aqueous Electrolyte Consisting ofNaCl0 4 100 mM + KCN 25 mM
Crystallographic PZC without CN- (V/SCE) CN- adsorption Potential energy of
orientation (Trasatti [60]) potential (VISCE) adsorption (V)
Au(llO) -0.05 -1.30 -1.25
Au(lOO) +0.10 -1.10 -1.20
Au(lll) +0.25 -0.80 -1.05

It is noteworthy that the DFG resonance is
dramatically reduced around 0 V for all three
orientations. As a result, the kinetics and the dynamics
of the CN- adsorption processes are faster on Au(111)
and slower on Au(100) and Au(l1 0). The rate of CN-
adsorption as measured by the positive slope of the
increasing segment is roughly the same for all surface
orientations, whereas the rate ofCN- desorption is much
higher for the 111 orientation. This behavior should be
connected to the thermodynamics of the system. The
upper stability potential limit ofCN - on the surface elec-
trode is the same for all the orientations, whereas the
lower limit is more negative for 110 than 100 and 111
orientations.
Figure 21 shows a set ofpotential evolved SFG spectra.
Fit to Eqs. (18) and (44) leads to a single resonance
centered at 2110 cm- 1 for E= -1 v/SCE, with a tuned
rate of 20 cm- 1 IV and a halfwidth of 15 cm- 1, in a good
agreement with data obtained by IR and Raman [63,64]
spectroscopy. Notice that IR spectroscopy of the same
system shows four bands, two of them being potential
dependent and assigned to surface species [55]. It is the
advantage of SFG to be sensitive only to the interface
2.0
1.5

1.0
c. Investigation of the Electrode Surface
-1.2V/SCE
Electronic Properties by SFG: CN- on 0.5
Silver
___......WIfII!'
0.0 asymetrie peak: phase>90"
As discussed in Sec. B. 3, the nonresonant SFG (DFG)
2.0
signal comes mainly from the substrate and is closely
dependent on the surface electronic properties of the i§ 1.5
substrate. Of interest here is the sensitivity of the ~

intraband contribution of the free electron to the static :e2! 1.0

~
electric field across the interface [Eq. (32)]. This effect Qj

can be used to probe the surface electronic properties of ..

c: 0.5
.2' -1.0VISCE

the electrode as a function of the potential, as shown by ~ 0.0

en symelrie peak: phase=90"
Tadjeddine et al. [42]. Our theoretical approach predicts 2.0
that not only the amplitude but also the phase of the
nonresonant signal carries out surface electronic infor- 1.5
mation and can then give access to the PZC. This is dem-
1.0
onstrated below for polycrystalline, 111 and 110 single
crystal silver electrode in contact with CN- containing 0.5 -0.7V/SCE
neutral solution. Details on the experimental procedure
are given elsewhere [62]. 0.0
1950 2000 2050 2100 2150 2200 2250
After polarization of the electrode at -1.3 V vs. SCE wavenumber (em")
for 15 min, SFG spectra were acquired at fixed potential,
increasing from -1.2 V to an upper limit below the silver Figure 21 SFG (circles) spectra of Ag electrode (continuous
dissolution, in a spectral range extending between 1950 line: results of the fits) in contact with an aqueous electrolyte
and 2250 cm- 1, within the CN- stretching vibrational consisting of 0.1 M NaCl0 4 and 0.025 M KCN at E= -1.2,
mode [12,63]. -1.0, and -0.7 V vs. saturated calomel electrode.
338 Tadjeddine and Le Rille

where the symmetry is broken, hence to bring direct As already stated, fit ofSFG spectra ofCN- lAg leads
spectroscopic information on the adsorbed species. to one resonance interfering with a potential dependent
However, one should note the capability of IR nonresonant signal. The latter contribution can be
spectroscopy to detect solution species in the vicinity of written, using Eqs. (32) and (36), as
the electrode surface that provides additional infor-
mation on the vibrational properties of the interface. x~~ ~ i . Y + rx . (Ede - E pze ) + <5 (52)
The dependence ofthe magnitude and the width ofthe
SFG resonance with the electrode surface orientation As demonstrated for SHG [66], <5 can be neglected in
and the electrode potential is analyzed elsewhere [12,62]. our experimental conditions, leading to
We discuss here only the nonresonant signal and its corre-
(53)
lation to the PZc.
Figure 22 shows the imaginary (a), the real (b) the
1. Determination of the PZC by SFG amplitude (c), and the phase (d) of the nonresonant sus-
ceptibilityas a function of the electrode potential. qJ and
The quantitative analysis of the structure of the electro-
C are given by Eqs. (54) and (55), respectively.
chemical interface requires the knowledge of the surface
charge, particularly the PZc. For dilute solution on
nonadsorbing ions such as CIO;;- on silver, the PZC is (54)
readily obtained from capacitance measurements.
However, there is no electrochemical technique able to
give directly the PZC in the presence ofstrongly adsorbed tan qJ ~ y (55)
rx . (Vde - Vpze )
ions [42,65]. An attempt has been made to derive the
PZC from the nonlinear optical response [65].We address As predicted by Eq. (53), the imaginary part of the
in this section SFG as a valuable tool for a direct determi- nonresonant susceptibility is constant, and its real part
nation of the PZC in concentrated electrolytes and in increases with the potential and is equal to zero at the
the presence ofa strong ionic specific adsorption. PZc. The amplitude of the nonresonant susceptibility

·0.4 E • • • • • • •
-0.2 [ a: imaginary part 01 the nonresonant
0.0

0.4 ICN/A9 I
0.2

0.0

-0.2

-0.4

0.6

0.4

0.2 d: module 01 the nonresonant

0.0 ........~...............L....................-L..~.....:J!'-1.............~....................-'-.......L~~-'-'- ..........~......J. ..........~........J
-'.2 ·1.0 -0.8 ·0.6
polential (ViSCE)

Figure 22 Potential dependence of imaginary part (a), real part (b), phase angle (c), and amplitude (d) of the nonresonant contri-
bution to the SFG susceptibility of Ag electrode (continuous line: results of the fits) in contact with an aqueous electrolyte consisting
of 0.1 M NaCl04 and 0.025 M KCN. Data are the results of the fits of the SFG spectra. The vertical arrow indicates the PZC and the
0
horizontal arrows indicates when the real part ofthe nonresonant is zero (b), when its phase angle is 90 (c), and when its module is mini-
mal (d), respectively.
SFG/DFG at Electrode Surfaces 339

Table 6 Potentials of Zero Charge Without CN- (Aqueous Electrolyte Consisting of NaCI0 4 100 mM)
[42,60] and with CN- (Aqueous Electrolyte Consisting of NaCI0 4 100 mM + KCN 25 mM) [12,42] for
Different Silver Electrodes
Crystallographic orientation Ag(IlO) Ag(100) Ag(lll) Ag(poly)
PZC without CN- (ViSCE) -1.0 [60] -0.9 [60] -0.7 [60] -0.95 [42]
PZC with CN- (ViSCE) -1.15 [12] -1.00 [12] -1.2 [12]
-1.05[42]

displays a well-defined minimum, located at the PZC, in
agreement with Eq. 54 and in accordance with the
behavior previously observed in SHG [65,66] and SFG
[42]. Finally, Eq. (55) predicts a phase q; of ± 90° at the
PZC, in agreement with the experimental data of Fig.
22d. It is worthwhile to note the unique advantage of
SFG to give access to the phase q;, which comes from the
interference between the nonresonant and the resonant
SFG signal. This interference effect has a drastic influ-
ence on the shape of the SFG signal, as shown in Fig. 21.
The SFG spectrum is symmetric at the PZC where the
phase is equal to 90 and asymmetric for q; i- ± 90°,
0
[71,72]. Brolo et al. [73] were able to record SERS spectra
of pyridine adsorbed on an unroughened Au(21O)
single-crystal electrode. However, the signal from the
bulk molecules can hide that of the adsorbed molecules
and careful data treatment is needed to extract the
interfacial spectrum from the overall signal. We have
studied the adsorption of pyridine at the
Au(ll1)-electrolyte interface by DFG in the spectral
range of the ring mode vibrations [74]. CLIO as a tunable
IR source has enabled us to investigate the ring vibrations
of pyridine around 1000 cm- I .

1. Five Modes of Vibration of the Pyridine Around

addressing the phase q; as a very sensitive probe of the
10/lm
PZC
Table 6 sums up the PZC of Ag(hkl) obtained by SFG Figure 23 shows the DFG spectrum recorded for Au(lll)
in CN- containing [12] and by capacitance measure- in contact with a solution of 0.1 M NaCl0 4 +0.002 M
ments in CN- free NaCl0 4 solution [60], along with data pyridine, at a potential of +0.3 V, between 900 and
obtained byTadjeddine et al [42] on polycrystalline silver 1150 cm- I . The experimental data were best fitted with
in contact with both electrolytes.
There is no measured value ofthe PZC ofsilver in con-
tact with of pseudohalide ions. Our results show clearly
the expected negative shift of the PZC upon CN-
adsorption.
2

D. Adsorption of Pyridine on Gold, Studied by

DFG
Pyridine has been extensively used as a model compound
for the study of bonding and coordination with metal
surfaces. This molecule contains a delocalized p-electron
system and a lone pair located on the N atom, both of
which participate in bonding. As early as 1971, Chao et o
al. [67] inferred from ellipsometric measurements a
change of the pyridine bonding on polycrystalline gold
electrode, from a flat line at negative potential to a vertical
orientation at positive potential. The potential depen- -I
dence ofthe adsorption geometry ofpyridine on Au(hkl) 900 950 1000 1050 II 00
electrodes has been studied by Stolberg et al. [68-70]. IR wavenumberlcm-
I

They found that the molecules adsorb in a flat orientation

at negatively charged surfaces and in an N-bonded verti- Figure 23 DFG spectrum ofAu(lll) electrode in contact with
cal orientation at positively charged surfaces. Therefore, (0.1 M NaCI0 4 + 0.002 M pyridine) at E = + 0.3 VlSCE. Also
pyridine undergoes a phase transition at PZc. Pettinger shown are the six bands obtained after deconvolution of the
et al. [71,72] also investigated this transition, using SHG DFG spectrum [74].
340 Tadjeddine and Le Rille

five resonances at 981, 1008, 1028, 1050, and 1092 cm-I.
Figure 23 also shows the deconvolution of the DFG
spectrum into five absorption bands.
2. Assignment of the Vibrational Modes
The pyridine molecule belongs to the C Zv point group
with two orthogonal mirror planes containing the C2
axis. The 27 fundamental modes of vibration of liquid
pyridine taken from and labeled following Corrsin et al.
[75] are listed in Table 7. They consist oflO A] , 3 A 2 , 9 B],
and 5 B2 , modes. In the gas phase, the A], B], and B2
modes are both Raman an IR active, the A 2 modes being
only Raman active. The Al and B1 modes account for
the in-plane vibrations, whereas the A 2 and B2 modes
represent the out-of-plane vibrations. The frequencies of
the bands observed for adsorbed molecules are likely to
be different from those of the free molecules due to their
electronic interactions with the metal.
The bands at 1008 and 1028 cm-] are in good agree-
ment with those obtained by Brolo et al. [73] on Au(21O).
They are assigned to the symmetric ring breathing mode
1 and the asymmetric ring breathing mode 12,
respectively. The bands at 1050 and 1092 cm- 1 are
assigned to the modes 18a and 18b, respectively. These
two modes have the same frequency of 1068 cm- 1 in
liquid pyridine. The band at 981 cm- 1 can be assigned
to the A 2 mode, which is IR inactive in the gas phase.
However, it has a weak IR activity in the liquid phase
[75,76], which explains the observed DFG spectrum.
3. Geometry of the Adsorption of Pyridine on Gold
The symmetry of the modes observed in the vibrational
spectra can give information on the adsorption geometry
of the molecule. For a given geometry, a mode will be
observed if it gives rise to an IR dynamic dipole normal
to the surface. The atomic displacements have been given
for each mode of vibration of pyridine by Long and
Thomas [77]. Pyridine can be bound perpendicular to
the surface via the N atom, in a way retaining both sym-
metry planes. In this case only A] modes will be
observed. The molecule can lie flat on the surface, the
mirror plane perpendicular to the molecular plane being

Table 7 Vibrational Frequencies of Liquid Pyridine [74,75]

Symmetry Notation Mode description Frequency (cm -1)

Al 6a In-plane ring distortion 605

I Sym ring breathing 992
12 Asym ring breathing 1029
18a C-H in-plane bend 1068
9a C-H in-plane bend 1218
19a C-C, C-N stretch 1482
8a C-C, C-N stretch 1580
20a C-H stretch 3036
2 C-H stretch 3054
13 C-Hstretch 3054
BI 6b In-plane ring distortion 652
18b C-H in-plane bend 1068
15 C-H in-plane bend 1148
3 C-C in-plane bend 1217
14 C-C ring stretch 1375
19b C-C, C-N stretch 1439
8b C-C, C-N stretch 1572
7b C-H stretch 3054
20b C-H stretch 3083
A2 16a oop ring distortion 374
lOa C-Hoopbend 886
17a C-Hoopbend 981
B2 16b oop ring distortion 405
4 oop ring distortion 675
11 C-H in-phase oop bend 703
lOb C-H oop bend 749
5 oop ring distortion 942
SFG/DFG at Electrode Surfaces 341

4. EVOlution of the Adsorption Geometry of the

Front view Side view Dipole Pyridine with the Potential
active
mode
Figure 25 shows the evolution ofthe oscillator strength of
N- B, the 1008- and lO92-cm- 1 bands as a function of the
applied potential. These bands corresponds to the ring
breathing mode 1 (AI) and to the C-H in-plane bend

lOJ
-"- [JJ A, mode 18b (Bd, respectively. We show that our results
are consistent with a reorientation of the molecules that
are adsorbed in a more vertical configuration at
positive potentials than at negative potentials.
(f) [,/ ] A,. B2 The oscillator strength ofboth the A 1 and the B I mode
is constant at negative potential and increases at potential
" positive of +0.05 V, close to the PZc. This behavior
indicates that a reorientation takes place around the PZc.

"
vJ [&J ] AI' BI' B2
Moreover, the activityofa Bl mode is possible only if the
molecule is rotated around the C 2 axis. This conclusion
is further supported by the observed change of the sign
of oscillator strength of mode B I, indicative of a change

~ [_I ] A,. B,
oforientation of the dipole of the vibrational mode.
Our observations are in agreement with the results of
Haq and King [79] for pyridine adsorbed on Pt(lll) in
UHV who found a rotation of the molecule when the

~ [L] A" BI' B2

coverage is increased and with the work of Stolberg et a1.
[68] who observed a phase transition from flat orientation
at a negatively charged interface to vertical orientation
at a positively charged interface.
Figure 24 Front and side views of the different adsorption
configurations of pyridine, with their vibrational dipole active
mode. oscillator strength/a. u.
• •
retained, in which case only out-of-plane modes will be
•
observed. Finally, the molecule can be tilted, due to sim-
ultaneous Nand n-bonding. If the mirror plane perpen-
0.5

•
I • • • •
dicular to the molecular plane is retained, B] modes will • •
not be observed. If the molecule is tilted and rotated
0.0
•
around the C 2 axis, all active modes will be observed.
Our spectra show A I, B], A2, and B2 modes. This means
that the pyridine molecule is bound via the N atom and
is tilted toward the surface and rotated around the C 2 axis -0.5
(Fig. 24). This geometry has been inferred, from AFM
observations, to the orientation of pyridine adsorbed on
heulandite 010 in aqueous solutions [78].
No significant frequency shift of the ring breathing
mode I was detected within our spectral resolution,
-1.0
•
whereas a shift of 10 cm- I V-I was observed for mode
18b.These results are in agreement with the shifts of mode
-800 -400 0 400
1reported for pyridine adsorbed on silver (6 cm- I V-I) Electrochemical PotentiaVm V
[64], on copper (10 cm- I V-I) and Au(21O) (no signifi-
cant shift) [73]. The weak potential dependence of the Figure 25 Potential dependence of the oscillator strength of
mode vibrational frequency is consistent with an the vibrational bands at ca. 1008 cm- L (circles) and at ca.
N-bonded adsorption geometry. 1090 cm- 1 (squares) [74].
342
v. CONCLUSION AND OUTLOOK
The nonlinear optical techniques of SFG and DFG are
now well established as a vibrational probe ofthe electro-
chemical interface. They offer the advantage of being
sensitive only to the interface between centrosymmetric
media, at the submonomolecular scale, and enable absol-
ute vibrational spectra of the electrode to be recorded at
each potential removing the need ofreference state. Com-
bination of these advantages with the time resolution
inherent to short laser pulses has also made possible the
investigation of the vibrational dynamics of the electro-
chemical interface. Exploitation of SFG and DFG for
surface studies is still beginning, and one expects an
increasing use of these techniques in the spectroscopy
and in the dynamics of the electrochemical interface. It
will be of special interest to investigate the kinetics of the
elementary steps involved in an electrochemical reaction.
Moreover, SFG and DFG also carry valuable infor-
mation on the electronic properties of the substrate. We
have shown theoretically and experimentally that the
nonresonant second-order susceptibility is indeed very
sensitive to the electronic transitions of the substrate.
Furthermore, the contribution of the intraband and the
interband transitions to the nonresonant second-order
susceptibility of the substrate are basically different and
their contribution to the experimental SFG (DFG) signal
can be clearly identified. These techniques are then also
a suitable electronic probe ofthe substrate and give access
simultaneously to the potential dependent vibrational
and surface electronic properties of the interface. Thus,
by using a tunable laser in the visible and near Uv, it is
possible to study the electronic properties and to probe
directly the interband transitions of metal clusters by
these techniques.
The complete quantitative analysis of the adsorption
geometry ofpolyatomic species requires the study of sev-
eral vibrational modes, thus the extension of the laser
tunability to the far IR. This is easy to obtain by using a
free electron laser. However, adequate laser systems are
now available commercially, and the continuous
advances in laser technology will certainly further
increase their performances.
ACKNOWLEDGMENTS
We are grateful to Dr. A. Peremans for many discussions
and advice and to the CLIO staff headed by Dr. 1. M.
Ortega.
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T
20
Vibrational Coupling Effects on Infrared Spectra of
Adsorbates on Electrodes
Carol Korzeniewski
Texas Tech University, Lubbock, Texas
ABSTRACT
Infrared spectroscopy is important for interfacial
characterization in electrochemistry. Several reviews
have appeared covering experimental methods and
applications. This chapter focuses on infrared spectra of
strongly bonded adsorbates and some effects that interac-
tions among similarly oriented molecules (vibrational
coupling effects) have on infrared band positions and
intensities. Information about adlayer structure that can
be obtained from spectral changes induced by vibrational
coupling is emphasized. The manner in which vibrational
coupling restricts detection of molecules at different
structural sites on surfaces and at different metal sites on
alloy and bimetallic electrodes is also discussed.
Examples are taken mainly from studies of carbon
monoxide adsorption on electrodes. References to litera-
ture on the physics ofvibrational coupling are provided.
I. INTRODUCTION
Infrared spectroscopy is widely used to investigate
interfacial processes in electrochemistry. The ability to
record infrared spectra of species at the electrode--
solution interface under reaction conditions (in situ),
often with submonolayer sensitivity, has led to advances
in the study of adsorption and electrochemical reaction
pathways. Progress in these areas since the 1970s is
described in several reviews [1-17].
In electrochemistry, in situ infrared spectra are often
used to identitY molecular analytes or assess changes in
their solution concentration or surface coverage. These
345
spectra are also applied to investigate analyte chemical
environment. Molecular chemisorption produces some
of the strongest environmental effects, because bonding
to the electrode surface can induce changes in molecular
geometry and electronic structure. Additional spectral
perturbations can arise from interactions among simi-
larly oriented neighboring adsorbates. This latter effect
is called "vibrational coupling"and can result from forces
between the external electric fields ofadsorbate transition
dipole-moments (known as dipole-dipole coupling)
[16,18-27] and from through-metal chemical bonding
interactions [18,24-26,28].
Vibrational coupling effects in in situ infrared spectra
have provided important information about the arrange-
ment of molecules on electrode surfaces. From these
effects on spectra of adsorbed carbon monoxide (CO),
for example, it can be distinguished whether at low to
moderate coverages the molecules are present in dense
patches or small dispersed islands. This knowledge has
enabled the chemical environment at the metal- solution
interface to be examined during adsorption of CO
[16,18,19,29-33] and electrochemical reactions of species
that progress through adsorbed CO [34-36]. However,
vibrational coupling can also complicate the relationship
between spectral band intensities and adsorbate surface
coverages. This limitation has impacted efforts to detect
molecules adsorbed at different structural sites on
surfaces [16,27,37,38] and at different metallic sites in
mixed metal catalysts [39,40]. For these systems, the
infrared band intensities do not always reflect the
populations of molecules at the different types ofsites.
346
In this chapter, some aspects of vibrational coupling
and its effect on infrared spectra of adsorbates on elec-
trodes are discussed. Emphasis is placed on adsorbed
CO and the relationship between spectral features and
adlayer properties. The use of \2COI l3CO mixtures to
investigate adlayer structure and the study of adsorption
on stepped and bimetallic surfaces are highlighted.
II. BACKGROUND
The importance ofadsorbate intermolecular coupling on
vibrational spectra has been understood since the early
infrared spectroscopy studies of molecular adsorption
on metal catalyst particles [41,42]. Bands associated with
C-O stretching modes of atop CO (CO coordinated to
a single surface atom [Fig. 1] [18,24,26]) were detected.
Coupling was indicated by a shift to lower energy of the
CO spectral bands with decreasing CO surface coverages
and by unexpected intensity ratios for l2CO and l3CO
bands when catalysts were dosed with known compo-
sition mixtures of these isotopes [41,42]. Since this early
work, coupling among adsorbates has been studied under
a variety of conditions ref. 10,13,19,24-27,29-32,37,38,
43-47].
The spectral changes that arise from vibrational
coupling result from collective motions of the adsorbed
molecules [cf. 18,25]. In the absence ofcoupling, the mol-
ecules respond to the infrared radiation field as indepen-
dent oscillators and vibrate at the frequencies
characteristic of the isolated adsorbates. When inter-
molecular coupling forces are present, the molecules
vibrate with a fixed-phase relationship. The modes that
result have transition energies and intensities that are dif-
ferent from those ofthe isolated adsorbates [25].
Spectral changes can be understood further by con-
sideration of the surface selection rule. For molecules
on metal surfaces, the infrared spectral band intensities
are proportional to the strength of the transition dipole
moment normal to the surface, which is determined by
o o
III
C
II
C III.
I I \
M M M Vibrational coupling is observed most often in infrared
Figure 1 Sketch showing adsorbed CO with atop (left) and
twofold bridging (right) coordination.
Korzeniewski
the relative phases ofthe molecular displacements during
a vibrational cycle. For CO, which bonds to transition
metal surfaces through the carbon atom with the C-O
bond axis toward the surface normal [48], the most
intense infrared transitions occur for modes in which
most of the adsorbates have in phase C-O stretching
displacements [25]. This condition is satisfied by the
highest energy modes of molecules in similar
coordination environments [18,25]. Because these
in-phase modes shift to higher energy as the coupling
strength increases, C-O stretching infrared spectral
bands tend to upshift as the distance between CO
molecules decreases (i.e., as the CO surface coverage
becomes greater).
The unexpected l2COI l3CO band intensity ratios
observed in experiments with mixtures of these isotopes
on metal surfaces result from vibrational coupling. The
high energy atop C-O stretching mode is mainly due to
the vibrations of 12CO, but with some contribution from
l3CO ref. 25]. In this high energy mode the C--O
stretching displacements of the 12CO and l3CO mol-
ecules are in-phase. The low energy atop C-O stretching
mode is mainly due to l3CO vibrations but with some
contribution from l2CO; in this case, the l3C-O
and \2C-O displacements are out-of-phase during a
vibrational cycle [25]. In an adlayer with equal numbers
of 12CO and 13CO, vibrational coupling causes the higher
energy mode associated with atop 12CO to have some-
what greater intensity than the lower energy atop l3CO
mode, because the out-of-phase vibrational motion in
the l3CO mode reduces the transition dipole moment
[16,18,25,43]. The disparity in the 12COI l3CO band inten-
sity ratio increases as the intermolecular interactions
become stronger. Similar considerations can explain
unusual intensity effects in infrared bands of CO
adsorbed at different surface structural sites, such as steps
and terraces [cf. 16,37,38,49-51], and CO adsorbed at dif-
ferent metal sites of bimetallic catalysts [39,40].
The sections that follow discuss examples of
vibrational coupling in infrared spectra of adsorbates on
electrodes. For more detailed descriptions of the physics
ofvibrational coupling, several other sources can be con-
sulted ref.
18, and references therein, and 23-26].
EXAMPLES
A. Surface Coverage Effects
spectroelectrochemical studies as coverage dependent
shifts in the C--O stretching modes ofadsorbed Co.This
behavior is depicted in Fig. 2, which shows in situ infrared
L
IR Spectra of Adsorbates on Electrodes 347

forces. Because the dipole-dipole interaction energy

scales as d- 3 , where d is the distance between molecules,
the bands shift to higher energy as the adlayer fills in
2048 1805 [18,23-25,33,49,52].
I
8 I
When the approximate CO surface coverage is known,
0.05 spectral perturbations that result from vibrational
coupling provide insights into the two-dimensional
arrangement of adsorbates on electrodes [10,13,
0.12 19,29,30,33].When the coverage is low, the appearance of
atop and bridging CO bands at the high energy side of
their spectral ranges indicates the CO is present on the
surface in dense patches [19,32,33,53,54]. A downshift in
these bands by 20-40 cm- 1 indicates the CO is in small
0.24 dispersed islands [19,32,33,53,54]. These effects are dem-
onstrated further in Fig. 3 for adlayers formed on a Pt(llO)
2056 electrode with two different dosing procedures. When
I
1816 the CO adlayer was formed by exposing the electrode to
electrolyte solutions that contained CO at dilute levels,
0.30
the atop CO band position shifted by about 50 cm- 1 for
coverages from near zero to saturation. In contrast, when
the adlayers were formed by the oxidative removal of
CO from a saturated adlayer, the atop CO bands showed
little dependence on surface coverage. The responses
suggest that with the controlled dosing technique, CO
populates the surface as small dispersed islands, which
2063 0.39 gradually increase in number and size as the CO

I 2 X 111"3 B.U.
1843
I ofthe interfacial environment during the electrochemical
0.55
Figure 2 on a Pt(lll) electrode in
0.1 M HCl0 4 at the indicated surface coverages. The electrode
potential was 001 Vvs. seE. (From Ref. 19, with permission.)
spectra ofCO adsorbed at different coverages on a Pt(lll)
electrode held at a potential in the double-layer region.
Bands at 2048-2063 cm- 1 and 1805-1843 cm- 1 arise
from modes of CO in atop and bridging coordination
environments, respectively [18,19,47]. The upshift in
transition energy with increasing CO surface coverage
is believed to result mainly from dipole-dipole coupling
surface coverage increases, whereas with the oxidative
treatment, the CO that remains after reaction is in a high
coverage environment, likely consisting of large CO
patches [53].
Knowledge ofvibrational coupling effects on infrared
spectra of adsorbed CO have been valuable for the study
oxidation of CO and other organic molecules
[19,29,30,36]. For CO, the rate ofoxidation appears slower
in adlayers that display stronger intermolecular coupling
[19,55,56]. This dependence is thought to be due to the
inability of water to penetrate dense CO islands and
undergo surface catalyzed activation for the conversion
of CO to CO 2 [19,29,30,55,56]. In organic oxidation
reactions, infrared spectroscopic detection of CO at
specific potentials has enabled determinations of the
extent to which reaction inhibition arises from surface
blocking by adsorbed CO [11,34,57]. Further, the pos-
itions and intensities of the CO vibrational bands have
been used to determine characteristics of the arrange-
ment ofsurface poisons on the electrode [34,57].
More detailed relationships between infrared spectra
and molecular adlayer structure are emerging from the
combined use of infrared spectroscopy and in situ
scanning tunneling microscopy (STM) [17,18,47,58-61].
These studies have demonstrated that the positions and
348 Korzeniewski

• •
20701-~ ~..
/ /::0," .-. • • e-;:?
/' T
,it ,, /
t'
A.~'
",t'
a. ~
~ "
2050 r ,,'
i ,,~
,"
po"
"
E
()
," " ,,
"- 4"6. '
_0
~u
If" 9'
N 6
2030 " ,I
9
I
I
I
I
I

°
I
9'
2010 ,'0
0/

0.2
e
Figure 3 Plot of atop CO peak frequencies vs. CO surface coverage for Pt(llO) in 0.1 M HCl04 at -0.25 V (circles) and 0.05 V
(triangles) vs. SCE. The open symbols represent spectra of CO adlayers that were formed by briefexposure to electrolyte solutions that
contained CO at dilute levels. The closed symbols represent spectra of CO adlayers that were formed by oxidative removal of CO from
a saturated adlayer. (From Ref. 53, with permission.)

intensities of adsorbed CO infrared bands depend disrupts the adlayer symmetry and leads to new infrared
critically on the coupling among molecules in d(fferent active vibrational modes [18,23-26]. Isotope mixtures
coordination environments and on subtle shifts in have been used in infrared spectroelectrochemistry
adsorbate coordination to positions intermediate experiments to measure adlayer interaction force
between atop and twofold bridging [18]. Better under- constants [18], investigate effects of surface structure
standing ofvibrational coupling and its effect on infrared and electrode potential on adlayer characteristics
spectra is developing from these molecular-scale [18,19,37,45-47,62], and compare differences in adlayers
experiments. formed on electrodes and surfaces in ultra-high vacuum
(ORV) [19,47].
Example mixed isotope spectra are shown in Fig. 4.
B. Mixed Isotope Experiments
Spectra are ofvarious 12eo/l3eo mixtures at saturation
Many spectroelectrochemical studies ofadsorption have coverage on a Pt(lll) electrode. For I2eo/l3eo fractions
used isotopically labeled compounds to investigate between 0.07 and 0.61, the separate atop e-o stretching
adlayer physical properties. Isotopic substitution bands between 2000 and 2100 cm- 1 are associated with
IR Spectra of Adsorbates on Electrodes
1 0 .002
0.13
0.07
0.00
2200 2100 2000 1900 IBOO 1700
Wavenumber em-I
Figure 4 Infrared spectra from mixtures of IlCO and 13CO
on Pt(lll) in 0.1 M HCI04 at +0.1 V vs. SCE. The numbers
above each spectrum are the IlCOI 13CO fraction. (From Ref.
18, with permission.)
modes of the different isotopes. As described in Sec. II,
bands at high and low energy mainly arise from the
vibrations of l2eo and l3eo, respectively. One conse-
quence of vibrational coupling is that the intensity ratio
for the two bands does not coincide with the isotope com-
position in the adlayer. For all IleOI l3eo fractions
above 0.13, intensity shifts in favor of the higher energy,
l2eo, band.
Severson et al. [18] demonstrated the striking
sensitivity of Ileo and 13eo spectra to potential induced
adlayer rearrangements. In this work, infrared spectral
349
features and specific adlayer structures were correlated
with in situ STM. Knowledge of the adlayer structures
allowed the coupling force constants to be determined
from the mixed isotope spectra.
Mixtures of IleOI l3eo isotopes have recently been
used to explore interactions among adsorbates at differ-
ent structural sites on surfaces [37]. On smooth Pt(lll)
electrodes, the dipole-dipole coupling was observed to
increase uniformly in proportion to the CO surface
coverage. However, on Pt(s)-[4(1ll)x(100)] (Pt(335))
electrodes, the coupling was weak at low coverages, as
molecules ordered along step edges, then increased
sharply as the adlayer started to occupy and grow across
the short (lll) planes [16,37].
C. Adsorption of CO at Different Structural
Sites on Surfaces
1. Surfaces with Steps and Terraces
Adsorption of CO at different surface structural sites
(i.e., steps, kinks, and terraces) has been studied in
detail with infrared spectroscopy [cf. 37,38,51,63,64].
Initial efforts investigated the coverage dependence of
CO at Pt(335) in UHV [49,52,63,65]. Similar to the
perturbations that arise in adlayers comprised of two
different CO isotopes, the infrared band intensities of
CO molecules adsorbed at different structural sites, such
as steps and terraces, do not reflect the CO coverages
at these sites. The spectra in Fig. 5 demonstrate this
effect. The atop CO band near 2020 cm -I in the lowest
coverage spectrum in Fig. 5 is associated with CO at
step edges (edge-CO). At 818max =0.49, CO occupies
both steps and terraces as indicated by the splitting in
the atop CO band. The higher energy feature in the atop
CO band pair grows as the CO coverage increases.
However, at saturation (8 I 8max = 1.0), only one atop fea-
ture appears even though CO is present at both steps
and terraces.
The vibrational modes that result from coupling
between CO molecules at step and terrace sites consist
of e-o bond stretching displacements for both types
of adsorbates. Because the highest energy mode has the
most in-phase atomic motion and the strongest transition
dipole moment normal to the surface, intensity shifts into
this band as the adlayer grows (vibrational coupling
increases). Similar considerations apply to the bridging
CO bands at 1800-1880 cm- I .
Shifts in band frequency also provide insights into
CO adlayer structure. The plot in Fig. 6 compares the
atop CO band positions with the fractional CO surface
coverage for adsorption on Pt(335) and Pt(557)
electrodes. In all cases, coupling causes a gradual
350 Korzeniewski

I4x10-4 au 2070 j Pt(557)/CO I

r .2067
• ••
XOo1L 1877
I

---"---__ 1.00
8/8 max

";"
2050 1

444
•
JJ •
2030 J::JJt. 4 4
E 4

x 0.25
CJ
en
0::
w 2010
1 lJi.
&4

0.60 m
:E
~
z Pt(335)/CO
w
2051 2030
> 2070]
• ••
, I
1801
~ • •
0.49 2050 •
AA
2030
x3 AAAA
0.16
2010
I .-
2000 1800 o 0.2 0.4 0.6 0.8 1.0
WAVENUMBERS, em-1 FRACTIONAL COVERAGE

Figure 5 Spectra of CO adsorbed on a Pt(s) - [6(l1l) x (100)]
electrode. The surface coverages are expressed as a fraction of
saturation (8/ 8max ). Spectra were recorded with the electrode
at +0.1 V vs. SCE in 0.1 M HCl04. (From Ref. 38, with
permission.)
Figure 6 Plot ofatop CO band energy as a function ofthe CO
surface coverage expressed as a fraction relative to saturation.
The top and bottom panels report results for CO adsorbed on
Pt(s) - [4(l1l) x 100] and Pt(s) - [6(1ll)x (l00)], respectively.
The open triangles and closed squares mark the positions of
the low and high energy atop CO vibrational modes,
respectively. (From Ref. 38, with permission.)

upshift in the atop CO band energy. However, the cover-

age range over which the separate branches of the
"edge-" and "terrace-CO" features are detectable is
larger for Pt(557) than Pt(335). The response indicates
the intermolecular coupling is weaker on the surface
with wider terraces and suggests that once the edges fill
CO occupies the terraces on platinum at random rather
than by ordering in sites adjacent to molecules on the
edges.
2. Bimetallic Surfaces
Infrared spectra ofmolecules adsorbed on surfaces com-
posed of two or more metals can be influenced by
vibrational coupling. The effects have been characterized
most quantitatively for CO adsorption on bimetallic
surfaces in DHV [39,40]. }n electrochemistry, vibrational
coupling among molecules adsorbed at different metal
sites can become important in in situ infrared
spectroscopic studies of underpotential deposition [cf.
66-68] and bimetallic electrodes [69].
Figure 7 demonstrates some effects of vibrational
coupling for CO adsorbed on Pt(1l1) containing partial
monolayers ofcopper.The bottom spectrum is each panel
a, b, and c shows atop CO bands for saturation coverages
of Co. When the copper coverage is below 1/3 monolayer
(Fig. 7a and b), bands assignable to CO on platinum sites
(2095-2098 cm- I ) and copper sites (2137-2132 cm- I )
can be observed, although in each case the modes are
likely perturbed weakly by CO molecules on the opposite
metal. These coupling interactions become more appar-
ent when the copper coverage exceeds 2/3 monolayer
(Fig. 7c), in which case separate PtiCO and Cu/CO bands
are not observable. In the bottom spectrum of Fig. 7c,
IR Spectra of Adsorbates on Electrodes 351

IV. SUMMARY
(c) CO/Cu/Pt(111 )
Infrared spectroscopy is a valuable technique for the
2096 study of adsorbed molecules on electrodes. However, for
adlayers comprised of similarly oriented adsorbates,
9cu = 0.68,270 K 10.5%
effects of vibrational coupling need to be considered in
spectral interpretation. Because of intermolecular
9cu = 0.68, 100 K interactions, infrared spectra of adsorbates on surfaces
that have different coordination atoms, or different types
w of metal atoms, may only reflect a certain population of
(,) (b) the adsorbates. Nevertheless, vibrational coupling effects
Z
<
a:l
in spectra ofmolecules on surfaces can also provide infor-
a: 9cu = 0.29, 270 K I 0.5%
mation about the strength of the intermolecular forces.
otJ) These can be investigated with mixtures of two different
a:l isotopes of an adsorbate. Experiments with 12CO/DCO,
< 9cu = 0.29, 100 K in particular, have provided valuable insights into effects
ofelectrochemical environment on adsorbate structure.
(a)
REFERENCES

9cu = 0.12, 270 K
2098
9cu = 0.12, 100 K
2100 1900
2300
WAVENUMBER, cm-1
Figure 7 Infrared spectra for CO at saturation coverage on
Pt(lll) surfaces containing 0.12 (a), 0.29 (b), and 0.68
monolayers (c) of copper. The Cu adlayers were deposited on
Pt(lll) at 100 K. The bimetallic surfaces were then exposed to
50 Langmuirs of CO at 100 K and infrared spectra were
acquired. These spectra are displayed in the bottom of each
panel. After spectral acquisition, the surfaces were flashed to
270 K to desorb the CO adsorbed on Cu sites, and a new set of
IR spectra was taken at 270 K. The spectra obtained at 270 K
are displayed at the top of each panel. (From Ref. 39, with
permission.)
the infrared active modes of the atop CO species
appear within the broad feature peaked at 2124 cm- I .
The lower energy pt/CO atop band, expected near
2095-2098 cm- I , is seen only after flash desorption of
CO from the copper at 270 K (Fig. 7c, top). The removal
of CO from the copper eliminates coupling between CO
molecules on Pt and Cu and restores intensity to the
Pt/CO band at 2096 cm- I . In each case, for spectra in
Fig. 7a, b, and c, desorption of CO from the copper sites
at 270 K produces an increase in the Pt/CO signal at
2100-2096 cm- I . This screening of CO on one type of
metal by CO on sites of a different metal greatly limits
knowledge ofthe distribution ofmolecules on the surface.
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21
A Fourier Transform Infrared Spectroscopy Approach to
Double-Layer and Electrocatalysis Problems
Teresa Iwasita
University ofSao Paulo, Sao Carlos, Brazil
Elena Pastor
University of La Laguna, La Laguna, Tenerife, Spain
ABSTRACT
The adsorption behavior ofseveral acids, as evidencedvia
in situ Fourier transform infrared spectroscopy, features
some important properties of the platinum surface at
the electrochemical interface. Acids having a very weak
proton-donor character in solution, dissociate upon
adsorption at Pt(hkl). This behavior, which is enhanced
at increasing positive potentials, can be extended to the
adlayer of water, as judged by results on adsorbed water
at Pt(lll). Electrocatalytic phenomena are discussed in
the light ofthe gained information on the electrochemical
interface. Data on the oxidation of small organic mol-
ecules correlate very well with a model suggested for the
interaction of water with the Pt surface.
I. INTRODUCTION
Vibrational spectroscopy has contributed, to a great
extent, to the advance in electrochemical surface science
attained in the last years [1-3]. In situ Fourier transform
infrared (FTIR) data on the interface in equilibrium
reflect the effect of potential on the chemical bonds of
reversibly adsorbed species. Under nonequilibrium
conditions, i.e., under conditions of current flow,
IR spectroscopy affords valuable information on
electrocatalytic processes. Both these aspects are dis-
cussed in the present work. We discuss examples on the
adsorption behavior of weak acids at Pt(hkl) and on the
353
adsorption of water at Pt(lll). We then analyze data on
the oxidation of small organic molecules at Pt(lll) and
discuss electrocatalytic phenomena in the light of the
gained information on the electrochemical interface.
II. ELECTROCHEMICAL INTERFACE IN
EQUILIBRIUM
The structure of the electrochemical double layer is a
central issue in electrochemistry. Basically, the double
layer consists ofa charged solid surface in contact with a
polar solvent (e.g., H20) and electrochemically inert ions
(e.g., SO~-, PO~-, CIO;, H30+, K +), i.e., species being
stable over wide ranges ofpotential, which can reversibly
interact with the surface as the potential is changed within
given limits. Figure I illustrates the cyclic voltammetry
response of Pt(lll) in the absence of strongly adsorbable
ions (0.1 M HCl0 4 ) (a) and in the presence of adsorb-
able sulfate species (0.05 M H 2S0 4 ) (b). The features
characterizing well-ordered Pt(lll) electrodes in both
these media have been described in detail elsewhere
[4-6]. Briefly, the charge between 0.05 and 0.40 V in Fig.
la corresponds to adsorption-desorption of hydrogen,
the region between ca. 0.50 and 0.85 V has been called
unusual states of the voltammogram; the peak at 1.06 V
is related to the adsorption ofabout 25% ofa monolayer
of oxygen [7]. The unusual states shift negatively in the
354
I
(a) ~ 100~
100l II
501- II I \
1 If
0
\ /\ J l
~
::L
-..
-f~
r
-50 RHE
-100
Figure 1 Cyclic voltammograms for a Pt(lll) electrode in (a) 0.1 M HCl04 solution and (b) 0.05 M H 2 S04 solution. Sweep rate,
0.05 V . S-I.
presence of adsorbable anions in solution as observed in
Fig. lb for sulfuric acid. It has been shown for several ani-
ons [3,8-10] that the onset of adsorption at Pt(lll)
coincides with the beginning of the unusual states. The
latter are related to a partial transfer of charge between
the adsorbed species and the metal surface [11]. In other
words, adsorbed anions undergo a reversible redox
process upon adsorption. However, in HCl0 4 solutions
(Fig. la), a pH-dependent unusual state is observed,
although perchlorate ions practically do not adsorb. IR
spectroscopy data presented here shed some light on this
issue, whose interpretation has been the subject of
discussions over many years [4-6]. The behavior of plati-
num toward the adsorption of acids having different
strengths as proton donors shows a fundamental
behavior of the metal at the electrochemical interface,
which can clearly be differentiated from that of the clean
metal-gas interface as studied in vacuum. Weak acids
can thus be taken as test substances to monitor
physicochemical properties of the charged metal-
solution interface. Examples of this are given below,
via the analysis of IR data for trifluoracetic acid, acetic
acid, and dissolved CO 2 interacting with Pt(hkl)
single-crystal electrodes. It is further shown how the dis-
sociative behavior of these weak acids can be extended
to the dissociation of water in a model for H20 adsorp-
tion at Pt(lll). Finally we discuss the consequences of
the interfacial properties of water on classic problems of
electrocatalysis.
Iwasita and Pastor
50
C}I
E
0
~
I ~ I I 0.2 0.4~/O.8 1.0
-50
-100
A. Adsorption of Anions
1. Trifluoracetic and Acetic Acid
Figure 2 shows the voltammograms obtained with
well-ordered Pt(100), Pt(l1O), and Pt(lll) electrodes in
(a) 10-2 M CF 3COOH and (b) 10-2 M NaCH3C02 sol-
utions using 0.1 M HCl0 4 as a base electrolyte. Note
that due to the presence of HCl0 4 , the acetate solution
has a pH ~ 1; under these conditions, undissociated
acetic acid molecules are the prevailing species in
solution. The sharpening of the adsorption states in the
hydrogen region at Pt(100) and Pt(l1O) suggests that
desorption of hydrogen is prompted by the adsorption
of the acids (or their respective anions). Furthermore,
the adsorption lowers the potential limit of the unusual
states in the voltammogram ofPt(lll) [9,10]. Several fea-
tures in the voltammograms can be taken as an indi-
cation of the differences in the strength of adsorption
of both acids: at Pt(100) and Pt(llO), the peak current
density for hydrogen desorption is higher for acetic acid
than for trifluoracetic acid; it has been shown that at
Pt(100) and Pt(l1O) the voltammetric charge related to
the partial charge transfer of the adsorbate is higher for
acetic than for trifluoracetic acid [10]; at Pt(lll),
residual features related to the anomalous states in pure
HCl0 4 , are observed in the presence of trifluoracetic
acid. Summarizing, these observations indicate that
the Pt surface interacts more strongly with acetic than
with trifluoracetic acid.
FTIR Approach to Double-Layer and Electrocatalysis Problems 355

Figure 2 Cyclic voltammograms for Pt(100), Pt(llO), and Pt(lll); v = 0.05 V s-1 in (a) 10- 2 M CF 3 COOH + 0.1 M HCl0 4 solution
and (b) 10- 2 M NaCH 3C0 2 + 0.1 M HCl0 4 solution. Dashed line: cyclic voltammograms taken in the supporting electrolyte [9,10].

To characterize the nature of the adsorbed species,
FTIR spectra were obtained in the respective solutions
using p- and s-polarized light [9,10]. Typical spectra for
Pt(100) are shown in Figs. 3 and 4 for trifluoracetic and
acetic acid, respectively. The positive-going bands at 1682,
1435,1262,1200, and 1150 cm- I in Fig. 3a are associated
with the consumption of trifluoracetate species upon
adsorption at 0.80 V (reference potential = 0.10 V) [10].
The negative-going band at 1224 cm- I in the spectrum
taken with p-polarized light, which is not observed with
s-polarized light, is assigned to the adsorbed species. In
Fig. 4a the positive-going bands at 1715, 1388, and
1278 cm -1 are assigned to acetic acid in aqueous solution
[9]. These bands are caused by the depletion ofacetic acid
in the cavity of the thin layer as the potential is switched
from the reference (0.10 V) to the adsorption value
(0.80 V). The band at 1424 cm- 1 appears only in the
spectrum taken with p-polarized light and is related to
the adsorbed species.
Acetate ions in solution present the v(CO) mode,
356 lwasita and Pastor

(a) (b)
1200

f5
....
....

Pt(110)

1110
RJRo = 0.001
1224
RJRo =0.001

2000 1500 1000 2000 1500 1000

1
Wavenumber I cm-
1 Wavenumber I cm-

Figure 3 (a) IR spectra for Pt(lOO) in a 10- 2 M CF 3COOH + 0.1 M HCl0 4 solution obtained at 0.80 V (reference
potential = 0.10 V); 1024 scans for pand 3072 scans for s-polarized light. (b) IR spectra for Pt(hkl) obtained with p-polarized radiation
in a 10- 2 MCF 3COOH + 0.1 M HCl0 4 solution at 0.80 V (reference potential = 0.10 V for Pt(lOO) and Pt(lll). andO.OS V for Pt(lIO));
1000 scans [10].

related to the symmetric stretching of the COO group at
1414 cm- I [12]. Also, bridging and bidentate acetato
complexes [13] present bands in the 1400-cm- 1 region as
shown in Table 1. It is therefore reasonable to relate the
band near 1420 cm- 1 in the spectra of Fig. 4 to twofold
coordinated (bridge or on top) acetate ions, bonded to
the surface by the COO group.
In a solution containing 10-2 M CF3COOH + 0.1 M
HCl0 4, the (CF 3COO-)/ (CF 3COOH) ratio is ca. 3
(pK a = 0.5 [14]). Therfore, both the nondissociated acid
and the salt could be expected to become adsorbed.
However, in the spectra of Fig. 3, there is no indication
of the presence of nondissociated trifluoracetic acid at
the surface, e.g., no feature in the spectrum can be related
to v(C=O) of the carbonyl group. There is a difficulty
for establishing the nature of the adsorbate, because the
C-O stretching oftrifluoracetate ions in solution is very
weak [15] (Fig. 3, band at 1435 cm- I ) and it could also be
very weak for the adsorbed species. However, the band
around 1220 cm- I , which is related to the v(C~F)
stretching vibration [16], can be of aid for the identifi-
cation of the adsorbed species. Its strong intensity
indicates that the dipole moment of the CF3 group lies
perpendicular to the electrode surface and suggests for

..I.......-
FTIR Approach to Double-Layer and Electrocatalysis Problems 357

(a} (b)

1278

Pt(110)

1424

RlRo =0.001
RlRo = 0.001
1640 1107

2000 1500 1000 2000 1500 1000

Wavenumber I em -1 Wavenumber I em -1

Figure 4 (a) IR spectra for Pt(lOO) in a 10- 2 M NaCH3C02 + 0.1 M HCl0 4 solution at 0.80 V (reference potential = 0.10 V); 1000
scans for p- and 2000 scans for s-polarized light; resolution = 8 cm -1. (b) IR spectra for Pt(hkl) in a 10- 2 M NaCH3C02 + 0.1 M
HCl0 4 solution at 0.80 V (reference potential = 0.10 V for Pt(100) and Pt(lll), and 0.05 V for Pt(lIO)); p-polarized radiation; 1000
scans; resolution = 8 cm -1 [9].

the adsorbed species a symmetry similar to that of metal

trifluoracetate complexes, exhibiting a bridging structure Table 1 Fundamental Modes of Some Acetate and
(see Table 1). On this basis, it is very likely that the surface Trifluoracetate Complexes [13]
species are CF 3COO- ions, bonded to the electrode sur-
Complex
face through the oxygen atoms of the COO group.
Although on the mere basis ofadsorption equilibrium Bidentate
it is not surprising to find mainly the dissociated form of RuH(02CCH3)(PPh 3)2 1526 1451
trifluoracetic acid at the electrode surface, the presence Mn(02 CCH 3)(COh(PPh 3h 1520 1437
of adsorbed acetate ions in the case of acetic acid Bridging
(pK a = 4.75 [17]) cannot be readily justified. Note that in [RU(02CCH 3)(COhpyb 1540 1415
the solution used above (pH~I), the concentration of [Rh(02 CCH3)2Pyb 1590 1430
[Ag(02 CCF3)b 1623 1454
acetate ions is ca. 10- 6 M. Thus, the primarily adsorbed
[Mo(02CCF3)b 1592,1572 1459
species could be acetic acid molecules, but in the
358
adsorbed state, the electron density on the oxygen atoms is
probably polarized toward the metal surface, and proton
dissociation would be facilitated. If, in addition, a partial
charge transfer occurs, the tendency of the acid to dis-
sociate can be additionally enhanced at the surface, par-
ticularly at increasing positive potentials. This may be
the main difference in adsorption behavior between the
metal-gas and the (charged) metal-solution interface.
At Pt(111) in ultra-high vacuum (UHV), electron
energy-loss spectroscopy (EELS) data show that acetate
is the species adsorbed at coverages e < 0.3, whereas both
acetate and acetic acid are coadsorbed at e > 0.5 [18]. In
contrast, no band indicating the presence of
un dissociated adsorbed acetic acid has been observed
the electrochemical environment over a wide range of
potentials (0.10-1.40 V) [9].
2. Adsorption of Carbonate-Bicarbonate
Single-crystal Pt(lll) electrodes in contact with a CO 2
containing solution exhibit a striking difference in
behavior as compared with the other two low-index
planes Pt(11O) and Pt(100) [3]. The latter surfaces are
active for the reduction of CO 2 to adsorbed CO via
adsorbed hydrogen [19,20], whereas Pt(111) is inert
toward this reaction. The differences in behavior of these
surfaces are attested by both cyclic voltammetry and IR
spectroscopy as illustrated in Fig. 5,a - f. After holding
the potential at ca. 0.10 V in the CO 2 saturated solution,
the voltammograms of Pt(100) and Pt(llO) exhibit the
characteristic current peak for CO ad oxidation (Fig. 5b
and c, solid lines), and the respective spectra show bands
for adsorbed carbon monoxide near 1835 and 2050 cm- 1
(Fig. 5e and 0. The stationary voltammograms for these
surfaces obtained in a 0.1 M HCI0 4 solution saturated
with CO 2 (Fig. 5b and c, dashed lines) approach those
obtained in the absence of CO 2 • In contrast, the station-
ary voltammogram for Pt(1ll) in the presence of CO 2
(Fig. 5a, dashed line) exhibits a clear modification of the
anomalous states, which do not exhibit the spike at 0.78 V
and are shifted toward lower potentials, as expected in
Table 2 Fundamental Modes of Some Carbonato Complexes [21,23]
Complex vI(cm- 1) v2(cm- l )
Monodentate v,(C0 2 ) v(C-O)
[Co(NH 3)sC03]CI 1488 1062
[Co(NH3 )sC03]CI0 4 1471
Bidentate v(C-O) v(C0 2 )
[Co(NH 3h C03]CI 1590 1043
[Co(NH 3)4C03]CI 0 4 1602
Iwasita and Pastor
the case of specific adsorption of anions (compare with
Fig. 1). Besides this, the Pt(111) surface shows low activity
toward CO 2 reduction: Holding the potential for 5 min
at full hydrogen coverage results in a small current peak
for CO oxidation, whose charge corresponds to adsorp-
tion on defect sites [19]. In agreement with this, the
spectrum obtained under similar conditions shows no
band for adsorbed CO but features at 1328, 1455, and
1537 cm- l (Fig. 5d). These frequencies coincide with
those of carbonato complexes (Table 2 [21]) leading to
the conclusion that carbonate ions are formed at the sur-
face [22]. The same bands are also present at Pt(llO)
(Fig.5e).
At Pt(111), sample and reference spectra were obtained
at 0.80 and 0.10 V, respectively. The positive-going band
at 2341 cm- 1 indicates the consumption of CO 2 in sol-
ution at the sample potential of 0.80 V, due to adsorption
in the form of carbonate ions. The intensity of the CO 2
band was used to estimate the surface coverage with
adsorbed carbonate species [22]. Accordingly, ca. 4 to 5
10 14 ions· cm- 2 cover the surface at saturation. This rep-
resents roughly 30% of the 1.5 1015 atoms/cm 2 at the
Pt(111) surface.
A series of spectra at different potentials is shown in
Fig. 6, together with the potential dependence ofthe band
centers. The band at 1330 cm- 1 , which is independent of
potential, has been assigned to the symmetric v(COO)
mode of adsorbed HC0 3 ions [22]. The 1400 cm- I
feature, which exhibits a very high slope between 0.55
and 0.70 V, has been assigned to the symmetric v( COO)
of CO~- ions, adsorbed through one oxygen atom. This
assignment is supported by the high v-E slope
(190 cm- I V-I), which could be, at least in part, due to a
high sensitivity of this mode to the environment. Besides
the fact that lateral interactions may be increasing as the
adsorbed layer is formed, the sensitivity of the frequency
to the potential change can be paralleled to the obser-
vation reported by Fujita et al. [23] that crystal water,
adsorbed water, and counter ions markedly affect the
symmetric v(COO) mode in monodentate complexes.
v3(cm- l ) v4(cm- 1) vs(cm-') v6(cm-')
b(C0 2 ) Va (C 0 2) MC0 2) IT
741 1351 694 877
760 1370 690 855
MC0 2) va (C0 2 ) MC0 2) IT
768 1282 673 885
762 1284 672 832
FTIR Approach to Double-Layer and Electrocatalysis Problems 359

(a) (f)
2343
50 I-

IR/Ro =0.001 Pt(111)

J
I I

(b) (e)
"5 400 I- 2057

~ IR/Ro = 0.005
-.
i!:' 200 I- Pt(110)
.U)
c:::
(J)
"C / \
1527 1428

i
::::l
()
2342
1110

200 f-----'--....l..--L.-----'-_....lI_--1
(c)

Pt(100)

2343
I R/Ro = 0.001
-200 I
O~ 02 OA OS O~ 1~ 2500 2000 1500 1000
Potential I V vs RHE Wavenumber I em"

Figure 5 (a)-(c) Cyclic voltammograms for Pt(hkl) in CO 2 saturated 0.1 M HCI0 4 solutions. Stationary voltammogram: dashed
line; voltammogram after holding the potential at ca. 0.10 V: solid line; sweep rate 0.05 V S-l. (d) FTIR spectrum for Pt(lOO) showing
adsorbed Co. (e) FTIR spectrum for Pt(llO) showing bands for CO and carbonate species. (f) FTIR spectra for Pt(lll) showing bands
for carbonate species. Sample spectra were obtained at 0.80 V after application of a potential step from 0.10 V (reference potential)
[19,22].

In this respect, it must be noted that adsorption takes
place in the potential region where pronounced changes
in the interaction of water dipoles with the substrate
occurs (see Sec. II.C). At 0.70 V; the v-E slope abruptly
changes to 25 cm- I V-I. This change occurs simul-
taneously with the appearance of a new mode at about
1530 cm-I and suggests a change in the binding geometry
of the ions from one- to twofold coordination. For such
a geometry, which can be paralleled to that of bidentate
carbonato complexes, v(CO) is expected at about
1590 cm- 1 [21]. Coordination to the surface via two oxy-
gen atoms presents one difficulty for the assignment of
the 1450-cm- 1 feature. In bidentate complexes this mode
appears at 1046 em-I (Table 2). But this frequency region
is covered by the asymmetric stretch of CIO; ions
(1110 em-I). Therefore, a series of spectra was measured
in fluoride electrolyte. However, these showed no
carbonate band near 1046 em-I [22]. Thus, the band at
1450 em-I was assigned to the symmetric stretch of the
group (COO) coordinated to the surface from a potential
of 0.70 Vonward.
An additional argument in favor of the assignment
of the 1450-cm- 1 band to v(COO) mode of twofold
coordinated CO~- ions is given by spectra obtained at
Pt(1lO). In this case, only two very weak features related
to adsorbed carbonate were observed (Fig. 7a). The
360 Iwasita and Pastor

(a) E/V

~0.55

~0.60

~O.~
0.70

0.80

0.90

R/Ro =510-4

1600 1400 1200

Wavenumber / cm- 1

Figure 6 (a) Sequence of spectra for adsorbed carbonate species at Pt(llI) in C02 saturated 0.1 M HCI0 4 solution.
Reference spectrum measured at 0.30 V vs Pd/H 2 . Resolution = 8 cm- l ; p-polarized light; 500 scans. (b) Potential dependence of
band center for adsorbed carbonate species.

potential dependence of the band centers is given in Fig. at Pt(IlO), and the effect oflateral coupling could prevail
7b. Here we observe the high frequency mode at ca. over that of the electric field, causing the frequency to
1530 cm- 1, which is assigned to v(CO) of twofold grow instead ofdecaying.
coordinated carbonate ions as for Pt(lll). The band We conclude that although the thermodynamic equi-
appearing at ca. 1430 ~I presents a negative slope for the librium at (pH ~ 1) strongly favors C02 as the main
potential dependence of the band center. This is the species, both CO~- and HC0 3 having negligible concen-
expected v-E behavior for a group oriented with the nega- trations in solution, both these ions are found as the sur-
tive charge of the dipole toward the electrode surface. face species at Pt(lll). It is very likely that adsorbed
Based on pure electrostatic considerations, it could be carbonate species are formed in a reaction with adsorbed
expected that increasing the potential in the positive water as follows:
direction (i.e., increasing the positive charge on the metal)
would result in an enlargement of the C-O bond [24] CO2 + 2(H 20)ad -+ (HC0 3)ad + H 3 0+
and consequently in a lowering of the vibrational
frequency. The reason for the different potential depen- (HC0 3)ad + (H2 0 )ad -+ (CO~-)ad + H 3 0+
dence at Pt(lIO) and Pt(lll) could lie in the difference of
coverage. The latter is somewhat higher at Pt(lll) than the equilibrium constants favoring the deprotonation.
FTIR Approach to Double-Layer and Electrocatalysis Problems 361

1550 I I
(a) (b)

,....
Eo 1500- -
-....
Qj
.c
E
::::J
c:
~
~ 1450 I- -
-4
RlRo =510
• --I-
1400 L-_ _----IJ ---l.I ---1

1600 1500 1400 1300 0.4 0.6 0.8 1.0

Wavenumber I cm-1 Potential I V vs RHE

Figure 7 (a) IR bands for adsorbed carbonate species on Pt(ll?) at ?80 V in CO 2 saturated ?.l
M HCl0 4 solution. Reference
spectrum taken at 0.30 V vs Pd/H 2 . Resolution = 8 cm- 1 ; p-polanzed lIght; 500 scans. (b) Potential dependence of the band center
for adsorbed carbonate species at Pt(llO).

B. Concluding Remarks on the Adsorption of
Weak Acids at Platinum
In solutions containing weak acids or their salts in strong
acidic media, as a general tendency, weak acids seem to
adsorb at Pt electrodes mainly in the dissociated form,
independently of the nature of the main species in
solution. This has been proved for trifluoracetic acid,
acetic acid, dissolved CO 2 , and, although not shown here,
for other weak acids such as HSOi [8,25] (pK a = 2 [17])
and H2POi [25,26] (pK a = 7.21 [17]). In the latter case,
dissociation is observed after adsorption at Pt(lll) and
Pt(WO), as the potential is positively shifted [26].
Clearly, the Pt electrode strongly affects the acid-base
character ofthe adsorbed species. This effect can be inter-
preted in terms of a Lewis acid character of Pt(hkl),
(justified in part by the high values of the work function)
and the partial electron transfer aided by the applied
potential. This idea is reinforced by the fact that on
Au(111) and Au(100), whose work function values lies
below those ofPt by ca. 0.7 eY, * H2POi does not dissocia te
even at high anodic potentials [25]. At the Pt surface, with-
drawal ofelectrons from the oxygen atoms causes a weak-
ening of the O-H bond and the acids dissociate. The
strength of acid dissociation is further enhanced at
increasing positive potentials. As we shall see in the next
section, this behavior, which can be extended to adsorbed
water at Pt(111), is a key point for understanding the
physicochemical properties of the Pt-so1ution interface
and has fundamental consequences in the electro-
catalytic processes taking place at this interface.
C. Adsorption of Water at Pt(111)
For a complete description ofthe electrochemical double
layer at a molecular level, the structure ofthe solvent plays
a deciding role. The solvent, being the predominant
component in electrolytic solutions, can exert an appreci-
able influence on the processes taking place at the
interface. Because of the unavoidable problem with bulk
contribution, it is a difficult task to obtain in situ IR
spectra of water at the interface, and accordingly,
vibrational data on water at the metal-liquid interface
are not very frequently found in the electrochemical
literature [28-30]. On the contrary, in UHY, the
metal-water (gas) interface has been extensively
explored using vibrational spectroscopy (lR, EELS) [31].
UHV data at Pt(lll) indicate the predominance of
intermolecular H-bonds in icelike structures matching
the pattern of the metal substrate [31].
The characteristic vibrations ofwater are:
' H H/'
'\./
~ / /'\
H
'\. /
H
'\./

°~ 0--+
°~
* Values of the work function (¢): for Pt(lll), 5.93 eV [27a], for
Au(lll), 5.26 eV [27b]. symmetric stretch asymmetric stretch bending
362 Iwasita and Pastor

Table 3 Infrared Frequencies of Water (21,32] E (Vvs RHE)

Aggregation
state
vasym(O-H)
(em-I)
V sym (O-H)
(em-I)
J(H-O-H)
(em-I)
0.1
0.2 ------...............- '---
0.3
Gas 3756 3657 1595
Liquid 3615 3450 1640
Bulk ice 3220 3140-3400 1650
Ads. Pt(111) 3400 (broad) 3400 (broad) 1625
0.45
0.5
The corresponding frequencies in the mid-infrared 0.6
region are given in Table 3 [21,32]. Taking as a reference 0.7
the frequencies in the gas phase, the actual values in the
liquid and solid states are shifted, accounting for the for- 0.77
mation of H-bonds. Thus, the 0 - H stretching frequency 0.8
decreases and the HOH bending frequency increases in
0.9
comparison with the respective values in the gas phase.
1.0
1. In Situ FTIR Spectra for Adsorbed Water at Pt(111)
1.1
A series of reflectance spectra from a pte Ill) electrode in
0.1 M HCI0 4 solution for potentials in the range 1.2
0.10-1.20 V are shown in Fig. 8. Surface and solution
features are superimposed, and most observed
intensity is due to a large contribution from bulk water. RjRo =0.05
However, the surface contribution is shifted toward lower
wave numbers than the solution bands and shows up a
clear potential dependence.
The bands near 3100 and 1600 cm- 1 correspond to the
O-H stretching (VOH) and the HOH bending (b HOH ), 3000 2000
respectively. Between 0.10 and 0.30 V, the spectra present
very low frequencies for the O-H stretch and positive- Wavenumber / cm- 1
and negative-going features for the bending mode of bulk
Figure 8 FTIR reflection-absorption spectra obtained with
and adsorbed water, respectively. Above 0.35 V, the
p-polarized radiation at Pt(111) in 0.1 M HC104 solution.
O-H stretch is shifted toward higher wave numbers,
Sample potentials as indicated, reference potential = 0.05 V;
and the negative-going band for the bending vibration 1040 scans, p-polarized light, resolution = 8 em-I.
becomes stronger and better defined. Besides the main
I
VOH feature, a second stretching band at 3270 cm- is
developed at higher potentials. Other less defined were made at Ru(OOl) [34] and Ni(llO) [35]. On this basis,
features, which are not sensitive to the potential changes, the frequency values for the O-H stretch in the 0.10 to
are observed at higher wavenumbers. 0.30-V range were assigned to VOH of H-down oriented
The O-H stretching appears at frequencies well water molecules at the Pt(lll) electrochemical interface
below the value observed in the Pt(lll)-gas interface [28].This orientation ofthe water molecule can be favored
(Table 3). In particular, at low potentials (0.10-0.30 V), by a negative charge on the metal at these low potentials,
I a hydrogen down orientation being consistent with a
VOH values are very low (around 3000 cm- ). On several
metal surfaces, EELS studies have shown O-H decrease of potential energy of the water dipoles in the
stretching bands for adsorbed water at very low fre- electric field at the interface.
quencies that were assigned to O-H··· M bonds, i.e., In Fig. 9a and b the potential dependence of the band
O-H stretching from water molecules bonded to the centers for both stretching and bending modes is given.
metal through a hydrogen atom. According to Ibach and Below 0.30 V the VOH mode exhibits a negative slope.
Lewald [33], O-H vibrations between 2850 and Between 0.30 and 0.35 Vafrequencyjumpofca.150 cm- 1
3020 cm- 1 at Pt(lOO) can be assigned to O-H··· M toward higher values is observed. It is likely that at about
vibrations. Similar assignments oflow O-H frequencies 0.35 V, a change of water orientation from H-down to
FTIR Approach to Double-Layer and Electrocatalysis Problems 363

3200 Lone pair electrons from the 3a[ and Ib l orbitals (Fig.
•• 10 [37]) are consistently found to take part in the bonding
3150
(a)
• • ••• • • • • of water to metal surfaces [31]. From these orbitals, the
f"
I lb l has nonbonding character and the 3al is partly
I
,
I
bonding and partly nonbonding [38]. It is therefore poss-
3100 I
I ible that in addition to the reason given above, the low fre-
I
,I
quencies are related to electron donation from the 3a[
I
3050 I
I
orbital of the water molecule, which causes a weakening
";"
• • !
I
of the O-H bond. These effects are slightly reinforced

-E
(,) 3000 • at more positive potentials, as shown by the small nega-
tive slope observed above 0.50 V
~
~ (b) ~
,,
.. • The bending mode gives important information on
the metal-water interaction in the potential region

-
1630
~ 0.50-0.80 V The frequency shift toward lower frequencies
,,
I
~
in this region could be an indication ofan increasing par-
~ •
-
1620 I
,
I ticipation of the 3a1 orbital with increasing positive
~ I • potentials. The 3a) orbital occupies a position between
~ 1610
•
I
I
• • • •
,, the two hydrogen atoms (Fig. 10) and produces a
(U I
a:l
screening effect on the proton charges. Therefore,
1600
• ,
I

I
donation of3a1electrons to the surface causes an increase
• ofthe H-O-H bond angle and consequently a decrease
1590 '----_-'----_.,-L--_--'-_----L_----'_ _"'-------' of the frequency for the bending vibration [31,39].
0.2 0.4 0.6 0.8 1.0 1.2
The red displacement of the bending mode indicates
Potential I V vs RHE an increasing interaction of the molecules with the
surface. A comparison of Figs. la and 9b shows the
Figure 9 Potential dependence of the band center frequency coincidence of the frequency shift with the onset of the
for (a) the O-H stretching and (b) the bending mode of unusual states in the voltammogram. In this respect,
adsorbed water on Pt(lll). Data taken from the spectra of Fig. 8. adsorption of water through the oxygen atom at Pt(lll)
can be paralleled to adsorption ofweak acids on Pt(hkl).
Considering water as a weak acid, it would not be
O-down takes place. This reorientation is probably surprising that following the trend of weak acids to dis-
associated with a change in sign ofthe charge at the metal sociate on the Pt surface, adsorbed water molecules dis-
surface, i.e., this result suggests that the potential of sociate on the metal surface forming adsorbed hydroxyl
zero charge of Pt(I11) could lie close to 0.35 V Between
ca. 0.45 and 1.20 V, a very weak band center shift
(dvIdE=-15±3 cm- I y-I) is observed.
The water-dipole orientation at the electrochemical
double layer can be paralleled to the effect ofalkali atoms
on adsorbed water at Pt(lll) in UHY [36]. In this
case, due to a significant charge transfer to the metal
substrate, adsorbed alkali atoms acquire a positive charge.
Under the effect ofthe electrostatic field around the alkali
adatom, coadsorbed water molecules are forced to change
their position from oxygen-down to hydrogen-down [36].

2. Strength of the Water-Metal Interaction

As stated before, the spectral features are strongly affected
by overlapping ofsurface and bulkwater bands. However,
no potential dependence is expected for the latter, and
therefore the sensitivity ofboth VOH and (jHOH to a change Figure 10 Representation of the 3al and Ib l molecular
in potential must be associated with water molecules in orbitals of H 2O. (From Ref. 37. Reproduced with permission of
direct contact with the metal surface. Academic Press.)
364
ions. This process was suggested by Jaaf-Golze et al. [6] to
take place under the unusual states ofthevoltammogram.
Thus, the charge should be related to a partial discharge
of OH- ions, similar to the partial discharge of anions
reported by Orts et al. [11].
At different metals under UHV conditions, (OH)ad
frequencies were observed in a wide range between 3160
and 3680 cm- I [31]. In the UHVenvironment, spectral
data can be obtained for sub monolayers of water, and
under these conditions, the bending mode disappears in
the course of (OH)ad formation, thus facilitating the OH
band assignment. On the other hand, in the electro-
chemical environment, the bending mode persists in the
spectrum due to the presence of nondissociated mol-
ecules (either as adsorbed or as bulk species). Therefore,
the band assignment for VOHad is in this case very difficult.
However, we observe a slow development of a shoulder
at 3270 cm- I in the potential region coinciding with the
anomalous states of the voltammogram. Moreover, it
has been shown [53] that a plot of the band height as a
function of potential exhibits an arrest in this region. In
spite of the difficulty that the band intensity is affected to
a large extent by a bulk contribution, this coincidence of
facts has led to a tentative assignment of the 3270-cm- 1
feature to adsorbed OH- ions.
3. Structure of the Water-Metal Interface
On most of metal surfaces at the metal- gas interface,
water is adsorbed via the lone pair electrons on the oxygen
atom. The 3al orbital sets the molecular plane perpen-
dicular and the Ib l parallel to the metal surface [31]. The
actual angle formed by the molecular plane and the metal
substrate results from the relative contribution ofthe Ib]
and 3al orbitals to the surface bonding. A tilted position
is observed in UHV, which favors the formation oficelike
structures on metal surfaces presenting an hexagonal
pattern [31]. On Ru(OOl), which has a similar surface
geometry as Pt(lIl), a (~3 x ~3)R30° structure was
deduced from LEED data. The corresponding model
consists of a bilayer of water molecules presenting a
tow-dimensional periodicity [40,41].
At the electrochemical interface, the decrease of the
bending frequency (Fig. 9) can be associated with an
increasing participation of the 3a 1 orbital in the surface
bond; this fact reveals an alignment of the water dipoles
under the influence of the static electric field. The
spectroscopic data presented here do not establish the
real structure ofthe water adlayer. However, it is likely that
long-range bilayer patterns as observed at low tempera-
ture in UHV can be ruled out, even at the potential of zero
charge (PZC).
Iwasita and Pastor
In the absence ofa static electric field, adsorbed mol-
ecules are not forced to align perpendicularly to the
surface. Hence, at the PZC (ca. 0.35 V), interaction with
the metal and intermolecular forces do equilibrate and
small H-bonded surface aggregates could be formed. In
addition, molecules in direct contact with the surface
can additionally present H-bonds toward the solution.
Above 0.45-0.50 V, due to the increasing change from
the tilted to the perpendicular position, the formation of
lateral H-bonds is unfavorable. Under these conditions,
the adlayer contains coadsorbed OH- ions from H 20
dissociation. At ca. 0.90 V the maximum of H 20
dissociation is reached and the band center for the
bending mode remains almost constant.
D. Concluding Remarks on Water Adsorption
at Pt(111)
Adsorbed water at the electrochemical interface is
characterized by a strong influence of the electric field.
This determines the orientation of the water dipoles on
the surface and the strength of the water--metal
interaction. The latter increases with increasing positive
potentials and causes dissociation of molecular water to
form OHad in the potential region corresponding to the
anomalous states of Pt(IlI). Like in the case of other
adsorbed anions, OH- becomes reversibly adsorbed in
this potential region. The OH layer is not a Pt oxide
film as that formed by site exchange at high anodic
potentials.
No icelike structure as in UHV is expected in the elec-
trochemical environment. The formation of H-bonding
with neighboring surface molecules is unfavorable for a
perpendicular orientation of the molecular plane,
H-bonds being probably formed toward the solution.
As discussed in Sec. III, the model for water interac-
tion with Pt(lIl) has important implications in the
electrocatalytical behavior of this surface toward the
oxidation of small organic molecules.
III. ELECTROCHEMICAL OXIDATION OF
SMALL ORGANIC MOLECULES
The electro-oxidation ofsmall organic molecules (formic
acid, methanol, formaldehyde, etc.) has been extensively
investigated for over ca. 40 years [42-44]. The repeated
interest in these substances has afforded a wealth ofinfor-
mation on the responses of the systems to different elec-
trochemical input programs and on the nature and
potential dependence of the reaction products as well.
Nevertheless, and even assembling this information as
the parts of a complex puzzle, progress in the knowledge
FTIR Approach to Double-Layer and Electrocatalysis Problems 365

ofthe electrooxidation mechanism is made only in small

steps, and several questions concerning these reactions 1.0
(a) CHpH
remamopen.
Apart from the specific properties inherent to the 0.8
nature of the particular substance under study, small
organic molecules present a common feature in the 0.6
current-potential response: They exhibit anodic maxima
during the reverse scan ofa cyclic voltammogram. This 0.4
behavior is discussed in the present section. Cyclic vol-
tammetry and IR spectroscopy data on the electrochemi- 0.2
cal oxidation of small organic molecules are analyzed in
0.0
the context of the water adlayer model described above.
C)I 5
A. Voltammetric and IR Spectroscopy Data E (b) HCOOH
on Organic Oxidations 0
c:( 4
1. CyclicVoltammetry Curves
Figure 11 shows current-potential responses during the
oxidation of methanol, formic acid, and ethanol at
-E
~
'ec:n
3

-
Q)
Pt(111). All three voltammograms exhibit current "C
2
maxima during the application of an anodic potential c:
scan. Typically, the oxidation maxima are also observed ~::J
when the direction ofthe applied polarization is reversed, U
i.e., anodic current peaks are present during polarization a
in the cathodic direction. This "symmetric" response
is also typical for other organic molecules. Further- (c) C2H5OH
more, the anodic maxima are observed under both 0.8
potentiodynamic and stationary conditions for both
directions of the applied polarization. This means that 0.6
the current-potential relationship does not fit the con-
ditions for diffusion plus kinetic control, featuring peaks 0.4
during the application ofpotentiodynamic scans. Several
interpretations of this phenomenon have been proposed 0.2
[42,45-48]. At high anodic potentials ( > 0.80 V for poly-
crystalline Pt), the current decays were explained in terms 0.0
of the formation ofa platinum oxide and the increase in
current during the polarization in the negative direction, 0.0 0.2 0.4 0.6 0.8 1.0 1.2
as due to the clean surface produced after reduction of
the Pt oxide [42]. Indeed, the PtO layer inhibits in several Potential I V vs RHE
cases the oxidation of small organic molecules and a
reactivation in the form of an anodic current can be Figure 11 Cyclic voltammograms for a single crystal Pt(lll)
observed during a potential sweep in the negative electrode in (a) 1 M CH 30H/O.l M HCl0 4, (b) 1 M
direction, as soon as the oxide starts being removed. This HCOOH/O.l M HCl0 4 , and (c) 1 M C 2 H sOH/O.l M HCl0 4 .
Sweep rate, 0.05 V S-I.
interpretation, however, cannot explain decays and
reactivations of current observed for some systems at
lower potentials. Figure 12, for instance, shows the
response ofa Pt(111) electrode to a potential scan between anodic currents during the cathodic sweep must be one
0.30 and 0.50 V, in 0.1 M HCOOH + 0.1 M HCl0 4 depending reversibly on potential and postulated the
solution. Similar curves have been shown by Capon and reversible formation of an intermediate of the type
Parsons [45] for polycrystalline Pt, when reversing the (C(OHh) as responsible for this behavior [45]. For meth-
potential at e.g. 0.75 V, i.e., well before the formation of anol in sulfuric acid solutions, Markovic and Ross [46]
Pto. The same authors indicated that the process causing considered that sulfate adsorption, which is a reversible
366 Iwasita and Pastor

in OJ M HCl0 4 as a supporting electrolyte. In these

spectra, negative-going features represent gain of species
1.6 at the sample potential. The bands observed near 2060
and 1850 cm- I correspond to adsorbed carbon
monoxide and that at 2341 cm- I to the product C02.
These are the only species detected during oxidation of
1.4
~ formic acid (Fig. 14a), In the case of methanol, the band
E at 1230 cm- 1 (Fig. 13a) is due to the C-O-C stretching
0
[51] of methyl formate, which is produced via a homo-
~
-
~
'iii
c
1.2
geneous reaction ofmethanol with formic acid, the latter
being a side product of methanol oxidation [44]. During
ethanol oxidation (Fig. l5a), adsorbed species are not
only CO (band at ca. 2050 em-I) but also acetate ions
G)

-~
'0
c
1.0
=s
(j
0.8
0.6' , ' I I I l5a.
Q3 OA 0.5
Potential IV vs RHE
Figure 12 Cyclic voltammogram for a Pt(lll) electrode in
0.1 M HCOOH/O.l M HCI04, The direction of potential scan
is reversed at 0.50 V Sweep rate, 0.05 V s-l,
process, hinders the adsorption of organic species.
Herrero et al. [47] suggested lateral sulfate- water inter-
actions to be responsible for the observed symmetric
current-potential dependence during the oxidation of
methanol. But it must be noticed that the reversible
behavior described above is also observed in H 3 P04 sol-
utions [47] and in the presence of other less adsorbable
electrolytes like, e.g" HCl0 4 [49]. Summarizing, the
symmetric current-potential response is observed for
different organic molecules, using different supporting
electrolyte, and on Pt surfaces with different surface
geometries,We must thus conclude that the reason for this
phenomenon lies in some general property of the inter-
face, common to all observed systems [48]. Further infor-
mation can be gained through the analysis of infrared
spectroscopy data obtained during the electrooxidation
of the model molecules,
2, Reaction Products Observed by Infrared
Spectroscopy
Figures 13a and 15a show spectra obtained during the
oxidation offormic acid, methanol, and ethanol at Pt(1l1)
(shoulder at 1406 em-I, compare Fig. 4). The feature at
1717 cm- 1 is typical for the carbonyl group [51] and can
be due to the presence of both acetaldehyde and acetic
acid, The only undisturbed band for acetic acid alone is
that at 1286 cm- 1 and for acetaldehyde a feature at
933 cm- 1 [52], which can be observed using a ZnSe
window, The latter has a lower cutoff frequency than
the CaF2 window used in the experiments of Figs, 13a to
From the point of view of the "symmetric"
current-potential response described before, it is
interesting to analyze in Figs. 13b to 15b the changes of
the band intensity during the application of potential
steps toward increasing positive potentials and back to
the initial potential. The species formed during the appli-
cation of potential steps in the positive direction are
formed again when the potential is reversed. This means
that the conditions responsible for the current maxima
during the positive-going potential scan are restored
during the negative-going scan,
Because the 'symmetric' response is a feature common
to all three systems under analysis, the discussion requires
the consideration of the factors affecting the reactions in
common. These could be established by considering the
schemes ofreactions given in Fig. l6c. For each particular
substance, these reactions have been discussed in detail
elsewhere [49,50,53]. Here we shall constrain the dis-
cussion to those aspects concerning these systems in
common. The first step in all three cases [Eqs. (a), (h), (k)]
is considered as an adsorption reaction on a Pt site that
is initially occupied by a water molecule; adsorption is
explicitly considered as a water replacement reaction [54].
Although this fact was probably kept in mind in former
papers, neglecting the "obvious" presence of a water
adlayer has led finally to ignore its importance in the
reaction mechanisms. Considering adsorbed water in
Eqs. (a), (h), (k) is consistent with the fact that the strength
ofthe H 20- Pt(lll) interaction increases with the applied
potential as discussed in Sees. II. C and D.
FTIR Approach to Double-Layer and Electrocatalysis Problems 367

(a) (b)

E IV vs RHE 0.16

0.12

0.08

0.04

0.00

6
:::i
to
>. 4
:t:
III
c:
Q)
"E 2
-c
c:
l'Cl
m 0

1111

RlRo = 0.02

0.1
2341
0.0
0.L..O~~O....L.2"----~--:O.J....4'----~-'-O.L.6~~O....L.8.,----~---J1.0
2500 2000 1500 1000
Wavenumber (cm- 1) Potential 0J vs RHE)
Figure 13 (a) In situ FTIR spectra during the oxidation of methanol at Pt(lll) in 1 M CH 30H + 0.1 M HCI0 4 solution. Sample
potentials as indicated. Reference potential 0.05 V; 256 interferometer scans were averaged at each potential. Resolution = 8 em-I;
p-polarized light. (b) Change of the band intensity with potential for the species formed during methanol oxidation; adsorbed CO
(ca 2060 em-I), C02 (2341 em-I) and formic acid (measured as methyl formate) (1230 em-I) [48].

B. Role of Water in the Electrocatalysis of
Organic Oxidations
It should be noticed that reactions (a), (h), (k) in Fig. 16
stress the fact that the initially adsorbed species is a
nondissociated organic molecule. Charge transfer and
dissociative adsorption steps can occur only ifthe organic
molecules come in close contact with the metal atoms.
Increasing the potential results in two opposite effects in
the reactions of Fig. 16. One of these is that all oxidation
steps are favored at increasing positive potentials, due to
the increased rate of charge transfer. (Note that also the
formation of the reaction partner Pt(OH) [Eq. (d)] is
favored in this way.) The negative effect of the potential
on the reaction rate is produced through the strengthen-
ing of the H 20-Pt interaction, which hinders the initial
368 Iwasita and Pastor

(a) (b)

0.20
I .,..•
0.15

0.10

--:- 0.05
:3
cu
......
>.
I ~ CO
:t:: 0.00
en

-c:
Q)

oS
"C
c:
cu
m 15

11~1 10

5
R/Ro = 0.01

0
2341
L......
3000 2500 2000 1500 1000 0.0 0.2 0.4 0.6 0.8 1.0 1.2
1
Wavenumber / cm- Potential N vs RHE

Figure 14 (a) In situ FTIR spectra during the oxidation offormic acid at Pt(111) in I M HCOOH + 0.1 M HCI0 4 solution. Sample
potentials as indicated. Reference potential 0.05 V; 256 interferometer scans were averaged at each potential. Resolution = 8 em-I;
p-polarized light [48]. (b) Change ofthe band intensity with potential for the species formed during oxidation offormic acid: CO (ca
2060 em-I) and C02 (2341 em-I) [48].

adsorption step. These opposite effects lead to a maxi-
mum in the current-potential dependence, and because
they are in equilibrium with potential, they cause anodic
maxima during both positive- and negative-going poten-
tial scan, i.e., symmetric current-potential responses
are produced. The potential dependence of the band
intensities (Figs. 13b to 15b) supports this interpretation.
It can be seen that for all reaction products and
intermediates the band intensities go through a maxi-
mum on the reverse scan. After diminishing to very low
values in the positive scan, the rate of CO formation,
which can only occur by increasing the rate ofadsorption,
increases on reversing the potential. These results empha-
size the blocking capacity of the Pt(HzO),(OH) layer and
suggest that in the cathodic scan, under the conditions
where the CO signals grow, adsorption of the organic
molecule (i.e., water displacement) is the rate-limiting
step.
C. Adsorption Energies Involved: A
Comparison of the Cyclic Voltammetry
Responses of Small Organic Molecules
with that of CO
The present model for the oxidation ofsmall organic mol-
ecules emphasizes the adsorption process as one where
the organic species has to compete with water for an
adsorption site. In other words, we assume an energy bar-
FTIR Approach to Double-Layer and Electrocatalysis Problems 369

(a) (b)

E IVvs RHE 0.08 CO

0.06
.
,

~
0.04

0.02
II
I'
0.00 :. • • • •
0.15
S'
~
>0
0.10
:c:
VI
c:
Q)
1: 0.05
'0
c:
C'CI
m 0.00
0.8

0.6

0.4

r- 0.2
.....
R/Ro =0.01 r-
.....
0.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2

2500 2000 1500
Wavenumber / cm- 1 Potential / V vs RHE

Figure 15 (a) In situ FTIR spectra during the oxidation of ethanol at Pt(lll) in 1 M C 2 H sOH + 0.1 M HCl0 4 solution. Sample
potentials as indicated. Reference potential 0.05 V; 256 interferometer scans were averaged at each potential. Resolution = 8 em-I;
p-polarized light [53]. (b) Change of the band intensity with potential for the species formed during ethanol oxidation: CO (ca
2060 em-I), CO 2 (2341 em-I), CH 3COOH (1280 em-I), CH3CHO(933 em-I). ForCOandC0 2, spectra were obtained usinga CaF 2
prismatic window; data for acetic acid and acetaldehyde were measured using a flat ZnSe window [53].

rier for the desorption ofwater, which is comparable with
that of the organic species. In addition, one has to con-
sider that H20 molecules are in large excess, so that even
in the absence oflarge surface water clusters, when com-
peting for adsorption sites, water should not be neglected.
A rough estimation of the adsorption energies
involved can be accomplished via TDS measurements of
gas-solid interfaces, because the peak temperatures of
mass signal-temperature diagrams are related to the
desorption energies. Data for Pt(lll) indicate a
chemisorbed state for water at 170-180 K [55,56].
Assuming a first-order kinetic and a pre-exponential
factor of 10 13 s-l, the chemisorption bond strength of
water was estimated to be in the order of 42 kllmol [31].
To compare, the peak temperatures for molecular
desorption in TDS experiments at Pt(lll) are 190 K for
370 Iwasita and Pastor

Methanol
Cl-hOH coo') + Pt(H,O) ~ Pt(CH,OH) + H,O (a)
Pt(CH,OH) + PI ~ X H+ + x e' + Pt(res) (b) 0.6
Pt(CH,OH) ~ PI(CO) + 4 If' + 4 e (e)
Pt(H,O) ~ Pt(OH) + If' + e (d)
0.5
Pt(CO) + Pt(OH) ~ 2 Pt + CO, + If' + e' (e)
Pt(res) + Pt(OH) ~ CO, + x' If' + x' e+ 2 Pt (f)
~
Pt(CH,OH) + Pt(OH) ~ HCOOlf<",,) + 3 If' + 3 e + 2 Pt (g) ~ 0.4

Formic acid
HCOOlf<,ol) + Pt(H,O) ~ H,O + Pt(HCOOH)
Pt(HCOOH) ~ Pt + CO, + 2 If' + 2 e
(il)
-i
~
E
0.3
(i)
~
Pt(HCOOH) ~ Pt(CO) + H,O (j) 1:
Pt(H,O) ~ Pt(OH) + F + e (d) ...l!!
:::J
0.2
U
Pt(CO) + Pt(OH) ~ 2 Pt + CO, + If' + e (e)

Ethanol
C,H,OH(,ol) + Pt(H,O) ~ Pt(C,H50H) + H,O
Pt(C,H,OH) + Pt ~ y If' + Y e + Pt(CO) + Pt(res)
Pt(C,H50H) ~ Pt(CH,CHO) + 2 If' + 2 e
Pt(CH,COH) ~ CH,CHOc,ol) + Pt
Pt(H,O) ~ Pt(OH) + H' + e
Pt(CO) + Pt(OH) ~ CO, + H' + e + 2 Pt
Pt(CH,CHO) + Pt(OH) ~ CH1C00lf<,ol) + H' + e + 2 PI
Pt(res) + PI(OH) ~ CO, + y' H' + y' e + 2 Pt
Figure 16 Schematic representation of the processes occur-
ring during the electro-oxidation of methanol, formic acid,
and ethanol at platinum. Pt stands for the metal surface (without
denoting the coordination) and the parentheses denote
adsorbed species. Pt(res) indicates poisoning species different
from Co.
CH 30H [55], 170 K for HCOOH [57], and 200 K for
C 2 H sOH [55]. Accordingly, the adsorption energy for
the molecular (undissociated) species should be of the
same order as that of water. Contrasting with these rela-
tively low values, the energy of desorption of carbon
monoxide, calculated from TDS data, lies in the order of
108 kllmol [58]. In a first approximation, we can assume
that approximately the same relationship between the
adsorption energies in UHV holds in the electrochemical
environment. Thus, in principle, a competition with water
for Pt sites can be expected from the organic molecules,
but not from co. From this point of view, according to
the present model, no increase in current should be
observed during the cathodic scan in a CO-containing
solution. This effect, i.e., the absence of a reactivation
peak for carbon monoxide, has been shown in
0.1
(k)
(I) 0.0
(m)
(n) 0.0 0.2 0.4 0.6 0.8 1.0
(d) Potential I V vs RHE
(e)
(0) Figure 17 Current-potential curves for a Pt(lll) electrode in
(p) CO-saturated 0.1 M HCl04 solution after adsorption of CO
during 4 min at 0.05 V. Sweep rate, 10 mY/so
voltammograms at polycrystalline [59] and single-
crystal Pt electrode [60] in CO-saturated solutions.
The current-potential curve of Fig. 17 was taken in a
CO-saturated 0.1 M HCI0 4 solution, after adsorption of
CO during 4 min at 0.05 V The features observed during
the positive-going scan have been explained in detail by
Caram and Gutierrez [59] for polycrystalline Pt and
Wieckowski et al. [60] for single-crystal Pt surfaces and
are not discussed here. For the purpose ofthe present dis-
cussion, we observe that only a decrease ofcurrent occurs
during the reverse scan, according to the expected
behavior for a system governed by the rate of charge
transfer. The adsorbed water layer does not represent a
barrier for CO adsorption and oxidation.
IV. CONCLUSIONS
The discussions in the present paper demonstrate the
importance gained by in situ FTIR spectroscopy in elec-
trochemical surface science. Adsorption data on the
interface in equilibrium reveal the strong Lewis-acid
character of the Pt surface, which leads to electron
FTIR Approach to Double-Layer and Electrocatalysis Problems 371

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12:4260-4265, 1996. 58. RW Mc Cabe, LD Schmidt. Surf Sci 66:101-124, 1977.
51. G Socrates. Infrared Characteristic Group Frequencies. 59. JA Caram, C Gutierrez. J Electroanal Chern 305:259-274,
New York: Wiley, 1966. 1991.
52. SC Chang, LWH Leung, MJ Weaver. J Phys Chern 94, 60. AWieckowski, M Rubel, C Gutierrez. J Electroanal Chern
6013-6021, 1990. 382: 97-101, 1995.
22
Second Harmonic Generation Anisotropy from Single
Crystalline Electrode Surfaces
Bruno Pettinger and Christoph Bilger
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany
Jacek Lipkowski
University ofGuelph, Guelph, Ontario, Canada
Wolfgang Schmickler
University of Ulm, Ulm, Germany
ABSTRACT
Interfacial second harmonic generation (SHG) is an
optical spectroscopy that is inherently surface sensitive.
All effects that modifY the electron density profile of the
interface are mapped into the SHG process. Therefore,
SHG depends on the exciting and SH frequency, on the
surface structure, and on adsorbates and adlayers. For
metal electrodes there is a remarkable dependence of
SHG on potential, adsorption, and charge density at the
metal and surface structure. Using the advanced form
ofthe SHG anisotropy, the interference SHG anisotropy,
one can determine the anisotropy of the SH field itself
and can pursue how the various isotropic and anisotropic
sources contributing to this field evolve with potential
and adsorption. This yields information on the geometric
and electronic structure of the interface and adlayer to
unparalleled details.
I. INTRODUCTION
Elementary electrochemical processes occur at the phase
boundary electrode-electrolyte on atomic and molecu-
lar levels. Their type and kinetics are determined by the
local electronic and geometrical structure of the surface
and by the adsorbate-substrate interaction. To evaluate
373
electrochemical processes on elementary levels, one
needs to know all electronic and structural parameters
of the interface, including their variation with potential
and adsorption. Solely electrochemical investigations
yield only global parameters such as potentials, currents,
and capacities, yet they have provided important insight
into the electric double layer.
In recent years, a series of methods were developed
dedicated for in situ investigations of interfaces. A variety
of them will be addressed in this volume, among them
scanning tunneling microscopy (STM), atomic force
microscopy, and X-ray reflection and diffraction. They
are suitable to reveal surface structures on an atomic level.
In addition, a number ofoptical methods have emerged,
for instance, infrared (lR) and Fourier transform
infrared spectroscopy, Raman and surface-enhanced
Raman spectroscopy (SERS), and visible and ultraviolet
spectroscopies. They are particularly useful to identifY
adsorbates and intermediates and to study their interac-
tion with the substrate.
Nonlinear optical spectroscopies of second order at
surfaces attracted much attention by two outstanding
reasons: They are inherently surface sensitive and the
created radiation is easily separable in space, frequency,
and time. In general, this nonlinear radiation is generated
374
only within the interfacial region and is emitted as a beam
into a distinct direction; its frequency is the sum or differ-
ence frequency, W = WI ± W2, and its phase relationship
with the exciting electromagnetic wave is well defined.
From the experimental point of view, these properties
are most attractive. Up to now, it is a great challenge for
theorists to develop models for the nonlinear interfacial
interactions that account for the major specific features
observed in this area. Not surprisingly, innumerable
experimental and theoretical works exist, illustrating that
the advent of nonlinear spectroscopies opened new
avenues for exciting research at interfaces.
In this review we focus on a restricted topic, second
harmonic generation (SHG) anisotropy at crystalline
electrodes. Results on other related topics, such as on
sum or difference frequency generation, are presented
byTadjeddine in Chapter 19. To begin with, let us empha-
size the following. The understanding of interfacial pro-
cesses, including the nonlinear optics at surfaces, can
only evolve on a microscopic level when we take into
account the interfacial structure. In terms of SHG, the
utilization ofcrystalline samples, which show anisotropic
behavior, provides a formidable challenge for experi-
mental and theoretical studies.
The paper is organized as follows. After the intro-
ductory subsections Brief Historical Survey, SHG
Applications, and SHG Anisotropy, we continue with
the section Theory. It contains the fundamentals of
interfacial SHG and presents detailed material on SHG
anisotropy, its concept, and analysis problems. Then, in
the subsection Basics of Interference SHG Anisotropy,
we outline the concept of our recently developed
experimental approach. Using this new method we can
perform a much more elegant analysis of the exper-
imental data and provide new insight into the origin of
SHG, that can not be achieved by the "classical" SHG ani-
sotropy technique, as we show later. In the section Results
and Discussion we first deliver early SHG experiments
on electrodes and then results on standard SHG
anisotropy. Finally, we arrive at the subsection Inter-
ference SHG Anisotropy. Here, we like to convince the
reader that using this method, one can extract infor-
mation from anisotropy measurements to unparalleled
details. Finally, we show that improvements in the theory
of nonlinear spectroscopy brings the theoretical
predictions closer to the experimental results.
Last, but not least, we would like to emphasize mutual
links between SHG at electrodes and electrochemistry,
and the results of classical electrochemical measure-
ments simply because these methods probe different
physical properties of the interfacial regime. Adsorption
and potential, charge density, surface structure, and the
Pettinger et aI.
formation of (ordered) adlayers have a significant impact
on both the behavior of the electric double layer and the
SH response. In turn, we expect that an improved under-
standing of SHG at electrode interfaces will also help to
deepen our knowledge on electrochemical processes.
II. SHG AND ITS APPLICATIONS
A. Brief Historical Survey
As with all nonlinear spectroscopies of second order,
optical SHG at phase boundaries is allowed in general
due to the absence of centrosymmetry [1-4]. This prop-
erty is particularly attractive if the SHG signal stems
from the interfacial regime formed between two cen-
trosymmetry media. Then the SHG signal originates
primarily from the interface, whereas the bulk contri-
butions are minor if they exist at all. The first measure-
ment of this type was performed by Brown et al. in 1965
[5], just after the development of pulse lasers and the
detection of harmonic radiation by Franken et al. [6].
Already in 1962, Bloembergen and Pershan [7] presented
the theoretical basis for surface SHG that is still valid
today. In this and subsequent papers, B10embergen and
coworkers investigated various interfacial configurations
[7-10]. They also addressed the question on how
adsorbates may affect the SH signal and concluded that
their influence should not be important because the inter-
face should contribute to SHG only via a weak
quadrupole type of interaction [11]. Contrary to that,
experimental evidence for the opposite behavior, a sub-
stantial influence of adsorbates on the SH intensity, was
accumulated [1,12]. To explain these observations,
Rudnik and Stern [2] reconsidered the case of an inter-
face formed between centrosymmetric media in a theor-
etical paper; the authors concluded that symmetry
breaking is occurring at the interface that therefore has
a noncentrosymmetric property. Consequently, electric
dipole contributions to surface SHG are permitted and
can represent the major source of nonlinear radiation
from an interface.
For more detailed information on the early develop-
ments of surface SHG, the reader is referred to a series
of interesting reviews [13-18].
B. SHG Applications
Because we restrict ourselves in this review to a specific
topic, the SHG anisotropy at single crystalline metal
electrodes, other applications, though also very
important, can be mentioned only briefly. The quotations
given in this section are necessarily arbitrary and
~
SHG Anisotropy 375

incomplete. They are basically given to serve as a starting surface temperature Ts (K)
point for interested readers and to illustrate the great var- -41200 1000 800 700 600 500
iety of SHG applications and outstanding research 10 0=0:,,....----,,----,--...,----,---,..---------,.
activities.
1. SHG at Distinct Interfacial Configurations
In the past decades, interfacial SHG emerged to a
0
versatile method for a large number of systems such as (/)

the solid-vacuum [19-31], the solid-electrolyte [32-59], "E 10~

<D
or the liquid-liquid and liquid-air [60-66] phase '13
:e<D
boundaries. Because there are several extended reviews 0
u
available on various investigation fields ofSHG, we refer 10-7
Ol
c: Experiment
the reader to these reviews [4,67-69] and only briefly :i:
0\ HiSi(100)
address some of the main topics. ~
(/)
41 o DiSi(100)
10
2. Time Resolved Studies
SHG processes occur nearly instantaneously. Together •.• HiSi(111)
o DiSi(111)
with a suitable apparatus, this property opened a new 10-9
avenue for anumberoftime resolved investigations invari-
ous disciplines and for time scales extending from seconds 0.8 1.0 1.2 1.4 1.6 1.8 2.0
to subpicoseconds [see also in 70,71]: Among them are 1000fTs (K- 1)
studies on the double-layer reorganization and metal
deposition by Robinson and Richmond [72,73], the Figure 1 Initial sticking coefficient of thermal H 2 and D 2
rotational relaxation at the air-water interface [74], the gases at Tgas = 300 K and Si(lll) 7 x 7 and Si(lOO) 2 x 1
intermolecular vibronic dephasing and intermolecular surfaces as a function of their inverse temperature. The
vibronic coherence transfer [75], the electric field experimental values are denoted by symbols; lines represent
dynamics at metal-semiconductor interfaces [76-79], theoretical calculations. (From Ref. 84.)
the measurement of transient electron temperatures of
metals [80,81], the phase transformations of a semicon-
ductor surface layer [82], the dynamics ofhydrogen inter-
action with silicon surfaces [83,84], the in situ and probabilities in the range of 10- 9 to 10- 5 using optical
real-time monitoring of surface reaction dynamics and SHG for H2 and D2 on Si(lll) 7 x 7 and Si(100) 2 x 1.
gas phase kinetics [85], the new time-domain surface Figure 1 shows the initial total sticking coefficient of H 2
phonon spectroscopy [86], the photoreduction kinetics and D2 on both surfaces as a function of the inverse
ofmalachite green adsorbed onto single crystal cadmium surface temperature. A rather similar behavior is ob-
sulfide [87], the photophysics, photochemistry and served on both surfaces and on both isotopes.
photodynamics ofdyes [88], and the photochemistry and
photophysics ofliquid interfaces [89].
4. Molecular Orientation
3. SHG and Adsorption-Surface Coverage
The adsorption of adlayers of metals, molecules, or ions The average orientation of adsorbed molecules is one of
at an interface changes its electronic configuration. This the key questions in surface science and technology.
is, in a sense, mapped into the SH response. Thus, there SHG has been used to determine this quantity. In general,
are unnumbered SHG investigations in this field. Among a configuration is used where the adsorbate dominates
them only a few can be mentioned here, for instance, the the SHG response. (However, there are few cases where
studies concerning adsorption and surface coverage molecular orientations of small organic molecules at
at surfaces in ultra-high vacuum (UHV) [90-93]; metal surfaces were elaborated [102].) To determine the
electrodes [94,95]; semiconductors [84,96]; oxides, average molecular orientation, the magnitude and the
insulators, and glasses [97,98]; and at liquid-liquid or phases of the nonlinear susceptibility tensor elements
liquid-air interfaces [61,99-101]. have to be measured. The results are compared with
The enormous sensitivity and power of SHG investi- predictions ofan appropriate model from which the aver-
gations has been shown recently by Brenig et al. [84]. age orientation is deduced. Details on this interesting
The authors observed extremely small sticking topic can be found in [61,68,69,98,103-105].
376 Pettinger et al.

5. Electric Field Measurements

Another major influence on SHG is the static electric [01 'f]
field across an interface. If the medium is centro-
symmetric, the action of such a field is to break this
(0)
symmetry, which means SHG is allowed in the region
where a sufficient field strength is present [1]. This effect,
also known as electric field induced SHG (EFISH), has
been reported for a variety of systems, in particular on 11]
semiconductor interfaces [54,77-79,106].
Note that also the potential dependence of the
nonlinear susceptibility on metal-electrolyte phase
boundaries was related to this EFISH effect. In fact, this
old concept is valid to date, and we address this feature
in later sections.

III. SHG ANISOTROPY: PROBE OF

INTERFACIAL ROTATIONAL SYMMETRIES
Light interacts with matter by inducing linear and
nonlinear polarization. Given sufficiently intense laser
[011]
pulses with w frequency, the nonlinear polarization of
second and higher order is strong enough to create (b)
radiation at 2w and higher frequencies. The
second-order polarization vector can be split into its
components perpendicular and parallel to the surface.
The former is sensitive, for instance, to the interfacial
electric field, and the latter probes the rotational [211]
symmetrics of the sample surface. Keeping the zenith
angle, 3, fixed and recording the SHG intensity as a
function of the polar angle, qJ, * i.e., recording the SHG
anisotropy, provide an easy way to monitor the
rotational symmetry of the sample and its possible
changes in the course of experiments. The SHG ani-
sotropy was first observed for crystalline semiconduc-
tors and insulators [107-109]. One of the intriguing
first examples was reported by Heinz et al. [108]; it is
reproduced in Fig. 2 and shows the SH intensity of a
Si(1ll)-7 x 7 surface in UHV as a function of the Figure 2 SH electric field as a function of the angular
orientation of the linearly polarized electric field vector orientation of the linearly polarized pump electric field vector
for a clean Si(l1l)-7 x 7 surface. The field amplitudes polarized
of the incident laser beam. The pattern illustrates the
along (a) the [211] (x-) direction and (b) the [OIl] (y) direction.
rotational symmetry of the 7 x 7 reconstructed surface. Open and filled points correspond to sign changes in the
Another example, the SHG anisotropy on a crystalline experimental data. The solid curves represent theoretical
metal surface, is given in Fig. 3. It presents the ani- predictions for the magnitude of the SH electric field under
sotropy variation with increase of the surface coverage 3 m symmetry. (From Ref. 108, courtesy of American Vacuum
Society.)
* In the literature, the rotational angle, cp, is often called the
"azimuthal angle." Here, let us stick to the following conven-
tions: The angle of rotation around the surface normal is of hydrogen on Ni(lll). Both examples clearly reveal
denoted as the polar angle, cp, and the angle of incidence the great sensitivity of SHG on the rotational
between the surface normal and the incident beam may be symmetries present in the surface and its power to
associated with the zenith angle 9. monitor symmetry changes.
SHG Anisotropy 377

90 the interface. This field is easily separable in its isotropic

and anisotropic components, contrary to usual case of
SHG anisotropy.

A. General Considerations on Optical

Nonlinear Processes
In the classic view, all interaction oflight with matter is
180 ........,p-...,.....+ 0
-f"--fe-)o.........
ruled by the Maxwell's equations that relate the electric
I r m- 8.,-=.. . ,0"""'.0'" and magnetic fields, E(r, t) and B(r, t), with the current
D 8=0.2 and charge densities, J(r, t) and per, t). Using the charge
.. 8=0.4 conservation law,
.. 8=0.6
v . J(r. t) + atp(r, t) = 0 (1)
• 8=0.8
• 8=1.0 and the definition for a generalized polarization, per, t),
with J dc being the dc current density [3,114],
270
J(r, t) = Jdc + atP(r, t) (2)
Figure 3 Hydrogen coverage dependence of p polarized SH
rotational anisotropy from Ni(lll) in UHV near 200 K P
the Maxwell's equations can be cast into the following
polarized 700-nm light from a Nd : YAG laser pumped dye form [3,115]:
laser incident at 60° from the surface normal. (From Ref. llO,
1
courtesy ofPhys. Rev. 8.) V x E(r, t) = - -atB(r, t)
c
1
V x B (r. t) = - at (E(r, t) + 4n: per, t))
c
Shannon, Koos, and Richmond were the first to 4n: (3)
+-Jdc
observe the SHG anisotropy at metal electrodes [111-113]. c
These findings started a new research field because at that V· (E (r, t) + 4n:P(r, t)) = 0
time SHG was basically the only structural sensitive
V· B(r, t) =0
method that could be applied in situ in electrochemistry.
We address this topic in detail in the following. where the operator at is defined as at!(t) = af(t)jat.
Obviously, per, t) is the only time-varying source term.
The general polarization can be expanded into various
IV. THEORY
orders [3,116]:
For a clear and profound understanding ofthe anisotropy
effects, we present in this section the theoretical back- P = p(l)(r, t) + p(2)(r, t) + p(3)(r, t) + ... (4)
ground of SHG, and we learn how symmetries govern
If the field E(r, t) is a sum over monochromatic plane
fundamental properties of SHG, among them its aniso-
waves, i.e., if E(r, t)= Li E(k i , w), then the Fourier trans-
tropic behavior.We then are confronted with the problems form of the nth-order polarizability, p(n)(r, t) ~ p(n)(k i ,
that one encounters in the analysis of the SHG anisotropy
Wi) leads to the relationship between the polarization of
data. Finally, we lay the theoretical foundation for the
nth order and the exciting field(s):
interference SHG anisotropy (ISHGA) experiment. It is
the first approach that permits the complete and unam- p(n)(k, w) = X(n)(k = k] + ... ± k n, (r, t),
biguous analysis of the anisotropy data to unparalleled
w =Wl + ... ± W n) : E(k], w])··· E(k n , w n )
details. It is also the first approach that yields the ani-
sotropy ofthe complex SH field, E(2w, rp), t generated at (5)
where X(n)(k, w) is the nth-order susceptibility tensor of
t Obviously, this is the main advantage of the ISHGA method n + 1rank describing the nth-order nonlinear interaction
over the standard interference technique. The latter was applied of light with matter. Evidently, nonlinear processes
to SHG to get the phase of the electromagnetic field in addition involve the generation of new electromagnetic waves with
to its intensity but not to get the anisotropy of the E(2w, rp) field. the frequencies wand the k-vector, k, defined in Eq. (5).
378
In principle, the use ofa full quantum mechanic approach
is necessary to calculate the susceptibility tensors
because only then microscopic events and macroscopic
observations are linked sufficiently.
1. General Symmetry Considerations
Fortunately, the consideration ofsymmetries can provide
remarkable insights into specific properties of the sus-
ceptibility tensors without the need of detailed
calculations. There are general and specific symmetry
properties of the susceptibility tensors X(n): the first arises
from the principles of time invariance and causality and
means that X~JI"'~n (w; WI, ... , w n) is invariant under all
n! permutations of the pairs (ai, WI), (a2, (2), ... , (an,
w n ) [116]. In the absence of resonance transitions, i.e.,
when the nonlinear medium is transparent to all relevant
frequencies, there exists an overall permutation sym-
metry for the pairs (fl, w), (ai, WI), (a2, (2), ... , (an, w n).
This symmetry is known as the Kleinmann symmetry
[117] resulting in a substantial reduction of the indepen-
dent susceptibility elements (e.g., a X(2) tensor with 27
elements can then be reduced to a tensor with 18
elements).
Spatial symmetries of the nonlinear medium can con-
stitute further important restrictions to the susceptibility
tensors: Here, the Neumann's principle applies in the
sense that the susceptibility tensors must remain
invariant under all coordinate transformations reflecting
symmetry operations characteristic for the nonlinear
system.
Because in this chapter we focus on second harmonic
processes, we obtain with WI + W2 = 2w and k=kl +k 2:
P(2)(k,2w)= PJ(k,2w):E(k j ,w)E(k 2,w) (6)
This is the so-called electric dipole contribution to SHG
(note in this context that higher order contributions to
2w radiation can arise if one or several frequencies in
Eq. (5) are zero, i.e., if WI :;;t:O, W2 :;;t:O, but Wi, ... W n ,
---+ 0, i, n > 2).We can then define an effective polarization
of second order that contains all contributions (see Sec.
IV.E).
The Neumann's principle has an important conse-
quence for materials exhibiting inversion symmetry or
centrosymmetry: The inversion operation is R~fJ = -b~fJ
with b~fJ being the Kronecker delta. The invariance under
this transformation requires that X~2;fJ = -X(2;fJ [116]. This
means that X~2;fJ = O! Thus, in dipole a;proximation
SHG is forbidden for matter exhibiting inversion or
centrosymmetry. Among them are gases, liquids,
amorphous solids, even crystals with fcc structure. This
rule can be extended to all higher order susceptibilities
Pettinger et at.
with an even order, i.e., x<2n) =0, n ~ 1, n E ~ for
centrosymmetric media. In turn, X(2m+I):;;t: 0, m ~ 0,
m E ~ for all media.
2. SHG at Interfaces
At phase boundaries, however, the centrosymmetry
is broken, and therefore interfacial SHG is allowed
in general. Most attractive is a configuration formed
by two centrosymmetric media, such as the
electrode-electrolyte. Then SHG originates-in dipole
approximation-exclusively from the interface, i.e., from
nearly the same region where also important electro-
chemical processes occur.
At interfaces (between medium 1 and medium 2)
there exist gradients of matter, fields, and properties
(such as X~n) ---+ X~n) ---+ x~nJ). Consequently, the effective
second-order surface polarization is composed of sev-
eral contributions [3,7]:
P~~~ff = a [E (w) . V E (w) ] + fJ E(w) [ V . E (w) ]
2iW) y [E (w)
+ ( ---;;- x B(w)] (7)
+ X~2)b(z) : E (w) E (w)
which can be identified with the electric quadrupole [the
first two terms on the right side ofEq. (7)], the magnetic
dipole, and finally the electric dipole contributions.
Using the delta distribution, b(z), Z = 0+, the nonlinear
electric dipole interaction is restricted to the surface (the
underlying concept is that only an infinitely thin dipole
sheet at the interface radiates at 2w; it is located between
medium 1and medium 2, having the same linear optical
properties as medium 2; see Fig. 4). Discussions on the
higher order contributions can be found in [3,4,118]
and are not repeated here. Instead, we proceed by
restricting ourselves to the electric dipole contribution,
which is often by far the dominating contribution to
SHG at metal electrodes; this holds in particular for
Ag and Au electrodes (when excited in the long wave-
length regime, e.g., at 1064 nm).
In the case of a single fundamental beam, the full
expression for SHG in the electric dipole approximation
can be written as [3,120]
2m 32n3w2sec296W I 2w. X(2): eWeW 212(w)
I
(8)
1 = e .
1/2
C3cI (w)cI (2w)
where the appropriate Fresnel factors are included
implicitly into each tensor element to simplifY the
notation [119-121].
SHG Anisotropy 379

o
~)
dIS
(2) ( 00 d24 0 (11)
X(lIO) =
d 31 o 0
where the subscripts (hkl) denote the surface orientation.
2w The symmetry notation for these surfaces is for 100 C 4v ,
for III C3v, for 110 C 2v . Because (in dipole approximation)
there are only onefold, twofold, and threefold rotational
symmetry contn'b' utlOns to SHG , t h e X(IOO)'
(2) (2)
X(lIO)' an
d
xm I) tensors contain only three, five, and six independent
terms; the rest of the elements are zero. That means a
2w SHG intensity vs. cp curve can exhibit quite distinct
patterns: Step and defect free unreconstructed surfaces
of 100, Ill, or 110 orientation show a purely isotropic
behavior, a threefold, or a twofold rotational symmetry,
respectively.
For a deeper understanding of the anisotropy, let us
consider a realistic surface exhibiting reconstruction,
microfacets, steps, etc. In terms of symmetries we then
have to consider a superposition of several rotational
symmetries. Thus, the overall rotational symmetry is
onefold; as an additional symmetry element, we assume
a vertical mirror plane. Such a surface is associated with
medium 1 s medium 2 a Cs symmetry. The corresponding nonlinear tensor of
third rank, denoted as X~;, reads in the expanded form as
Figure 4 Scheme of second harmonic generation from an
interface between two isotropic media. The interfacial layer of (2) -
XC, -
thickness d is specified by a linear dielectric constant £s and a
second-order surface nonlinear susceptibility X~2). (After Ref. 3.)
o o
X212
Xll3
0
0
X212
X122
o
0
X223
Xll3
o X223
X~3)
B. SHG and Anisotropy o
o X313 0 X322 0 X313 X333
The SHG intensity as described by Eq. (8) can vary when (12)
the sample is rotated around its surface normal. In other
words, it shows an anisotropic behavior: 12w = 12W (cp), Note, the Kleinmann symmetry is applied.
with cp being the rotation or polar angle. This anisotropy To account for a rotation ofa surface around its normal
is connected with specific symmetry properties of the by the polar angle, cp, a coordinate transformation has to
nonlinear susceptibility tensor X(2). By visual inspection be applied to the tensor using the rotation matrix R:
of the corresponding plots or by mathematical analysis
of the anisotropy pattern, one may identify rotational
R =
COS cp
si~ cp
- sin cp
cos cp
0)
0 (13)
symmetries present in the surface.
Most instructive is to compare the reduced form ofthe
(
o 1

l2) tensors referring to a 100, Ill, and 110 orientation: The general form of this transformation is

(2)
n =0-3 (14)
X(lOO) = (9)
where X~;; are the rstth elements of the susceptibility
tensor. The result is shown in Table 1. Note that for the
transformation the expanded form of the l2) tensor has
(2)
X(lll) =
o
o
0
dIS
dIS
0
0)
-dOll (10)
to be used, not the contracted one, because the latter does
not transform as a tensor of third rank. As evident from
d 33 0 0 Table 1, most of the 27 tensor elements carry a depend-
380 Pettinger et aI.

Table 1 SusceptibilityTensor X~;

xx xy xz yx yy yz zx zy zz
(3) 3 (3) . 3 (2)
2cp (3) . (3) 3 (2) 2
a l13 cos cp
aliI COS cp -alii Sill cp a l13 cos -alii Sill 3cp -alii cos cp

+ + - +
(2) . 2
- a l13 Sill cp +
(2) . 2
- a 113 Sill cp a(I)
l33 cos cp
(I) (I) . (00) (I) . (1) (00)
alllcosCP a l12 Sill cp a l13 a l12 Sill cp a l22 cos cp a l13

(2) _ (3) . (3) (3) (3) . (2) 2 cp (2)

XCs - -alII Sill 3cp -aliI cos3cp -alii cos3cp a lll Sill 3cp - a l13 cos l13 -a cos2cp
+ + - 2'
(1) . (1)
_a(2)
113
sin 2cp
(1) (I) .
+ (2)
- a 113
.
slll cp + (I) .
- a l13 slllcp
(00) (00)
a l22 slllcp a l12 cosCP a l12 cosCP alllslllcp a l13 a l13

2cp - a(2) 2
311 cos cp
a(2) COS
311 (2) . (I) (2) . 2 (I) . (I) (I) • (00)
+ - a 311 SIll2cp a 313 COS cp - a 311 slll
.
cp +
( 0 0 ) '311
.
-a slllcp a 313 cos cp - a 313 Sill cp a333
(00)
a 311 a 311

ence on the rotational angle: X~;~ => [120, 121]. /tl(mp) ships can be easily deduced from the above equations.
Although the second-order interaction oflight with a sur- Note again that in the presentation, the Fresnel factors
face having a Cs symmetry seems to be inevitably are implicitly included in each a~;2 term [120,121].
complicated, one can simplifY the experiment and its One should also bear in mind that the aY;2 elements are
theoretical description substantially using specific composed ofthe original X~;~ tensor elements in quite dif-
polarization conditions. The standard approach is to use ferent ways:
linear polarization of the light, set either to p or s
polarization (parallel or perpendicular to the plane of (3) _ I (
incidence). This applies to the exciting laser beam and alll -4 XIII - (X122 + 2X212))
for the emitted radiation where a polarizer projects out alii
(I)
=41(3 XIII + Xl22 + 2X212)
its p or s polarized components. (I) I (
For the four polarization conditions,pp, sp,ps, SS, and a ll2 =4 Xlli - (X122 - 2X212))
for the case of Cs symmetry, it is worthwhile to summarize am
(I) I (
=4 XIII + (3Xm - 2X212))
the relationships between SHG intensities and the (00) I (
rotation angle (where x~:l(mp) ---+ a~;2 cos or a~;2 sin mp a ll3 =2: Xll3+X223)
mp): a l13
(2) _ I(
-2: Xll3 - X223) (16)
(I)
a 133 =X133
(00) (I) (I) (00)
I pp ex a 333 + a 313 cos <p + a l33 cos <p + a 3ll (00) I (
I a 3l1 = 2: X311 + X322)
(2) (00) (2) (I) I (
+ a 3l1 cos 2<p + a ll3 + a ll3 cos 2<p a 3l1 = 2: X3l1 - X322)
2 (I) (I)
(3)
+al1lcos 3<p+all1cos<P
(I)
I L2 1
a 313 = a 332 = X313
(00)
(00) (2) (3) a 333 = X333
I sp ex a 311 - a 311 cos 2<p - alII cos 3<p
I
2 (15)
+ a (1)
ll2 cos <p I L
2 1
For each polarization condition, one can group the
. 2 (3)· 3
terms in Eq. (15) into the order ofcos n<p or sin n<p terms.
I ps ex a (2) (2)·
I l13 Sill <p + alii Sill <p + a l22 Sill <p For pp polarization we obtain
2
+ am
(1).
Sill <p
1
I L2

3
(3) .
(I). 1-12L 1 li;: ex lAPP + lJPP cos <p + cPP cos 2<p + IYP cos 3<P12
Iss ex -alii Sill <p + alii Sill <p

~ It, k:' co, n~12

1

Low-indexed unreconstructed surfaces have higher

rotational symmetries.Their simpler intensity-<p relation- (17)
SHG Anisotropy
with
k~P = {APP, J3PP, CPP , lJPP}
PP (00)
A = a 333 + a(00) (00)
311 + a l13
p (I)
J3P =a 313 +a 133
(I)
+a(I)
lll (18)
CPP - a(2) + a(2)
- 311 113
lJPp -
-
a(3)
III
Analogically, one can proceed for the other
polarizations. Evidently, for each of the uv = pp, ps, sp,
or ss polarization conditions and for a rather low surface
symmetry, such as Cs , the SHG anisotropy is described
by a superposition of up to four effective susceptibility
terms having a complex character in general. The first
term is associated with the so-called isotropic
susceptibility, denoted by the complex term AUv, whereas
the other three are connected with the anisotropic
susceptibilites, BUv, CUV, and DUv, multiplied by the appro-
priate trigonometric function. The latter three terms
indicate the possible presence (and superposition) of
onefold, twofold, or threefold rotational symmetry
elements in the surface. Because we are interested in the
angular dependence, we set the proportional constant to
c = 1. In addition, we omit the uv indices at the four terms
where appropriate.
C. Problems in Evaluation of Susceptibility
Coefficients
Various promising attempts were made to correlate the
SHG anisotropy patterns of a sample and their changes
in the course of experiments with the presence and vari-
ation of its rotational symmetries. There is, e.g., the early
study ofthe symmetry and disordering ofa reconstructed
Si(111)-(7 x 7) interface by Tom et al. [19]. At silver (lll)
electrodes surface reconstruction is absent (i.e.,
B = C = 0). The analysis of such simple cases according
to Eq. (17) appears to be straightforward [4]. If surface
reconstruction is present, as in the case of Au( Ill)
electrodes, but the Band C coefficients are still small
enough, the coefficients A and IDI can be determined
together with the relative complex phase (5 A-D [122]. In
all these cases, a priori information was used to simplifY
the expression according to which the data were analyzed.
Severe difficulties arise, however, when the anisotropy
becomes rather complex and a priori information is not
available. For example, the SHG anisotropy pattern of a
Au(1 10) electrode has such a rich content that their analy-
sis yielded unsatisfactory results, when using usual con-
cepts [123,124].
381
Moreover, the data analysis itself bears additional
problems. According to Eq. (17), a SHG anisotropy curve
is composed by superpositions of a few harmonics (in
general, n::::6). A Fourier analysis leads to a nonlinear sys-
tem of equations, which can have multiple solutions. In
fact, either by solving this system of equations or by a fit
procedure, one can find multiple solutions. This holds
even for the case of a simple rotational symmetry, such
as that of an unreconstructed 111 oriented surface. One
can find several usually distinct sets of coefficients that
reproduce the same anisotropy curve [125]. Thus, among
the various sets of coefficients, only one describes the
physical situation of the sample but which is unknown
in advance.
D. Concept of SHGA
1. Fundamentals
The above sketched difficulties and problems can be
traced back to the fact that in the analysis of the usual
anisotropy curve, one operates with intensities,
2
/SHG oc IE(2w, <P )1 , and not with experimental results
being linear to the SH field, E(2w, <p). To overcome this
limitation, one has to combine the methods ofSHG inter-
ference and SHG anisotropy to a new experiment such
that the corresponding analysis allows us to extract all
the coefficients and other not yet discussed terms in a
simple, easy, and reliable way without ambiguities. This
new approach is denoted as ISHGA [126]. It is nothing
else than an experimental procedure to get the anisotropy
ofthe complex SHfield, E(2w, <p). It can be easily extended
to the (up to now neglected) contributions of higher
multipoles and to other optical spectroscopies.
To begin with, we describe the variation ofthe SH field
with the polar angle, <p, in a more general form compared
with that used in Eq. (17):
EPP(2w, <p)ocAPP+J3PP cos (<p + IX)
+CPP cos (2(<p + {3)) (19)
+lJPPcos (3(<p + y)) + ...
where we introduce, offhand at this stage, angular shift
terms IX, {3, and y. Their physical meaning is discussed
below. Note, analogous relationships hold for all
polarization combinations.
Next, let us consider the case of the interference of
two SHG waves, the first created by a quartz lamella
and the second by the sample surface. As shown in Fig.
5, the quartz lamella is placed additionally into the laser
beam, but in front of the sample at a location x, where
x denotes its distance from the sample. The s or p
polarized laser pulse passes the quartz lamella and
382
.. •..,
~.-
(1: J;
laserspot
05mm
•••.,;..ll'
:.
fundamental
00 :.
:. greenfilter
200 quartz
200 sample
X2
Figure 5 Interference SHG anisotropy experiment. The first
SHG wave is created by the quartz lamella (dotted line) located
at Xl or X2; it propagates together with the fundamental beam
toward the sample where the second SHG wave is created
(dashed line). Upon reflection at the sample, both SHG waves
travel on parallel routes and interfere at the observer point.
(From Ref. 126.)
creates the first SH signal there. Both the laser pulse and
the first SH wave travel colinearly toward the sample
and are reflected there. The laser pulse interacts with
the sample surface and generates the second SH wave.
A filter, placed behind the sample, only blocks the fun-
damentallaser beam. Both the first and second SH wave
pass this filter and subsequently a polarizer. The latter
projects out either the s or the p polarized components
of both 2w radiations. Their interference intensity is
recorded by the detector during a polar angle scan of
the sample (Fig. 5). For the mathematical description
of this process, we benefit from the arbitrariness of the
(absolute) phase of EU V (2w, cp) and define the relative
phase relationship of the two SH waves such that
E q = IEqI is real if the quartz lamella is moved to a
location Xl using the identity
IE UV
(2w, cp)leib"ffiPldlpl + IEqleibqu"'''1
IIE UV
(2w, cp )lei(b"ffiPI«lpl-bquaml + IEql1
Then the quartz lamella is moved to a specific location
X2 (such that Llx = X2 - Xl ~ 3.18 cm). This means that
the phase relationship changes by nl2 because ofthe dif-
ferent optical path lengths for the wand 2w beams in air
(n(w) i n(2w» thus, E q -+ i E q. For this configuration,
the second ISHGA curve is measured. Subsequently, the
quartz lamella is moved offthe beam and a third, the stan-
dard SHG anisotropy curve, is recorded. Obviously, this
Pettinger et al.
approach records three anisotropy curves, one without
the quartz lamella and two with the quartz lamella at
locations XI and X2. The intensities ofthe three anisotropy
curves are
suprasil
electrolyte I;pHG ex: IRe (EPP(2w, cp» + iIm(EPP(2w, cp»1 2 (21)
2
I~;HG(XI)ex: IEq+Re (EPP(2w, cp»+iIm(EPP(2w, cp»1
(22)
2
I~;HG(x2)ex: IRe(EPP(2w, cp»+i (Eq+lm(£pP(2w, cp»)1
(23)
Depending on the location of the quartz lamella at Xl or
X2, its SH field appears in the Eqs. (22) and (23) either
via the terms E q or i E q • This concept can be used for all
possible polarization combinations. Here, pp polar-
ization is used.
The next step is to compute the difference curves, i.e.,
the difference of Eqs. (22) and (21) and of Eqs. (23) and
(21); in addition, the SHG intensity of the quartz lamella
alone, E; ex:lq, is subtracted (for the sake ofclarity we omit
the polarization indices such as pp, ps, etc.). Then the dif-
ference data are divided by 2Eq:
ESHG(xj) = 2~ (IISHG(Xj)_ISHG -E~); j = 1,2
q
(24)
We arrive at
ESHG(XI) ex: Re (E (2w, cp» (25)
E SHG (X2) ex: 1m (E(2w, cp» (26)
where ESHG(xj) are the experimental data proportional
to the real and imaginary parts of the SH field E(2w, cp),
respectively. Because the ESHG(xj) data are recorded vs.
the rotation angle cp, they represent the experimentally
measured anisotropy of the SH field. The composition
= of E(2w, cp) is given by Eq. (19). Note that the Eqs. (25)
(20)
and (26) are derived on a rather fundamental level
because there are neither restrictions nor assumptions
made concerning the SH field E(2w, cp). If higher order
contributions are present in E(2w, cp), they are measurable
in principle. In particular, higher order contributions
giving rise to n-fold rotational symmetries with n > 3
[indicated by Eq. (19)] are easily identifiable, provided
that their amplitudes are above the noise level [126-128].
As is well known, the complex phase of E(2w, cp) (or of
its constituents) is defined and measurable only against
L.-
SHG Anisotropy 383

a reference phase, here relative to the phase ofthe SH wave

from the quartz lamella at location XI. Because both
curves, Re(E(2w, cp)) vs. cp and Im(E(2w, cp)) vs. cp, can be
composed of an isotropic and a few harmonic terms, a
Fourier analysis

(27)

[ITO]
yields the Fourier coefficients an,j and bn,j. They contain
all symmetry information and therefore permit an easy
evaluation of the full set of isotropic and anisotropic
coefficients A, B, C, D, ... and also the "geometric" angu-
lar offset terms, a, f3, y. This is shown by
1
Ar = lao,l

k n . r = {Br, Cr,Dr, ... } =ja~.1 +b~.II_

n-I,2,3. ., Figure 6 Scheme for superposition of three onefold contri-
'n,,, = {a", f3", Ya. ...}= arctan (~) butions due t..0 the presence of reconstruction domains along
the three [110] equivalent directions (onefold polarization
an.1 n=1.2,3, ..
1 vectors hold for the case ofpp polarization),
A·=-a02
I 2 ' [110] directions at a 111 surface, the surface rec-
kn,i = {Bi, Ci , D i, ... } = /a~,2 + b~'21_ ,
n-l,_,3,
onstruction occurs in three domains, as shown by Barth
et al. [130]. If the reconstruction domains are equally
distributed, all onefold (vectorial) contributions vanish,
'n,b = {ab, f3b' Yb- ...} = arctan (~n'2) The observation of Cs for a reconstructed Au(lll) surface
n,2 n=I,2,3, ...
means an unequal distribution of the domain, and its
(28) rotational symmetry term shows an angular offset B
where the polarization indices have been omitted, and cos( cp + a) [129]. This is illustrated in Fig, 6. For the
again the dots mean a possible extension ofthis approach onefold contribution it shows a superposition of three
to higher rotational symmetries than n = 3. The angular vectors to an effective one having a distinct orientation
offset terms, a, f3, }', have a clear geometric meaning, dis- (see also Sec. v'B.3). In addition, preferentially oriented
cussed below. steps exhibit their own onefold contribution, as shown
by Friedrich et al. [131] for stepped Au(lll) surfaces.
2, Angular Offset Terms a, f3, Y Evidently, there are multiple, possibly physically dis-
Surprisingly enough, the angular offset terms appear in tinct, sources for the onefold symmetry element. Similar
Eq. (28) as two possibly different sets, as a,,, f3'" Y", .. , considerations hold for all other rotational symmetries.
and ab, f3b' Yb' .. " contrary to the view that each For a deeper understanding let us consider the nonlinear
rotational symmetry term should have a single offset polarization vector of second order, p2w(cp), instead of
angle common to its real and imaginary parts, in the sense the SH field (E(2w, cp)oc.e 2w . p2w(cp)). The former is
that k n cos (n(cp + Sn)) = Re(kn) cos(n(cp + sn))+i 1m regarded as a sum over n different polarization vectors
accounting for the isotropic contribution and n rotational
(kn) cos(n( cp + Sn))'
Such an angular offset term was first addressed by symmetry contributions:
Pettinger et al. [129] for the case of a Au(lll) electrode as
a result of a superposition of three reconstruction p2W(cp) = P6w + P;'" (cp + a) + P~W(2cp + 2f3)
(29)
domains, Au(lll) is known to reconstruct in the form of + P~W(3cp + 3y) + .,,
.J3 x 23 due to compression of the top layer in [110]
direction by about 4%. Because there are three equivalent where is dipole approximation n = 0, 1, 2, 3. Thus, we
384 Pettinger et al.

achieve a clear understanding of the angular terms a, {3, y

and y. Each of the P~~I vectors in general represents a
real parts
vector sum over indivIdual contributions and therefore
can have an orientation different from the standard
orientation. This is described by the angular offsets a, {3,
y, ....
At a first glance, however, it is not comprehensible why x
the real and the imaginary parts ofP~w can have different
spacial orientations.To understand this peculiar property,
let us discuss the superposition of only two distinct
nonlinear onefold polarizabilities described by the ~ B]
coefficients B I and B 2 having different orientations 'I
and '2. Both B I and B 2 are complex numbers. The ~ B2
measured angular dependence results from the projection imaginary y
. . . Beff
ofthe effective polarization onto the field vector direction parts ----t-.
defined by the polarizer. This would be trivial if the
coefficients B I and B2 were both real numbers, but they
are unequal and complex. Thus, the superposition has to
be separated into a superposition of the real and of the
imaginary parts as sketched in Fig. 7. The real and the x
imaginary parts are displayed as vectors in an abstract
xy plane (which should not be confused with the surface).
In this way, we can describe both the projection of the
polarization vectors, oriented in 3D space on the field
direction and their vectorial superposition [127]. As seen Figure 7 Superposition oftwo polarizability vectors. The two
from Fig. 7, the spatial orientation of B 1 is different from initial vectors (white and hatched vectors, here with!, = 00 and
that of B 2 . As required, however, the real and the !2 = 125°) are complex quantities. Their real and imaginary
imaginary parts of B I show the same orientation, parts have the same orientation in thexy plane, The black vectors
indicated by the angle 'I. The same holds for B 2 with the represent the effective complex quantities that arise from
superposition of the white and the hatched vectors. The real
angle '2. The black vectors, Beff, in Fig. 7 illustrate the
and the imaginary parts of the resulting effective polarizability
resulting coefficients describing the effective nonlinear
(black vectors) have distinct orientations in the xy plane. (From
polarizability after the superposition of the two Ref. 127.)
polarizabilities described by B I and B 2 . Evidently, the
effective vectors resulting from the superposition have dif-
ferent orientations for the real and the imaginary parts where kn.eff , 'n.a, and 'n,a are obtained by trigonometric
of Beff . The experimental consequence is that the relationships.
measured real and imaginary parts of the onefold sym- The original sources of n-fold rotational symmetries
metry reaches their maxima at distinct rotation angles cp. are characterized by k n.b ... , kn,m (complex numbers)
In turn, if different geometric angles for the real and and their orientations as 'n.l, ... , 'n,m. They are hidden
the imaginary parts are observed experimentally, then because from the analysis of the SHG anisotropy pattern
this evidences the presence of at least two physically dif- we obtain "only" the following four parameters of the
ferent SHG sources having different spatial orientations resulting effective polarizability: Re(kn), Im(k n), 'n.a, 'n.b
and different complex planes. An extension of this con- (here and in the following we omit the index elf [127,128].
cept to all rotational symmetries and to more than two
distinct sources is straightforward: E. Potential Dependence of the Nonlinear
Polarization
k n.1 cos(n (cp + 'n.I)) + k n,2 cos(n (cp + 'n,2)) + ...
+ kn,m cos(n (cp + 'n,m)) 1. Potential Dependence of SHG Within the
Phenomenological Model
= Re (kn,eff) cos(n (cp + 'n,a))
In an electrochemical environment, both the applied
+ i 1m (kn,eff) cos(n (cp + 'n.a)) potential and the ionic or molecular adsorption deter-
(30) mine the charge density of the metal. The potential drop
SHG Anisotropy
across the electrochemical double layer results in a large
static electric field, Edc , perpendicular to the surface. Its
strength can reach 10 9 Vim and higher. Consequently,
the high static and the intense electromagnetic fields can
induce third-order nonlinear processes leading to a
supplementary nonlinear polarization with frequency
2w:
P~~(2w) =/2): E(w)E(w) + /3): EdcE(w)E(w)
= x~;i (4)) : E (w ) E (w )
(31 )
Thus, the various elements ofthe resulting effective tensor
x~J( 4» depend on the cell potential 4> but in quite distinct
ways. In particular, the Xzzz component is expected to
show a linear dependence on the electric field existing
across the interface. Therefore, the response on the poten-
tial should show a parabolic behavior, as long as the Xzzz
dominates the potential dependent SHG response. Split-
ting the polarization into its potential dependent and
independent parts, one yields in analogy to
Guyot-Sionnest and Tadjeddine [40]:
P~;i(2w) = P~2(2w)b d- I ~<1> + P(2)(2w)
where P~2(2w) and p(2 1(2w) are the third- and
second-order polarizations, d is the thickness ofthe elec-
tric double layer, and b takes into account that only a
fraction of the total potential drop takes place in the
region where the SH response is generated. ~<1> is defined
by ~<1> = (<1>-<1>pzc) with <1> representing the applied poten-
tial and <1>J)zc the potential of zero charge. De~ning
a = e2m • P~c (2w) bd- 1 and b = e2m • P(2)(2w), we arnve at
known as the parabolic model [1,40,132]. Guyot-Sionnest
and Tadjeddine [40] studied the potential dependent SH
response on Ag(lll) and Au(lll) electrodes at various
exciting wavelengths. They found that the cubic
nonlinearity makes an important contribution to SHG
in the free electron regime. In this regime, the parabolic
model is valid, but not in the interband transition regime.
At single crystalline electrodes, different contributions
to the potential dependence of the SH response can be
discerned. Besides the Xzzz element of the susceptibility
tensor, other elements, in particular those reflecting the
transition from a reconstructed to an unreconstructed
surface, also exhibit an (indirect) influence of the
potential. Anisotropy measurements are the method of
choice to extract distinct potential behavior of the A, B,
C, and D terms [4,102,121-123,133]. For the A term, the
385
isotropic contribution to SHG, linear relationships with
the induced metallic charge density, O"M, were reported
for a variety of systems [121,123,129,134-137].
2. Potential Dependence of SHG Within a Jellium
Model
Semiempirical models, as those discussed above, are
powerful when symmetry considerations play an import-
ant role. They do not, however, give an answer on quanti-
tative questions, such as on the strength of interaction or
the dependence on potential or charge density. This is
the field ofquantum mechanical formalisms used to cal-
culate the nonlinear response of a free electron metal
modeled by a jellium. Within its framework, many
experimental findings can be explained at least qualitat-
ively [see, e.g., 138-140]. For a structureless model
surface, such as that of jellium, the SHG response is
characterized by three coefficients, a, b, and d, that have
the following meaning: a characterizes the SHG response
caused by currents driven in the z direction, perpendicu-
lar to the metal surface; b specifies the contribution by
currents induced parallel to the metal surface; and d is
due to the magnetic dipole moment from the bulk. Within
the jellium model, b = -1 and d = 1. In the framework of
the jellium model, only the coefficient a depends on the
electronic structure of the interface, i.e., on the electronic
density of the bulk and on the charge density at the
surface. The comparison of theoretical predictions and
experimental results concerning the potential depen-
dence of the SHG response for silver electrodes are
reviewed in Sec. V CA.
To account for the crystal structure, one has to
incorporate, e.g., a lattice of pseudopotentials into the
electron gas [141]; Leiva and Schmickler [142] used this
approach to calculate the coefficient a as a function of
the surface charge density for the principal single crystal
surfaces ofseveral metals in the low frequency region.
Recently, Petukhov [143] investigated the origin of the
rotational anisotropy of a Ag(lll) surface. According to
his results, the anisotropic SH response in the low fre-
quency region is caused by the necks ofthe Fermi surface
near the L-points of the Brillouin zone [144]. This
practically implies an independence on the surface
charge or on the electric potential. This is not consistent
with the experimental experience.
V. RESULTS AND DISCUSSION
A. Early SHG Experiments on Electrodes
SHG at electrodes has become a hot topic in the early
1980s. It found great interest first in connection with
SERS investigated mostly on silver surfaces. SERS was
386 Pettinger et al.

T I

• 50 mM Urea
... £> 5 mM Pb 2 - I
•I
• 0.1 M Na CI0 4
I
I
/
I

/
ctl
C ~ /
OJ '£>""1 /
en £> '\.
I \. I
en £>~\. /
~ ""-.\. /
I
-
£>\ ~ I /
!~ II
£> ~~ I
"~ ./..
£>r/:'~ ~././
\
, I ....... I::::o.~_.---.-. I

o -500 -1000
mV vs. Ag/AgCI

Figure 8 SHG from a thin silver film (45 nm) in contact with a solution of 0.1 M NaCI0 4 (solid circles), with 0.1 M NaCI0 4 + 50 mM
urea (solid squares), and with a solution of 0.1 M sodium acetate + 5 mM lead acetate (open triangles). (From Ref. 148.)

observed for a few noble metals but only when the surface
was activated by electrochemical or other means [145].
One result of the activation is the roughening of the
surface. It was shown that the presence of roughness
supports the excitation of (more or less localized) surface
plasmons that causes a substantial increase ofthe electro-
magnetic field at the surface. At that time, one of the key
questions in the SERS field was whether at all and to
which extent SERS is related to such a rise in the local field
near a metal surface [see refs. in 145]. Because interfacial
SHG depends on the 4th power of the surface EM field
produced by the incident laser, a field enhancement at
rough silver surfaces should lead also to a significant
enhancement of SHG at these surfaces compared with
SHG at smooth ones. In fact, large surface enhancements
for SHG by several orders of magnitude were reported
[146]. This was considered as clear evidence for an
important role of the electromagnetic enhancement
mechanism in SERS [147].
In these measurements a remarkable dependence of
SHG on potential was observed. Consequently, the
research interest turned also toward the relationships
between SHG and electrochemical processes.
Corn et al. [148] presented a nice investigation on the
surface plasmon-enhanced SHG at thin silver film elec-
trodes in which they used a field enhancement for SHG,
this time on smooth optically flat films composed of
crystallites showing mostly 111 orientation. The surface
plasmons were excited by the technique of attenuated
total reflection. Figure 8 reproduces the potential depen-
dence ofSHG intensity at a thin silver film in contact with
0.1 M NaCI0 4 electrolyte. The curve shows a minimum
around - 750 mY, which is close to the PZC for Ag(lll).
The authors noted that although their films were
polycrystalline, mostofthe crystallites were oriented with
the III face parallel to the surface. The adsorption of urea
at the film electrode should occur around the PZc. It
should induce a little shift of the PZC and change the
dielectric constant and the nonlinear susceptibility
within the interfacial region. In fact, a little shift of the
PZC was observed and also a significant decrease of the
SHG intensity negative of the PZC point. The deposition
of a monolayer of Pb caused a dramatic decrease in the
SHG intensity. These observations indicate that the
SHG signal arises from the metal surface [148]. The
authors consider the parabolic model [1,40,132] and relate
T
I
I
SHG Anisotropy
the SH signal to the square of the excess charge on the
I electrode (which is roughly proportional to the static elec-
t tric field at the interface) [148].
The adsorption of ions and their influence on SHG at
polycrystalline silver electrodes became another field of
interesting surface studies [34]. Monolayer coverages of
sulfate adsorbed on silver electrodes were detected using
surface SHG. This observation illustrated the enormous
sensitivity of this nonlinear optical method [149]. Biwer
et al. [150] showed in their study on film formations on
iron electrodes that surface SHG is not restricted to noble
metals.
One of the first SHG studies in nonaqueous sol-
utions were conducted by Campbell and Corn [151],
who investigated the hydrogen evolution from poly-
crystalline silver electrodes in acetonitrile. The authors
proposed a two-step reaction process consisting of an
initial ion discharge reaction creating an adsorbed
monoatomic hydrogen and a diatomic surface combi-
nation process.
Evidently, surface SHG became more and more an in
situ tool for electrochemical processes, first at rough, then
at smooth metal surfaces, and finally at crystalline
samples.
B. SHG Anisotropy at Metal Electrodes
The use ofcrystalline materials turned out to be a big step
forward in vacuum surface science. In electrochemistry,
the crystalline electrodes were used on a large scale, once
techniques had been developed that characterized the
surface and adlayer structures. Among them is the tech-
nique of the emersion ofelectrodes and their subsequent
transfer into a vacuum chamber to perform detailed sur-
face structural studies [152]. To the optical spectroscopies
applied in situ to crystalline electrodes belong electro-
reflectance [153], surface plasmon spectroscopy [154],
IR [155] and Raman spectroscopy [145], and last but not
least SHG [14].
The rotational anisotropy ofthe SHG intensity from an
Ag(lll) single-crystal electrode was first reported by
Shannon, Koos, and Richmond [111-113]. The authors
correlated its pattern with interfacial symmetries and its
variation by changes of the nonlinear susceptibility and
surface structure.
A SHG anisotropy was reported also for crystalline
gold [156], copper [157], and platinum electrodes
[158,159]. A broad study was started by several groups to
eludicate the various sources and parameters of the
nonlinear response: The main questions were: how is
SHG affected by the optical resonances, the electrode
potential, by adsorption and chemisorption, the influ-
387
ence of surfaces structure and reconstruction, and what
are the major sources ofthe nonlinear response? Clearly,
these effects show mutual dependences.
The effect ofthe exciting frequency on SHG at Ag(1l1)
and Ag(llO) surfaces was studied by Georgiadis et al.
[44,160]. The authors noted differences in the 1064- and
532-nm excitations attributed to an increased contri-
bution of surface interband transitions for higher exci-
tation energies and possible participation of surface
states in the SH processes for excitations between 610
and 640 nm. The authors also observed a potential
dependence of the anisotropic contribution when the
SH frequency lies in the UV region, but not when it is in
the visible region. Figure 9 illustrates this remarkable
behavior by showing the potential dependence of the
SHG response at Ag(lll) electrodes. The intensities were
recorded at pp and ss polarization and at a polar angle
of 30°. Thus, the former experiment only yields the
isotropic and the latter the anisotropic components of
the SHG intensity. These data are plotted vs. electrode
potential for four different exciting frequencies.
Wong and Richmond [161] examined the SH response
ofAg(lll) and Au(lll) electrodes at infrared wavelengths.
For both electrodes the anisotropy remains significant
in the absence ofresonances, and the SH intensity roughly
follows the dielectric functions of the two metals.
Guyot-Sionnest and Tadjeddine [40] compared the SH
potential dependence of Ag(lll) and Au(111) electrodes
at wavelengths within and above the free electron regime.
In the former, the cubic nonlinear susceptibility is
dominant, whereas for the latter the quadratic nonlinear
susceptibility of the d-electrons is prevailing. This causes
the distinct potential dependence seen for the two elec-
trodes [40].
The influence of adsorption of iodine and CO on
Pt(111) was studied by Lynch et al. [158]. The authors
attributed the anisotropic response from the surface
either to a reduction of the average surface symmetry
from C3v to C3 or to an adsorbate-induced additional
anisotropic nonlocal contribution. In a subsequent paper
the authors showed that the SHG signal from the
well-ordered Pt(111) surface in perchloric acid also
reveals the presence ofan ordered chemisorbed overlayer,
probably ofa hydrogen species, at all electrode potentials
negative of the butterfly peaks [159].
Friedrich et al. [156,162] demonstrated that rec-
onstruction at Au(111) and Au(100) electrodes has a sig-
nificant impact on the SHG anisotropy. The authors
monitored the transition from reconstructed to
unreconstructed surfaces in situ. One example is given in
Fig. 10. It contains two groups of three polar plots of ani-
sotropy curves with the polarization conditions and the
388 Pettinger et at.

Ag (111) cp=30 Ag (111) cp=30

o
o
o 0 (0) 532nm (b) 532 nm
oo~
o 0
o 0 0 0
{l.
00 0
0
0 0
° ... ~
q, 0
I-+:J 00
0#~{l.~..R.. ~_h ~~ ~
6ilt0 {J
~':'0G\9
{J0 0 0 till
0°r1J..{) ;fal6"'" 0° W-qj9
o o,ptlllaJ 0-JIf} till
000 0 ttl""!:
#
°r¥ °
~

....en 610nm .........

c:::
::l
610nm ....
en
c:::
° ::l
O-~c9'ldb~~
o
...0
...
'-"
o ...o
...0

'-"
>.
~
~
>.
U1
c::: en
Q) c
~

c 640nro g"
....c:::
Q)

0° 640nm
I I
(f)
(f)

o o
0- 0-
I r
0- U1

1064 nm 1064 om

-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2

Applied Voltage vs Ag/AgCI (V) Applied Voltage vs Ag/ AgCI (V)

Figure 9 Comparison of the potential dependence of the isotropic (a) and anisotropic (b) components to the SH intensity
from Ag(lll) at the indicated wavelengths. The solution was 0.25 M Na2S04 at a pH of 3.5. An incident angle of 45° was used. (From
Ref. 44.)

potential denoted in each plot. The first group on the left
side holds for an unreconstructed Au(lll)-(l xl) surface
and the second group for a reconstructed
Au(IIl)-(.J3 x 23) surface, respectively. Evidently, the left
group shows distinct anisotropy patterns, but all of them
exhibit the expected C3v symmetry, whereas the right
group shows the superposition of threefold and onefold
rotational symmetries such that the overall rotational
symmetry is Cs . It was shown that this Au(lll)-
(l xl)+---+Au(IIl)-(.J3 x 23) transition is potential or
adsorption controlled and reversible [42,121,122,156,162].
In a series of papers, Pettinger et al. investigated the
influence of ionic and molecular adsorption on surface
reconstruction and also on the isotropic part of the
SH response at Au(IIl) and Au(llO) electrodes
[42,102,121,122,129,134-137,162,163].
SHG Anisotropy 389

r I I "I
I
. pip
I

180 0 180 [ll~._.~l • 0 0

0

I
I
[1l2J i
L -.J L -.J
I I "I I "I
I
. pis
I

lRO [Jl~._._ . . _._._.

0 180 0

L
* 0

[112J
I
I
i
o 0

-.J L -.J
I "I I "I

180 o 180 o

L L
Figure 10 Polar plots ofSHG intensity vs. rotational angle, cp, for positive (left) and negative (right) potentials. (Upzc = +270 mY),
and for pp, ps, and ss polarization of incident ill and emitted 20) beams. Electrolyte: 0.1 M HCl04; (open circles) experimental data;
f;pH f;r
(solid lines) fit by or ~ o:::~=o d;n) COS(ncp))2, U = pp or ps), or f~r ~ (dl3) sin 3cp - d(l) sin 3cp). (From Ref. 121.)

In two three-dimensional plots, Fig. 11 shows the
potential-induced changes ofthe Au(110) anisotropy pat-
tern in the absence and in the presence of specific
adsorbing bromide ions in solution. The left plot exhibits
a gradual change of the pattern with potential shifting
from negative to positive values. The right plot first shows
a similar development at negative potentials, but in the
potential regime of bromide adsorption a fast change
toward an unreconstructed Au(110) surface can be clearly
seen.
The molecular adsorption can be monitored by using
SHG anisotropy. Recording the SHG intensity of a
Au(lll) electrode vs. potential for three polar angles at
qJ = 0 30°, 60°, one can compute the complex isotropic
0
,
390 Pettinger et al.

(a) (b)
If .-.. _- ----:~==:==~::--

~
U
rJ)

-0.9 V

-0-100-200 -300 ·0-100-200-300-

.cp -----I.~ cp
Figure 11 Three-dimensional plots of the SHG anisotropy for an Au(1W) electrode vs. the rotational angle cp and vs. the electrode
potential U (a) Pure 0.1 MNaCl0 4 ; (b) 0.1 M NaCl0 4 + I mM NaBr.The potential is stepped from -0.9 Vto +1.2 V. (From Ref. 129.)

term and the threefold rotational term vs. potential, using d-band located about 2 eV below the Fermi level. For
the approximation /sHG(<p)=IAr+i A;+D cos (<p)1 the pure solution of the supporting electrolyte, the phase
(where we use the arbitrariness ofthe total phase to define angles changes little with potential until the onset of
D as a real quantity) [134]. Figure 12 reproduces the vari- OH adsorption (at E> 0.5 V [SeE]). The phase angle
ation ofthe phase angle, c5 = arctan(A;jA r ) with the elec- is apparently shifted toward lower values by adsorbed
trode potential. The line (1) is the curve for the pure
supporting electrolyte, the line (3) depicts the curve deter-
mined in the presence of 2,2/-bipyridine (22BPY), and
the line (2) shows the change of the phase angle in the
presence of adsorbed pyridine described in a previous
work [102]. The phase angle in the pure solution of the 70
supporting electrolyte is equal to 60° at the PZC of the
--
0

Au(111) electrode. This value is close to the phase angle t-o

000 determined under similar experimental conditions ~ 60
0

by Wong and Richmond [161]. The phase angle reported c~

by them was determined from the interference pattern ~
1;1)
between the SH fields generated by the Au(llI) surface ~

and a quartz reference [16]. In contrast, the value deter- ..cc. 50

mined by Yang et al. [134] is an estimate based on the
assumption that the phase of the threefold symmetry
amplitude does not change and that c5 shows the true 40, I , I "

phase variation of the isotropic term. -500 0 SOO 1000

Wong and Richmond [161] demonstrated that the
(relative) phase angle is expected to be 90° when
interband transitions are absent. A smaller value of the
phase angle indicates that the interband transitions con-
tribute to the observed SH signal. In the case of the Au
electrode when the energy of the input photons is 1.17 eV,
the interband transition involves the upper edge of the
ESCE/mV
Figure 12 Dependence of the phase angle (j = arctan(A,j A r )
on the electrode potential for: (1) 0.1 M NaCl0 4 supporting
electrolyte, (2) 0.1 M NaCl0 4 + I x 10- 3 M bipyridine, (3)
0.1 M NaCl0 4 + 2 x 10- 3 M pyridine solutions. (From Ref.
134.)

,
..............
SHG Anisotropy 391

organic molecules. The decrease of the phase angle pro-

ceeds in two well-defined steps in the presence of := ps polarization (a)
.Q 300
adsorbed pyridine. The first step corresponds to adsorp- ~""
tion of the n-bonded molecule, and the second step is 200
E
observed at potentials where pyridine assumes the til

N-bonded geometry. The change of the phase angle is ....=

...
.5
gradual in the case of 22BPY, and this behavior is
consistent with the gradual character of the transition
=
~
1+---lf--+---:+-=--I--+----:::.r-77"i-:I 25
from the n-bonded to the N-bonded state of adsorbed 20
15 ~
bipyridine. The lowering of the phase angle by adsorbed ;;:
organic molecules suggests that adsorbed pyridine and =
= 10 ~
22BPYenhance the participation of the resonant chan- .Q
5 ~
nel to the generation of SH photons, due to orbital ""
o:l
o ..
mixing of the molecular orbitals of the adsorbate with
the electronic states from the d-band of the group IE
:!:!
... -5 !<:>

metals [164].
l;::

'a""<:>
25 g
20 fir
The above discussed results illustrate the great poten- e
tial of SHG for interfacial studies. Because mainly SH ""
o:l
.c
15 .,
Ql

intensities were measured, the information present in
the SH field is lost to some extent. In addition, more infor-
mation is lost when using simple models in the analysis
of the data, thereby neglecting the influence of steps
and other irregularities and of surface reconstruction.
By wavelength and (relative) phase measurements one
can achieve additional, valuable, and important
information, but quite more information on the interface
and on the SH process itself can be revealed when one
determines the anisotropy of the SH field and
decomposes it into its various symmetry contributions
without using restricting assumptions.
C. ISHGA at Au and Ag Electrodes
The following section presents first results and insights
gained by applying the interference SHG anisotropy to
crystalline gold and silver electrodes. The aim of these
investigations is to extract information on how the
rotational symmetries of the two classes of electrodes
evolve with the variation of the electrode potential. The
main objectives are to understand the complicated struc-
tural changes occurring at Au(lW) electrodes as seen by
SHG, to monitor the influence of adsorption of halide
ions on the SH response of an Au(ll1) surface, and to
compare the variation of the A term (of Ag(ll1) and
Ag(lW) electrodes) with quantum mechanical calcu-
lations of the nonlinear response ofa free electron metal
modeled by ajellium.
1. Geometrical Offset Angles at Au(110)
In the theoretical section we showed that the ISHGA
method yields the full set ofthe susceptibility coefficients
A, B, C, and D but also the geometrical offset angles rx,
"0 10 ::r
=
<:> 5 =
e.
~
..."" o 1il"
-5
o 50 100 150 200 250 300
Angle of rotation qJ ;0
Figure 13 SHG intensity and SH field at a reconstructed
Au(llO) surface ys. angle of rotation recorded under ps
polarization at -600 mV YS. SeE. (a) SHG anisotropy of the
Au(llO) surface (open circles; measured values; solid line, result
from ISHGA). (b and c) Real and imaginary parts (Re(EPS (2w,
qJ)) Im(EPS (2w, qJ)) of the SH field. The filled circles are
experimental difference curves according to Eqs. (25) and (26).
The thick solid line in the upper part of the graph results from
Fourier analysis of these curves using Eqs. (25) and (26). In the
lower part of the graphs band c the symmetry components
(onefold, twofold, and threefold) are shown that constitute the
SH field. (From Ref. 127.)
[3, and y that were not considered in literature up to now.
However, they must be regarded to fully render a complex
SHG anisotropy pattern such as that of an Au(110) elec-
trode [127]. For ps and pp polarization, Figs. 13a and 14a
show the SHG anisotropy patterns that clearly do not
possess a C2v symmetry (as expected for an ideal 110
surface). The graphs in Figs. 13b, 14b, 13c, and 14c display
the anisotropy of the real and imaginary parts of the SH
field generated at the Au(110) surface, respectively. The
data shown by the filled circles in Figs. 13 and 14 represent
experimental data calculated from the original
experimental curves ofthe ISHGA experiment using Eqs.
(25) and (26). From the experimental difference curves
392 Pettinger et al.

in Figs. 13b, 13c, 14b, and 14c, one can easily evaluate the
pp polarization
nonlinear susceptibility coefficients and the geometrical =
.Q 800
offset angles [see Eq. (28)]. ""
~
(a) Reconstructed Au (110), ps Polarization. For ps .~
III
polarization the SH anisotropy shows five maxima having =
~
different heights and being not equidistant (Fig. 13a), a .5
behavior similar to that reported by Keefe et al. [124] for ==
rJl
the same system. Using the ISHGA, we obtain from the 15
curves in Fig. 13b and c the following values for the sus- (b)
ceptibility coefficients APs, J3fJS, Cps, and [)IJS:
-=
III

'8
10 aa
rJl

APS =- 2.9 + i1.2 = 3.1eil58°;

J3Ps = - 2.1 - i1.7 = 2.7ei219 ';
.Q

--""
0=
5
-
~

~
""
"0 0 ~
Cps = 9.0 - i2.8 = 9.4e i343 '; QJ
I;:
.S:I
g
~
15
f)Ps =4.5 + n.8 = 9.0e i60° =
0 =
! ij
e --
Now let us consider the geometric angles. As noted in ""
0=
.c:
10 ~

?-
Sec. IY.D.2, there are two equations, (25) and (26), from "0
=
0 5 =
=
which these offset angles can be calculated. They are, ""
Q; ~
rJl
therefore, distinguished by the indices a and b: 0
(n.a = {lX a , fJa' 'Ya} and (n,b = {lXb' fJb' 'Yb}' This labeling
indicates the distinct origins of the two sets of geometric
angles and does not associate a complex character to
o 50 100 150 200 250 300 350
Angle of rotation <p / 0
them. As discussed in Sec. IY.D.2, differences in (n,a
and (n.b give evidence that the nth symmetry contri-
Figure 14 SHG intensity and SH field at a reconstructed
bution results from several physically distinct sources.
Au(IlO) surface vs. angle of rotation recorded under pp
Figure 13b and c illustrates this by showing, in addition polarization at -600 mY vs. SeE. (a) SHG anisotropy of the
to the experimental data, three of four symmetry com- Au(IlO) surface (open circles, measured values; solid line; result
ponents that, together with the isotropic term, consti- from ISHGA). (b and c) Real and imaginary parts (Re(EPP (2w,
tute the SH field (thick solid line). There is also a weak q»), Im(EPP (2w, q>)) of SH field. The filled circles are
fourfold symmetry component originating from an elec- experimental difference curves. The computation of the data
tric quadrupole contribution to the total nonlinear and the notation of the curves are analogous to Fig. 13. (From
polarization. It is not presented in this figure, but it is Ref. 127.)
necessary to take it into account to reproduce the
experimental data shown in the graph.
Next let us compare the location of the maxima of the
symmetry superimposed by a smaller threefold
onefold symmetry component displayed as dotted lines
amplitude. From the presented middle and bottom
in Fig. 13b and c. Obviously, the real and the imaginary
panels, the susceptibility coefficients are calculated:
parts of the onefold symmetry reach their maximum at
different polar angles cp. The same is observed for the
APP = - 17.6 - il3.0 = 21.9 ei216°;
threefold symmetry component (solid line), also dis-
played in these figures. The following table presents the J3PP = - 1.2 - i 1. 7 = 2.leil34c ;
two different sets of offset angles: CPP =3.3 - i 1.1 = 3.5ei34oo;
IX~S = _ 64°; RPS
Pa
= 320.
'
~S = -110; f)PP =0.9 + i 3.3 = 3.4e'"J50
rxf,s = + 7°; fJf,s = 32°; Yj,s = -170
As for the case ofps polarization, there are also two dif-
ferent sets ofgeometric angles for pp polarization:
(b) Reconstructed Au (110), pp Polarization. Figure 14
presents the results for pp polarization in the same way
as Fig. 13. The upper panel of Fig. 14 displays the standard
1X~f' = - 86° PI = -44° ~P = 5°

SH anisotropy that clearly shows a twofold rotational rxf,P = - 29° fJf,P = _5° Yj,P = _10
f
SHG Anisotropy 393

The displacement between the real and the imaginary

Re(E PP(2w,cp)) 10
parts of the twofold symmetry component is illustrated
in Fig. 14. Note that because of the different signs of the 8
real and imaginary parts of CPP the maxima and minima 6
are reversed between the real and imaginary parts. 4 '"
'<
2 8
The above presented results provide clear evidence for
the effective onefold, twofold, and threefold rotational
symmetries arising from two or more physically distinct
0
-2
-
8
.,
~

'<
t"l
0
sources. In this view, it is obvious why earlier models for -4 8
the Au(llO)-SHG anisotropy failed [123,124]: They did 10 ~
'8
=
not account for the structural complexity inherent to a 8 It =
-..
AuOW) surface that is in a sense "buried" within the offset
angles.
6 .,
Ql

4 5"

2. Potential Dependence of Susceptibility at AU(110)

~) General Potential Dependence. Thevariation ofthe
potential changes the free energy of the surface and thus
the forces driving the reconstruction and microfaceting.
The full picture ofstructural changes, as far as is seen by
SHG, can be achieved only when each effective rotational
symmetry contribution to total the SH field is monitored
as a function ofpotential, adsorption, etc.
Figure IS shows the angle dependence ofthe real part of
the SH field and their harmonic contributions for two dif-
ferent electrode potentials at pp polarization. The open
circles represent the experimental values calculated
according to Eq. (25). The thick solid line is computed
from the corresponding susceptibility and angular offset
terms, obtained from the first five elements (an, bn,
n = O· .. 4) ofthe Fourier series according to Eq. (28) (the
meaning of the fourth element is discussed below). In the
lower part ofeach panel of Fig. 15, only the first three sym-
metry components are shown for the sake ofclarity (dotted
line, onefold; dashed line, twofold; solid line, threefold).
Comparing the anisotropy curves for the two applied
potentials ( -600 and 600 mY) in Fig. 15, it is evident that
both the amplitudes of the symmetry components and
their angular position vary. So shifts the twofold sym-
metry component (real part) by about 500 between the
reconstructed (-600 mY) and the unreconstructed
(+600 mY) surface. The maxima of the onefold and
threefold symmetry components also show small shifts
in their positions. The nature of these shifts is discussed
below. Analogous observations were made for the
imaginary part of the SH field.
Let us now discuss the variations of nonlinear
polarizability for pp polarization presented in Fig. 16.
For the sake of clarity, we only display the curves calcul-
ated in the same way as described for the thick solid line
of Fig. 15. Between -600 and 0 mY, the shape of the
curves in the upper panel flattens somewhat. Around
2
0
-2
-=
2.
'"
-30 ,.. . .,.,.. .
...."" "" .
-4
o 50 100 150 200 250 300 350
angle of rotation cp r
Figure 15 Real part ofthe SH field Re (£(201, rp)) generated at
a AuOW) electrode for two different potentials (upper graph,
-600 mY; lower graph, +600 mY). The open circles represent
the measured SH field [see Eg. (25)]. The thick solid line is cal-
culated from the Fourier analysis using the first five (n = 0 ... 4)
Fourier elements. The first three symmetry elements ftz = I, 2,
3) are shown in the lower part of each graph. Especially for the
twofold symmetry part (n = 2) there is a considerable shift in
the geometric angle ({31 i- Ih)' (From Ref. 128.)
o mY, the large maximum at 240° diminishes, and at
300 mY, the three maxima from a threefold symmetry
component become more pronounced.
In contrast, the shape of the imaginary part of the SH
field remains nearly unchanged over the whole potential
range. As shown in the lower panel of Fig. 16, there are
clearly three maxima at all potentials that shift slightly
with potential in the orderof ± 10°. The distinctly varying
vertical offset of the curves, seen in both panels, arises
from the potential dependence of the isotropic term. This
behavior is discussed elsewhere in detail [126]. For ps
polarization the potential dependence is less pronounced
Fig. 17). In particular there is only a minor variation of
the APs term.
(b) Potential Dependence of the Symmetry Com-
ponents. Each effective rotational symmetry contri-
bution must be characterized by four parameters. In the
following, we denote the list of these parameters in a
slightly different but compact form: The twofold
rotational symmetry we characterize by {C} = {IC!, be,
f3a' f3b}' Analogous notations are applied for the onefold
394 Pettinger et al.

pp polarization ps polarization
tl ",
Re(E PP(2w,<p» 'S Re(E(2w,<p» /.: ...
.-._ .... .' .... - ............
.cr..=
••.. -0.'.
,.,.
,. .!~\.'.
.;l
=
=
.c
.................. ~'
, -
-'"
iE
'.\
\;"

; " , ... - ............ -

~-"
~
:.c ·600mV
OmV
·30 I- " , , " ~
...... _... 'C 600mV
iE
:.c
-·600mV
OmV
300mV
600mV ~Q,
r..
~
'C
'"
"S
.~
Q,
§ 0
r..
~
=
.5
==
o
·20 ~.~..~..~.=.~.~.:.:.~.; . : .: ~.::.::."._ ~. . . . . . .
.>••.>••.>•• •
..... ~.<#
~." •
·10
, ..... - .....
·30
.... ,
......... ..
.,' ............ _ - _ . ..-' o 50 100 150 200 250 300 350
angle of rotation <p I 0
o 50 100 150 200 250 300 350
angle of rotation <p r Figure 17 SH field generated at the Au(1lO) surface at various
electrode potentials for ps polarization. In the upper and lower
Figure 16 SH field generated at the Au(1lO) surface at various graph the real and imaginary parts of the SH field, Re (E(2w,
electrode potentials for pp polarization. In the upper and lower cp» and Im(E(2w, cp», are displayed. (From Ref. 128.)
graph, the real and imaginary parts of the SH field, Re (E(2w,
cp)) and 1m (E(2w, cp», are displayed. (From Ref. 128.) '"
§ 4.0
.. •
o
I C PP I (twofold symmetry)
I D PP I (threefold symmetry)
-e~ 3.5 I~
i:j'1J"
and threefold rotational symmetries. Important is that all 00.0

four parameters can depend on potential and (specific) oO°1:looocoool;lo0 010l

adsorption. 2:
~ 3.0 001:).. 0
(c) TIvofold Symmetry Component. The twofold sym-
metry component exhibits a very distinct potential 2:'-l 2.5
dependence for pp and ps polarization. This is evident
from the comparison of {cPP } with {cPs}, shown in Figs.
18 and 19 and Figs. 20 and 21, respectively. Let us first
consider the amplitude and the complex phase for
ps polarization. The amplitude ICPS I increases continu-
_ .10 iP
o

~
'"~
·20
...----.-..
1···tr·'fi·.c··.c··t1··~··C"··I:I··.c······o .. c.··tl"1iJ
,0 .90 0

ously with potential, showing a small change in the Q,

slope around 0 mV where the lifting of ~
reconstruction/microfaceting begins (Fig. 20). The "S. ·30
complex phase iY'~ of the twofold symmetry remains § • a/P (twofold symmetry)
nearly constant over the whole potential region. -40 o alP (threefold symmetry) •
Contrary to that, IcPP I and iY'! behave completely dif-
·600 ·400 ·200 0 200 400 600
ferent (Fig. 18). The amplitude IcPP I is nearly constant
potential vs SeE I mv
until -200 mY. At more positive potentials it varies in a
parabolic manner, with a minimum around 300 mY.
The complex phase iY'! changes by about 25°. The onset Figure 18 Symmetry components ofthe SH field generated at
an Au(1lO) electrode for pp polarization displayed vs. electrode
of these changes corresponds roughly with the lifting of
potential. Upper graph: amplitudes (ICPPI and IlYPI) of the
the reconstruction. Lifting of the reconstruction of the twofold and threefold symmetry components. Lower graph:
Au(lW) surface must be understood as a gradual complex phases ({it' and 01'£) vs. electrode potential. For a better
transition from a microfaceted to an unreconstructed representation, the complex phase of the threefold symmetry
Au(llO)-(l xl) surface. In STM experiments performed component was subtracted by 90°. (From Ref. 128.)
SHG Anisotropy 395

pp polarization
.l!l 16 • I cpr 1 (twofold symmetry)

twofold symmetry
........ - .. "§ [JI D pr I (threefold symmetry)
O •••
O" 0
• tl a PP , 0 tl bPP • of 14
8::.Q .. 10
0:).
.. ...... Q
',0,
••,,'
.'-
"
o ...... 20 .......... ".' l!. 12
- 8::= 0 .. 0 9 e'# I::l •
~= ·30 0 -:.- -, - -Q, _ n 0 10
'!
[J [J [J
c' . -e.. l j ' . D •• i:i ---[J .
~ ~ ~ .... C" • -I!I' •• _•• 0 - ••••• EI- ••
".40 •.... -', '0-' - -,,'"
'C 0 .~ g[J

I ~~
20

15
threefold symmetry
- y /P, [J YbPP

~......
•
_

-
",
-
'
-
0
65
60 • • • • /
• .
•
• • •
• •
'\ III • +50·
~W . _ ./ \,
OJ
III
55.
!5: CIIl -- ~ .",\
"
.:
c.
50
[J
[J
..!?.···--e···_···_···· .. 11
[J

~ 5 •• · .. •• - .il OJ
~
[J p •• " ··c·',.
"6.
..
[J
.-e•. o ·· Et
e 45 ••••• [J
o Q._c-.oQ.-[j
[J •• Ip"' i3 _.0.. -e.• 1:7' 'c"
Q

'"' ..0 • ScP' (twofold symmetry)

-600 ·400 ·200 0 200 400 600

40
...11 [J SDPS ( threefold symmetry)
35
potential vs SCE I mV ·600 ·400 ·200 0 200 400 600
potential vs SCE I mV
Figure 19 Geometric angles calculated from the SH field gen-
erated at an Au(llO) surface under pp polarization, displayed Figure 20 Symmetry components ofthe SH field generated at
as a function of electrode potential. Upper graph: geometric an Au(llO) electrode for ps polarization displayed vs. electrode
angles ofthe twofold symmetry component, f3~P and 13ft Lower potential. Upper graph: amplitudes (IOSI and 11)I'sI) of the
graph: geometric angles ofthe threefold symmetry component, twofold and threefold symmetry components. Lower graph:
"laP and Itt (From Ref. 128.) complex phases «(/'~ and rY'd). For a better representation 50 0

was added to the complex phase of the twofold symmetry

component. (From Ref. 128.)
by Gao et al. [165,166] in perchloric acid, consistent
atomic resolution could only be obtained above 200 mV
vs. SCE and below -300 mV In the potential regime in
between these potentials, an atomic resolution was either dependence of the SH sources. Thus, if multiple SH
not observable or not reproducible. Probably, this is due sources exist, the measured quantities like amplitude,
to a relatively unstable surface where reconstructed and complex phase, and geometric angles result from a con-
unreconstructed parts of the surface are rapidly trans- structive or destructive interference of these sources.
formed into each other. In a SHG experiment, one Such a behavior is evident in Figs. 18 and 19 for the twofold
averages over a macroscopic surface region with symmetry component {CPP}. For ps polarization we con-
reconstructed and unreconstructed parts. Both have a clude that only one SHG source is present because the
twofold symmetry but ofdifferent nature. Associated with offset angles are equal, i.e., ~s = f31: s, and they do not vary
them, there exist distinct sources for the twofold sym- with potential. Consequently, IcPS I rises nearly linearly
metry contribution to SHG. The parabolic shape of the with increasing potential, whereas its complex phase (jP~
amplitude ICPP I is possibly due to the interference of these remains nearly constant.
two sources having distinct potential dependences. (d) Threefold Symmetry Component. The threefold
Let us further pursue the idea that, depending on the symmetry component of a Au(llO) electrode arises by
polarization condition (ps or pp), one or several sources two reasons: there is a microfaceting of the Au(llO) sur-
constitute the effective twofold symmetry contribution. face exhibiting 111 oriented surface elements and there
This conclusion is supported by a corresponding exist plaI!es with III orientation formed by steps running
behavior of the geometrical offset angle 13. In fact, the in the [110] direction. When the reconstruction is lifted,
upper panel of Fig. 19 displays a distinct variation of f3a the microfacets vanish. As a consequence, the amplitude
and f3h for pp polarization. This is not the case for ps of the threefold symmetry component should decrease
polarization shown in the upper graph of Fig. 21. Next, dramatically. But this is not the case, neither for pp nor
one has to take into account the possiblydistinct potential for ps polarization as seen in Figs. 18 and 20. For pp
396 Pettinger et a1.

ps polarization 1.6
[]
- I QPPI [] "" ••• I!I_tl_...lJ.

!.
38
36
twofold symmetry
• l'>/', 0 ~bPS
o Q
~

-e
=
1.4

= 1.21-
[] I QP'I

[] ' - ,[3 , tf '15

,lJ.,"'[]

-
[]
. -
,,-;----.
-13

.... .' -
10

o
,Jf

B.cd:
•
34
32
~ ••
•
a
···.v··.··.··.·..··..
•• 0 ··.··i1
Q
~

1.0-
-
[]
_.,.-
.,
--~
~
30
28
000 o 0.81=- -.- -_- -
~
-

=~ 160

-.
°5"
-- ~
- boPP •
......_---",,"-i
o

--~ ~ 140 [] boP' --'

I "',e
. 121-······ .. ·· .. ··_······~.
_
threefold symmetrv
- ....... _
- ••••• _ J]"
l: ..c:
Q,
_.
"""
- ,.,-'

~': ·14
"'~
_ y P' [] Y P' •
a 'b
...
:.:.'~ tf'
[] . ' .'~'" ' ..
>(
Q,
~e
120
----[]----c------_
."...
[]
- - +65
0

"...

.16ic
c ., c. '-13" EJo·····tJ
[]
.'
[]

9.····· []
, . ' [] ".
." . e 100
[]
[]
[]
[] - - - .[J. _ ~_ ¥
{]..
./
.I;!, _
-.........
[]
[]
[]

·600 ·400 ·200 0 200 400 600 -600 ·400 ·200 0 200 400 600
potential vs SCE / mV potential vs SCE / mV

Figure 21 Geometric angles calculated from the SH field gen- Figure 22 Fourfold symmetry contribution due to a
erated at an Au(lW) surface under ps polarization displayed as quadrupole interaction at an Au(lW) electrode as a function of
a function of electrode potential. Upper graph: geometric the electrode potential. Upper graph: amplitudes QPP and QPs
angles ofthe twofold symmetry component, fJ~s and f3~s. Lower measured for pp and ps polarization, respectively. Lower graph:
graph: geometric angles ofthe threefold symmetry component, complex phases flJ
and biQ. (From Ref. 128.)
}'~' and y;,s. (From Ref. 128.)

as the magnetic dipole or the electric quadrupole

polarization there is only a small decrease about 25% interaction. Measuring SHG or interference SHG
in the amplitude IlYJPI of the threefold symmetry intensities, higher order contributions may be present in
component starting with the lifting ofthe reconstruction, addition to the second-order nonlinear contributions.
and for ps polarization the amplitude IlYJS I remains nearly The former involves tensors of rank four and higher,
constant over thewhole potential range. Obviously, a con- and therefore n·fold rotational symmetries with n > 3
siderable amount of sources for threefold symmetry is and 4 are then observable also [168-173]. Using the
always present on this surface. As noted above, the lifting ISHGA approach, the components of the quadrupole
of the reconstruction leads to a strong inhomogeneity of term, contributing to a fourfold rotational symmetry
the surface [167]. The unreconstructed surface will there- element, can be straightforwardly determined with suf-
fore contain a great amount of steps with III orientated ficient accuracy in spite of its weak amplitude [126--128].
planes having threefold symmetry. As shown in Figs. 19 Figure 22 shows the amplitude and the complex phase
and 21 for pp and for ps polarization, the analysis yields of the fourfold symmetry component calculated for pp
distinctly varying offset angles (y~P, I"P and y~S, I"s) from and ps polarization. Evidently, even the quadrupole term
the real and the imaginary parts of the threefold sym- is potential dependent. At a first glance, this behavior
metry contribution. Evidently, more than one source exist seems to be incomprehensible because the quadrupole
(susceptibility element) with a threefold symmetry, each term should originate from the bulk and not be influenced
having its own potential dependence. by variations ofthe interfacial electric field. But consider·
(e) Higher Order Contributions to SHG. Several ing the explicit deduction of the quadrupole term given
papers [168-173] are concerned with the question to by Guyot·Sionnest and Shen [169], this term is composed
which extent bulk contribution from centrosymmetric of two contributions, one constant quadrupole term
media is present in the interfacial SHG signal, although referring to SHG processes in the bulk of the material
it is forbidden in dipole approximation. Most of them, and the second term arising from the gradient of the
except [172], contain theoretical considerations on the quadrupole term across the surface. Obviously, only this
contribution of higher order multipole interactions, such second term is sensitive to reconstruction processes and
r SHG Anisotropy 397

to changes of the electric field perpendicular to the sur-

face taking place in the course of electrochemical
~.=+. =.-=;.i=l.t=;.;:::::;_ _
28 r::---.....
26
..
;::=:--::.:--....-.--.--.-=;:-=:;::::::-l
experiments. Note also that under both polarization con- 24_...... _~_

ditions, one observes a similar potential dependence of

the amplitude of the quadrupole term (I Q'JS 1and 1QPP I). 22 Au(lll)

However, their complex phases cY'Q and cY'Q (lower graph 20 • CI04'
• cr
of Fig. 22) change in different directions. 18 • 81"'

16 ~.=.._I_·--...l._ _~!:a:~~!!.-....J.... _
3. Halide Ion Adsorption on Au(111)
Compared with Au(llO), the Au(lll) electrode is structur-
~ ·120
ally simple. There is only one type of reconstruction, the ~

well-known .j3 x 23 reconstruction, occurring in all 5il

~

three equivalent [1 TO] directions. It is present at negatively ~ ·130

charged surfaces, and it is lifted at positively charged
metal surfaces. This reconstruction and its dependence
~
-140
on potential and adsorption on it have been studied exten-
sively by several groups using a variety of methods, such -500 o 500
as LEED [173-178], STM [179-183], x-ray [184-189], and
SHG [121,122,156,190]. With SHG the reconstruction potential U I mV
can be monitored only if the reconstruction domains are
Figure 23 Potential dependence of the D term of an Au(lll)
distributed unequally. If not, the Au(lll) surface must
electrode in four different electrolytes: (a) 0.1 M NaCI0 4 ; (b-d)
show an anisotropy pattern typical for a C3v symmetry.
0.1 M NaCI0 4 +1 mM NaX, X=CI, Br, 1. Top: IDI vs. U;
However, surfaces are not perfect. Because of the Bottom: 6D vs. U.
presence of steps and slightly unequally distributed rec-
onstruction domains, weak additional onefold and
twofold symmetry contributions to the anisotropy pat-
independent. If halide ions are added to the electrolyte,
tern are present, hampering (earlier to ISHGA) to some
the IDI term decreases upon adsorption. The amount of
extent a precise determination of the various sus-
decrease increases in the sequence of Cl-, Be, and 1-.
ceptibility coefficients.
For the latter, a drop by about 30% can be noted. These
In earlier publications the influence of adsorption on
observations confirm earlier results [121]. The new
the isotropic term has been investigated, and linear
finding is shown in the bottom panel: The complex phase
relationships of A r = Re(A) with the metallic charge
b D varies rather linearly with potential in the absence of
density, O"M, have been found, whereas the imaginary part,
specific adsorption. In the presence of halide ions in
Ai = 1m (A), behaves less systematically. In these
solution, the complex phase bD shows a kind of s-shaped
measurements the phase of the A term could only be
variation in the potential region where the adsorption of
determined relative to the phase of the threefold term D.
the ion occurs.
That means bA-D = bA - bD was computed and not bA.
Now let us turn to the potential dependence of the A
This is not a problem, as long as bD is a constant.t
term. Both the A and bA curves are shown in the top
1 I
However, if the D term has its own phase variation, i.e.,
and bottom panel of Fig. 24. For each halide ion, the IA 1
if bD of: const., then the quantities Re(A) and Im(A) are
vs. potential curve now displays a broad peak, with a
not correctly defined. In fact, by using the ISHGA
maximum at potentials coinciding with the correspond-
method, a significant variation of bD was found even in
ing current density maximum seen in the CV curves upon
the absence of specific adsorption. This is shown in Fig.
adsorption. The decrease of IA at more positive 1
23 displaying the potential dependence of the D term, in
potentials indicate either a partial charge transfer from
the top and bottom panel arrangement for IDI, and bD.
the ion to the metal or a substantial change of the SHG
The four curves in each panel refer to distinct electrolytes.
resonance. The complex phases in Fig. 24 show a kind of
In the absence of specific adsorption, i.e., in pure per-
s-shaped curve, with the rise coinciding roughly with
chlorate solution, the IDI term is nearly potential
the potential region ofadsorption.
Using the charge density vs. potential relationships,
t Here, only the variation of 6A vs. potential is of importance. well known for Au(lll) and for each of the five
The absolute value of the phase is meaningless. electrolytes, the complex phase can be redrawn vs. charge
398 Pettinger et al.

38
Au(lll) ~

5 I Ao(111)
:l • CI04 ' • cr 80
'S U

~I
36 ... Br' • r ::t ....... CI04'
=
.Q 34
..... ...... 804=
...
~ ...... CI·
..... 32 0-:;' 40
.......Br·
30 ~ 20
:'!: til
cQ,l -0-1"
28 "Cl 0
Q,l

...
OJ)

=
.:: ·20
~
20 <.l

f:OJ) ·800 ·400 0 400

~
"Cl electrode potential U I mV
..... 0
I
~ 30f Au(I11)
20
<I:
00
-500 o 500 ~ 10
potential U / m V =
.::
c. 0
:-:
oS:!
Figure 24 Potential dependence of the A term of an Au(l1l) c. -10
electrode for the same four different electrolytes as in Fig. 23. §
<.l
Top: IA Ivs. U; Bottom: bA vs. U.

density, aM' Figure 25 shows how the phase angles change

with aM, for pure 0.1 M NaCI0 4, and for this basis elec-
trolyte with the addition of four different anions in
millimolar concentrations, respectively. In the same plot
but vs. potential (Fig. 24b), the phase angles follow four
different curves, showing a clear and distinct influence
of the nature of the anion. These changes support the
assumption that intraband transitions are involved in
the SHG processes. Because the amount of phase angle
shifts increases in the order of CI0 4 ~ S04 <
CI- < Be < 1-, it parallels the increasing adsorption
strength. However, in the plot bA vs. aM, below
60 pC cm- 2 all five curves essentially follow the same
curve; that means in this regime they exhibit a common
relationship and show nearly no dependence on the
nature of the anion.
Another presentation of the A term should not be
withheld. It is its plot in the complex plane given in Fig.
26, i.e., a plot ofIm(A) vs. Re(A) of the same data shown
above as IA I and b A vs. potential. The curves were shifted
in the complex plane to highlight common properties (the
shiftdo notalter their form). Theseshiftswereapplied only
to four ofseven curves, to curves for iodide, chloride, and
the two curves for bromide (corresponding to different
measurements on the same system). That means each of
them is shifted by adding a specific constant complex
number with two objectives: All curves should coincide
o 20 40 60
2
80
charge density aM II-lC cm·
Figure 25 Top: Charge density aM vs. potential U for an
Au(lll) electrode in contact with the same four electrolytes as
in Fig. 23. Bottom: Complex phase ofthe isotropic term, bA vs.
charge density, aM. bA data are the same as in Fig. 24.
at most negative potentials and all curves for halide and
sulfate ions should coincide in addition at the curve sec-
tionsasorderedadlayer. In this complex plane plotitis evi-
dent that overall the Ai term varies from about -19 to
about +12, whereas the A r term increases from +26 to
+38 and decreases again to +28 (all reI. units). Obviously,
the strongest dependence on potential or on charge den-
sity occurs for the Ai term, whereas the A r term shows a
minor variation. Thus, the phase variations given above
arise mainly from the Ai term (i.e., b A ex Ai)' Most negative
Ai values correspond to most negative potentials or charge
densities and vice versa for the most positive Ai values.
In this plot (Fig. 26) one can clearly distinguish four
different sections: (1) the linear region marked as
"non-specific adsorption": It is valid for CI04', SO; at
all negative Ai values, for CI- only at rather negative Ai
values, and for CI- in 0.1 M HCI0 4 at all negative Ai
values; (2) the transition region marked as "specific
adsorption (disordered layer)": It includes all curve sec-
SHG Anisotropy 399

20
charge density etc., i.e., if A r = feu, UM, r, .. .) then Ai
Isotropic SHG response at Au(111): The A • term obeys the same function, besides a proportionality factor
rx. In short, in the linear sections we have Ai =
compressed layer ordered odlayer rxA r + b = rxf(U, UM, r, .. .) + b, whereb is an appropriate
-o-r offset and the functionf(U, UM, r, ...) can be curvilinear
-6- Br'
and may also depend on the nature of anions. The
• Br'
10 __ CI' linearity only requires that Ai ocrx A r .
Now back to the complex phase. It is related to the
-~ CI' in 0.1 M HClO.
..... S04=
arcustangens of the quotient AjAr. For all anions the
...... CI04· complex phase vs. charge density curves follow a common
relationship below 60 JiC cm -2. That means Ai ~
.~ 0 g(uM)A r = g(UM) j~(U, uM, r, .. .), where the index g
~ indicates that we relate A r to a more general functionj~
compared with the functionfvalid for the above discussed
linear sections of Ai vs. A r . Thus, for the complex phase,
nonspecific 6A ~ arctan(g(uM)) mainly a dependence on the charge
adsorption density remains, whereas both the A r and Ai terms con-
-10 tain a complicated dependence on potential, charge
density, surface coverage, etc.
specific adsorption
(disordered layer) Changes in the complex phase (ofsusceptibility terms)
mean in general that the electronic configuration of the
surface is altered by potential and/or adsorption of ions
and molecules. This can occur via the influence of the
-20 interfacial electric field acting on the electronic configur-
LL- ~----____::'_=__----___::_:

25 30 35 40 ation ofthe metal surface or by orbital mixing. For charge

Ar
Figure 26 Plot of the A term in the complex plane.
Electrolytes: pure e: 0.1 M NaCl0 4, 0.1 M NaCl0 4 + 1 mM
NaX, X=Cl (#), Br (6 and .A.), J (D), S04 (*), and 0.1 M
HCl0 4+1 mM NaCI (x). The thick solid lines are guides for
the eye.
tions deviating from the straight lines shown in the graph.
Most strikingly, the curves for bromide and iodide closely
coincide (besides the final section at most positive Ai
values); (3) the upward oriented linear sections for posi-
tive Ai values: They are denoted as "ordered adlayer"
because here the Ai values correspond to charge densities
where ordered adlayers are formed ( > 60 JiC cm- 2 for
halide ions and> 35 JiC cm- 2 for sulfate ions) [191,192];
and (4) the last section denoted as "compressed layer": It
corresponds to charge densities where compressed
adlayers are established. Connected with that, there is
no change in Ai but a decrease in A r . A similar tendency
is seen for bromide but not for chloride.
Altogether, in the various curve sections this complex
plane plot shows a common behavior ofthe Ai vs. A r vari-
ation for distinct ions. For bromide and iodide, the total
Ai vs. A r curves coincide aside from the last section (once
the above described shifts were applied). The linear sec-
tions mean the following: If A r is a function of potential,
densities below 60 JiC cm -2, disordered layers exist that
are rather mobile. Therefore, a substantial orbital mixing
must be ruled out [193], and thus the phase variation
is driven by the electric field, because the latter
is proportional to the charge density UM. Thus,
6A = 6A(UM) obeys a common functional for all anions
in the region of nonspecific adsorption or in the dis-
ordered adlayer region, but there is no common relation-
ship for the ordered adlayer region [193].
The Ai vs. A r curves clearly show the impact ofadlayer
formation and their structural changes. In addition, the
plot of the A term in the complex plane yields a comp-
lementary picture to that of 6A vs. UM: The various curves
deviate from each other in the disordered adlayer region
but coincide in the ordered adlayer region.
4. IsotropicTerm on Ag Electrodes: Comparison of
Theory and Experiment
Silver is free electron metal to a greater extent than gold
because oflower d-band contributions to the conduction
band. Its low indexed crystalline surfaces are not
reconstructed. These properties make silver rather
attractive to compare experimental SH results with corre-
sponding theoretical studies where the metal is modeled
by ajellium and the crystal structure is incorporated into
the electron gas by a lattice of pseudopotentials [141,142].
Because the calculations are focused on the behavior of
400 Pettinger et al.

Sipe et al. [120], the isotropic amplitude is expected to

have a dependence on the charge density [40] (see also

7l
3~
the theoretical Sec. IVE):
---1:l * Ag(lOO) (JM
~.
~ 2 D Ag(llO)
A = Ao + AIEH(::::' 0) ~ ao + al-- (32)
...... . eHeo
....., • Ag(lll) .I
---
1:l where we omit the pp indices on A, A o, and A I here and in
~.
,i
.'f the following. At the PZC we have IA( (JM = O)I~IAo I.
~ 1

/* The relationship between the charge density and the

I

---
~. electrode potential was determined in independent
S ,..* measurements for Ag(lll) and Ag(lOO) and is used in
0 the following. Figure 28 compares the A term determined
in the ISHGA experiment and the theoretical calculation
of the a term, using density functional theory and intro-
ducing the crystal structure via pseudopotentials [142]
.e'''''·-''
-e'-..•*"~*""~~~
(unfortunately, there are no theoretical data available for
150
Ag(llO)). To establish a comparison, only the real part of
.,* the experimental A term (for pp polarization) could be
.",

;~( used: A r = Re 0). In addition, it is given in a normalized

!!.... 100 fashion, as the ratio of (Ar((J) - Ar(PZC))/ A r (PZC).
, //
The comparison shows a fairly good agreement for low
r.o"'" ," '¥..~ charge densities [194,195]. For higher charge densities,
,fi ,
50 , I

• ./ *'
./
.' 2 Ag(100)
o *. o theory
U-
N • experiment
-1400 -1200 -1000 -800 ·600 -400 -200 C.
'-(.
~
potential E / m V .....
U-
N
Figure 27 Potential dependence of the A term for Ag C.
'-(.

electrodes. Top: IA I ys U; bottom: Complex phase bAYS. ~ 0

potential. Electrolyte: 0.1 M NaCI0 4. (From Ref 195.)
~
~
-I
the isotropic term, A, we present only experimental and
theoretical findings concerning this term. For a clear dis-
2 Ag(111)
tinction we denote the experimental data as APP (for pp
o theory
polarization) and theoretical data as a. The behavior of U-
N • experiment
C.
the anisotropic terms (C, B, D) for Ag(lll), Ag(llO), and '-(.
~
Ag(lOO) is discussed elsewhere. Here we like to emphasize .....
that for Ag(lll) the threefold susceptibility, DPP, is rather G
N
independent of potential, whereas the IJPP and CPP terms e.
and the hypothetical fourfold term, denoted as are EfJ,
~
.
§:
0

of the same height as the noise level, as expected for an

~
unreconstructed surface. Therefore, the potential depen- -I
dence of the SH response at Ag(lll) electrodes lies solely
within the isotropic susceptibility, APP. Figure 27 illus- ·10 0 10 20
trates this with a plot of three lAPP I curves vs. potential charge density (J / J.LC cm' z
for Ag(lll), Ag(lIO), and Ag(lOO). The curves show a Figure 28 Normalized form of A r = Re(A), (A r - AfZC)/AfzC
minimum around the PZC, as proposed by Leiva et al. YS. charge density aM. Top: Ag(100); bottom: Ag(lll). Electro-
[142]. In the framework of the semiempirica1 model of lyte: 0.1 M NaCI0 4. (From Ref. 195.)
SHG Anisotropy
we expect a deviation between theory and experiment ACKNOWLEDGMENTS
because the model describing the electric double layer is
We are grateful to Professor G. Ertl for stimulating
then no longer adequate. This is also evident from the
interest, various discussions, and continuing support in
comparison. There are two reasons for these deviations.
these studies. This work was partly financed by the
First, at high negative charge densities, the electrons spill
Deutsche Forschungsgemeinschaft.
out further into the solution. Therefore, the details of the
interaction of the electrons with the solvent become
important. These are not accounted for in the model.
REFERENCES
Second, at high positive charge densities, an oxide layer
starts to form on the surface, which is also not incorpor- 1.
ated in the model.
2.
3.
VI. OUTLOOK
4.
SHG represents an in situ optical nonlinear spectroscopy
that is inherently sensitive to the interfacial region. Using
SHG anisotropy, one can probe not only rotational and 5.
mirror symmetries present in the surface but also the
static electric fields at the interface. This holds in particu- 6.
lar for its advanced form, the ISHGA. It directly yields
the anisotropy of the SHG field, E(2w, cp), which is 7.
proportional to the complex susceptibility coefficients
A, B, C, and D. By decomposition of E(2w, cp) = A + B 8.
cos (cp + a) + ... into its various terms, information can
9.
be achieved on the geometric and electronic structure of
the interface and their changes upon potential and 10.
adsorption. We have shown this in detail for the usually 11.
microfaceted Au(llO) where each rotational symmetry
contribution to SHG has to be characterized by four 12.
parameters; otherwise, the anisotropy curves cannot be 13.
matched sufficiently. This reflects the structural com- 14.
plexity and variability of this electrode. For a Au(ll1)
electrode, we illustrated the sensitivity of the isotropic 15.
term, A, on potential and specific adsorption of halide 16.
ions. When plotted in the complex plane, it clearly shows
17.
distinguishable regions for nonspecific adsorption and
18.
for the formation of disordered, ordered, and com-
pressed adlayers in the case of specific adsorption.
Finally, we demonstrated for Ag(111) and Ag(lOO) 19.
surfaces that theoretical prediction of the SH potential
dependence agrees well with experimental results. 20.
One can expect that the use of the interference SHG
anisotropy (or other equivalent methods) will provide a 21.
maximum of information on both the interface and the
surface SH process itself, when it is combined, e.g., with 22.
wavelength dependence studies. The electronic con-
figurations ofthe interface, surface states, orbital mixing,
23.
surface structure, and, last but not least, the static electric
field at the interface were key issues in the past, but they 24.
remain on the agenda. The use of nonlinear optical
spectroscopies will help to deepen the understanding of 25.
these issues.
401
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L
 ..~

23

Amphiphilic and Ionic Surfactants at Electrified Interfaces

Dan Bizzotto
University ofBritish Columbia, Jimcouver, British Columbia, Canada

Vlad Zamlynny, Ian Burgess, Craig A. Jeffrey, Hong-Qiang Li, John Rubinstein, Rod A. Merril, and
Jacek Lipkowski
University ofGuelph, Guelph, Ontario, Canada

Zbigniew Galus
University of Warsmv, Hilrsaw, Poland

Andrew Nelson
Plymouth Marine Laboratory, Plymouth, England

Bruno Pettinger
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany

ABSTRACT cases, the surfactants were repeatably desorbed and

The adsorption of insoluble surfactants spread as a
monolayer at the gas- solution (G- S) interface onto elec-
trifiedmetal- solution (M - S) interfaces is described. Sur-
factants used include octadecanol, pentadecyl- pyridine,
12-AS, and the lipids dioleyl phosphatidylcholine(DOPC)
and dimyristoyl phosphatidylcholine (DMPC). The
adsorption of surfactants that do not display any specific
interaction with the metal surfaces used [Au(lll) and Hg]
reveal thatthetransferofthemolecules from the G- S inter-
face to the M - S interface is strongly dependent on
potential. The transfer ratio between the two interfaces is
I : I at an uncharged electrode surface and decreases to
zero at sufficiently negative charge densities. A compari-
son of the adsorption of DOPC on Au(lll) and Hg is
described. Surfactants with head groups that specifically
interact with gold (i.e., pyridine) were also studied. This
type of adsorption (chemisorption) displayed stable low
capacitance layers, and in one case, spontaneous forma-
tion of a bilayer from a monolayer was observed. In all
405
readsorbed at negative potentials.The fate ofthe desorbed
surfactants was investigated using in situ spectroelectro-
chemical techniques. The mechanism ofthe adsorption-
desorption process involves formation of the aggregates
near the electrode surface at negative potentials. At less
negative potentials, the aggregates are contact adsorbed
onto the electrode surface and hemiaggregates are formed
that then spread to form the adsorbed layer. Confocal flu-
orescence images illustrate the adsorption-desorption
process. The potential controlled spreading from hemi-
micelles to an adsorbed layer as observed by atomic force
microscopy (AFM) for the adsorption of sodium
dodecylsulfate (SDS) onto Au(lll) is described.
I. INTRODUCTION
Surfactants are ubiquitous in our daily activities and find
use in a host oftechnologies. Knowledge ofthe forces that
control the assembly of surfactant molecules at the
406
solid-liquid interface is vital for such traditional fields as
detergency, flotation, oil recovery, and tribology [I]. Thin
organic films deposited at solid surfaces also find appli-
cationinthefabricationofoptoelectronicdevices, sensors,
biosensors, and chemically modified electrodes [2].
Monolayers and bilayers of phospholipids deposited at
solidsupports areused as models ofbiological membranes
in biomimetic research [3-5]. It has long been established
that the assembly of surfactants at the solid-liquid inter-
face depends on the charge at the solid surface [6]. It has
also been observed that the spreading of vesicles into a
phospholipid bilayer requires that the surface of the solid
support is negatively charged and hydrophilic [3,4],
However, the present understanding of the role played by
charge on the interaction of a surfactant molecule with
the charged solid surface is far from complete.
Electrochemistry provides a unique opportunity to
study the influence of charge on the properties of
amphiphilic and ionic surfactants at the charged
solid-liquid interface. We recently used electrochemical
techniques, surface spectroscopies, and scanning probe
microscopy [7-10] to study the full cycle ofthe interaction
ofa surfactant molecule with the solid surface. This cycle
involves adsorption of a micelle or vesicle, formation of
surface aggregates (hemimicelles), spreading of the
micelles into a condensed film, reformation of the hemi-
micelle, transformation of the hemimicelle into an
adsorbed micel1e, and desorption of the micelle.
The purpose of this chapter is to review our recent
studies of adsorption of surfactants at electrified inter-
faces and to present a comprehensive model of the inter-
action of surfactant molecules with solid surfaces. First,
we give a brief description of experimental method and
methodologies used in our studies of surfactant adsorp-
tion at electrode surfaces. Next, we describe the surface
properties ofsurfactants weakly interacting with the elec-
trode surface and oriented with their hydrocarbon tails
toward the metal and with their polar heads toward the
solution. We refer to these phenomena as physisorption.
This section is followed by a discussion of the surface
properties of surfactants whose head groups display suf-
ficient affinity to the metal so that molecules are oriented
with their head groups toward the electrode and their
hydrocarbon tail toward the solution. We refer to such a
case as chemisorption. The chapter is concluded with a
discussion of a general model describing adsorption of
amphiphilic and ionic surfactants at solid surfaces.
II. EXPERIMENTAL
We described experimental techniques and
data-processing procedures in a series of recent
publications [7-17]. Figure 1 shows the space-filling
Bizzotto et al.
models of surfactants used in our studies. They included
octadecanol (C180H), 12-(9-anthroyloxy) stearic acid
(l2-AS) 4-pentadecyl-pyridine (C15-4-Py), 1O-decyl-9-
[2-(4-pyridyl)ethyl] anthracene (OPEA), sodium dodecyl
sulfate (SOS), dioleyl phosphatidyl choline (OOPC), and
dimyristoyl phosphatidyl choline (OMPC). In addition,
octadecanoic acid and 1-l'-dioctadecyl-3,3,3/,3/-
tetramethylindodicarbocyanine perchlorate (OiIC 18)
were used in some experiments [12]. A special glass cell
or a homemade Langmuir trough converted into an elec-
trochemical cell were used in our studies. Figure 1is a dia-
gram of the trough and the cell. The glass cell had a port
through which a Wilhelmy plate (WP), attached to a
microbalance, measured the film pressure of surfactant
spread at the gas-solution (G-S) interface during the
electrochemical experiments. The Langmuir trough was
equipped with a reference electrode and a counter elec-
trode so that the electrochemical experiments could be
performed on a monolayer compressed to a desired value
of the film pressure at the G-S interface. The surfactant
was dissolved in chloroform and spread onto the surface
of the electrolyte. When experiments were performed in
the glass cell, enough surfactant was spread onto the sur-
face to cover the surface twice over. This created a
monolayer on the surface of the electrolyte whose film
pressure was characteristic, known as the equilibrium
spreading pressure. When the experiments were
performed in the Langmuir trough, the pressure of the
monolayer spread at the G-S interface was controlled by
the position of the movable barrier. The films of sur-
factants were deposited onto the surface of a gold
single-crystal electrode using the horizontal touching
procedure. Only a few experiments were performed in
which the film was deposited onto the surface ofa hanging
mercury electrode.The gold electrode was flame annealed
and cooled in Ar and then touched to the monolayer at
the G- S interface. The electrode was then slightly pulled
away from the plane of the aqueous surface to form a
hanging meniscus. This was termed a single-touch layer.
This hanging meniscus orientation ensured that only the
polished surface of the working electrode was exposed to
the solution. Multiple-touch layers could also be pro-
duced by immersing the electrode at potentials near the
potential of zero charge (PZC), removing the (typically)
small drop of electrolyte, and then retouching the
monolayer-covered G-S interface as before, resulting
once again in a hanging meniscus. The adsorbed surf-
actant was characterized using cyclic voltammetry (CV),
differential capacity, and charge density measurements,
details ofwhich are described in our previous publications
[7,11-13,18]. The chronocoulometric measurements com-
bined with the electrocapillary equation al10wed the film
AmphiphiIic and Ionic Surfactants
WE
HE CE
HE
SDS
Figure 1 Top: Schematics of the glass cell and the electrochemical Langmuir trough. Bottom: Space-filling models of surfactants
used in our studies.
pressure of the adsorbed film to be determined and
directly compared with the film pressure of surfactant at
the G- S interface measured using aWP.
Electroreflectance, fluorescence, and elastic light-
scattering experiments used to study the mechanism by
which surfactants spread at the metal-solution (M -S)
interface were described in [15]. Monochromatic linearly
polarized light was focused onto the electrode surface at
407
WP WE CE
I
DOPC DMPC
a 45° angle. The specularly reflected light was collected
in electroreflectance experiments. Fluorescence and
elastically scattered light were collected at an angle of
90° with respect to the plane of incidence and 45° with
respect to the electrode surface.
Atomic force microscopy (AFM) images of the
film-covered electrode were captured using a Nanoscope
E AFM (Digital Instruments, CA) using silicon nitride
408
tips (Digital Instruments) that had a nominal spring con-
stant of 0.06 N/m [10]. The tips were exposed to ozone
in a UV laminar flow cabinet for 30 min before use. All
images were acquired in deflection mode with both inte-
gral and proportional gains below 1 using scan rates
between 7 and 12 Hz. No filtering of images was
performed other than that inherent in the feedback loop.
The working electrode for AFM experiments consisted
of 2000-A-thick gold film vapor deposited onto a glass
slide pretrated by deposition of a 20-A-thick layer of
chromium to ensure a better adhesion ofgold to the glass
substrate. The electrode was annealed with a hydrogen
torch before each experiment. The all-glass AFM cell
was equipped with a gold oxide quasi-reference electrode
and a platinum wire counter electrode. Before and after
the experiment. the potential of the gold oxide
quasi-reference electrode was measured vs. a saturated
calomel electrode (SCE), and all potentials are reported
vs. SCE.
III. PHYSISORBED FILMS
Gold and mercury electrodes display ideally polarizable
behavior in a broad range of electrode potentials. The
properties of these two metals are complementary.
Mercury is a liquid and has an ideal, physically smooth,
and energetically homogeneous surface. In contrast, gold
is a solid and its surface contains many defects and
imperfections. Most experiments described in this review
were acquired using the flame-annealed Au (I II)
electrode. Its surface is a mosaic of well-ordered 111
domains separated by steps, domain boundaries, etc.
The flame-annealed surface is known to reconstruct.
and its surface has the so-called (23 x.)3) structure
[19,20]. The reconstructed surface is stable at a negatively
~h!rge<-!~rface, and the reconstruction is lifted when
the electrode is positively charged. Adsorbed organic
molecules stabilize the reconstructed structure and slow
down the rate of the surface reconstruction phenomena
[21.22]. However, the effect of the adsorbed surfactant
on the structure of the underlying Au(ll1) surface has to
be taken into account if adsorption is studied over a suf-
ficiently broad range of potentials such that the charge
on the metal surface changes sign. The adsorption of
surfactant molecules at the Au(111) surface is therefore
more complex than adsorption on the surface of the
mercury electrode. However, using a gold electrode one
can use a host ofspectroscopic and surface imaging tech-
niques to acquire information concerning the character
ofthe interaction ofthe surfactant molecul~ with the solid
surface and the character of the surface aggregation
Bizzotto et at
phenomena at the molecular level. In contrast, surfactant
adsorption on mercury can be investigated chiefly using
electrochemical techniques.
The adsorption ofoctadecanol onto gold and mercury
electrodes displays behavior representative of physi-
sorbed surfactants. Figure 2 shows the cyclic voltam-
metry and differential capacity curves determined for
Au(lll) and Hg electrodes horizontally touched to the
G-S interface that was film free (dotted lines) and
covered by a film of octadecanol (solid or dashed lines).
To compare the adsorption of insoluble surfactants at
the two metals, all curves are plotted vs. the rational
potential defined as Erational = E - E pzc , where E is the
electrode potential measured vs. the SCE and E pzc is
the potential of zero charge for a given metal
[E pzc = 275 mV(SCE) for Au(111) and E pzc = -450 mV
for Hg]. The octadecanol film lowers the electrode
capacity at potentials close to the PZC, indicating that
surfactant molecules are adsorbed at the metal surface
in this range of potentials. At the Hg electrode, the
adsorption of octadecanol was investigated in a broad
range of both negative and positive potentials. At the
Au(l1l) electrode, oxidation of octadecanol took place
at positive potentials, and for this metal the studies were
restricted to negative polarizations. The adsorption of
C180H was therefore investigated at a reconstructed
gold surface [18-22]. At mercury. the adsorption of
octadecanol is quite symmetric with respect to the PZC
and extends over a range of 300-400 mV in the negative
and positive directions. The characteristic sharp peaks
mark the desorption ofthe surfactant molecules at either
more positive or more negative potentials. The peak
potentials recorded in the positive and negative half
cycles differ somewhat. These differences between the
desorption and adsorption cycles indicate that the film
desorption and readsorption processes are slow. The slow
kinetics of the desorption-adsorption phenomena is
responsible for the hysteresis and the absence of the
absorption -desorption peaks on the differential capacity
curves.
The adsorption of octadecanol at gold displays a
number of similarities to the adsorption at mercury.
The capacity of the film-covered electrode has a com-
parable value, the desorption of the film takes place at
approximately these same potentials, and a similar )
adsorption hysteresis is observed for the two metals.
The main difference between the behavior of the film
at the two electrodes is the presence of multiple
desOI;ption peaks on the CV recorded for gold and a
single desorption peak on the CV measured for mercury.
This behavior indicates that the adsorption -desorption
~
kinetics are more complex on a solid than on a liquid
 Amphiphilic and Ionic Surfactants 409

6 6
CIIOH on Au(111) C,.OH on Hg
N 4 N 4
I I
E E
._---..r. .
,'.
u 2 .........: u 2
c( c(
::L 0
....... .. '
........
::L 0
....... ~---""'I .
".
--2 '.
'.'
--2

-4 -4
1 N 40 :
N 40
I I
E E
u 30 .... u 30
u.. u..
::L ::L
....... 20 ....... 20
...>- ...>-
u
IV
10 u 10
IV
Q, Q,
IV IV
0 0 0 0
-1.2 -0.9 -0.6 -0.3 0.0 0.3 0.6 -1.2 -0.9 -0.6 -0.3 0.0 0.3 0.6
Erational I V Erational I V
Figure 2 Cyclic voltammetry (top panels) and differential capacity (bottom panels) recorded for Au( III) (left) and hanging mercury
drop electrode (right) in contact with 0.05 M KCI0 4 in the absence (dotted line) and in the presence (solid line, voltage scan in the posi-
tive direction; dashed line, voltage scan in the negative direction) of CI80H spread at the G-S interface. Cv, 20 mY/s; capacity,
5 mY rms; 25 Hz for AuOll) or 253 Hz for Hg; 5 mY/s sweep rate; a series RC circuit was assumed in the calculation. (From Ref. 8.)

metal. Tentatively, we explain these differences in terms
of homogeneity of the liquid electrode (mercury) and
nonhomogeneity of the gold single-crystal surface
(presence of steps, defects, etc.).
The transfer of the insoluble film from the G-S inter-
face onto the M - S interface of a gold or a mercury elec-
trode can be described quantitatively in terms of the
surface pressure ofthe film transferred onto the electrode
surface. The film pressure at the metal solution interface
nM-.5 = }'sw - }'SL' where }'sw and }'SL are the surface
energies of the film-free and the film-covered electrode
surfaces, respectively, can be determined through inte-
gration of the electrode charge densities measured in the
) absence and presence of the film [7-18]. Using a
Langmuir trough converted into an electrochemical cell,
we can measure simultaneously the pressure of the films
at the G-S and M-S interfaces. In this way, the transfer
of the film from G-S onto M-S may be studied
quantitatively. Figure 3 shows the film pressure data deter-
mined in a series of experiments in which the film press-
ure of octadecanol spread at the G- S was varied and for
each value of the film pressure at G-S the film pressure
at the Au(lll) electrode was determined. The nM-.5 are
plotted in a three-dimensional (3D) diagram in which
the calculated values of nM-.5 are plotted on the vertical
axis, whereas the film pressure at the G-S interface
(nG-S) and the electrode potential are plotted on the two
axes of the basal plane. The 3D representation provides
a condensed description of the dependence of nM-.5 on
the two independent experimental variables nG-S and E.
These data clearly show that spreading of the insoluble
surfactants from the G-S interface onto the electrified
M - S interface depends strongly on the electrode
potential. For a fixed value of nG-S, the nM-.5 may change
from a maximum value at the PZC to zero at the most
negative potentials. Apparently, the insoluble surfactant
spreads easily from the G-S onto the uncharged M-S
interface. The straight line joining the maxima on the
nM-.5 vs. E curves has a slope of unity. It corresponds to a
1 : 1 transfer of the insoluble monolayer from the G-S
onto the M - S interface at the PZc. The transfer ratio
drops below unity as the potential departs from the PZC
410 Bizzotto et al.

25 I I
(8) aDA 15 mN m- 1
.-
• Au( 1111
.
50
20
.' ., ~.'
• d,S
\
.
\
I ,.// \
45 E ! .'''' Au(100) •
40 z 15 .'
/
s:
--....
S5 E
...... ./ . •
/
I

Z: SO
",10 / i
s: ~5 i i
--....

en
~O : i j
i i/
i ,.,/..,."
15 5
~ 10 Au(110)
~5 I ~. it.
T I", _.... ~
......,
I
O r •• , • • • • • • • i
o
-O~ -0.6 -0.4 -0.2 i
-0.0 I
0.2
oP

Erational I V
0'1.-
00

-,,>" -,,>'1.-/" " - 35 Ti- - - - - - - - - - - - - - - - ,

(b) Diethyl ether O.25M
<5b ~o
<2-- <. co.,,-...p<:'~
-,,>'<>
~ -,,>'P
30 /.-~ Au(111)
0..:.....9 /.
Figure 3 Three-dimensional representation ofthe film press-
i
E
25
./.
ure at M- S interface as a function of the film pressure at the
G-S interface and ofelectrode potential. (From Ref. 8.)
z 20
E / .-.-........
...... 15 / ./' ".

'" /. ./. / ... Au(100) '\.

.
./. ./
:10
and it eventually becomes equal to zero at very negative
potentials where the charge density at the metal is suf- 5 /
""
/
............ . . . . . . . . . .,. ... .,........, Au(110)
. I
ficiently large. o I • I - ........
j, =;r....... I
, I i

An intersection of the curves in Fig. 3 with a plane
parallel to the basal plane of the figure shows how nG-S
has to change with potential to maintain a constant value
of nM-S. The dotted line in Fig. 3, corresponding to nM-S
equal to 10 mN m- I , displays a quasi-parabolic depen-
dence on E. The quasi-parabolic line lying in the basal
plane (nM-S = 0) denotes the potential at the onset of the
spreading of the insoluble monolayer from the G-S onto
the M -S interface. At potentials located beyond this line
the surfactant will not spread from the G-S onto the
M - S interface regardless of the value of nG-S.
The adsorption ofinsoluble surfactants at an electrode
surface is clearly dependent on the electrode potential
(charge density). From this point of view, the adsorption
of long-chain insoluble surfactants is not too different
from the adsorption of small organic molecules that are
soluble in water [23,24]. In fact, one can find many
similarities between the surface behavior of these two
classes of compounds. For example, a change of the sur-
face crystallography ofgold electrodes has a similar affect
on adsorption of long-chain surfactants and small ali-
phatic molecules. Investigations ofmolecular adsorption
at electrodes of a different surface crystallography sheds
-0.8 -0.6 -0.4 -0.2 o 0.2
Erational I V
Figure 4 (a) Pressure ofthe aDA film atthe M- Sinterface for
Au(lll), Au(lOO), and Au(llO) electrodes when the aDA film
pressure at the G-S interface was equal to 15 mN m -I. (b)
Pressure of the diethyl ether film at the M-S interface for
Au(lll), Au(lOO), and Au(llO) electrodes in equilibrium with
0.25 M diethyl ether concentration in the bulk of the solution.
(From Ref. 8.)
light on the role of defects such as steps and domain
boundaries, always present at a solid electrode surface.
Figure 4 shows film pressures of octadecanoic acid
(ODA) at three low index gold single-crystal electrodes.
These data were acquired by keeping a constant pressure
ofthe film ofODA at the surface of the Langmuir trough
(15 mN m- I ) and recording the charge density curves or
the three gold single-crystal electrodes. These results
show that for an identical film pressure at G-S, the film
pressure at the M -S interface decreases by moving from
the Au(1ll) to the Au(11 0) plane. The insoluble surfactant
Amphiphilic and Ionic Surfactants
spreads less onto the more open 110 surface than onto the
densely packed 111 surface. Figure 4b shows the film
pressure curves for the adsorption of diethyl ether, a
soluble organic molecule, onto the same gold surfaces.
These data were taken from [11,25]. For this same bulk
concentration of the diethyl ether, its film pressure at the
M -S interface displays a similar dependence on the sur-
face crystallography ofgold to that observed for adsorp-
tion of ODA molecules in Fig. 4a. Apparently, the same
dependence ofadsorption on the surface crystallography
is observed regardless of whether the surfactant mol-
ecules arrive at the M - Sinterface from the bulk ofthe sol-
ution or from the G-S interface. This fact sheds light on
the mechanism of spreading of an insoluble surfactant
from the G- S to the M - S interface. It is well established
that the dependence of adsorption of diethyl ether on
the crystallographic orientation ofgold can be explained
in terms of a solvent-substitution mechanism of adsorp-
tion from solution and variable hydrophilicity of different
gold surfaces [25]. The similarity between adsorption of
an insoluble surfactant from the G - S interface and a
soluble surfactant from the bulk of the solution suggests
that the adsorption of insoluble surfactants at gold elec-
trodes is also a solvent substitution reaction.
The strong dependence of the adsorption of an
insoluble surfactant on the solid electrode surface
crystallography also explains the differences between
spreading of the insoluble film onto the liquid surface of
Hg and the solid surface of the Au(ll1) electrode that we
discussed previously. Defects inevitably present at the
surface of a single-crystal electrode may be treated
as adsorption sites of different crystallographic
orientations. Figure 4 shows that surfactant will spread
differently at the 111 terraces and at the defect sites.
Clearly, the film is likely to be less evenly spread on a
single-crystal surface of a solid than on a surface of a
liquid electrode.
Phospholipids constitute a very important class of
insoluble surfactants that exhibit physisorption charac-
teristics upon adsorption at electrode surfaces.
Monolayers of these compounds are used as models of
biological membranes, and hence the properties of these
films at electrode surfaces has attracted significant
interest. Miller [26,27] was the first to show that a film of
lipids spread at the G-S interface ofa Langmuir trough
can be transferred onto the surface ofa Hg electrode. He
demonstrated that the field-induced changes of the film
properties may be conveniently studied using electro-
chemical techniques. Miller's approach was applied later
by Nelson and colleagues for biomimetic research. They
deposited films ofphospholipids onto a Hg electrode sur-
face [2S-31] and investigated either the incorporation of
411
a number of toxins [32,33] or ion transport through lipid
layers with and without incorporated ion channels
[34-40].
Figure 5 compares the differential capacity and
charge density curves for an Au(111) electrode covered
by films of CISOH and DOPC transferred from the
G-S interface at the equilibrium spreading pressure.
DOPC is a phospholipid that has a very low liquid
crystal-gel transition temperature (-22°C) and hence
at room temperature it forms 2D liquidlike films. There
are apparent similarities in the adsorption behavior of
these two surfactants. They display a tendency to
adsorb at the gold surface at potentials close to the
PZe. In each case, the potential of the maximum
adsorption corresponding to the intersection of the
charge density curve for the film-covered electrode with
the curve for the supporting electrolyte coincides with
the PZe. The values of the differential capacity at the
PZC are equal to 6.5 pC cm- 2 for DOPC and
S.7 IIC cm- 2 for CISOH, and hence they are quite
comparable. For each surfactant, the capacity and
charge density curves recorded using positive and nega-
tive potential scans display a hysteresis. The hysteresis
is more pronounced for CISOH than for DOPe. The
adsorption of DOPC takes place in an apparently
broader range of potentials than CISOH. However. this
may reflect a higher value of the equilibrium spreading
pressure for DOPC (51 nM m- I ) than for CISOH
(31 mN m -1). The two surfactants are desorbed from
the gold electrode surface at the negative limit of
applied potentials. All these features suggest that
CISOH and DOPC belong to this same class of
surfactants.
Figure 6 compares the adsorption of DOPC at an
Au(ll1) and a mercury electrode. In this case, the differ-
ences are very significant. The differential capacity at the
PZC has a much lower value at mercury (~1.S pC cm- 2)
than on gold (~6.5 pC cm- 2). The low value of the
differential capacity at mercury is consistent with the
value predicted for the electrode covered by a compact
condensed monolayer of this surfactant. This result
indicates that at mercury, DOPC forms a virtually ideal
defect-free monolayer. In contrast, the high value of
capacity measured for gold indicates that at this electrode
the DOPC film is defected. Referring to the earlier dis-
cussion, we recall that the defect sites inevitably present
at the solid electrode surface have properties ofhigh index
surfaces, at which the adsorption of physisorbed
surfactant is much weaker than at III terraces. The higher
value of the differential capacity at gold may therefore
indicate that the defect sites are either partially covered
or not covered at all by surfactant molecules.
412 Bizzotto et at.

DOPC on Au(111) C 0H on AU(111)

30 18
(b)
1
, ....."'... , ....... 1 '

E
u 20 1IIi'...

U.
::l
........
()
10

0' . " ,. ,
(c)

"
(d)
o ; .,:-'-
..~.." "
~

// 'f
1 ".'
".., l

L 1""",',. . ,
E -10
u /
()
::l i"
~ ..
/
........ -20
::i:
t:>

...
-30 . """
L
-800 -400 0 400 -800 -400 0 400
E I mV vs SCE E I mV vs SCE
Figure 5 Comparison ofdifferential capacity and charge density curves for DOPC and Cl80H adsorption at the Au(lll) electrode.
Capacity recorded using 5-mV rms, 25-Hz ac perturbation, and 5-mVis sweep rate, ( ) in absence ofsurfactant ( - - - - ) anodic
scan, (- - -) cathodic scan. (a) DOPC adsorbed onto Au(lll), (b) Cl80H adsorbed on Au(lll). Charge density measurements
( ) in absence ofsurfactant, anodic process, L':,. cathodic process. (c) DOPC adsorbed onto Au(lll), (d) Cl80H adsorbed onto
Au(lll).

The differential capacity curve for gold displays three
peaks. The most negative peak corresponds to the
adsorption-desorption process, whereas the middle
and the most positive peaks represent phase transitions
in the DOPC monolayer. To each capacity peak on gold,
one can assign a counterpart on the differential capacity
curve for mercury. However, for mercury, the most posi-
tive peak is split into two sharp spikes and the middle peak
is much taller. Apparently, the phase transitions are very
sharp for a nearly ideal film on mercury and are rounded
off for a defected film on gold. The bottom panels in Fig.
6 show the charge density curves. Consistent with the
differential capacity curve, the charge curve for mercury
displays multiple well-defined steps at potentials at which
peaks are seen on the differential capacity curve. For gold,
steps on the charge curve are essentially washed out and
the charge increases gradually with potential.
The area contained between the charge density curve
for the film-covered and the film-free electrode is equal
to nM-S. The film pressure vs. potential curves for DOPC
adsorbed at a gold and a mercury electrode are plotted
in Fig. 7. At the PZC, film pressure values for gold and
mercury are similar and are approximately equal to the
equilibrium spreading pressure at the G-S interface
(51 mN m- I ). This behavior is quite general for all
physisorbed films investigated by us so far. At the PZC,
Amphiphilic and Ionic Surfactants 413

DOPC on AU(111) DOPC on HMDE

30
(a)

~
E 20
u
U.

-
::1.

o 10

0
(c) (d)
0 - _ _ ..
:
, .. , "
.'
.....j .. .' "
,,~'
~
.' "
.." .'
,.,."
E
u
-10
..' ..
...........
,
"
.'.' .'"I'
,.' .'.'
0

- .'..
.' ""
::1. '"
.........

0
:!: -20
. ...'.'
,.'.'
'

-30
-1200 -800 -400 o -1200 -800 -400 o
E ImV E ImV
rational rational

Figure 6 Comparison of DOPC adsorption at Au(11l) and Hg electrodes at the equilibrium spreading pressure of DOPC at the G- S
interface (51 mN m -1). (a and b) Differential capacity curves recorded in the absence (dotted line) and in the presence of DOPC (solid
line), using voltage scan in the positive direction. 20 mYls, capacity 5-mV rms, 25 Hz for Au(lII) or 75 Hz for Hg, 5-mV/s sweep rate,
a series RC circuit was assumed in the calculation. (From Ref. 15.)

these films are transferred from G-S onto the Au(lll) or
mercury surfaces with a transfer ratio equal to unity.These
two metal surfaces are essentially hydrophobic and at
the PZC they characteristically behave as conductive
walls.
IV. CHEMISORBED FILMS
The surfactants for which the adsorption and desorption
behavior has been discussed so far contained either a
hydroxylic, carboxylic, or phosphate functional group.
These groups display weak affinity toward the gold sur-
face [41], and at the M-S interface the molecules display
a preference for adsorption with the polar head turned
toward the solution and the hydrocarbon chain toward
the metal surface. In this section, we describe the adsorp-
tion of insoluble surfactants at a gold electrode whose
functional groups display sufficient affinity toward the
metal, so that the adsorbed molecules are oriented with
the polar head directed to the metal and the hydrocarbon
tail toward the solution. We are interested in studying
films that could be repeatedly adsorbed and desorbed
from a gold electrode surface. Therefore, the interaction
between the functional group ofthe surfactant molecules
414 Bizzotto et a1.

60, ' i , : , I' : i u, , ' I face properties of chemisorbed to the previously

described physisorbed surfactants. Figure 8 shows the

?~
electrochemical characteristics of a film of DPEA mol-
ecules deposited onto an Au(lll) electrode surface by
.... horizontally touching the G-S interface at the equilib-
E 40 >
"
"
rium spreading pressure (32 mM m- I ). The top panel is
z f" a plot of the differential capacity curve. The differential
f
-E

~
£Q
:::2:
20
l
6-
6-
l
6-
6-

50 I- (a)
DPEA on AU(111)

6-
f
" ~ 40
O~t"""
E
u
-1200 -800 -400 o U.
30
E
rational
ImV
- ::1.
( .)
20 I: "~

Figure 7 Comparison ofthe film pressure vs. potential curves 10

for DOPC adsorption at Au(lll) C&.l and Hg (0) electrodes.
(From Ref. 15.) o I , , ,

(b)
and the metal had to be much weaker than in the case of ~ o I--'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'=;'-;;'-~"l
...
thiols deposited at gold by the self-assembly technique.
We have selected surfactants with a pyridine moiety as
E
u ,."..'.
..........
...~...,:.
~.#.
,~

(.) -101- I' ... ~......

the best candidates for these studies. Extensive investi-
gations of pyridine adsorption at gold single-crystal
electrodes, performed in our laboratory, taught us that
pyridine molecules coordinate to the gold surface either
-::1.

t:l
~
·20 I- -I,"
~\~
;"'01'
.........:,.-
:.'
~~...

through the n-bonds of the aromatic ring or through the

lone pair ofelectrons of the nitrogen heteroatom [41-50].
.•.•. " "
",.

This ligand-metal interaction was moderate in strength

and the adsorption of pyridine onto gold was reversible .....
in character. Two surfactants, C15-4-Py and DPEA, were E 60 ~ (c)
therefore synthesized [9]. Their space-filling models are
shown in Fig. 1. The first has an alkyl tail of 15 carbons z
attached to the pyridine head group at the para position.
The second surfactant studied has an anthracene moiety
incorporated into the aliphatic chain with the short axis
- E
£Q
t:!.~
40

lying parallel to the alkyl chain. In this section we contrast 20

the physical properties of monolayers and bilayers
formed with C15-4-Py and DPEA molecules adsorbed
onto the Au(llI) electrode surface to the properties of 0
physisorbed films described earlier. -800 -400 0
The surface behavior of DPEA and C15-4-Py are E/mVvsSCE
somewhat different. The first surfactant forms stable
monolayers and does not form a bilayer. In contrast, we Figure 8 Differential capacity, charge density, and film press-
demonstrate shortly that the monolayer of C15-4-Py is ure curves for a film of DPEA deposited at the Au(lll) electrode
unstable and converts spontaneously into a bilayer. We surface by the single-touch technique. Capacity recorded using
describe the DPEA adsorption first to contrast the sur- 5-mV rms, 25-Hz ac perturbation. and 5-mV/s sweep rate.
Amphiphilic and Ionic Surfactants 415

capacity displays a single capacity and a deep minimum C15-4Py SingleHT, initial
(pit) in the potential range between -200 and 200 mV 30
(SCE). In the minimum, the capacity has a low value of (a)
" , ..
6 /lC cm -2. At the most negative potentials, the capacity
.'"
ofthe electrode that was initially film covered merges with .' "

.. .,,-
••>
~
the capacity of the film-free electrode, indicating that I I I .... ,.....

E 20
the film is desorbed from the electrode surface. The (.)
··.
adsorption-desorption peak is apparently absent.
...
-
LL
Instead, by moving from the negative end in the positive ::::I.
".
~.
direction, the curve for DPEA progressively drops below
the curve for the film-free electrode. The capacitive peak () 10 ~.
'.
seen at potentials ~ -330 mV (SCE) corresponds to a
phase transition in this organic layer.
The character of DPEA adsorption may be even better
explained with the help of charge density curves shown
in the middle panel. The charge curve for DPEA has two o .800 -400 0 400
steps, a feature characteristic for a two-state adsorption. E/mVvs SCE
The first step at E:::::: -600 mV corresponds to
adsorption -desorption of DPEA molecules. The
C15-4Py Single HT, 17 h
absence of the adsorption-desorption peak on the C(E) 30
curve indicates that the adsorption-desorption pro- (b)
cesses are slow. The second step at E :::::: -330 mV (SCE) .,> II'"
~,,4. .....,..
corresponds to a reorganization ofthe film ofDPEA.This
process is apparently faster because quite a pronounced ~ . I I I .........
...1 1.... .'
peak is seen on the capacity curve at this potential. Inte- E 20
gration ofthe charge density curves gives the film pressure
(.)
··
··
-
plotted vs. the electrode potential in the bottom panel. LL
::::I.
In good agreement with the behavior ofphysisorbed films
discussed earlier, this curve also has a quasi-parabolic ()
10
shape. However, the maximum film pressure at the ··
M- Sinterface is more than twice the value ofthe equilib- ··
rium spreading pressure at the G-S interface ·.
(32 mN m -1). The surfactant is more strongly adsorbed
at the M-S than at the G-S interface and that must 0
.-... -.....
involve a direct interaction of the polar head of the
-800 -400 0 400
surfactant molecule with the metal surface. This feature E/mV vs SCE
may be used as a criterion to distinguish chemisorbed
from physisorbed films. Figure 9 Evolution of the differential capacity of the Au(l1l)
The monolayer of DPEA deposited onto the Au(lll) electrode in the presence of C15-4-Py at the G-S interface with
electrode surface is stable, and if the film covered elec- the exposure time. (a) Differential capacity curves recorded just
trode is left in contact with the film at the G-S interface, after the transfer ofthe film from G-S interface onto the Au(l11)
no change in the electrochemical characteristics of the electrode surface using the single-touch technique. (b)
Differential capacity curves recorded after 17 h ofequilibration
film was observed, even after 18 h. In contrast, a film of
between the M - Sand G - S interfaces. Capacity recorded using
CI5-4-Py deposited onto the Au(lll) electrode by the 5-mV rms, 25-Hz ac perturbation, and 5-mVis sweep rate.
single touch technique and left in contact with the film
at the G-S interface is unstable. Figure 9a shows the
differential capacity curve recorded after horizontally capacity curve for the film covered electrode is not too dif-
touching a CI5-4-Py covered G-S interface with the ferent from the curves recorded for other surfactants. We
Au(lll) electrode. The lowering of the differential emphasize, however, that we observed quite a significant
capacity at potentials more positive than -700 mV irreproducibility of the differential capacity curves for
indicates that the film was transferred from the G- S onto the Au(lll) electrode covered by single touch films of
the M - Sinterface. In general, the shape ofthe differential CI5-4-Py. For example, the curve shown in Fig. 9a has a
416 Bizzotto et al.

C15-4Py on Au(111} molecules. The bilayer is desorbed at E ~ -700 mVand

reformed again at potentials higher than -600 mY. The
20
formation ofthe bilayer apparently proceeds in two steps
(a) that initially involves a less compact film characterized
10 byasomewhathighercapacityof2-3 f.1C cm- 2 .Thisfilm
j
~
s l
is then transformed into a compact bilayer at potentials
E
0 0 ._._._._._._._._·_~;,i·.7·~~- more positive than -200 mY.
Figure lOa and b shows the charge density and film
. .,.. . . . ~,.#.,

-
() pressure curves for the bilayer of CI5-4-Py deposited
:::t "..:",-.#-"
-10 either by a single touch followed by a 17-h waiting time
........ :;~.,
~ ~. .#.' or by the double-touch technique. These films are charac-
~ .".~.
terized by a much larger change of the electrode charge
.,..',.,
-20
........' density and by significantly higher film pressures. The
data in Fig. 10 also demonstrate that the differences
,"
-30 between films produced by a slow transport of surfactants
from the G-S onto the M-S interface and by the double
deposition technique are very small indeed. This is a
160
remarkable result. It demonstrates for the first time that
surfactant molecules present at the G-S interface can
.... spread from the G - S onto the M - S interface. The trans-
120
E port of surfactants across the two interfaces most likely
involves a 2D diffusion. This is therefore a very interesting
z
- E
~
t:!.~
80
case of an exchange of mass between two two-
dimensional phases. We emphasize that we observed this
spontaneous formation of a bilayer only for a
chemisorbed film. Spreading of surfactant molecules
40 from the G-S onto the M-S interface is apparently
facilitated when the molecules in the first layer of the
bilayer are turned with their polar heads toward the metal
o and their hydrocarbon tail toward the solution. The archi-
tecture of the bilayer most likely involves a tail-to-tail
-800 -400 0 400 orientation of the two layers.
E/mV vs SeE
V. SPECTROSCOPY
Figure 10 Charge density and film pressure curves for the
Au(lll) electrode surface covered by a film of CI5-4-Py The experiments described in the preceding section indi-
deposited either by the double-touch technique or by a prolong cate that the exchange of surfactants between the G-S
equilibration of the M-S and G- Sinterfaces, lasting 17 h. and M-S interfaces is very slow (a spontaneous
transformation ofa monolayerofCI5-4-Py into a bilayer
required 18 h). The slow kinetics of the mass transport
different shape than the differential capacity reported in between the two interfaces cannot explain the repetitive
our recent publication [9]. However, ifthe electrode is left character of potential controlled desorption and re-
in contact with the film-covered G-S interface, the adsorption ofsurfactant molecules. To record differential
differential capacity curve evolves with time, until after capacity, cyclic voltammetry or charge density curves,
about 18 h it attains a final (equilibrium) shape shown in presented in the previous sections, a film of surfactant
Fig. 9b. Identical differential capacity curves may be molecules was repetitively desorbed and readsorbed by
obtained if the electrode covered by the single-touch film applying either a very negative potential or a potential
is disconnected from the G-S interface at the PZC and close to the PZc. The desorption and adsorption pro-
then horizontally touched to the CI5-4-Py covered G-S cesses were very repeatable, and the film formed by
interface (double-touch film). This aged or doub- readsorption of the surfactant molecules retained all of
le-touched film is characterized by a very low capacity of its initial characteristics, even after multiple
0.9 f.1C cm -2, which is typical for a bilayer of surfactant adsorption-desorption cycles that continued for hours.
Amphiphilic and Ionic Surfactants 417

In addition, we can transfer a film-covered electrode to
another cell with the clean surfactant-free G- S interface.
The Cv, differential capacity, or the charge curves
recorded in that cell are essentially identical to the curves
recorded when the electrode is in contact with surfactant
at the G~S interface. This behavior is consistent with
the slow kinetics of the mass exchange between the M - S
and G-S interfaces. However, where do the surfactant
molecules go when they are desorbed from the electrode
surface by applying the most negative potentials? The
most likely explanation of the observed phenomena may
be given if one assumes that desorbed surfactant
molecules form micelles, flakes, or vesicles trapped in
the subsurface region and that the repeatable film
desorption - formation processes involve potential-
induced micellization (flake or vesicle formation) and
micelle (flakes, vesicles) adsorption.
To understand the mechanism by which the surfactant
is repeatedly desorbed and readsorbed, we performed
light-scattering experiments using the Au(lll) electrode
covered by films of Cl80H and DOPC molecules. A
beam of electromagnetic radiation was directed at the
electrode surface at a 45° angle of incidence. The
radiation scattered from the electrode was then detected
at an angle that was 45° with respect to the electrode sur-
face and 90° with respect to the plane ofincidence. Figure
11 shows the result of the combined electrochemistry
light-scattering experiment. A slow voltage sweep was

DOPC on Au(111), L-B Deposition. C OH on AU(111), Double HT.

40 1s
(a) (b)

=> 30
··
.
..
..
......
'

10 .......
'. ....-................._.r.ro.
'.,

0
30
(c) (d)
..........".''10
•..•,..,..• ......
"

C)l
"".",1'"
E 20 ' ...
0

U. ···
:::t
....... ·..
(,) ....
10 ..
.'
................
.........

o -800 -400 0 400 -800 -400 0

ElrnVvs SCE E / rnV vs SCE

Figure 11 Capacity and intensity ofelastically scattered light from an Au(lll) electrode with C180H adsorbed as a double- touch layer
and DOPC deposited using the Langmuir- Blodgett technique.The incident light was 550 nm and s-polarized. Dotted line, differential
capacity for the film-free interface; solid or dashed lines, differential capacities for the film-covered electrode. The relative scales for
the scattered light intensity are shown. Supporting electrolyte 0.05 M KCl0 4 .
418
applied to the electrode initially covered by a film pro-
duced by the double-touch procedure for Cl80H and by
the Langmuir-Blodgett technique for DOPC, the
differential capacity of the electrode was measured, and
simultaneously the elastically scattered light from the
electrode surface was recorded. The results show a very
weak signal of scattered radiation measured for
potentials at which the film was spread onto the electrode
surface. However, at potentials at which the differential
capacity shows that the surfactant desorbs from the elec-
trode surface, a dramatic increase in the amount of
scattered radiation is observed. The scattered radiation
reaches a plateau at the negative limit of potentials, where
the film is totally desorbed from the electrode surface.
When the curves are recorded using a potential scan in
the positive direction, the scattered radiation is quenched
at potentials at which a characteristic pit appears on the
differential capacity plot, indicating that film is spread
at the electrode surface. The changes of the intensity of
the scattered radiation apparently follow the changes of
the differential capacity. The appearance of scattered
radiation at potentials at which surfactant molecules are
desorbed from the electrode surface suggests that the
desorbed molecules form aggregates in the subsurface
region, which later spread back onto the metal surface at
potentials close to the PZc. We do not know the actual
shape of these aggregates; however, we refer to them as
micelles.
The potential-induced adsorption and desorption of
insoluble surfactants was investigated further using
l2-AS, an insoluble surfactant-dye molecule adsorbed
onto the Au(lll) electrode surface. The l2-AS molecule
is a popular fluorescent probe used to study the fluidity
and polarity of biological membranes and phospholipid
monolayers [51-55]. Figure 12 shows a space-filling
model of the molecule. It is an anthroloxy derivative of
stearic acid in which an anthroloxy moiety is attached to
the 12th carbon on the alkyl chain. The long axis of the
anthroloxy group is collinear with the alkyl chain. The
UY spectrum of this dye displays two absorption bands
due to (n*~ n) electronic transitions in the anthroloxy
group. The first corresponds to the transverse transition
at 360 nm and is linearly polarized along the short axis
of the anthroloxy moiety. The second is a longitudinal
transition that is linearly polarized along the axis of the
anthroloxy group.
Because of complications caused by light scattering,
the presentation of the electroreflectance spectra will be
restricted to the single-touch film for which only very
weak elastic light scattering was observed at the
desorption potential. The electroreflectance spectra
were recorded by measuring the spectrum at
Bizzotto et al.
~
+OOO~
I Mnnol DR • ~PMf
(260nm)
PMf
Figure 12 Right: Space-filling model of12-AS molecule and
the directions of the optical transitions. Left: Geometry of the
electroreflectance experiment.
E ads = + 100 mYl SCE, the potential where the monolayer
is adsorbed onto the electrode, and then stepping the
potential to Edes = -550 mY/SCE at which the surfactant
is desorbed and recording the second spectrum. The
two spectra were subtracted to give !':..R and then divided
by the spectrum at the adsorption potential, resulting in
the calculated electroreflectance spectra !':..R/R. Signal
averaging was used to increase the signal to noise and
typically four spectra were averaged before calculating
!':..R. Sand p linearly polarized incident light was used,
spanning a wavelength range of200-300 nm. The direct-
ions of the electric field of the photon with respect to the
electrode surface are shown in Fig. 12. The electro-
reflectance (MVR) spectra are presented in Fig. 13.
The changes in reflectivity (M/R) for 12-AS on Au(111)
can be described to a first approximation by
!':..R _ R(Eads )- R(Edes) _ B[cos 2 8(Edes)E(Edes)r(Edes)
R- R(Eads )
2
- cos 8(Eads)E(Eads)r(Eads)]
(1)
where R is the electrode reflectivity, 8 is the angle between
directions of the electric field of the photon and the
transition dipole moment in the dye molecule, E is the
molar absorption coefficient, r is the surface concen-
tration of the dye, and B is a constant that incorporates
all other parameters of a specific model of the interface.
The magnitude of !':..R/R depends on the mechanism by
which the surfactant molecules are desorbed and
readsorbed at the electrode surface. Ifthe surfactant mol-
ecules are exchanged between the M - Sand G - S inter-
faces by moving out and onto the electrode surface, no
dye molecules should be present in the optical path at
potentials outside of the capacitive pit region at Edes.
The first term in Eq. (1) should then be equal to zero
Amphiphilic and Ionic Surfactants
0.05
0.04
0.03
a: 0.02
~ 0.01
~ 0.00 - ,....... .,"" YI''''''¥jY of'< . . WI\- ....
-0.01
-0.02
-0.03
0.05
0.04
0.03
a: 0.02
~ 0.01 s-pol
~ 0.00 -UI.JI~
-0.01
""
-0.02
-0.03 -t--'-""'--'--'--'--'--'--.--.--.--.--.--r--1
220 240 260 280 300 320 340 360
wavelength I nm
Figure 13 Electroref'lectance spectra (s- and p-polarized
light). Solid line, single-touch film of l2-AS adsorbed onto
Au(lll); dashed line, background spectrum recorded without
an adsorbed monolayer. (From Ref. 7.)
[r(Edes) = 0] and the measured AR/R should be
monopolar in character resulting in a typical absorption
spectrum of the film of 12-AS molecules. According to
the definition of AR/R given in Eq. (1), the spectrum
should have a negative sign. In contrast, if the surfactant
molecules are desorbed as micelles trapped under the
electrode surface, the dye molecules would remain in the
optical path even if they are desorbed from the electrode
surface. In this case AR/R represents the difference
between the absorption spectra of the dye molecules in
the film at potentials within the pit and clustered as
micelles at a potential outside the pit. The measured
spectrum should then be differential (bipolar) in
character. The electroreflectance spectrum should be
distinctly different for each of the two mechanisms,
and hence the e1ectroreflectance experiments should
lead to unambiguous identification of the surfactant
desorption - readsorption mechanism.
The electroreflectance spectra, shown in Fig. 13, dis-
play absorption bands around 260 nm due to the longi-
tudinal electronic transition in the anthroyloxy moiety of
the surfactant molecules. The absorption band for
419
p-polarized radiation is bipolar with the positive and
negative sections having comparable amplitudes. The
band for s-polarized light is predominantly unipolar;
although the optical signal for this band changes sign at
280 nm, the negative portion of the spectrum is much
p-pol weaker than its positive section. This band is dominated
by the positive signal and hence we refer to it as a unipolar
band. In view of the above discussion, the behavior of
the p- and s-polarized bands may appear as con-
tradictory. However, the predominant positive sign of
the band recorded for s-polarized light indicates that the
dye molecules are essentially optically inactive (or weakly
active) at potentials in the capacitive pit (when they are
spread as a film at the electrode surface) but become
optically active at potentials outside the film (when they
are desorbed from the electrode surface). The positive
.. sign of the unipolar band recorded for s-polarized light
and the bipolar character of the band recorded using
p-polarized radiation indicate that the desorbed
surfactant molecules remain in the optical path, trapped
in the electrolyte layer near the electrode surface probably
in the form of micelles (or other clusters such as flakes or
vesicles). Therefore, the electroreflectance experiments
provide the second evidence that the repeatable
desorption and readsorption processes described above
involve potential-induced micellization of the film at
negative potentials and spontaneous spreading of the
micelles onto the electrode surface at more positive
potentials.
Further insight into the mechanism of the potential
controlled adsorption-desorption of insoluble sur-
factants comes from fluorescence measurements. 12-AS
is a known fluorescent dye and hence is an ideal choice
for such studies. The fluorescence of 12-AS adsorbed at
a metal surface will be quenched due to the reduced life-
time of the excited state. In contrast, the fluorescence is
weakly quenched if the surfactants desorb and form
aggregates in the subsurface region away from the
electrode. Therefore, little fluorescence should be
observed in the potential range in which the film is spread
at the gold surface and fluorescence should appear at
potentials at which the film is desorbed, assuming the
surfactant molecules form aggregates in the subsurface
region. More specifically, because the efficiency of
quenching depends on the fourth power of separation of
the fluorophore from the metal, the measurement of flu-
orescence monitors changes in the separation between
the surfactant and the metal surface.
Figure 14 illustrates the changes measured for the
adsorption of a double-touch layer of 12-AS on Au(1l1).
The top panel shows the values of the electrode capacity
recorded during the positive-going and negative-going
420 Bizzotto et al.

60 capacity rises again upon approaching the negative

N
I potential limit and becomes equal to the capacity of the
E 45 film-free electrode, indicating that the film is desorbed
CJ
from the surface. This increase of the capacity correlates
LL. 30 well with a sharp increase of fluorescence and intensity
::::L .....- :.::.:..:.< .
...... of scattered light. The optical signals attain their highest
~~~
15
values for potentials at which the film is desorbed from
()
0 the surface. The hysteresis displayed in the differential
capacity curves is also observed on fluorescence and
elastically scattered radiation plots. This hysteresis may
~
l'\~
.Q
... indicate that somewhat different mechanisms are
4(
" :~"\"\\:
,,:.
involved in adsorption and desorption processes. In con-

\
\. clusion, the appearance ofthe strong fluorescence at the
...... \
: most negative potentials suggests that the desorbed

.$
..
0
~ \
\ : :'", aggregates of surfactant molecules move away from the
"'(l,"b......
\: : M ... " ..
"
: .....,. ......
• -..,
~.,Jior'W...... ""'""."
tr..M electrode surface at a distance that may be as large as
10 nm or more.
. The detection of fluorescence was used recently to
~
.Q
... ,".~~..\.\
I :
.
, :
image the desorbed and intermediate stages of surfactant
adsorption using a double-touch layer of C180H with

"
4(
~ \ 3 mol% ofa dye OiIC 1S (5) [17]. Independent capacitance

\ --
\
......
..• \:
\ :
.\
: ~-...
measurements indicated that the incorporated dye did
not significantly disturb the adsorption-desorption of
u
\ \:: :: ..........."'....... C180H and thereby imaging fluorescence of the dye
en

-800 -600 -400 -200

.

E I mV vs
Figure 14 Capacity, fluorescence, and light-scattering inten-
sity measurements as a function ofpotential for a double-touch
film of l2-AS adsorbed onto Au(lll). (From Ref. 7.)
voltage sweeps, the middle panel shows the fluorescence
(emission measured at 470 nm, excitation at 360 nm),
and the bottom panel shows the corresponding changes
of scattered radiation (at 550 nm; away from the absorp-
tion bands for the chromophore). In Fig. 14, moving from
the negative potential limit in the positive direction, we
note that a decrease of the capacity is paralleled by a
decrease of fluorescence and scattered radiation. At the
bottom of the first capacitive minimum, about 70% of
the fluorescence and about 50% ofthe scattered radiation
are quenched. The fluorescent and scattered radiation
decrease further with potential until they become com-
pletely quenched at E> 100 mY. Changing the direction
of the voltage sweep and moving toward negative
potentials, the differential capacity increases somewhat
at E < -200 mV(SCE). This change in the capacity is
not accompanied by a parallel small increase of fluor-
escence and the elastically scattered radiation. The
o
'-200
could be considered representative of the octadecanol
behavior. The images (100 x 75 .urn) were acquired using
a line scanning confocal microscope arrangement with
seE piezo-controlled movement of the scanned line across
the sample achieving the 20 image. A HeNe laser was
used for excitation, and the integrated fluorescence inten-
sity (650-678 nm) is presented in Fig. 15. Each image
was acquired on a new spot to avoid any bleaching effects.
The images shown in the figure are referenced to the
capacity measured for the interface. The fluorescence
could be seen as a bright spot in the image, whereas the
quenching of fluorescence produces a dark image.
Overall, the images support the previous
spectroscopic studies. The fluorescence is quenched
(except for residual effects) at potentials of adsorption
and is large at the potential of desorption. Significant
structural details are evident at the desorption potential
compared with the adsorption potential. These structures
are diffuse, and the brightness is unevenly distributed in
the image, indicating some sort of aggregation of the
surfactant molecules. The potential was then scanned
positively, and the adsorption of the aggregates was
initiated as indicated by a small decrease of the capacity.
The shapes of the aggregates are more pronounced,
having sizes in the tens of .urn range, and the distribution
of surfactant across the surface is very uneven. As the
potential is scanned to more positive values, the capacity
drops to an intermediate value and the image changes.
Amphiphilic and Ionic Surfactants 421

40.0

o 100 200 300 400 500 600

30.0
t)l
E
o
LL
:1.
~20.0
'0
eo
0-
eo
U

10.0

O'---'-~~~~~'---'-~~'--'-~~'---'-~~'--'-~~'---'-~~~~~'---'-~~~~--'------'

-800.0 -600.0 -400.0 -200.0 o 200.0

-E /mV vs SeE

Figure 15 Confocal microscope image ofthe adsorption and desorption ofa double-touch film of C180H containing a fluorescent
dye. (From Ref. 17.)

The aggregates have similar sizes and a significant
fraction of the electrode area is dark, indicating
quenching ofthe fluorescence. Once the potential reaches
the positive limit, the fluorescence is essentially
quenched, although a small bright spot may still be noted.
The capacity curve for the desorption process exhibits a
large hysteresis, which is typical for these double-touch
surfactant layers. The capacity increases only slightly on
the cathodic scan and is below the intermediate value
observed for the positive scans. The image taken at a
potential just before the jump in capacitance shows a
number of interesting features. The layer begins to desorb
and aggregates are forming, which again leads to the
appearance ofdiffuse bright spots in the image.
This series of images supports the contention that the
adsorption-desorption process proceeds through for-
mation of aggregates that is coincident with the abrupt
changes in capacity. The adsorption process involves con-
tact adsorption of the aggregates near the electrode and
aggregation of these surfactants into hemiaggregates on
the surface. The fluorescence in these intermediate states
is not evenly distributed. This feature may suggest that
the hemiaggregates are large in size, more like droplets
or massive crystals of material, or that only a fraction of
surfactant is adsorbed and the rest remains in the aggre-
gate state in the subsurface region. At sufficiently positive
potentials, the surfactant respreads and the quenching is
quite efficient, so that only a minute amount of material
remains fluorescent. The fluorescence imaging exper-
iments on the dye-containing film of Cl80H are in full
accord with the fluorescence and elastic light-scattering
measurements for adsorption of l2-AS described earlier.
VI. MICELLES AND VESICLES
The light-scattering, electroreflectance, and fluores-
cence-quenching experiments described previously offer
considerable evidence that the repeatable potential con-
trolled desorption and adsorption of insoluble sur-
factants involves formation and spreading of micelles.
We provide further support for this mechanism by
demonstrating that monolayers and bilayers of sur-
factants may easily be formed at an Au(lll) electrode sur-
face by fusion of micelles or vesicles from solutions that
contain suspensions ofthese aggregates.We first compare
the properties ofa bilayer ofDMPC formed at the Au(lll)
surface by fusion of small unilamelar vesicles (SUV) to
the bilayer deposited by the transfer of the film ofDMPC
422 Bizzotto et al.

spread at the G- Sinterface. The solution ofSUV was pre-
pared according to the Barenholtz procedure [56].
Dynamic light-scattering experiments gave a mean
radius of 14.7 nm for the SUVs. The distribution of par-
ticle sizes around the mean value was very narrow and
nearly normal. The liquid crystal-gel state phase
transition for DMPC takes place at 24C. To ensure that
the film of DMPC is in the liquid state, the solution of
SUV solution was prepared and the fusion ofvesicles onto
the Au(lll) was studied at a temperature of 30°C. The
bilayer formed by the double horizontal touch procedure
was also deposited at 30°C, and this temperature was
maintained during all electrochemical experiments.
Figure 16, taken from our recent studies [57], shows
differential capacity curves recorded for the Au( Ill)
electrode surface in contact with the SUV solution and
Apparently, the same film of the phospholipid is formed
by the fusion of vesicles and by deposition from the G-S
interface. These two films may be repetitively desorbed
and readsorbed, and it is very likely that in each case these
adsorption-desorption phenomena involve the same
mechanism.
The adsorption of ionic surfactants such as SDS has
long attracted the attention of the electrochemical com-
munity [58-63]. Figure 17, taken from our recent paper,
describes the electrochemical behavior of SDS at an
SOl (a)
60 ,
,
I

,,
for the electrode covered by the double-touch film in
~ ,,
, .
contact with the pure supporting electrolyte solution. ' ,
·.
···, ..,,
E
Consistent with the results presented in the previous () 40 ,
sections, the pit on the differential capacity curves u.
indicates that molecules of DMPC adsorb at the
:. ·
, ,
,

electrode surface in the range -400 < E < 400 mVand

........
U 20
': .......
I •
~:., .........

desorb at E < -800 mV(SCE). Significantly, very similar

differential capacity curves were obtained when the film
ofDMPC was produced by the fusion ofvesicles and for 0
the film deposited by the double-touch technique.

r
40
(b)

60
~
E
20
t . '
J . . .':
() ~ .. :
U 0 I~"""
N
:.
E
u
40 ........
E

-
IL
:.
o
t:I
-20

-800 ·400 0 400

-800 -400 o 400
ElmVvsSCE
Figure 16 Differential capacity curves recorded for the
Au(11I) electrode in (dotted line) pure 0.05 MNaF, (dashed line)
solution ofSUVofDMPC in 0.05 M NaF, and (solid line) elec-
trode covered by the double-touch film of DMPC deposited at
E=O V (SCE), using 5-mV rms, 25-Hz, 5-mV/s sweep rate,
and a series RC circuit assumed in the calculation. (From Ref.
57.)
E/mV vs SeE
Figure 17 (a) Differential capacity of the Au(11I) electrode
recorded in 16 mM SDS solution. Solid line, positive-going
potential sweep; dashed line, negative-going potential sweep.
The dotted line represents the differential capacity curve for
16 mM KCI0 4 solution. The curves were measured using
25-Hz, 5-mV rmsacperturbation, anda 5-mV/spotential sweep
rate and were calculated assuming a series equivalent circuit.
(b) Charge density vs. potential plots for (solid line) 16 mM
SDS solution and (dotted line) 16 mM KCI0 4 solution. (From
Ref. 10.)
Amphiphilic and Ionic Surfactants 423

Au(lll) electrode surface, when its concentration in the
solution is twice the critical micelle concentration. The
differential capacity curves shown in panel a resemble
differential capacity curves presented earlier for the
Au(lll) electrode in the presence of neutral amphiphilic
surfactants. The capacity curves for the adsorption on
gold also bear many similarities to capacities reported
for SDS adsorption on mercury [58-63]. SDS is appar-
ently desorbed at the most negative potentials and
adsorbed at E> -500 mV(SCE). Clearly, its adsorption
has a two-state character. Panel b shows that state I of
the film exists at small absolute values of the charge den-
sity and state II is observed when the charge density on
the surface exceeds 30 J.1.C cm- 2 . For mercury,
Satiropoulos et al. [59] suggested on the basis of theoreti-
cal arguments that state I of the film corresponds to the
formation of surface aggregates of SDS (hemimicelles)
and state II to the spreading ofhemimicelles into a con-
densed monolayer.
In fact, direct atomic force microscopy images of sur-
face aggregates of SDS (and some other surfactants) at
graphite [64-72] and at gold [73] were recently
published. These images were acquired without poten-
tial control. The coupling of electrochemistry with
AFM imaging was accomplished in our laboratory,
and we have succeeded in providing the first direct
visualization of the potential control transformation of
hemimicellar aggregates of SDS into a condensed
monolayer at the Au(lll) electrode surface. Figure 18 is
an image of the SDS film at the gold electrode surface

Figure 18 AFM deflection images of stripe-shaped SOS aggregates adsorbed at an Au(lll) electrode at E= -100 mV (SeE). (a)
500x500 nm image, (b) 100x 100 nm image of the well ordered domain ofSOS aggregates with a height profile taken in a direction
normal to the stripes.
424 Bizzotto et al.

at a potential of -100 mV(SCE), which is in the middle 35 i I

of the region corresponding to state I of the film.

Incidentally, the open circuit potential is very close to 3H a)
E= -100 mV(SCE). The image shows stripe shaped sur- N

face aggregates of this ionic surfactant. The film is a eu 25

mosaic of three domains of parallel stripes rotated by \I.
::L.
60°C. The section of the image characterized by the _2:1
~ I "
longest range order has been imaged to show the regu- c
larity of these stripes. The plot of the height in the direc- S 15
U
tion normal to the stripes illustrates that the pattern II
has an almost ideal periodicity and a constant tj 10
amplitude. The distance between the stripes is equal to
5.0 ± 0.5 nm in good agreement with the results pre- 5

sented at the open circuit potential by Jaschke et al. [73]

for gold and Wanless and Ducker [69] for graphite. This o' " " " " ' ,.... " ' ," .... t ... " ' ...... ' .. ' " " ' .. ' i
200275:m3253f03754CD42i4004755D
distance is very close to the diameter of a spherical
micelle formed by SDS in the bulk of the solution. The EI mV \IS seE
stripes are therefore interpreted as representing 400

half-cylinder shaped aggregates of SDS lying on the

substrate surface [64-73].
To image the phase transition between states I and II
300
of the film, the electrode potential was changed to a
value +250 mV(SCE), just before the onset of the phase
transition, and then the potential was scanned in the
positive direction across the phase transition. Move- 200
ment of the AFM tip was synchronized with the change
of the electrode potential. A differential capacity curve
was collected simultaneously with the image. In this
way the changes of topology could be correlated to 100
the change of the electrode capacity. Figure 19 com-
pares the 400 x 400-nm image of the film to the
change of the differential capacity of the interface.
These figures offer a direct visualization of the o 100 200 300
transformation of the aggregates into a condensed
monolayer. The left side of the image corresponds to Figure 19 (a) Differential capacity of the Au(lll) electrode
the potentials of state [ with the discreet recorded in 16 mM SDS solution using 5-mV/s positive-going
hemicylindrical aggregates. The characteristic pattern potential sweep, 25-Hz and 5-mV rms ac perturbation, and cal-
of parallel stripes is clearly visible in this region. At culated assuming a series equivalent circuit. (b) 400 x 400 nm
potentials corresponding to the capacitive peak, the AFM deflection image recorded at a scan rate of 10.2 Hz with
stripes melt and transform into the condensed the scan axis moving from left to right while simultaneously
monolayer. On the right side of the image, the surface changing the potential of the gold electrode by applying a
is covered by a compact layer and the characteristic positive-going potential sweep at a sweep rate of 5 mYls. (From
Ref. 10.)
stripe pattern is totally lost. The transition between
the hemimicellar and condensed states of the film is
fully reversible. Reformation of the hemicylinders was VII. MECHANISM
accomplished by reversing the scan. These images con-
stitute the first molecular level evidence that the nature The desorption/spreading of surfactants has similarities
of the adsorbed surfactants is potential controlled. They to the potential dependent spreading ofoil droplets onto
demonstrate that depending on the value of the applied the Hg electrode surface described recently by Zutic
potential, surfactants may form either surface and colleagues [74-76]. In addition, it has also been dem-
aggregates (hemimicelles) or may spread to form a onstrated that the so-called reductive desorption of
condensed film. self-assembled monolayers ofthiols involves formation
Amphiphilic and Ionic Surfactants
30 ....--r;:====;;-----:-----.....,
N
I
E the hemimicelles spread onto the metal surface to form
0
20
u.
:L
.....
->-
' 0 10
lQ
Q
~
lQ
U solid-liquid interface.
O+-........- r -......---r-"'T"'"".....,..-.,............---.-"'T"'""~
-1.0 -0.8 -0.6 -0.4
EritiOMl / V
Figure 20 A schematic of the proposed mechanism for the
adsorption-desorption of a film of insoluble surfactants
from/to the Au electrode. (From Ref. 8.)
ofmicelles in the subsurface region [77,78]. It appears that
all these phenomena may be described by a common
model shown in Fig. 20 using the film formed by 12-AS
as an example. At potentials near the PZC, the surfactant
spreads to form a condensed film. As the potential
becomes negative, the film becomes less ordered and the
organic layer is either porated or surface aggregates are
formed, a prelude to desorption that occurs at the most
negative potential. At this potential, the surfactant exists
asan organized structure near the electrode surface.
Interestingly, these organizations do not diffuse away
from the interface and are easily readsorbed when the
potential is made less negative. The respreading of the
micellular structures occurs in a fashion similar to the
spreading oforganic droplets onto solid surfaces. Initially,
the micelles adhere to the metal surface and form
hemimicelles.The shape ofthe hemimicelles is controlled
by the magnitude of the contact angle. The contact angle
0 0
changes from 90 to 0 as the electrode potential becomes
more positive and the film pressure increases. This
progressive change of the contact angle explains a
progressive quenching of light scattering and fluor-
escence within the potential range where hemimicelles
are formed [8]. When the contact angle is large, the
hemimicelle-covered electrode surface is rough and
scatters electrode radiation. In addition, a significant
fraction of the surfactant molecules contained in a
hemimicelle are sufficiently far from the metal surface
so that their fluorescence is not quenched.When the con-
tact angle decreases, the surface becomes smoother and
425
the surfactant molecules come closer to the electrode
surface. The light scattering decreases and the fluor-
escence is quenched. At potentials where 1tM-S < YLW,
initially a loose and later the more ordered film. The sig-
nificance of our results is that they show that the shape
and size ofthe hemimicelles formed at the M - S interface
may be conveniently controlled by the electrode
potential. This control offers a new possibilities to study
the mechanism by which surfactants adsorb at the
ACKNOWLEDGMENT
-0.2 -0.0 Supported by a grant from Natural Sciences and Engin-
eering Research Council ofCanada.
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24
Ordered Organic Adlayers at Electrode Surfaces
Claudine Buess-Herman, Sandra Bare, Mireille Poelman, and Michel Van krieken
Universite Libre de Bruxelles, Brussels, Belgium
ABSTRACT
The adsorption oforganic molecules at the electrochemi-
cal interface can result in the formation ofhighly ordered
monolayers that are easily detected by the presence of
two-dimensional (2D) phase transitions. This review is
mainly concerned with the role played by the electrode
substrate in the ordering and the disordering of 2D
organic films made of nonelectroactive molecules. The
current status of our knowledge is summarized by
reporting recent experimental results obtained at various
single-crystal electrodes and by emphasizing some fun-
damental advances made earlier at the mercury
electrode. In particular, the kinetics ofthe adlayer order-
ing and disordering are discussed in some detail.
I. INTRODUCTION
Greatly stimulated by the potentialities ofapplications of
thin organic films in many fields such as molecular
electronics, biosensors, electrocatalysis, or corrosion
inhibition, the assembling of molecules into highly
ordered structures has become a major research area in
material science during the last years. When prepared at
an electrode-electrolyte interface, the growth and the
structure ofthe film may be flexibly controlled by varying
the electrode potential. The formation of condensed
organic monolayers onto electrodes has extensively been
studied by electrochemists, starting from the pioneering
systematic investigations on mercury [1~5]. Those
researchers have shown that some compounds form
monolayers that may range from a dilute to a
self-assembled or condensed film. The creation of
427
organized thin films of organic compounds has devel-
oped into an increasingly important research area at the
frontier of analytical chemistry [6]. These films can be
used to create interfaces for manipulating reactions in
electrochemical analysis but also in electrosynthesis.
Condensed organic monolayers can indeed provide,
locally around the electrode, a hydrophobic environment
so that free radicals can be stabilized even when the elec-
trode is immersed in an aqueous electrolyte [7-9].
Until recently, the fundamental work dealing with the
two-dimensional (2D) condensation of organic sub-
stances was performed at the mercury electrode, which
provides smooth atomic surfaces easily renewable, so that
repetitive and reproducible results were readily obtained.
From the studies carried out at the mercury electrode, it
is generally concluded that the driving force for ordering
originates, as for a 3D crystal formation, from mutual
interactions between the adsorbate molecules, so that
organized monolayers (OM) are essentially formed when
strong attractive interactions exist between the adsorbate
molecules. These interactions are enhanced by the ability
ofmolecules to form hydrogen bonds and by the aromatic
character. Despite the large amount of studies that have
been carried out at the mercury-solution interface and
the advances made in the thermodynamics and kinetics
of 2D condensation, some important questions remain
unanswered. Among these, the role played by the
substrate is of particular importance. The adsorption at
the electrochemical interface is known to be a complex
process that is the net result of interactions between the
adsorbate, the metal, and the solvent. In contrast to the
liquid mercury electrode, solid electrodes display
428
complex surface structures, and the difficulty of their
renewal makes them very sensitive to trace impurities.
However, experimental procedures for the preparation
and treatment of well-defined solid electrodes [10-13]
and their electrochemical characterization are presently
available, so that a few groups have been recently
exploring the adsorption and self-ordering of organic
molecules onto metal single crystals.
In contrast to previous reviews, here we are mainly
concerned with the role played by the electrode in the
occurrence of ordered organic monolayers. Several new
findings dealing with recent investigations at various
single-crystal electrodes and fundamental advances
made earlier at the mercury electrode are presented to
give a picture ofthe state ofthe art ofthefield. An essential
part focuses on the kinetics associated with the ordering
and disordering of the films. Overall, this chapter pro-
vides the reader with a summary of the most salient fea-
tures of the 2D condensation of organic monolayers
presently recognized and reveals that the use ofsolid elec-
trodes has opened exciting new research perspectives.
II. PHASE TRANSITIONS IN ORGANIC
MONOLAYERS
A. Monolayers Adsorbed on Liquid
Electrodes
The adsorption ofneutral organic molecules is gener-
ally characterized by smooth variations ofthe differential
capacitance, the electrode charge density, and the surface
excess with the adsorbate concentration and with the
electrical parameter before desorption takes place at high
electric fields. Several reviews [14-18] describe the numer-
ous studies of molecules adsorbed at metal electrodes.
For dipolar surfactants, changes in the electrocapillary
parameters are expected because the molecules tend to
reorient gradually with the potential to adjust their dipole
to the imposed electric field. The adsorbed states may
then range from gaslike to condensed films so that phase
changes take place in the adsorbed layer. For a long time
most of the reported data dealing with the condensation
of organic monolayers were collected on mercury
electrodes. Phase transitions and condensed monolayers
have been observed at the mercury electrode for a large
number of neutral organic compounds (see references in
[5]), including mainly camphor and related compounds,
pyridine and bipyridine derivatives, thiourea, coumarin,
quinolines, purine, and pyrimidine derivatives.
Similar to 3D phase transformations, the transition
point corresponds to the intersection of the free energy
curves representative ofthe states prevailing at both sides
Buess-Herman et al.
r w 00 ~ (d)
'-T--- ~
f
~,., J3... -~'--.
a\ -..n.----- -.-'. , _" ,
a a j3o;·'~ ..
Ia P;;"
:1/ / / r
l=
a aU"LJ -E
Figure 1 Effect of the increase (a-d) of bulk activity of the
surfactant on the interfacial tension, charge density and
differential capacity. The lowering of y (arrows) is larger for the
most compact film {3. (From Ref. 19.)
(Fig. 1). Strong changes in the slope ofthe electrocapillary
curve describing the adsorption of the surfactant lead to
discontinuities along the potential that markedly affect
the charge density and capacitance values. According to
their set of capacitance, their potential of zero charge
(PZC) and their maximum surface tension, the two y-E
curves may present two, one, or no intersection. An
abrupt change in the charge-potential curve and a capaci-
tance tending to infinity at the transition point are
expected features [19]. However, the latter is not detected
due to experimental limitations. Such infinite peaks
would be indeed only observed if capacitance measure-
ments were performed at a sufficiently low frequency. In
most cases, the existence ofa condensed phase results in
a capacitance pit encompassed by two transitions. The
transition points or transition potentials Eo depend on
the variables affecting the electrocapillary plots. By
increasing the concentration of the surfactant, the most
condensed layer will expand its domain of prevalence
according to the difference between the surface excesses
of the two immiscible films (Fig. 2a). A decrease in tem-
perature promotes the extension of the most condensed
phase (Fig. 2b), the difference in the entropic terms
characterizing each of the two films being responsible
for the shift of the transition potentials.
The correct delimitation of the domain of stability
of the condensed phases requires the evaluation of
the thermodynamic transition potentials Eo. The
discontinuities present in the capacitance and
charge-potential curves arise generally at potentials that
deviate from the equilibrium transition potentials Eo.
Ordered Organic Adlayers at Electrode Surfaces
(a)
O'--------:+::------t:-----"*"- -....,.-
05 to t5 - E SCE IV
Figure 2 (a) Capacitance-potential curves recorded for adenine in 0.5 M at 25°C for various surfactant concentrations: (1) 0 M, (2)
2.3 mM, (3) 3 mM, (4)4 mM, and (5) 6 mM. (b) Capacitance-potential curves recordedforlO mM uracil in 0.4 MNa2S04 at various
temperatures: (1) 25°C, (2) 15°C, (3) lOoC, and (4) soc. (From Ref. 5.)
Potential scan experiments reveal the presence of an
hysteresis that is indicative of a kinetic control of the
interfacial process. Transitions leading outside the pit
region are generally independent on the scan rate so that
in many cases their positions will be considered as the
thermodynamic transition potentials. However, to
localize more accurately the transition potentials Ee, a
double potential step program has been designed [20] to
achieve a true equilibrium between the two competing
films: the first step triggers the condensation process
and before the completion of the transformation (usually
at 50% coverage by the condensed phase), the potential
is stepped to a value such that the capacitance or charge,
both representative of the degree of coverage by the new
film, are no longer time dependent.
In the early works [21-24], 2D condensation was dis-
cussed theoretically on the basis ofthe Frumkin isotherm
that predicts a discontinuity when the attraction
coefficient between adsorbed molecules is greater than
2. Classical thermodynamics has been used by Nikitas
[25-28] to derive rigorous criteria for the occurrence of
surface phase transitions. The thermodynamic treatment
predicts abrupt changes of the adsorbate concentration
and of the charge density when they are plotted against
the potential in the transition region.
The experimental dependences of the transition
potential with temperature and with the logarithm of the
bulk concentration of the surfactant, easily derived from
429
(b)
30
20
4 3 3 4
10
0'------+1-----+1------+1---;--"
05 10 -ESCE/V
classical thermodynamics, are also found when the phase
transition is discussed in terms ofa two-state Ising model
[29]. Several papers have recently based the interpret-
ation ofphase transitions on statistical mechanical treat-
ments [29-38].
2D condensation requires a close packing of the mol-
ecules that is only possible when short-range attractive
forces predominate. From the studies at the mercury
electrode, it appears that condensed monolayers are
formed for amphiphilic molecules having a dipole and
that the ability of H-bonding of the molecules and their
aromatic character may enhance modes of close
interaction. Obviously, there is a correlation between the
packing in a 3D solid and in a 2D condensed film because
all surfactants for which a phase transition between
adsorbed films has been reported have a melting tem-
perature higher than room temperature. Although
numerous studies of the adsorption behavior of parent
molecules at the mercury electrode have been reported,
it remains difficult to establish more precise molecular
requirements for the condensation of an organic
monolayer.
From the limited number of papers [39-46] dealing
with the occurrence of 2D condensed phases formed
from nonaqueous solutions, the influence of the solvent
can hardly be assessed. Additional studies are needed
involving surfactants other than sulfur derivatives to
minimize the interactions with the metal.
430
To examine the role played by the metal in the 2D con-
densation of organic molecules at the electrochemical
interface, it is more convenient to resort first to other
liquid electrodes to avoid all the problems associated with
the use of solid electrodes. Liquid gallium and molten
metals are not suitable because the formation of con-
densed phases is favored at low temperatures. A more
appropriate choice is to dissolve another metal in the
mercury phase to obtain a liquid amalgam electrode. We
have recently reported on the condensation of coumarin
at the indium amalgam-aqueous solution interfaces [47].
Indium amalgams have been selected because of their
wide range of compositions and their suitable potential
domain of ideal polarizability. They have also been the
object of investigations aimed at analyzing the
double-layer characteristics [48,49]. Similar to the
adsorption behavior on mercury, coumarin molecules
can form on indium amalgam electrodes a monolayer
presenting all the characteristics ofa 2D condensed layer.
An increase of the indium content of the amalgam leads
to an extension of the stability range of the condensed
monolayer. However, for each amalgam composition,
when the transition potentials are referred to the corre-
sponding PZC, they become independent of the indium
concentration. This feature can be explained by the fact
that when the indium concentration increases, more
negative potentials are required to reach an electric field
sufficiently high to reorient the adsorbed molecules and
promote the formation of the condensed monolayer.
B. Monolayers Adsorbed on Solid Electrodes
Except for the workon the adsorption ofcamphor on zinc
or tin electrodes [50-52] where the unusual capacity
curves have been interpreted in terms of the existence of
strong lateral interactions leading to condensation
phenomena, it is only very recently that the study of
formation of organic condensed monolayers at solid
electrodes has become an active field of research.
Single-crystal electrodes have increasingly been used in
electrochemical studies, and reliable results are now
obtained on well-defined surface structures that enable
a study of the surface specificity of interfacial processes.
Detailed studies of the adsorption ofpyridine on various
gold and silver single-crystal electrodes [53] and more
recently on bismuth electrodes [54] have provided clear
evidence of the importance of the nature and of the
crystallographic orientation of the electrode. Presently,
the most detailed studies on 2D organic condensation
have been carried out at the gold-aqueous solution
interface. Gold electrodes have been selected because
they display a broad double-layer region and have
Buess-Herman et al.
been the object of many investigations aImmg
at characterizing the interface in the presence of various
electrolytes [e.g., 55-58]. Gold single crystals may,
however, undergo potential-induced surface recon-
struction [59,60]. The stability range of the reconstructed
surface in the presence of organic molecules and their
influence on the potential-induced reconstruction
phenomenon are both important for defining the struc-
ture of the surface onto which the adsorption really takes
place.
The formation of organic adlayers of uracil,
methyluracils, and uridine has been investigated on metal
single crystals by means of cyclic voltammetry and
capacitance measurements [46,61-79]. Typical expanded
voltammograms recorded at the Au(lll) electrode in the
presence of these compounds are characterized by the
presence of broad peaks and sharp spikes that indicate
that the interfacial region undergoes important modifi-
cations (Fig. 3).
As was previously reported for such systems
[46,63,69,71], up to four distinct interfacial regions can
be distinguished for the adsorption of uracil, thymine
(5-methyluracil), 6-methyluracil, and uridine on the
gold(lll) face. The qualitative properties of the four dis-
tinct superfacial states are briefly summarized here. The
first adsorption state (region I) refers to arandom adsorp-
tion of the organic molecules and a gradual desorption
takes place at rather high negative potentials. Much more
interesting is the region II confined between regions I
and III by the presence ofa sharp spike at the negative side
and a steep step at the positive side. The domain of
stability of this film extends when the surfactant con-
centration increases and/or when the temperature
decreases (Fig. 4).
All these characteristics indicate that the region II may
be associated with a 2D-condensedfilm. A surface excess
of (3.0 ± 0.4) 10- 10 mol· cm- 2 for uracil [78] together
with a small shift of the PZC to less positive potentials
are consistent with a planar orientation of the molecules
that may form a hydrogen-bonded network similar to
their arrangement in the 3D solid. Region III shows very
large charge values (60 pC . cm- 2) that point to a
charge-transfer process associated with the passage from
a physisorbed (region II) to a chemisorbed-like state
(region IV). Roelfs and Baumgartel [68] were the first to
show that this complex transformation is pH dependent,
indicating that the charge transfer is accompanied by
the deprotonation of the molecule. At positive potentials,
region IV is associated with a highly ordered
chemisorbed phase. In contrast to region II, the extent
of region IV is only slightly affected by a temperature or
concentration change, indicating the distinct nature of
Ordered Organic Adlayers at Electrode Surfaces 431

30 30
(a) (b)

20 20

10 _ 10
N N
E IV E
u u
...... 0 ...... 0
< <
.=- .=-
---10 ---10

-20 -20

-30 -30
-0.6 -0.4 -0.2 0.0 0.2 0.4 -0.6 -0.4 -0.2 0.0 0.2 0.4
E/E sCE [V) E/E sCE (VI

30 30
(c) (d)

20 20

10 ..... 10
N
--IV N
E II E II
u u
...... 0 ...... 0
< <
.=- .=-
--10 ---10

-20 -20

-30 -30
-0.6 -0.4 -0.2 0.0 0.2 0.4 -0.6 -0.4 -0.2 0.0 0.2 0.4
E/E sCE (V) E/E sCE (V)

Figure 3 Cyclic voltammograms recorded for Au(lll) at 15 C in aqueous solution in the absence (.....) and the presence (--) of
D

four different compounds: (a) 0.5 M NaF + 12 mM uracil, (b) 0.1 M KC104 + 0.1 M uridine, (c) 0.5 M NaF + 20 mM thymine, and
(d) 0.5 M NaF + 28 mM 6-methyluracil.

the interactions leading to the formation oflayers IVand

II. The high temperature stability ofthe film in region IV
requires strong adsorbate-substrate interactions. In 20
region IV, the molecules adopt a vertical orientation that
favors the interactions between the substrate and one of 10
N
the nitrogen atoms. Experiments with 1,3-dimethyluracil E "
o
[70], where both nitrogen atoms are blocked, do not show <
:l.
0
any evidence of the presence of the chemisorbed
monolayer. It is therefore suggested that the molecules ---10
ofuracil and related compounds are connected via N(3)
or N (l) atoms to the gold surface. Recent XPS measure- -20
ments on the Au(111) electrode showed a significant shift
of one N(3) core level for thymine in the chemisorbed - 30 +----r-..----,---.--~!.....;--_.__---r-.....---I-
state [46]. However, for coordination complexes of gold -0.6 -0.4 -0.2 0.0 0.2 0.4
ions, the N(1) ring nitrogen atom seems to be the E/E sCE (V)
preferred reaction site [80].
Acomparison ofthe adsorption behavior ofuridine on Figure 4 Cyclic voltammograms recorded for Au(lIl) in
Hg, Au(111), and Ag(111) (Fig. 5) shows that the con- 0.5 M NaF aqueous solution + 12 mM uracil at IO C (--)
D

densed physisorbed layer is observed at very similar and 20 C (- - -). (From Ref. 75.)
D
432 Buess-Herman et al.

40 I I , , , 'I
solid substrate has been discussed for uracil and some
Hg
methyluracils [66,71]. Cyclic voltammograms on the III
and 100 faces ofgold and silver have revealed the presence
30
of the four distinct regions and in particular of the
N
E physisorbed and the chemisorbed films, Thymine on
u
;;:: 20 Ag(100) was the first example of a 2D condensation in
:I. "
an organic adlayer occurring on an unreconstructed 100
u
surface [64].
10 ," "
On the basis of the temperature dependence of the
condensed physisorbed phase,Wandlowski [66] has given
o I • I' • I I 'i I the following stability sequence: Hg < Ag(lll) < Au(lll).
-900 -600 -300 0 300 600 This order does not coincide directly with the order of
(a) E-E pze (mV) hydrophilicity (Hg::s Au < Ag) that has been derived
from the adsorption studies ofdiethylether and aliphatic
40 I I I
, , I alcohols [53]. The surprisingly large stability range of the
Au(lll) condensed physisorbed phase of uracil on gold can be
I
explained if one invokes a possible overlap of n-orbitals
30 .'.'
, ".' and nonbonding orbitals of a nitrogen atom of the mol-
',~I 'I
N
E ecule with the d-band of the metal. Such an interaction
u
;;:: 20 has been found to be in the case offlat-lying pyridine mol-
2- , '
ecules higher on gold than on silver [53]. The observed
u sequence is correlated to the energy of the d-bands of
10 the metals because these are located at 8, 4, and 2 eV
below the Fermi level, respectively, for Hg, Ag, and Au.
The Gibbs energy ofadsorption determined on the basis
o I I I I i I
-900 -600 -300 0 300 600 of chronocoulometric measurements indicates a weak
(b) E-E pzc (mV) chemisorption of uracil derivatives on Au(lll) [71]. At
more positive potentials, a partial charge transfer takes
40 I I I , , I place and a much stronger interaction can then be estab-
Ag(lll) lished between the deprotonated molecules and the posi-
tively charged electrode. According to Wandlowski [66],
30 the superposition of the Fermi level of the electrode and
the HOMO of the deprotonated molecule leads to the for-
N
E
u
~ ; : mation of a chemically modified adlayer. This expla-
;;:: 20 :J ~
:I. nation based on the N-coordination of vertical oriented
"
u deprotonated molecules with gold or silver can also
10 account for the absence ofa region IVat the mercury elec-
trode for which a d-band with too low energy may likely
be responsible for the lack of strong interactions between
oI i i I , I the absorbate and the electrode.
-gOO -600 -300 0 300 600
The difference in bonding ofthe uracil and derivatives
(e) E-E pzc (mV)
to the gold surface in regions II and IV is also revealed
by carrying out experiments on electrodes presenting dif-
Figure 5 Double-layer capacitance-potential curves record-
ferent crystallographic orientations (Fig. 6).
ed at 15°C for three different interfaces: (a) Hg 0.5 M
Surface defects may indeed affect the stability of the
Na2S04 +0.5 M uridine, (b) Au(lll) 0.1 M KCl0 4 aqueous
solution + 100 mMuridine, and (c) Ag(lll) 0.1 M KCl0 4 aque- films and the condensation kinetics. In contrast to the
ous solution + 100 mM uridine. case of metal deposition processes where the influence
ofsteps, kink sites, or screw dislocations has been for long
qualitatively recognized, the role played by the atomic
potentials when these are referred to the PZC character- surface arrangement in the formation of non-Faradaic
istic of the electrodes in the presence of an inert adlayers has presently received very little attention
electrolyte. The influence of the chemical nature of the [46,63,65,76-79]. Contrary to the physisorbed layer, the
 Ordered Organic Adlayers at Electrode Surfaces 433

40 40
(a) (b)
35 35
1
30 30

~ 25 ~ 25
... ...
;;: 20 ;;: 20
::>..
t -=-
U 15 U 15
10 10

5 5

0
t -0.6 -0.4 -0.2 0.0 0.2 0.4
0
-0.6 -0.4 -0.2 0.0 0.2 0.4
E/E sCE (V) E/E sCE (V)

40 40
(e) (d)
35 35

30 30

~ 25 ~ 25
... ...
;;: 20 ;;: 20
-=-
u 15 -=-
u 15
10 10

5 5

0 0
-0.6 -0.4 -0.2 0.0 0.2 0.4 -0.6 -0.4 -0.2 0.0 0.2 0.4
E/E sCE (V) E/E sCE (V)

Figure 6 Double-layer capacitance-potential curves recorded at 15°C for four different gold surfaces in 0.1 M KCI0 4 aqueous
solution + 100 mM uridine: (a) Au(l3,13,12), (b) Au(554), (c) Au(332), and (d) Au(221). (From Ref. 77.)

existence of the chemisorbed film seems to be rather
indifferent to the crystallographic orientation of the gold
electrodes. This is not surprising because chemisorption
merely results from a chemical interaction between the
organic molecules and the metal. By resorting to several
stepped surfaces, we observed that the sharp spikes
characteristic of 2D phase transitions detected on the
j- E curves on Au(lll) are no longer present even for high
surfactant concentrations and low temperature con-
ditions on Au(221) and Au(332).
To get a better understanding of the influence of the
surface structure, additional experiments have also been
performed on other stepped surfaces that present larger
111 terrace widths such as Au(554) and Au(l3,13,12). The
curves recorded with the 554 face present only very little
indications in favor of 2D phase transitions taking place
in the adlayers. For the 13,13,12 face that presents a larger
terrace width, marked peaks are detected and the adsorp-
tion behavior seems to be rather similar to the one
observed on Au(lll). These experiments have con-
vincingly demonstrated that the increased sharpness of
the transition spikes can be explained by an increased
domain size due to larger terraces. Condensed
physisorbed monolayers can only be formed when the
terraces are sufficiently large to permit the establishment
of an ordering of the adsorbate. The average width of the
terraces allowing the condensation can be expected to
depend on the nature and size of the surfactant. For the
closely related molecules uracil and uridine, similar
terrace widths are involved, and this is most probably
linked to the fact that uracil and uridine molecules are
both adsorbed flat at the electrode with a similar area
per individual molecule.
These results are of particular interest because they
emphasize the importance of a well-prepared surface
for the study of 2D condensation phenomena. For
instance, the observation of the 2D condensation of
thymine on silver electrodes was only possible on very
434
high quality single crystals that were pretreated by chemi-
cal etching and flame annealing [64]. Evidence in favor
of a flat surface as a prerequisite for the occurrence of
2D phase transitions has also been provided by exper-
iments with Au(llO) and Au(100) reported by H61z1e
and colleagues [65,71]. These authors have shown that
the 2D condensation ofuracil on gold is not restricted to
the close-packed surfaces like Au(111) and Au(100)-(hex)
but is also formed on Au(lOO)-(1 x 1), provided that the
gold islands due to the lifting of the reconstruction of the
electrode surface have been removed by an appropriate
procedure. All these results indicate that the atomic
corrugation of the substrate structure plays a critical role
for the occurrence of 2D phase transitions.
Among the new experimental tools available for the
study ofordered organic monolayers on solid electrodes,
only near-field techniques such as scanning tunneling
microscopy (STM) and AFM have been so far the subject
of intense efforts to obtain structural informations. STM
images ofguanine adsorbed and condensed on a graphite
HOPG electrode [81] were the first reported observations.
Presently, available in situ STM studies deal with purine
and pyrimidine bases [46,67,73,82,83], thio-derivatives
[84-86], and bipyridines [87,88] on Au(lll) and with
purine bases on a HOPG electrode [81,89-92].
Very recently, high-resolution STM images have been
obtained for thymine and uracil adsorbed on Au(lll)
[46,73]. Figure 7 shows the in situ STM images obtained
for the various superficial states ofuracil on Au(lll).
With both systems, the images of the physisorbed film
confirm that the molecules are lying flat and form a 2D
network via hydrogen bonds. The images of the
physisorbed film of uracil on Au(lll), Au(lOO)-hex, and
Au(100)-(1 xl) [73,93] are very similar and reveal only
small variations of the dimensions of the respective
coincidence cells. Although the imaging of the
chemisorbed film seems to be less problematic, the
interpretation remains difficult. In the case of thymine
on Au(lll), Roelfs et al. [46] observe images with a com-
mensurate .J3 x .J3 overstructure. They are interpreted
by stacks of upright standing thymine molecules con-
nected via N(3) atoms to the surface, and these stacks
are connected by coadsorbed water molecules.
Dretschkow et al. [73,93] propose for uracil a packing
arrangement where the molecules occupy the
(.J3 x .J3)R30° positions of the substrate lattice.
Moreover, the contrast pattern between adjacent rows of
molecules is explained by the formation of molecules
rotated +45° or -45° with respect to the [llO] direction
of the metal lattice. The chemisorbed uracil film on
Au(lOO)-(1 x 1) is of oblique symmetry and consists of
interdigitated regular arrays of four molecules stacks.
Buess-Herman et al.
These various studies clearly show that the description
ofan ordered molecular packing ofthe molecules derived
from the images obviously gains interest when it is con-
sistent with macroscopic data obtained from classic elec-
trochemical experiments and moreover provides
structural information that allows us to better
differentiate the films on the basis of their 2D ordering.
III. KINETICS OF ADLAYER ORDERING
Many kinetic studies have shown in the past that when
the adsorption process on electrodes is slow, the
rate-determining step is usually governed by mass
transfer. Other limitations than diffusional, however, are
responsible for the slow kinetics of formation of con-
densed monolayers. This is not surprizing because order-
ing is known to proceed when fluctuations are sufficient
to form clusters of a minimum size such that growth of
the new phase becomes spontaneous. The presence of a
significant activation energy associated with the forma-
tion of a critical nucleus is responsible for the fact that,
similar to 3D condensation processes, the ordering of a
2D phase at the electrochemical interface does
generally not take place at the transition potential but
requires an overvoltage that depends on the experimental
conditions.
The formation of an ordered monolayer can be
triggered at the electrochemical interface by an appropri-
ate change in concentration, temperature, or potential.
The phase transformation is, however, usually initiated
by applying a potential step that may very rapidly trigger
the formation ofa new thermodynamically stable phase.
The kinetics of the process can be followed by recording
capacitance, charge density, or current transients as a
function of time. Charge and capacitance transients give
fully equivalent results because these are both linked to
the extent ofcoverage by the new phase according to
Co - C (J - (Jo
8- ---
- Co - Coo - (J 00 - (JO
(1)
where Co, Coo and (JO, (J 00 are the capacitance and charge
density values before and after the transformation,
respectively. For practical reasons, charge measurements
are preferred for fast relaxation processes and capaci-
tance measurements for slow processes because these
are limited by the fact that the ac signal should have a
period much shorter than the relaxation time. They have,
however, for slow processes the advantage of being less
sensitive to the presence of minute electroactive species
than charge density transients recorded over a long time.
Current transients representative of the variation of the
Ordered Organic Adlayers at Electrode Surfaces 435

~'. ~ .•.
. . .' : .'".:.:. . . C
...: \........
. "'. -; "'. .......
"'.
... . . ..
.......... :... .
~
......:.. ...
". ..:~..-
'."
"
.. '", .... ..
" ....
'. ".. "0...
.... " .. .....• .
• .

30nm
... "
-a, ;'.',
.. :... .. -' ....
•• •

P2
:::~:': ;-:.:. .'..:::···:/'tA
. .. . . ~

·· .
.

100nm

I ····
100nm

~ .
"
:;:~

II ,:'.
.,' .
"
4.'"
..
.' ,
Esee IV .............. _. _ ,,'

III
P3

P2'

100nm 20nm

Figure 7 Cyclic voltammograms (scan rate 10 mV/s) for Au(l1l)/O.05 M H 2 S0 4 in the absence (thin dashed line) and in the
presence of 12 mM uracil: first scan with a reconstructed electrode after immersion at 0, 10 V (solid line) and steady-state
voltammogram (dotted curve). Illustration with typical 'steady state' in situ STM images. (A) thermally reconstructed AU(lll)-(px.J"3)
surface, (B) uracil physisorbed film, (C) unreconstructed Au(lll)-(l x I) in the presence of the uracil chemisorbed film (D), and (E)
island-free area ofreconstructed Au(lll)-(px.J"3). (From Ref. 73.)

overall rate of transformation as a function of time are
also recorded. These curves, although similar to those
characteristic of the formation of metal deposits by
UPD and OPD, differ, however, by the amplitude of the
measured current because only currents of capacitive
nature are involved in the organic monolayer
transformation. Consecutive to a potential step beyond
the transition, a metastable state is reached from which
the condensation can start as indicated by the slow modi-
fication ofthe capacitance, charge, or current. The analy-
436
sis of the transients is possible by selecting optimal
experimental conditions such that no significant overlap
between the initial part controlled by the time constant
of the equipment and the subsequent relaxation occurs.
In the absence of mass transfer limitations, potential
step measurements performed to follow the 20 order-
ing yield usually transients typical of a nucleation and
growth process. Complex kinetic results are associated
with the phase transition taking place within an organic
monolayer formed on solid electrodes. This is not
surprising because the kinetics at solid electrodes, even
if high-quality single crystals are available, are com-
plicated by the presence of surface defects that are
known to play an important role in nucleation and
growth processes. After a brief survey of some general
aspects of the nucleation process, the discussion starts
with the ordering kinetics of monolayers adsorbed on
liquid electrodes before considering some more
complex situations involving surface structure
specificities of the substrate.
A. Formation of Nuclei
By analogy to 3D phenomena, the nucleation step can be
explained on the basis of the classical nucleation theory
(CNT) successively developed mainly by Volmer and
Weber [94], Becker and Doring [95], and Zeldovich [96].
As soon as a cluster has reached its critical size, it has
a one-half probability to expand by incorporating
additional molecules and become macroscopically
detectable. The stability of the critical nucleus is con-
ditioned by two opposing factors, which are both function
of the nucleus size but with different dependences. The
free energy of formation (dG F ) of a 20 circular cluster,
as a function of its size, is given by the sum of the energy
gained by the formation of the disk and the work spent
to overcome the peripheral boundary:
dG F = 2nre + nr2dY# (2)
where e is the line tension, r the radius of the cluster, and
dl a negative quantity that is the driving factor or
supersaturation term externally imposed on the system
to trigger the transformation.
The free energy (dGj,) and the radius (r*) ofthe critical
cluster, which are obtained at the maximum of the
G = fer) plot, are given by
ne2 e pendently controlled, besides the potential, by the
dGj, = - dl and r* = - dY# (3)
Clusters with r > r* tend to grow spontaneously to a
macroscopic size. During the transformation, the
Buess-Herman et al.
electrode becomes a patchwork of zones made of
distinct phases, each phase being characterized by its
own interfacial tension because intermediate I' values
are forbidden.
According to the CNT that assumes that the
rate-determining step is the incorporation of one
additional molecule to the critical cluster, the 20
steady-state nucleation rate J can be expressed by
ne2 )
J = Z[3* N] exp ( dlkT (4)
where Z is the Zeldovich factor accounting for the
deviation from the Boltzmann distribution, [3* the supply
rate of a molecule to the critical cluster, and N] the
number of nonclustered molecules per unit area.
As a first approximation, Z and [3* can be considered
as nearly invariant with the supersaturation term so that
the equation for the steady-state rate of nucleation
becomes
ne2 )
J = J oo exp ( dlkT (5)
where J 00 is akin to a collision factor, being the value of
the nucleation rate for infinite supersaturation. Key
parameters such as the line tension, the radius, and
free energy of formation of the critical nucleus can
be obtained from the dependence of J with the
supersaturation term. Despite its widespread use, the
CNT remains only a semiquantitative approach to
describe the nucleation process by experimentalists and
has raised many problems that have been thoroughly
reviewed elsewhere [97,98].
Irrespective ofthe theory considered, the evaluation of
the supersaturation of the system is essential to interpret
the kinetics of phase transformations. Contrary to the
case of electrodeposition involving a Faradaic process,
the driving force for the formation of an ordered phase
of nonelectroactive molecules is no longer given by the
overpotential (Fig. 8).
The actual driving factor is the surface free energy gap
between the final and metastable states and is therefore
given by -dl. This quantity associated to the
supersaturation of the system must be necessarily equal
to zero at the transition point. According to the elec-
trocapillaryequation, the amplitude of dl can be inde-
temperature, the surfactant bulk activity, and the
pressure. The evaluation of the supersaturation term is
generally achieved by the following integration proce-
dure that involves, at constant pressure, temperature,
Ordered Organic Adlayers at Electrode Surfaces
2
" "- "-
\
\
\
, .
'\'"
Figure 8 Relaxation path when the potential is stepped from
£1 to £2. The fast polarization (full arrow) is followed by the
transition (arrow in broken line) that is driven by the energy
gap between the final and metastable states ~l. The
supersaturation term (-~l) equals zero at £8 and passes
through a maximum when £2 is varied. Broken lines refer to
metastable states. (From Ref. 5.)
and concentration, the charge density-potential plots
representative of the two distinct phases C( and p:
t,"'/ = JE u~dE - JE Uf3dE
Eo Eo
According to the amplitude of the supersaturation term,
the ordering process on a defect-free substrate can show
a deterministic or stochastic behaviour. Defects or
impurities are known to assist the nucleation process so
that the supersaturation term associated with the
self-nucleation process is no longer controlling the over-
all kinetics.
B. Ordering Kinetics of Monomolecular
Films on Liquid Electrodes
When the probability offormation ofthe critical nucleus
is low, the formation of the OM can become a stochastic
process. By potential step experiments it is possible to
obtain nonreproducible transients characteristic of the
growth of one single nucleus that appears stochastically
in time and space. Besides a low supersaturation, the
reduction of the electrode area also helps in lowering the
437
4
I(s)
0+----,-1----,-------,---,------,----+
-010 000 0.10 020 0.30
t (s)
0.40 0.50
Figure 9 Stochastic mononucleation charge transients
obtained after a single potential step from £1 = -450 mY to
£2 = - 510 mY on mercury with a saturated coumarin solution
in 0.5 M NaF at 10°C. These transients can be mathematically
described by the growth of a spherical cap at constant radial
growth (inset).
probability offormation of a nucleus. Nevertheless, even
when the probability of nuclei formation is small, no
stochastic behavior may be observed because of the
slowness of the growth process.
For a series of repeated potential step experiments
performed under strict identical experimental con-
ditions, the mononuclear transients are scattered along
the time axis as shown in Fig. 9. Such behavior has been
(6) observed for example for coumarin at the mercury
[99-102] and the indium amalgam electrodes [47] for a
wide range of overpotentials. Mononuclear transients
can provide both the growth rate and, ifa statistically sig-
nificant set of transients is recorded, the nucleation
kinetics that can, by the use of Poissonian statistics [1],
be extracted from the moments of nucleation detected
by the onset of the growth curve. Unfortunately, in most
cases, the stochasticity of the behavior is affected by the
presence of edge nucleations probably taking place near
the lumen ofthe capillary [103]. Evidence for such a cata-
lytic effect is provided by a statistical analysis of
experimental data obtained with electrodes of various
sizes. In contrast to foreign nuclei present in the solution,
the probability of occurrence of a spurious nucleation
induced by the capillary must remain constant when the
electrode area is varied. Meaningful values of the
steady-state self-nucleation rate are extremely difficult
to obtain from the sole analysis of the stochastic
responses.
438
Whatever the nature of the nucleus (intrinsic or
extraneous), the shape ofthe mononuclear transients pro-
vides a unique opportunity for evaluating the absolute
rate ofgrowth. Irrespective ofthe starting time, the charge
or capacitance transients reflect the progressive covering
ofthe electrode surface by the ordered phase and can thus
be directly related to the growth rate. For a 2D cluster,
growth is only possible by the expansion of its periphery
and a constant radial growth rate can be expected for
circular clusters. The use of a spherical electrode such as
the DME or HME leads to mononuclear transients ident-
ical in shape, although scattered along the time axis. All
sites for the formation ofa nucleus on a sphere are equiv-
alent so that a same coverage- time relation is expected.
The instantaneous coverage of a spherical electrode of
constant area by a circular nucleus is easily expressed in
terms of a growing spherical cap [103]:
8= ~ [I _
cos vet ~ to)] (7)
where 8 denotes the fraction ofthe surface covered by the
condensed film, v the radial growth rate, r the electrode
drop radius, and t - to is the time since the nucleus is for-
med.
Experimental verification of Eq. (7) proves that the
radial growth rate is not time dependent (Fig. 9). The
radial growth rates can then be evaluated from the slope
vir ofthe linearized form of Eq. (7). The rate of incorpor-
ation of additional molecules into the growing nucleus is
typically ofthe order ofa few mmls and is, compared with
the nucleation rate, only slightly dependent on the
supersaturation of the system.
The occurrence of single events in a wide range of
supersaturations is the result of assisted nucleations.
These essentially arise from the presence ofthe capillary
that may act as a nucleation site. Phenomena such as the
nonuniform distribution of the two constituents of an
amalgam at the capillary wall or the presence of oxide
traces and other impurities may catalyse the formation
ofa nucleus.When the formation ofthe ordered film starts
from an extraneous single nucleus, it is generally possible
to obtain the growth rate over a fairly large potential
range. As a result, an extrapolation of the growth rate
at potentials where prevails a deterministic behavior
is much easier so that data concerning the nuclea-
tion rate may be obtained from the combined analy-
sis of mononuclear transients and deterministic
measurements.
As can be expected, extraneous nucleations induced
by surface defects complicate markedly the detection of
a single event when a solid electrode is used. Moreover,
Buess-Herman et al.
for nuclei and electrodes presenting geometries different
from that, respectively, of a circle and a sphere,
mononuclear transients may present rather contrasted
shapes according to the location of the nucleus on the
surface.
When more than one critical nucleus are formed,
competition between the growing nuclei for the limited
area takes place and internuclear collisions may no
longer be discarded. It is generally considered that growth
stops at the points where nuclei meet and that coalescence
may be ruled out [104]. Simulations ofthe growth process
have shown that when a cluster grows by direct incorpor-
ation (Eden model) the resulting object has a compact
structure. Its Hausdorff dimension is equal to the
dimensionality of the lattice (here 2D) and as such is
not a fractal object. On the contrary, in the
diffusion-aggregation model, the resulting cluster has
an open structure with a fractal dimension of 1.66. Most
often the formation of 2D condensed monolayers at the
electrochemical interface is not diffusion controlled and
the growth of the nuclei leads to a compact structure with
no true fractal properties.
Deterministic transients have been by far more fre-
quently recorded, but unfortunately their analysis is more
complex and yields no absolute values of the rates of
nucleation and growth. Complications arise from the
internuclear collisions that occur when many nuclei grow
to cover all the available electrode area. The problem of
the overlap between growing nuclei has been derived
independently by several authors [105-110]. The fraction
ofthe surface covered by the nuclei at any time is given by
8 = I - exp( -8 x ) (8)
where 8x is the coverage that would have been reached in
the absence ofoverlap.
This expression often called the Avrami theorem is
valid for a random distribution of a large number of
nuclei, each of them having to be small with respect to
the total available area. When the formation and growth
of circular nuclei proceed simultaneously, the coverage
of the new phase is given by the Avrami equation for 2D
progressive polynucleation and growth (PPG)
8 = I - exp ( -"3
TC
Jv 23)
t (9)
where J and v are, respectively, the nucleation rate and the
growth rate.
PPG transients provide information that is exclusively
related to the product Jv 2• Transients resulting from a
single potential step ofvariable amplitude reflect directly
the dependence of this product on the potential and
Ordered Organic Adlayers at Electrode Surfaces
6
2
0.1 03 Q5 0] -EIEC
(V)
(a)
Figure 10 Influence of the potential (a) on the logarithm of the half-life times of the condensation transients and (b) on the
supersaturation term for 4 mM adenine in 0.5 M NaF at 15°e ('Y), 20 e ( • ), and 25°e (.A.).
consequently also on the supersaturation of the system.
This is illustrated in Fig. 10, which presents the logarithm
of the half-life times of the transients (T) as a function of
the potential together with the !!y# -Eplot.
When growth occurs from a constant large number
NN ofpre-existing nuclei, Eq. (8) takes the form
(10)
which is the Avrami equation for instantaneous
polynucleation and growth (IPG). Equations (9) and (10)
represent two limiting cases of a one-step nucleation
according to an exponential law. Polynucleation
transients are usually analyzed using a double logarith-
mic plot or Avrami plot that gives straight lines with
slopes 2 and 3, respectively, for IPG and PPG transients.
Deviations from the classical equations for PPG and
IPG have been encountered with a few systems. These
have generally been overcome until now by considering
a one-step nucleation according to an exponential law
orland a diffusional controlled growth.
439
--1v'(mNfm)
OJ 03
(b)
0
IPG transients can be triggered by the double poten-
tial step method because the nucleation rate is usually
a much steeper function of the potential than the growth
rate. A large number of nuclei are formed after a first
potential step that is aimed at applying a high
supersaturation during a short time. The potential is
then stepped further to a value where the nuclei can
grow and where further nucleation is unlikely. From
double-step experiments where the nucleation potential
and the nucleation duration are kept constant, it is poss-
ible to determine the influence of the potential on the
growth rate. The v- E relation obtained by this way is
generally consistent with the dependence established
from the analysis of mononuclear transients triggered
by single potential step experiments. The variation of
the nucleation rate with the potential is very difficult to
establish from the analysis of mononuclear transients
because the nucleation rate can be estimated only in a
very narrow potential range. When double potential step
experiments are carried out in a way such that the poten-
tial of nucleation is the only variable, the dependence
of the nucleation rate on potential can be obtained. A
440
13 I I I
.'Ei
I
II! 11
z
.5
:;
.....
9
~ '"
7 I i i I
-0.7 -0.6 -0.5 -0.4
1Itq"'{m.10- 3 N-')
Figure 11 Experimental test of the dependence of the
nucleation rate with the supersaturation term (-L'1'l) according
to CNT. Nucleation rates J are calculated from three different
sets of experiments where the perturbation in L'1'l is induced
by the potential (.), the concentration CA.), and the tempera-
ture (.) respectively. The value common to the three sets of
experiments is indicated by •. (From Ref. Ill.)
same value of the nucleation rate [111] has been found for
a given !1l value irrespective of the variable (potential,
temperature, or concentration) used to control the
amplitude of !1l (Fig. 11).
According to the CNT, the line tension can be
evaluated from the slope of the In J vs. 1I !1l plot.Values
of the line tension range from about I xlO- 12 to
15xlO- 12 Jim according to the nature of the surfactant
and the nature of the interfacial process associated with
the transition. When the line tension and the
supersaturation are known, the free energy and the radius
of the critical clusters can be calculated according to
Eq. (3).
c. Ordering Kinetics of Monomolecular
Films on Solid Electrodes
Recent data have shown that the transients corresponding
to the formation of a physisorbed condensed layer on
solid electrodes present complex shapes. This was to be
expected because it is known that surface defects such as
monoatomic steps influence markedly the kinetics of
interfacial processes where adsorption and nucleation
growth are rate-determining steps. Besides well-ordered
20 films, the formation of patchworks of random or
Buess-Herman et a1.
less-ordered structures may therefore not be excluded.
This complicates the kinetics of an overall phase
transformation because random aggregation is usually
governed by relevant adsorption-desorption kinetics
and condensation by a nucleation and growth process.
The kinetics of formation of a physisorbed mono-
layer made of uracil, methyluracils, and uridine have
been investigated by the potential-step technique at
gold single-crystal electrodes [63,67,69,74,75]. Typical
current-time curves obtained after a single potential step
triggering the formation of the ordered monolayer are
shown in Fig. 12.
The most commonly recorded transients present an
initial current decay followed by a shoulder (Fig. 12a). A
similar initial portion is also obtained when the initial
and final potentials are both located in the random
adsorption region. Therefore, the initial part ofthe transi-
ent is due to the combination of the charging of the initial
double-layer capacitance and the fast rearrangement of
the interface to a metastable state involving the gaslike
adsorption ofuracil molecules. The decoupling ofthe dif-
ferent parts of the transients can be facilitated by
performing the measurements in concentrated electro-
lyte solutions and selecting initial potentials close to the
transition point.
When the rate of the condensation process becomes
very fast, only monotonic curves are detected at short
times (Fig. l2b) and no further analysis is possible. The
most striking feature of the kinetic data is the presence
ofa pronounced maximum in the current transient (Fig.
12c) when the potential is stepped into region II. To
analyze these condensation kinetics, two parallel
pathways are postulated: random adsorption (RA) and
polynucleation and growth (PG). All the models con-
sidering simultaneous RA and PG predict current time
curves with a fast decay of the current that precedes a
rising portion itself followed by a gradual decay toward
zero [112-114].
The initial part of the j-t curves is generally satisfac-
torily fitted by an exponential law that can reasonably be
established from a set ofexperimental data. The analysis
of the decay in terms of the kinetics ofa Langmuir-type
adsorption of the molecules is too restrictive because the
adsorption process is also concommittant with the
charging of the double-layer capacitance characteristic
of the gaslike film when a potential step is applied to the
electrode. The kinetic results for the formation of the
chemisorbed layer of uracil on Ag(ll1) [72] have been
satisfactorily explained by a model that accounts for
diffusion-controlled random adsorption ofthe molecules
according to a Frumkin isotherm, followed by the
progressive nucleation and growth ofclusters.
Ordered Organic Adlayers at Electrode Surfaces 441

3.5 +----'--------'------'-------'-----+ O+-----'-------l.---'----_...L..-_ _-+

3.0

2.5 -2

(I)
I
140mV
~ -4
T slope 1.59
gOmV E
1.0

0.5 -6

0.0 +-----,-------..------,----,------+
a 0.01 0.02 0.03 0.04 0.05
-8 +----,-------r----,------r----+
(a)
t (s) -9 -8 -7 -6 -5 -4
In (tl s)
1.00 t-------'------'-------'---------+
Figure 13 Avrami analysis of a transient recorded at 15°C for
Au(1l1) in 0.5 M NaF solution + 30 mM 6-methyluracil after
0.75 applying a single potential step from £1 = -600 mV to a final
potential of -200 mY.

1§ 0.50
The curves obtained after subtracting the RA contri-
bution present a characteristic bell-shape morphology
0.25
and have been analyzed according to the linearized form
OmV -200mV
of the Avrami equation. A combination of a
Langmuir-type adsorption running in parallel with a
0.00 -l-----,---==~==~======i 20 growth process has also recently been used to describe
0.00 0.01 0.02 0.03 0.04
(b) the kinetics of deposition of metals [115]. In most cases,
t (s)
the Avrami plots of the transients reveal complex
situations since slopes ranging between I and 2 are
obtained (Fig. 13).
2.5
No indication of 20 progressive nucleation is found,
but the results show that the formation of the ordered
2.0 film proceeds from nuclei created instantaneously or
probably during the first moments of the overall relax-
ation curve. This is not surprising because the surface
~u 1.5
of a solid, even a single crystal, may present some
1 1.0
defects that may assist the formation of the nuclei.
Noninteger values of the Avrami exponents between I
and 2 are generally modeled by considering the
-IlOmV
0.5 exponential law of nucleation in combination with sur-
-120mV face diffusion controlled growth [116] or by taking into
0.0 account a "truncated nucleation" combined with a sur-
0.000 0.005 0.010 0.Q15 0.020 face diffusion controlled growth [117]. To explain
(c)
t (s) deviations from the classic Avrami equations for
instantaneous or progressive nucleation and constant
Figure 12 Current-time curves recorded at 15°C for Au(111) growth, attempts have recently been made, taking into
surfaces in 0.5 M NaF solution + 14 mM uracil after applying consideration a time-dependent supersaturation [118],
a single potential step from £1 = -650 mV to various final a progressive nucleation with decay of the nucleation
potential as indicated. centers [72], and the simultaneous processes of adsorp-
442
tion of the molecules from the bulk, surface diffusion of
the adsorbed molecules and their consumption at the
edge of the growing nuclei [119].
Of particular interest for the elucidation of the mech-
anism is probably the experimental fact that the Avrami
exponent may abruptly change from 2 to 1 as detected
for uracil on Au(l1 1). We have proposed to describe the
peaked transients obtained for the condensation ofuracil
on Au(111) by considering the succession in time of two
regimes for the growth process [75]. At short times,
molecules can directly be incorporated, whereas later a
limitation slows down the growth process. Generally,
surface diffusion is considered as responsible for a poss-
ible limitation of the growth rate. A completely rigorous
solution of the diffusion problem is difficult, and an
equation is given only for the simplified case where the
radius r ofa nucleus grows according to r = A .Jl5i, with
D the diffusion coefficient and A a constant that depends
on potential, molecular weight, and density of the
surfactant. The 2D instantaneous nucleation and growth
transient may then be described by the following
equation [120]:
i = qrnon n A 2 D exp( -nA 2 DNot) (II)
A diffusion controlled growth of pre-existing nuclei is
therefore characterized by a unity slope in the Avrami
plot. Incidentally, a similar time dependence is also
expected for a process controlled by the adsorption
kinetics. On the basis of a slope of 1, no distinction can
be made between RA and PG controlled by diffusion as
rate-determining steps. However, with uracil, a unity
slope is only obtained at longer times, and the presence
of pre-existing nuclei is indicated at shorter times by a
slope of 2 in the Avrami plot, so that we may decide here
in favor of a change in the growth rate. Detailed studies
on the kinetics associated with 2D phase transitions on
stepped gold surfaces are in progress [79] and tend to indi-
cate that the growth rate limitation is more likely con-
nected to the finite geometry of the surface and in
particular to the terrace widths.
The presence of surface defects is clearly responsible
for the shape modification of the transients. Depending
on the experimental procedure shoulders or pronounced
maxima can be observed in the current- time curves. We
have observed that the peaked current transients are
essentially obtained with an electrode after flame
annealing of the surface [78]. When some additional
potential excursion is made in region IV before triggering
the formation ofthe physisorbed layer, the current maxi-
mum rapidly vanishes. These facts demonstrate that the
kinetics are extremely sensitive to the surface character-
Buess-Herman et aI.
istics and that different results may be obtained for a same
system depending on the experimental protocol. In the
presence of surface defects, the random adsorption
pathway predominates over the nucleation and growth
process. As a result, the quality ofa surface can therefore
also be indicated by the charges involved, respectively, in
the adsorption and in the growth process.
The effect oftemperature on the transition kinetics has
also been examined by recording current transients
triggered by a potential step at various temperatures [75].
The data show that an increase of the temperature
decreases the rate of the transformation. Such a result is
expected for a condensation process because the acti-
vation energy is related to the formation of the critical
nucleus and consequently to the supersaturation of the
system. The influence of the temperature on the rate of
condensation of uracil on Au(I 11) is properly accounted
for by referring the potentials to the transition potentials,
themselves varying with temperature. Such an influence
of the temperature on the rate of monolayer
transformation is typical ofa non-Faradaic condensation
process controlled by a nucleation and growth
mechanism.
IV. KINETICS OF ADLAVER DISSOLUTION
On the basis of kinetic results obtained for the
disaggregation of physisorbed condensed films at the
mercury electrode, we suggested a defect-mediated dis-
solution process [19,121] because experimental facts have
indicated that the history ofthe film formation influences
markedly the kinetics. The disaggregation or dissolution
of monolayers directly compares with the dissolution or
melting of 3D crystals [122,123], which are known to be
complex phenomena occurring by the reverse process of
growth. For real 3D crystals, the dissolution rate is differ-
ent from the growth rates because the crystal perfection
has a stronger influence on the dissolution process. The
problem of the limiting process in dissolution is exactly
the same as in growth. Dissolution of 3D crystals limited
by bulk diffusion may occur, but the kinetics are mostly
complicated by the distinct dissolution rates at different
faces of a crystal and the presence of many structural or
chemical imperfections.
As shown in Fig. 14, the condensed film can be
described as a lattice arrangement of line and point
defects, so that two limiting disaggregation mechanisms
can be considered: the process may start either from lines
or from points. Point defects may be active sites from
which the dissolution starts. This can be viewed as the
creation ofa hole in the film or an island ofthe new phase
that will grow. This mechanism can be completely
r Ordered Organic Adlayers at Electrode Surfaces 443

6 +----'-------'-----'-----'----+

(a)

4
§
U 3
time
-3 ~2
• t> o
<J 2 ~1

0. +----+---+------1-----l
0. 0.005 0.01 0.015 002
(b) 1(')

0+--'----,.-----,----,------.----+
o 0.01 0.02 0.03 0.04 0.05
t (s)

Figure 14 Simplified scheme for the disordering of a con-
densed film (a) starting from lines or (b) via nucleation and
growth of holes.
described by the classic equations for polynucleation and
growth of circles so that peaked j-t or sigmoidal (J-t
curves may also be associated with a dissolution or
disaggregation process. Models based on the nucleation
and spreading of holes have been applied in the past to
the reduction and dissolution of anodic layers [124] and
the electric breakdown of membranes [125] and more
recently to the desorption of organothiols on gold [126].
Ofparticular interest is the case when a defect-free sur-
face such as the mercury electrode is used and the con-
Figure 15 Charge transient obtained after a single potential
step (E 1 = -530 mY; E2 = -400 mY) allowing the disordering
of the coumarin condensed film formed by mononucleation.
This transient can be analyzed using Eq. (7) (inset). Conditions:
Mercury in contact with a saturated coumarin solution in NaF
0.5 Mat 5°C.
ferent ages are presented in Fig. 16. Slower kinetics are
associated with older films where rearrangements
minimizing the defects similar to those associated with
an annealing process were possible.
-2.3

3
densed phase formed from one single nucleus. The
-2.2
dissolution transient reflects thus the growth of the new p
..
phase starting from one site that is most probably located '"-2.1
.£

at the place where the formation of the condensed phase ~

'-' 2
is completed. The transients are consequently expected U -2
-3 0 50
t(s)
100 150
to follow the equation for mononucleus growth. Figure t>
<J
15 shows an example of a dissolution transient obtained
for coumarin that nicely fits Eq. (7).
When the condensed layer is formed from a large
number ofnuclei, line defects resulting from the collision
fronts constitute additional sites for the disaggregation o-l-l---.,--------,------,-----==:::::;:======+
process. The kinetics depend not only on the dissolution o 10 20 30 40 50

overpotential but also on the overpotential where the t (s)

condensed film has been formed and on its age. By
increasing the condensation overpotential, the number
of nuclei is larger and the film is formed of a greater
number of patches. A larger number of line defects and
consequently a faster dissolution are expected. Exper-
iments have also been designed to examine the import-
ance of an aging effect of the condensed film on the
kinetics ofdisaggregation. Dissolution transients of con-
densed films formed at the same potential but having dif-
Figure 16 Disordering charge transient measured after a
double potential step with a first step (from -1l60 mV to
- 720 mY) allowing the formation of the condensed film by
polynucleation; after IS s, a second step to -1140 mV is applied
to trigger the disordering ofthe film. The inset presents the log-
arithm of the half-time of the disordering transients as a func-
tion of the time spent in the condensed region. Conditions:
Mercury in contact with a saturated coumarin solution in NaF
0.5 M at 10°C.
444
Until now, little work has been carried out to describe
the disaggregation from lines. In an early work [121], we
considered the shrinkage at constant rate ofa distribution
of squared patches and predicted monotonic transients.
A similar trend has been obtained by Mulder [127], who
proposed a model that describes the shrinkage ofcircular
patches at a constant rate. The patches have an average
size that is related to the nucleation and growth rates
and also to the birth time of the nucleus from which the
patch is originated. These models can nevertheless not
satisfactorily describe most of the experimental data
presently available.
Very recently, we proposed a model for the
disaggregation of a 20 condensed film where the rate of
disorder propagation is not constant but depends on the
different energetic contributions involved in the
transformation [128]. Experimental data obtained for
the disaggregation of a 20 ordered film of coumarin
adsorbed at the mercury-solution interface have been
analyzed in detail to test the validity of the model.
As discussed earlier, the kinetics of formation of a
condensed film are markedly dependent on the surface
characteristics of the substrate, so that it is much more
difficult to properly control the defects of the condensed
film when solids, even single crystals, are used as
electrodes. These defects are most probably also related
to the underlying defects of the metal surface. So far,
little attention has been focused on the kinetics of dissol-
ution of ordered monolayers formed on single-crystal
electrodes. The dissolution of the physisorbed layer of
uracil and derivatives is rather fast and has not been
studied in detail.
The effects of the crystallographic orientation of the
substrate on the dissolution kinetics of the chemisorbed
layer made of uridine molecules have been investigated
by using distinct gold faces. Complex current transients
presenting a fast decay followed by a pronounced peak
are generally observed. Similar to the procedure
adopted to analyze the condensation transients, a
nucleation and growth transient can be decoupled from
the initial exponential decay of the overall transients.
In the present case, the analysis of the peaked curves
gave Avrami exponents ranging between 1.4 and 1.8.
The transients can be fitted by the equation taking into
account a nucleation process following an exponential
law in combination with a surface diffusion controlled
growth [1l6]:
. silver, and cadmium single-crystal electrodes, con-
i=qnc KexP(-K(t - ~(I - eXP(-kt)))) (1 - e<-kl))
(12)
Buess-Herman et aI.
where qnc is the charge associated with the whole
nucleation and growth process, k is the nucleation rate
constant, and K a rate constant related to the growth
process. The two kinetic parameters involved in the
model vary markedly with the crystallographic
orientation of the substrate [77].
On the basis ofthis model it may be concluded that the
rate of the hole nucleation is enhanced by the presence
of defects present in the film, whereas the radial growth
ofthe holes is slowed down by the presence ofthe defects.
Our group is presently actively involved in the modeling
of dissolution transients to correlate the rate of dissol-
ution to the modalities offormation of the ordered layer.
It seems that peaked current transients may also be
obtained when the dissolution does not start from points
as described here but well from linear defects [128]. The
use ofsuch a model or ofa model that combines a dissol-
ution starting from points and from lines may provide
another description of these dissolution transients. Pre-
liminary data obtained with faces presenting a higher
step density show that the shape of the transient changes
and that the transformation becomes much faster.
Experimental arguments in favor of the use of a com-
bined model to describe the current transients come from
in situ STM images obtained for layers of adenine and
guanine on HOPG [89-91] or cytosine on Au(111) [83]
that clearly show that the films detected at rather positive
potentials dissolve from edges but also by developing pits
within the organic layer.
v. CONCLUDING REMARKS
Because of their interest in both fundamental research
and technology, ordered monolayers have in recent years
received increasing attention from electrochemists.
Despite the large amount of studies carried out at the
mercury electrode, an ideal substrate for these studies,
and the advances made in the thermodynamics and
kinetics of 20 condensation, some important questions
remained unanswered. Among these, the role played by
the substrate is a major issue that has only recently started
to be addressed by resorting to amalgams or solid
electrodes. Investigations carried out with single-crystal
electrodes presenting well-defined crystallographic
orientations have revealed that the occurrence of 2D
phase transitions within organic monolayers is no longer
restricted to the use of a mercury electrode. On gold,
densed physisorbed layers, originating from attractive
interactions between the adsorbate molecules, have been
detected for various surfactants. The adsorption of mol-
ecules such as uracil and derivatives on gold and silver
Ordered Organic Adlayers at Electrode Surfaces 445

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25
Capacitive and Voltammetric Responses from Stepped
Faces of Gold
A. Fernando Silva and Ana Martins
Centro de Investiga~clO em Quimica, Porto, Portugal
ABSTRACT
Voltammetric and capacitive studies were carried out on
13 gold single-crystal electrodes, single and stepped
faces, in the presence of oxoanions with tetrahedral and
planar geometry, but with variable 0-0 distances, per-
chlorate, nitrate, sulphate and phosphate. The results
indicate that the effect of the introduction of steps on
single crystal is seen as "regular" features on
surface reconstruction, Au-water interactions, and
oxoanion adsorption. When the terraces are wide the
predominant effects are related to the orientation of the
terrace. However, the relation between terrace-step
orientation also plays an important role in the behavior
ofstepped faces.
I. INTRODUCTION
Reactions and phenomena occurring at solid metal
electrodes can be strongly dependent on the nature and
structure of the metal surface. The use of single-crystal
faces has proven to be useful in electrochemical studies
concerned with the effect of surface reactive sites like
regular arrays of steps or kinks and the role of the
dimension and symmetry of atomically ordered flat
domains.
Most detailed studies on gold surfaces have been
restricted to the low index faces, through a wide selection
of ex situ and more recently in situ surface physics tech-
niques [1]. Stepped faces of gold have also been used to
assess the effect of "surface regularities" on a wide range
449
of electrochemical phenomena such as UPD [2-4],
electrocatalysis [5-7], ionic and organic adsorption
[8-14], two-dimensional film condensation [15-17],
double-layer parameters [18-22], etc. Nevertheless, fun-
damental aspects of the role played by the presence
of steps and their orientation on the stability of the sur-
faces in electrochemical environments, metal-solvent
interactions, and ionic adsorption are still scarce.
A. Experimental Details
Thirteen single-crystal electrodes were prepared at
"Laboratoire d'Electrochimie Interfaciale," CNRS,
Bellevue, according to procedures published elsewhere
[23,24]. The position ofthe surfaces on the stereographic
triangle, their Lang notation [25], and relevant geo-
metric parameters are given in Table 1. The last step of
the surface preparation, before any measurements, con-
sisted of a flame treatment followed by cooling in air
for 5 s and then quenching in Milli-Q water before
transferring to the electrochemical cell, where contact
with the solution was achieved by the hanging electro-
lyte method [26]. Previous studies showed that this sur-
face treatment was the most appropriate to produce a
surface that is clean, ordered, and reconstructed,
though partially [27].
A gold wire was used as counter electrode and was also
previously flame annealed; the reference electrode (SCE
in saturated NaCl) was kept in a separate compartment
of a two water-jacketed compartment cell connected by
450 Silva and Martins

Table 1 Summary of the Lang Notation, Geometric II. SURFACE RECONSTRUCTION OF GOLD
Parameters, and Position on the Stereographic Triangle of the STEPPED FACES
Gold Faces
It is today well established that gold surfaces undergo sur-
(111 ) face reconstruction, faceting, or relaxation to minimize
(755) their surface energy. These phenomena can be induced
(332) by thermal treatment under DHY conditions, or simply
(533)
/ through flame annealing, if followed by the appropriate
(511). cooling procedure [27].
(331) The reconstructed surface "survives" in electrochemi-
(311 )
(771 ) cal media, depending on the applied potential and the
species in the solution [30]. Furthermore, once lifted,
(100) (410) (210) (320) (110) the reconstruction can be partially recovered if a suf-
ficiently negative polarisation is applied to the electrode.
Density of In situ studies of the reconstruction ofgold surfaces in
steps Terrace width electrochemical media have been most performed on
Face Lang notation (10 6 em-I) (A) low index faces. The results for Au(lll), Au(lOO), and
Au(llO) have been recently reviewed by Kolb [30,31].
(100) Moreover, most studies carried out so far were conducted
(511) 3 (100)-(111) 13.3 7.5 in nonadsorbing media, although it was shown, for the
(311) 2 (100)-(111)/2(111)-(100) 20.9 4.8
low index faces, that anion adsorption plays an important
(533) 4 (111)-(100) 10.6 9.5
(755) 6 (111)-(100) 7.0 14.4
role in both surface reconstruction and its lifting
(111) [30,32,33].
(332) 6 (111)-(111) 7.4 13.5 The effect of the introduction ofsteps, on both the rec-
(331) 3 (111)-(111) 15.9 6.3 onstruction of gold single-crystal surfaces and its lifting,
2 (111)-(110)/2(110)-(1ll) cannot be deduced at an atomic level from the electro-
(771) 4 (110)-(111) 7.0 14.4 chemical data; however, the average effect is bound to be
7/3(111)-(111) 22.0 4.6 reflected, if existent, on the stability domains of the
(110) 2 (111)-(111) 34.6 4.1 reconstructed and nonreconstructed structures, and on
(320) 3 (110)-(100) 13.6 7.4 the surface transition mechanisms and reconstructed
(210) 2 (110)-(100)/2(100)-(110) 21.9 4.6
area. Indeed, it was the electrochemical behavior (cyclic
(410) 4 (100}-(110) 11.9 8.4
voltammetric and the differential capacity) of freshly
flame-annealed Au(lOO) and Au(lll) that led to the pro-
posal of existence of reconstructed surfaces in electro-
chemical environment. The proposal was later
a salt bridge filled with the solution under study. The tem- confirmed by in situ x-ray diffraction and scanning
perature in both compartments was controlled ( ± 0.2°C), tunneling microscopy (STM). Electrochemical tech-
and the reference compartment was maintained at 25°C niques are sensitive to surface charge distribution, and
during all the experiments. When studying the effect of therefore they are used simultaneously with surface
temperature, the nonisothermal arrangement was indeed imaging to correlate and interpret the results. In this sec-
preferred, so no correction for the temperature tion the aim is to show the electrochemical data obtained
coefficient of the reference electrode is necessary and for stepped surfaces subject to thermal annealing and
the experimental variations ofthe potential ofthe capaci- potentiodynamic perturbations and the correlations
tance minimum are more easily measured. existing with the extensive information available for the
The differential capacity-potential curves were calcul- low index faces.
ated from automatically acquired values of the in-phase Electrochemical evidence of thermal/electro-
and out-of-phase components (obtained from a lock-in chemically induced surface reconstruction was con-
amplifier) of the ac response to a 40-Hz sine wave cluded for some of the studied stepped faces (Table 2),
superimposed on a linear voltage scan of 5 mY s-I. based on the same criteria that are used to identifY the sur-
For all these surfaces, the experimental potential time face reconstruction and its lifting for the low index faces
program used was adjusted to the objectives of the study of gold. For Au(lll) and Au(lOO), the lifting of the rec-
[21,28,29]. onstruction is detected, on the cyclic voltammogram,
Capacitive and Voltammetric Responses 451

Table 2 Data Available in the Literature and our Results Concerning the
Surface Reconstruction of Gold Single-Crystal Faces
Surface reconstruction

Face UHV Air Solution Our work

(100) (5 x20) [30] (5 x20) [30] Reconstructs

(511) Stable [65] Stable
Magic [66]
(311) Stable [65,67] Relaxation [68] Stable
Magic [66] Stable [69]
(533) Relaxation [68] Reconstructs
(755) Faceting [70] Faceting [71] Stable [20] Reconstructs
Stable [20,72]
(111) (1 x23) [30] (l x23) [30] Reconstructs
(322) Faceting [71] Reconstructs
(331) (1 x2) [73] Reconstructs
(771) Reconstructs
(110) (I xn) [30] (1 xn) [73] Reconstructs
(320) Stable [67] Stable
(210) Stable [65] Stable [73] Stable
(410) Stable [65] Rough [73] Reconstructs

through the occurrence of a sharp current peak due to
changes of the potential of zero charge, Eu=o, and of the
amount of specifically adsorbed anions between
reconstructed and nonreconstructed surfaces (this elec-
trochemical evidence has been confirmed by various in
situ; observations [I]. For Au(llO), no sharp peak arises
during the lifting ofthe reconstruction because the poten-
tial of zero charge (PZC) shift is small; however, the
transition between reconstructed and nonreconstructed
surface can be diagnosed by the irreversibility of the
cyclic voltammogram, as is also observed for Au(lOO)
and Au(lll). On the other hand, the differences observed
between the first (just after surface flame annealing)
and following consecutive cycles reflect the structural dif-
ferences between the thermal and potential induced rec-
onstruction [30].
A. Thermal Reconstruction
Figure 1 shows that the first consecutive cyclic
voltammograms obtained for the stepped faces with wide
111 oriented terraces, Au(755), (332), and (533), exhibit a
sharp anodic current peak similar to the one assigned to
the surface structure transition between reconstructed
and non-reconstructed Au(1l1) surfaces [(.J3" x 23)
-+ (1 x 1)]. For these four faces, the peaks occur at the
exact same potential value, but their current intensity
decreases with increasing density ofsteps, i.e., decreasing
width of terraces.
The comparison of the CVs obtained in the same
experimental conditions for Au(100) and Au(41O) lead
to similar conclusions, i.e., the stepped face exhibits a
sharp peak at the same potential value as the peak
assigned to the (hex) -+(1 x 1) transition on Au(100).
It must be emphasized that the current peak corre-
sponding to the lifting of the thermal-induced rec-
onstruction can appear associated to a shoulder or split
into two peaks in the case of the stepped surfaces (detail
in Fig. 1), suggesting a complex mechanism due to the
presence of steps on the single faces. Similar behavior
was detected by Eberhardt et al. [34] for the rec-
onstruction on Au (100) in the presence of strongly
adsorbing bromide ions.
B. Potential Induced Reconstruction
As mentioned earlier, the reconstruction ofsingle-crystal
gold surfaces can be electrochemically induced when
enough negative polarization is applied. This rec-
onstruction is further lifted and thus detected on the
voltammetric profile, although it emerges at slightly
lower potential values compared with the lifting of the
thermal reconstruction.
The stability domains of the reconstructed and
nonreconstructed surfaces are delimited by the potential
at which the lifting occurs and in the cathodic scan by
the "critical potential" at which the electrochemically
induced surface reconstruction is triggered. This poten-
452 Silva and Martins

Au(111) Au(110)

,:\\+.._-
~.
r~
l' : H
0.,
<'f'
~·l i 11 1
:11 .
E
u
1 ~ ~.

iL
II

~I AU(755) Au(410) Au(771)

.!)1\ \
I

Au (332) Au (111)
Au (755) I~
11'\ '.
10 . \~ I
f' ii, ,i

o
_-( I :
III
I j
iii I
=::1 tcj/,J:!
.
il;
il
II I
II
N'i--'
I ! 1

~I:
~_J \ JI ...,. '\\.~II',
! Figure 2 CVs with decreasing cathodic limit for Au(lll),
Au(755), Au(lOO), Au(41O), Au(lIO), and Au(77I) obtained in
\Vf J i ;
\v"',·__··
H2S04 0.01 M solution.

-0.25 0.25 -0.25 0.25 -0.25 0.25 By contrast, the critical potential values for Au(lOO)
and Au(41O) are different, as the potential induced rec-
E IV (SSCE)
onstruction is triggered at less cathodic potential values
Figure 1 First consecutive CVs obtained just after flame for the stepped face. This behavior may result either of
annealing, with increasing anodic limit, in solution of H2S04 an earlier anion desorption on Au(410) or, more probably,
om M for Au(332), Au(lll), and Au(755): ( - ) 1°, (- - -) 2°, of an enhanced reconstruction kinetics in the presence
(_._) 3°, (...) 4°, and (-... -) 5° cycle (detail ofthe lifting peaks). ofthe 110 oriented steps that may act as nucleation centers
for the (hex)-structure formation [35].
The characteristic irreversibility observed during the
surface transitions on Au(lIO) is also observed for some
tial can be evaluated by progressively increasing the
of the stepped faces with 110 oriented terraces, Au(nI)
potential limit, during the cathodic incursions until the
and Au(33l), whereas the voltammetric profiles and
lifting peak is detected in the following reverse scan (Fig.
capacitance curves for Au(210) or Au(320) are totally
2); for the faces with 110 oriented terraces, the critical
potential is reached when the voltammetric profiles
become irreversible. The results show that once it Table 3 Values for the Reconstruction
emerges, the position of the lifting peak is independent "Critical Potential", Erecons, of Stepped
of the increasing cathodic limit ofthe potential excursion Faces and its Lifting, Elifling, in Comparison
but its intensity increases progressively. with the Low Index Faces (H2S04 0.1 M)
Under the assumption that this peak is indeed
Gold Elifling Ereconstruction
associated with the lifting of the freshly reconstructed face (mV/SSCE) (mV/SSCE)
domains, the data show that for the faces with III
oriented terraces, the presence of the steps does not Au(lll) 100 200
affect the critical potential of the reconstruction (Table Au(755) 100 200
3) nor the potential of its lifting. These observations Au(332) 100 200
may suggest that any eventual kinetic effect due to Au(533) 100 200
Au(lOO) -220 210
the presence of steps is not detected at the sweep rate
Au(41O) -90 210
used.
Capacitive and Voltammetric Responses
reversible in the double-layer region. Although these four
faces have 110 oriented terraces with comparable width,
the perpendicular orientation of the steps on the latter
faces may prevent the reconstruction "movement."
In summary, the sharp current peak and irreversibility
emerging on the voltammetric profiles at the same poten-
tial values for the low and high index faces points to the
suggestion that the structure ofthe reconstructed stepped
faces is dictated by the orientation of the terraces, i.e., it
is expected that new domains are formed with a structure
similar to that of reconstructed Au(lll), (100), or (1l0).
However, the reconstruction is observed only for the
stepped faces with wide terraces, which may be inter-
preted as a prerequisite for the accommodation of the
reconstruction unit cell. Besides the terrace width
requirement, the direction of the steps must not hinder
the reconstruction movement.
The current of the sharp peaks, corresponding to the
lifting of the reconstruction, is always lower for the
stepped faces when compared with the low index ones.
This implies a smaller PZC shift and/or a smaller vari-
ation of the amount of specifically adsorbed anions. On
the assumption that the reconstructed structures are
the same, regardless of the presence of steps, this result
is only consistent with the hypothesis that coherent
reconstructed domains do not cross the steps [36], thus
limiting the area for the reconstruction to occur when
the density of steps increases.
The differences that emerge when using different
oxoanions confirm that the potential at which the surface
reconstruction is lifted is highly dependent on the
adsorbability of the anion, i.e., the potential is shifted
toward more negative values and the current increases
following the same order as the adsorbability ofthe anion:
perchlorate < nitrate < sulphate < phosphate. The effect
of the lifting peak current is most likely related to the
differences of the adsorbed charge between the
reconstructed and nonreconstructed surfaces; this
"amplification" effect is actually useful in the detection
of the reconstruction and its lifting for stepped faces, for
which the signal is weaker compared with the low index
faces, thus probably justifYing the reason why previous
studies had failed to reveal its occurrence (Table 2).
Moreover, the effect of anion adsorbability on the lifting
peak can be used as a criteria to establish the adsorbability
order in a series of anions, provided there are no differ-
ence in the kinetics.
Although the electrochemical evidence seems con-
vincing, it may be argued that the terraces of some of
the surfaces are too narrow to accommodate the
reconstructed unit cells, as already pointed out by Ross
and DJ\gostino [37]. Because there are no concluding in
453
situ studies, the interpretation is only tentative and
speculative. Nevertheless, the presence of adsorbed ani-
ons may enhance the movement of the step atoms, as
was already reported in the presence of halide anions
[32,33]; moreover, due to the probable existence of
miscuts inherent to the single-crystal preparation
method, the terraces may have more than the expected
nominal number ofatoms.
III. TEMPERATURE COEFFICIENTS OF THE
PZC OF GOLD LOW AND HIGH MILLER
INDEX FACES: RELEVANCE TO
GOLD-WATER INTERACTIONS
In the absence of specific adsorption, the metal-water
interactions would explain the differences of the electro-
chemical behavior ofsingle gold electrodes with different
faces [18,38].The temperature coefficients ofdouble-layer
parameters are believed to be relevant to the understand-
ing ofthe composition and structure ofthe electrochemi-
cal interface because they would provide an interesting
insight into the double-layer structure [39--41].
For the low and high index faces ofgold, a single value
of E I1 =o exists, which can be identified with the potential
value of the capacitance minimum in absence of specific
adsorption. Values of E I1 =o were determined by polyno-
mial fitting around the minimum ofdigitized differential
capacity curves recorded during the anodic scan. The
capacity at the minimum, Cmin, was found to decrease
whereas the potential at this minimum, E I1 =o, shifted
toward less negative potential values when the tempera-
ture was increased.
Figure 3 shows an example of typical results [in this
case for Au(771)] obtained for the effect ofincreasing tem-
perature on the voltammetric profiles and capacitance
curves that were used to determined the temperature
coefficient of E I1 =o. The values of this coefficients,
dEI1 =o/dT, are summarized in Table 4, along with the
values of ElI =0 obtained at 298 K.
The values ofthe temperature coefficients are all posi-
tive and surface structure sensitive though lower for the
stepped faces when compared with the low index faces.
Positive values of dEI1=o/dT have also been reported for
single crystal faces of Cd[42], Ag[43-46] in contact with
aqueous solutions, except for Ag(llO).
The results inTable 4 show that the value of dElI = 0/ dT
decreases when the step density increases, which parallels
the effect of steps on the values of ElI =0 for the same
surfaces and electronic parameters such as the surface
energy [47] (Fig. 4). The faces with the higher density of
steps, also designated by "turning points" [48] in each of
454 Silva and Martins

125 C IIlFcm-2 E cr=ol mV (SSCE)

<:' Au (771)
E

-
Co)

~ r-
~
Y f
I
,.1 ••

" .•••'
-'\,~

~ ,'.,'
I,' .
/-'\.\
". ",,::"\.
. "'
I,'"
'I
I

f·· ..... ~ 1f
-125 30 -~~~ 1~(
\\ ' - 'I,.,
·,,/f
E I V (SSCE) T 1°C
... I.
0.5 -0.2 .. :~ -0.2 10 20 30

Figure 3 Effect of the increasing temperature between 3 and 40°C on the cyclic voltammograms, capacitance curves, and PZC
observed for Au(771) in HCI04 0.01 M solution.

the main zones of the stereographic triangle, have the
lowest value of E,,=o and seem to have as well the lowest
value of dE,,=o/dT.
A closer observation of the data indicates that the
range of values of dE,,=o/dT for the stepped faces is
characteristic of the zone where they are situated. The
faces situated in the [01 I] zone exhibit the lowest values
of dE,,=o/dT; by contrast, the faces situated on the two
Table 4 Values of E,,=o and dEu=o/dT for
Single-Crystal Gold Electrodes (0.01 M
HCI04 )
other zones have similar values of dE,,=o/dT, though
slightly higher for the [110] zone. The values of
dE,,=o/dT obtained for the three single faces are the
highest, which confirms that the introduction of steps
reduces the values ofboth E" = 0 and dE" = 0 / dT. However,
the amplitude of the variations observed in each zone
suggests that it is not only related to the step density but
also to the orientation of the steps compared with the
orientation of the terraces, i.e., the effect of the presence
0 50 100 0.0
I I I
I r 0.6
W +
0

Face
Eu=o
(mV/SSCE)
dEu=o/dT
(mVK- 1) 200-i ~
(/)
• m
~ 1- 3
> 'il
(100) 80 1.0 [74] §. 0

;:;: I f- 0.8
(511) -33 0.2 100-i ~ -t -2
w
3'
,~
(311) -31 1.3 [74]
~

(533) 49
0.05
0.2 O-i t, .-. ,j
I
\ .....
, ...... '
"'j>~ -1
/...;
~'!~
(111) 196 3.0 [74] \
+/ ./ \ ~ -
\
(332) -21 ·100-1 ~ ~
(331) -48
0.5
0.6 • e
(771) -60 0.7 0;:- ;: C:;-U;-;:-N";::--;::--SS6 S S
Cl .... ... C"')1t) ... C"')C"') ........ N ... .-O
(110) -72 0.9 [74] ~a ~ ~t:..~~~t:..~!:l~ ~!:.
(320) -108 0.4
(210) -136 0.4
0.5 [74] Figure 4 Variation of the values of Eu=o, dEu=o/dT. and the
(410) -44 0.6 surface energy (Y(hkn/}'(210») with the crystallographic
orientation ofthe gold face.
Capacitive and VoItammetric Responses
of steps seems more effective for the combined
terrace- step orientations in the following order:
(111) - (100) < (100) - (110) < (111) - (111)
A. Gold-Water Interactions
To extract further information from the values ofthe tem-
perature coefficients concerning the structure of the
interface in the absence of specific adsorption, the
relation between the PZC, Eu=o, and the electron work
function, <1>, ofthe face of a metal electrode has to be con-
sidered [38]:
Eu=o(hkl) = <1>(hkl)
(1)
+ [.5X M - gS(dip)]u=o(hkl) + constant
where .5X M is the perturbation ofthe electron distribution
at the metal surface upon contact with the solution and
gS(dip) is the contribution to the interfacial potential drop
due to any preferentially oriented molecules ofthe solvent
(the constant term depends only on the reference elec-
trode). The term [.5XM - gS (dip)] is not accessible to direct
experimental determination, and it has been considered
to represent the metal-solvent interactions.
The corresponding temperature coefficient of Eu=o,
for a non isothermal cell, is given by
(2)
From Eq. (2), it follows that the sign and magnitude of
dEu=o/dT is determined by the sign and relative
magnitude of the temperature coefficient of the
metal-solvent interaction term and the temperature
coefficient of the electron work function. Because theor-
etical calculations of d<1>/dT for the low index faces
of Cu, Ag, and Au [49,50] led to negative and
face-dependent values, it seems reasonable to expect that
the same coefficient will also be negative for the stepped
faces. Consequently, the experimental positive values of
dEu=o/dT lead to the conclusion that the values of
d[.5X M - gS(dip)]u=o/dT must also be positive and face
dependent.
If the assumption is made [51] that the temperature
coefficient of .5XM can be neglected in the small explored
temperature range with respect to the solvent contri-
bution d[gs(dip)]u=o]/dT, it can thus be suggested that
the decrease of dEu = 0/ dT is a consequence ofa decrease
in the net solvent dipole orientation, which must be the
result of a disorder in the solvent distribution induced
455
by the large number of surface defects existing on the
stepped surfaces.
On this account, it is possible to suggest that the
decrease of dEu=o/dT observed in each zone of the
stereographic triangle with the increasing density of steps
can be explained using the model for the water dipole
adsorption on stepped faces proposed by Lecoeur et al.
[18] to explain the decrease in Eu=o with increasing step
density. According to these authors, the adsorption of
water dipoles on steps occurs with the oxygen atom away
from the surface, thus leading to a positive contribution
to the total solvent dipole and to a simultaneous reduction
in the metallic dipole moment. This effect is expected to
be stronger on quaternary step sites 100 than on ternary
oriented sites 111, i.e., adsorption is stronger on the former
sites; consequently, a higher density of steps will lead to
a higher decrease of the metallic dipole, plus a larger
randomizing effect of the solvent dipoles distribution,
particularly in the presence of 100 oriented steps.
Accordingly, the randomizing effect ofa thermal increase
is expected to be smaller for the stepped faces where the
solvent dipole distribution is already more randomly dis-
tributed. On the other hand, under the assumption that
water dipoles are more strongly adsorbed on the steps
than on terraces [18], the thermal effect is expected to be
larger on the dipoles adsorbed on the terrace, which can
be held predominantly responsible for the variation of
dEu=o/dT. Consequently, the temperature coefficient is
higher when the terraces are wider, as is actually con-
firmed by the fact that the higher values are obtained for
the single faces. The combination of step-terrace
orientation, in particular the geometry of the step sites,
is expected to induce different degrees of perturbation
and may explain the variation of dEu = 0 / dT on each zone.
The variation ofthe net dipole ofthe solvent layer with
the metal surface structure, at zero charge, is confirmed
by the charge dependence of the entropy of formation of
the double layer (Fig. 5), which is expected to reflect the
important contribution of the structural rearrangement
of the interfacial water [40,41,52]. The general shape of
the curves is similar for all the faces. The entropy falls as
the charge becomes more positive with the charge, and
the value of S~ax appears to be face dependent and shifts
toward less negative charges with the decreasing width
of the terraces. It can also be suggested that the
face-dependent value of S~ax charge reflects the existence
of a different arrangement of the interfacial water at the
uncharged gold face electrodes: the lower the charge of
S~ax' the less structured the interfacial water. Moreover,
because S~ax occurs at negative charges, a residual net
orientation of the water dipoles with the oxygen atoms
pointing toward the surface is confirmed.
456 Silva and Martins

Table 5 Interatomic Distances

Between the Oxygen Atoms For-
10 9 S* I JK-1cm- 2
ming the Triangular Base of the
(100) [011] Oxoanions and Between the Gold
............. Atoms
o (~)~. Oxoanion 0-0 Distance (A)
(533Y,'-"·
I Nitrate 2.11
-10 (311) Perchlorate 2.36
Sulphate 2.47
Phosphate 2.59
-20 Au-Au 2.89

[001] crystal faces [53,54], OH- chemisorption in the

(419~00)
o (210) -~­
(320)
-10
..........
-20 a/JlC cm-2
Figure 5 S* (a) curves obtained in HCI0 4 0.01 M solution for
the faces in the [001] and [OIl] zones.
In conclusion, the positive values of dE(J = 0/ dT may be
interpreted as reflecting that the contribution ofthe water
dipoles to the potential drop decreases with the increasing
temperature. The presence of monoatomic surface steps
induces a disorganization of the water dipole layer that
is zone dependent, i.e., it depends on both the density
and orientation of the steps regarding the orientation of
the terrace and leads to smaller net dipole. In this sense,
the presence of steps causes a weakening of the average
gold-water interactions.
IV. REGULARITIES ON THE INTERFACIAL
CAPACITY FOR THE ADSORPTION OF
OXOANIONS ON STEPPED FACES OF
GOLD
Ion adsorption has already been tested as a probe for the
study of the surface structure details using for example
metal cations in UPD [3,4] studies, partially discharged
halides [8-10], H+ reduction on Au [11] and as a "tool"
for "counting" terraces and steps sites on Pt single
electrocatalytic reduction of O2 [7], oxoanions, and
their effect on the gold surface oxidation [29,55-57]. In
these studies, a systematic influence of the surface was
observed, and it was proposed that adsorption on steps
can be structure sensitive, depending on the nature
and size of the adsorbed species; moreover, it occurs at
lower energy and is stronger on the step sites than on
terraces.
Adsorption of species or intermediates is anticipated
to be ruled by the reactivity of sites, i.e., by the
microheterogeneity of the surface but also by the
matching ofthe symmetry ofsuch sites with the geometry
of the adsorbed species. Moreover, the eventually domi-
nant effect may depend on the extent ofa possible charge
transfer upon adsorption.
The study ofadsorption ofoxoanions with tetrahedral
and planar geometry but with variable 0-0
distances-perchlorate, nitrate, sulphate, and phosphate
(Table 5)-provides a useful tool to emphasise the import-
ance of the matching requirement; although charge
transfer cannot be ruled out.
Figure 6 shows the C(E) curves obtained in acidic sol-
utions of these four oxoanions for the 13 gold surfaces.
Two distinct situations can be identified, according to
the degree of adsorbability of the anion. In the presence
ofperchloric and nitric acid solutions, the curves exhibit
a simple and similar shape with a pronounced capacity
minimum, whereas in sulphuric and phosphoric acid
solutions, it is possible to follow a systematic effect ofthe
surface "regularities" on the adsorption phenomena,
through the systematic evolution of the C(E) curves.
A. Influence of the Surface Structure
The C(E) curves obtained in adsorbing electrolyte for the
faces with 111 terraces of variable width are presented in
Fig. 7. For the faces with the widest terraces, Au (1 11), (755),
Capacitive and Voltammetric Responses 457

"I
70
.__
-
....
--Au311
100
AU!511
Au 1 ,r, I~~~"
!"
" ..
E .~ '- - - AUl5331 /
u 50
LL. f
t-, '~ ......
---Au755
,~I \, ~-",. - - Au(111)
I 1/'" • '-'
1'1:
<-
0
I/I' J
;/1
\,
,,- __ I"
,tf -.=--
......
I"'~- I. 1
30 ~_ ... __ '..c.---
'~:'::~:,1
'-.".,
. . -_:;,
/' ,,/

70

50

30

- - AU111°1
70 --Au 320
·.·Au(210)
- . - AU(410) •
", -Au(100L, .,/ \ ..... - ._
50
.,< 1;, _ ...., ,iV"',·" .. -
:1,', '\. ....... /.,' :~' ',,_ .~~-

30
, '·-::~:~~11 . ',--.- [001]

~.4 o 0.4 o 0.4 0.8

E I V (SSCE)

120
"I
E
u
LL. 80
<-
o
40

120

80

40

120

80

40

Figure 6 C(E) curves obtained for all faces in each of

~.5 o 0.5 o 0.5
the main zones of the stereographic triangle in O.l-M
E I V (SSCE) solutions offour different oxoanions.
458 Silva and Martins

~ ~ 1: 1:~
11 - - - - AU(331)

100
_ Au 332
- A T
- - Au 331
_ .Au 755
1 ~
.... 100
-Au(100)
- - Au(410)
1 ~
....
- - Au(771) F
--Au(110) ,~ :'\
<:;
• -. Au(533) I
u 40 - ·Au(111) u
- Au(n1)
,l -;;~~_ "'
70 t_ '
I ,
~ ~70
60 - - AU(320)
---Au(210) 1/ ~" ...~

--" -- J/ f/
I 40 -=
~ -~.-
~
" ...... !J I
40:::=::
$-
~ ---... .-,
r7')

-0.2 0.1 0.4 E I V (SSCE) I -0.4 0 0.4 E I V (SSCE)' 20 -0.3 -0.1 0.1 E I V (SSCE)

Figure 7 C(E) curves obtained in 0.05 M H 3 P0 4 solution for the faces with Ill, 100, and 110 terraces.

(332), and (533), it is possible to observe the occurrence of
three adsorption peaks; each is situated at the same
potential value for all the specified faces and varies sys-
tematically with the terrace width. These results suggest
that the three peaks correspond to anion adsorption on
nonreconstructed III terraces bearing in mind that the
more cathodic peak occurs on surfaces that are still
partially reconstructed, i.e., where the area covered by
(1 xl) domains increases when the density of steps
increases. The preference for nonreconstructed terrace
sites may be rationalized in terms of surface relief, i.e.,
adsorption ofpoliatomic species is expected to be favored
on the flat (1 x 1) structure than on the slightly buckled
(.J3 x 23) reconstructed structure [30]. The capacity of
the three adsorption peaks increases with increasing
anion concentration and shifts toward more negative
potential values as expected from the Gouy-
Chapman-Stern model [58].
For Au(100) and (410), the adsorption peak observed
during the anodic scan occurs before the reconstruction
is lifted, i.e., on the (hex) structured surface that is very
similar to a 111 structure [59] and is therefore observed
at a potential value close to that for the first adsorption
peak on Au(111). Au(511) and Au(311) faces also have
100 oriented terraces but do not reconstruct; for these
faces, the adsorption peaks is observed at more
cathodic potential values compared with Au(100) and
(410); furthermore, the capacity is much lower and,
moreover, it increases when the density of steps
increases.
Adsorption on other faces with a high-density of
steps-Au(1IO), (320) (210), (331), and (nl)-exhibit
similar capacitance profiles as Au(511) and (311);
nevertheless, there is a clear influence ofthe step- terrace
combination near the step site [60] on the adsorption
peak potential in the following order: (110)-
(100) < (111)-(111) < (100)-(111). This result suggests
that adsorption on steps is significant for these faces
and therefore is stronger when the density of steps is
higher, probably because adsorption of oxoanions is
disfavored on narrow terraces.
Curiously, Fig. 6 also shows that the C(E) curves in
each zone of the stereographic triangle meet in a
isopotential point that seems to delimit, at more positive
potential, the occurrence of adsorption on 100 or 111
terraces and at more negative potential, the adsorption
on steps for the faces with small terraces width.
Isopotential points have already been reported for the
study of the effect of the temperature on the behavior
of gold single crystals and other metals [40,42,61]. Our
results, nevertheless, bring out the additional relevance
of the electrode surface structure, besides the import-
ance of the surface concentration of anions and solvent
molecules, and the temperature of the system, already
pointed by these authors.
It has been suggested that adsorption of
sulphate/hydrogenosulphate is energetically favored
close to the steps [60], similarly to the adsorption of
monoatomic ions such as halides [8-10] and protons
[11]. However, the adsorption of oxoanions on wide
terraces seems to be preferred, presumably as a result
of geometrical constraints around the steps. Con-
sequently, the C(E) curves will not bring out evidence
of adsorption on steps unless terraces are at least four
atoms wide.
B. Compared Adsorbability of the Oxoanions
In the absence of enough data for a proper
thermodynamic analysis, only qualitative assessments
can be made using the data obtained. The negative poten-
tial shift of the capacitance minimum, Cmin , caused by
an increase of the anion concentration in the presence
of adsorption usually parallels the shift of Ea=o and can
be used as a criteria to infer its adsorbability order [58].
The potential shift measured as dEmin/ d log c is reported
Capacitive and Voltammetric Responses
Table 6 Potential Shift of E min with the Increasing Concen-
tration of Oxoanions
-dEmin/dlogc o 20 40 60
mY/decade
in Table 6 and suggests the following order of increasing
adsorbability:
The shift of Emin is almost zero in HCI0 4 solutions, in
agreement with the literature [62], whereas it is slightly
higher in the presence ofHN0 3 [63].
The order of adsorbability on each gold surface can
also be deduced comparing the CVs curves obtained in
solutions with the same concentration of the different
oxoanions, through the negative shift of the surface
oxidation onset potential due to surface blockage for the
OH discharge due to competitive adsorption with the
oxoanions (Fig. 8). The order of adsorbability of the
oxoanions is not structure sensitive, as already reported
in the literature for the adsorbability of halides on sd or
sp metals [9,64]. Moreover, the order of adsorbability of
these oxoanions may be related, on one hand, to the
increasing congruence between 0-0 distance and gold
interatomic distance (see Table 5) and on the other hand
to the ability of H-bonding of the anions.
The important role ofthe symmetry ofadsorbing sites
is further emphasized comparing the adsorption of
sulphate from constant ionic strength solutions on several
faces. The study of adsorption of sulphate from constant
ionic strength solutions [75] at several gold surfaces indi-
cate that the Gibbs energy of adsorption given in Table 7
seems to decrease slightly with increasing step density
but cannot explain the significant difference observed
for the charge adsorbed (assumed to be SO~-) on each
surface. The large value observed for Au(lll) (identical
to the value reported by Shi et a1. [76]) and Au(533) com-
Table 7 Gibbs Energy of Adsorption of Sulphate from Con-
stant Ionic Strength Solutions on Faces Situated in the [011]
Zone
Face Au(lII) Au(533) Au(311) Au(100)
113.0 119.9 95.1 104.3
Source: From Ref. 75.
459
200
-"-
o
1 1.25
E I V (SSCE)
Figure 8 VoItammetric profiles obtained for Au(100) in the
surface oxidation region in O.OI-M solutions of (--) HCl04,
(- - -) HN0 3 (_._) H2S04, and (- - -) H3 P0 4.
pared with Au(lOO) and Au(5ll) can be due to the
favorable threefold adsorption sites, i.e., III oriented
terrace sites.
In summary, it is possible to propose that for the
faces with at least four atoms wide terraces, the
adsorbability of anions increases as the terrace width
increases, and it seems particularly favored in the
presence of III oriented terraces. This is probably
related to threefold symmetry of the adsorbing site
and the degree of matching with the symmetry of the
adsorbed anions. For the faces with high density of
steps, the adsorption is smaller, but it increases as the
step density increases, and the potential at which it
occurs depends on the combined orientations of adjac-
ent terraces and steps. Adsorption on the terraces
occurs at higher potential values than adsorption on
the steps, which is in agreement with the fact that steps
are more energetic sites.
V. CONCLUSIONS
The systematic study of the effect of the introduction of
steps on single-crystal faces reveals that "regular" fea-
tures can be observed on surface reconstruction,
Au-water interactions, and anion adsorption. Deeper
analysis of the effects suggests that when the terrace are
460 Silva and Martins

wide, the predominant effects are then related to the 26. D Dickertmann, FD Koppitz, JW Schultze. Electrochim
orientation of the terrace, but the relation between Acta 21:967,1976.
terrace-step orientation also plays an important role in 27. N Batina, AS Dakkouri, DM Kolb. J Electroanal Chern
the behavior of the stepped faces. 370:87,1994.
28. AF Silva, A Martins. Electrochim Acta, to be published.
29. AF Silva, A Martins, to be submitted.
ACKNOWLEDGMENTS 30. DM Kolb. Prog Surface Sci 51:109, 1996.
31. DM Kolb. In: J Lipkowski, PN Ross, eds. Frontiers in
We thank Mme. Antoinette Hamelin for her support in
Electrochemistry. Vol. 2. Dordrecht: Kluwer, 1993.
the preparation of single crystals and introduction into
32. J Wang, BM Ocko, AJ Davenport, HS Isaacs. Phys Rev
the study of gold single crystals. We also acknowledge B46:10321,1992.
the financial support of JNICT-CIQ L. 4. 33. JM Dona, J Gonzalez-Velasco. Surf Sci 274:205, 1992.
34. D Eberhardt, E Santos,W Schmickler. J Electroanal Chern
419:29,1996.
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26
Electrochemistry, Spectroscopy, and Scanning Tunneling
Microscopy Images of Small Single-Crystal Electrodes
V. Climent, R. Gomez, J. M. Orts, A. Rodes, Antonio Aldaz, and Juan M. Feliu
University ofAlicante, Alicante, Spain
ABSTRACT
A general approach to the investigation of electrochemi-
cal surface properties is described through several
examples. The use of well-defined electrode surfaces
obtained from small single-crystal beads accurately
oriented in careful electrochemical experiments allows
us to obtain an initial picture of the system under scope.
The techniques used in the proposed examples are cyclic
voltammetry, the most commonly used technique in
surface electrochemistry, and the eo displacement
technique, which leads to the determination ofthe poten-
tial ofzero total charge. This is a key magnitude in adsorp-
tion studies that provides valuable criteria for coulo-
metric coverage determinations. This initial picture is
then completed by using other techniques such as in situ
raurier transform infrared spectroscopy and scanning
tunneling microscopy. These new data improve our
knowledge on the system under study. As illustrating
examples, we present the influence ofanion and hydrogen
adsorption of eOad oxidation at Pt(lll) and NO ad
reduction at Pt(lOO). The study of irreversibly adsorbed
Br adlayers on Pt(lll) and Pt(IOO) and urea adsorption
on Pt(lOO) are also summarized.
I. INTRODUCTION
The electrochemistry ofwell-defined electrode surfaces is
a growing field in which more and more research groups
are involved. The development of this subject has been
handicapped by the intrinsic limitations of most of sur-
face science techniques that are not applicable in the
presence of the solution layer. This has limited a faster
463
growth of the knowledge of the behavior of solid metal
surfaces in condensed media and has motivated the
development of different approach strategies.
It is clear that the first requirement is the use of in situ
clean and well-ordered electrode surfaces. This has been
achieved, in a simple and elegant way, by the flame treat-
ment [1; see Chapter 14] originally applie<'l to platinum
single crystals and later extended to other lfietals [2,3]. In
some cases, i.e., Pt(lll) and some ofits vicinal surfaces [4],
the surface is ordered after the flame treatment and sub-
sequent protection with water to maintain its cleanliness
during the transfer through the laboratory atmosphere.
In other cases, some small modifications are required,
mainly in the cooling and water protection steps, that
need to be carried out under reductive conditions to
obtain electrode surfaces approaching nominal surface
structure [5-7]. It is important to remark that most
characterization criteria were empirically inferred from
the analysis ofelectrochemical experiments, mostofthem
by using cyclic voltammetry. They were thus uncertain
to some extent until their conclusions were supported by
well-established surface science techniques [8,9]. In this
way, the utility of electrochemistry in giving surface
science information in condensed media was proved.
The implicit assumption used for the characterization
of the single-crystal platinum surfaces was the existence
of structure sensitive reactions that involved atomic (or
molecular, ionic, etc.) adsorbed species. In fact, the devel-
opment of the electrochemistry ofwell-defined electrode
surfaces has paralleled the knowledge of the electro-
chemical behavior of these adsorbed species. In the case
464
of platinum, atomic hydrogen was naturally the first
species to be considered [10], because the voltammetric
profile for polycrystalline platinum was originally
explained through reversible adsorption/desorption of
hydrogen atoms [11]. The adsorption and desorption of
underpotential deposited hydrogen was also accepted
for interpreting platinum single-crystal voltammetric
currents observed in the low potential range (below 0.5 V
vs. RHE [reversible hydrogen electrode]) in acidic blank
solutions (solutions containing only a supporting electro-
lyte such as sulfuric or perchloric acids). In fact, the
voltammetric profile of a platinum single-crystal elec-
trode in these electrolytes is used today as a fingerprint
to check both the solution cleanliness and the quality of
the electrode surface. However, anion adsorption was
also considered, mainly in the case ofPt(Ill), as respon-
sible for the voltammetric current [12-14]. Although the
nature of the species that originate the blank
voltammogram is not important for characterization
purposes, it has a great importance in other instances,
i.e., evaluation of coverages. The anion contribution was
implicitly used for explaining the oxidative stripping of
adsorbed CO [15,16]. It was observed that coverages
obtained from the stripping ofadsorbed CO were always
greater than those obtained from the amount of CO 2 in
solution, which could be measured by Fourier transform
infrared spectroscopy (FTIR). The correction required
to bring the stripping CO charge to the measured amount
of the reaction product suggested that the voltammetric
profile obtained from the blank solution could not be
explained simply through adsorbed hydrogen. The anion
contribution to the voltammogram observed in the blank
solution was fully accepted when the particular processes
that take place during the adsorption of CO were fully
understood [17]. As seen below, the adsorption of CO
was used as a probe reaction for discriminating between
both interpretations of the clean electrode voltammetry.
In these experiments, a molecular surface probe (CO
molecules that adsorb on the electrode at constant poten-
tial and displace all the previously adsorbed species) pro-
vides information on the adsorbed species (e.g.,
hydrogen adsorbed at 0.1 V). This experiment showed
that the comparison between surface reactions on
well-defined surfaces is a good strategy for a greater
understanding of single-crystal electrochemistry.
On the other hand, the combination of electrochemi-
cal results and those obtained by other techniques
improves our knowledge of the fundamental aspects of
surface electrode reactivity. Some techniques may be eas-
ily available in many laboratories. FTIR spectroscopy
and scanning tunneling microscopy (STM), for instance,
can be used to try to gain information about the adsorbed
Climent et al.
species and its relation with the species present in
solution. The convergence of results obtained from the
use ofdifferent independent techniques on the same elec-
trochemical problem is necessary for the full understand-
ing of the process.
This chapter tries to emphasize our approach to the
study of single-crystal electrode surfaces. The approach
begins by obtaining electrode surfaces from small
single-crystal beads ( ~ 2 mm diameter) that are oriented,
cut, and polished in such a way that misorientation is
minimized [18]. The experimental protocol continues by
using electrochemical techniques, first voltammetry and
also charge displacement experiments. These techniques
supply information not only on the behavior ofthe system
under scope, which provides a preliminary model about
the process occurring at the interface, but also on the sol-
ution cleanliness and the surface order of the electrode.
This model is then tested by the application of techniques
capable of furnishing information on complementary
aspects of the process. We believe that the first electro-
chemical step should be rigorously accomplished if the
results given by other techniques are to be considered
meaningful.
II. CHARGE DISPLACEMENT EXPERIMENT
The initial interpretation ofthe voltammetry ofplatinum
single crystals consisted in ascribing the currents appear-
ing in the low potential range to the reductive adsorption
of hydrogen during the negative-going sweep and its
oxidative desorption during the positive-going one [1,10].
This interpretation was supported by the fact that the
charges integrated from the voltammetric profile could
be satisfactorily correlated to a surface concentration of
one hydrogen atom per platinum surface atom. On the
other hand, it was not fully accepted due to the particular
behavior observed with Pt(Ill) electrodes. In sulfuric
acid, the voltammogram (Fig. 1, dashed line) shows two
well-defined zones of current separated by a minimum
at 0.37 V in this case, but its position depends on the con-
centration of the acid: a low-potential usual adsorption
state between the onset of hydrogen evolution and 0.37 V
and the unusual adsorption states at potentials higher
than 0.37 V. When the voltammetric profile is recorded
in perchloric acid solutions, the low-potential region
remains unchanged, but the unusual states appear at sig-
nificantly more positive potentials (Fig. 1, solid line). The
adsorption potential of the latter region implied
extremely high adsorption energies for hydrogen that
had never been observed in the solid-gas interface. An
alternative explanation was that anion adsorption
accounted for the unusual adsorption states [12-14].
Small Single-Crystal Electrodes 465

<"I
e
~
60

so

0.1 j).?/
,..- ,-/
::'~-.:J
-
-<::::L
'~ -5
"I

-
8(,/
-<:1-
.....
B
tis

/.-1 ' __
E/VRHE
I,..--.-----~ II 400
II
I

200
Figure 1 Yoltammograms corresponding to a Pt(lIl) elec-
trode in 0.1 M HCl04 (solid line) and 0.05 M H 2 S04 (dashed
line). Sweep rate, 50 mY S-I.

This discussion was at the origin of the charge dis- x4

placement experiment, which aimed at deciding between
both interpretations in an unambiguous way. This exper-
iment essentially consists in dosing CO under
potentiostatic conditions and recording the current that
flows through the circuit. The experiment is based on the
fact that CO adsorbs strongly and irreversibly on
platinum, being capable of displacing from the surface
any other species that had been previously adsorbed. Pro-
vided that CO is a neutral probe, this displacement
involves a charge density opposite to that appearing
during the adsorption of the species present on the sur-
face at the working potential but equal in absolute value.
Therefore, the relevant magnitudes are the sign ofthe cur-
rent (that gives information on the anionic or cationic
nature ofthe dominant adsorbed species) and the charge
density displaced during CO dosing at constant potential
(related to the net amount ofadsorbed species).
In the case of a Pt(111) electrode in sulfuric acid, it is
invariably observed that dosing CO at potentials within
the usual adsorption state gives rise to positive currents
(oxidation processes), with the charges increasing as the
displacement potential diminishes [19,20]. Figure 2A
shows the j -t curve recorded during the CO displacement
at 0.08 V for a Pt(111) electrode in 0.5 M H 2 S0 4. The cur-
rent appearing during the displacement is attributed to
the desorption of hydrogen induced by the adsorption
of CO, schematically
Pt(lll) - H + CO~Pt(1ll) - CO + H+ + e
a,d c
.10 b 1.00
E/V RHE
Figure 2 (A) and (B) Curves j-t recorded during the
potentiostatic adsorption of CO at 0.08 (A) and 0.50 (B) Y vs.
RHE; (C) Curve a: voltammogram for Pt(lll) in contact with
a 0.5 M H 2 S04 before the CO displacement experiment; curve
b: control ofthe degree ofblockage by CO after the CO adsorp-
tion (enlarged by a factor of 4); curve c: subsequent oxidation
of the CO adlayer; curve d: voltammetric profile showing the
recovery ofthe adsorption capability of the electrode in the test
electrolyte. Sweep rate, 50 mY S-I.
On the other hand, the experiments done at potentials
within the unusual adsorption states or positive to them
showed a net reduction current, the absolute value of the
charge increasing with the dosing potential. Figure 2B
shows a displacement performed at 0.50 V The most
straightforward interpretation is that CO is displacing
adsorbed anions
Pt(1ll) - A + CO + e ~ Pt - CO + A- (2)
It was concluded that the unusual adsorption states are
directly linked to the adsorption of specifically adsorbed
anions, a process involving charge transfer. However,
the nature of the anion cannot be identified from this
(1) experiment.
466 Climent et al.

In this way, it is possible to discriminate between
reductive desorption of anions and reductive adsorption
of cations, two processes that contribute to the
voltammetric profile but cannot easily be discriminated
by means of this electrochemical technique.
The conclusions derived from the charge displace-
ment experiments need to be validated: It is necessary to
explicitly check that CO is a neutral probe, i.e., that the
molecule does not transfer charge during its adsorption.
The easiest way ofdoing so is to perform the displacement
experiment with a well-known system from both chemi-
cal and structural standpoints. The selected system was
iodine adsorbed on Pt(lll) [21] because it is well
documented that the iodine adlayer is fully displaced by
CO in a process that preserves the surface order [22], it
is irreversibly adsorbed on Pt(lll) and remains stable at
constant coverage in acidic electrolytes over a wide poten-
tial range, it is known that the adlayer is formed by neutral
iodine atoms (bond polarization does not involve free
charge that could be displaced), and the saturation
coverage is well known and two structures have been
described: the (3 x 3) and the (.17 x .j7)R17 with D
coverages 0.44 and 0.43, respectively, both in situ [23]
and ex situ [24]. The small difference in coverage (2%)
is indistinguishable for the charge displacement
experiment.
The process that is expected to take place during the
experiment is
pte Ill) - I + CO + e -----+ pte Ill) - CO + 1-
Hence, negative currents are expected, irrespective of
the dosing potential (because the adlayer composition
does not depend on the potential in this case), and charge
values should amount to around -104 flC cm- 2 , as
obtained in the actual experiment. Thus, CO is a neutral
probe: Its adsorption does not contribute to the charge
measured when the iodine adlayer is fully displaced. It
should be mentioned that the adsorption of another
probe, 12 molecules, used as displacing agent for Pt(lOO)
and Pt(lll) in sulfuric or perchloric acid solutions [25],
leads to results that correlate well with those obtained
with CO, taking into account that the experiment is done
at significantly higher potentials. Hence, there is a set of
self-consistent experiments involving neutral probes that
point to the existence of two different contributions to
the voltammetric current. Once we had confidence in
the meaningfulness of the technique, we went further in
the interpretation of the experiment.
At this point, it is important to remark that the agree-
ment between voltammetric and displaced charges is
quantitative: The difference between displaced charges
at two potentials equals, within experimental error, the
charge measured in the voltammogram between these
two potentials. This has been systematically checked with
different electrodes and supporting electrolytes [20,26].
Some results are shown in Table 1.
III. POTENTIAL OF ZERO TOTAL CHARGE
The thermodynamic treatment ofthe platinum-solution
(3) interfaces leads to the introduction of the concept of total

Table 1 Charge Displacement Experiment on the Platinum Basal Planes for Different Electrolytes

QI QI - Q2 QV(l-2)
Electrode Electrolyte (,lC cm- 2) Q2(pC cm- 2)! £2 (V) (pC cm- 2) (pC cm- 2)

Pt(lll) 0.1 M HCI04 152 -20/0.40 172 172

0.5 MH 2S0 4 161 -92/0.50 253 264
0.1 MHCI0 4+ 147 -104/0.50 251 249
0.01 M H2C204
I MHCI04+ 147 -85/0.45 232 244
0.1 MHAc
0.1 M HCI04+ 150 -98/0.50 248 250
0.01 M NaCI
0.1 MHCI0 4+ 158 -125/0.30 283 269
0.01 MKBr
Pt(100) 0.1 M HClO4 196 -56/0.50 252 255
0.5 MH2S04 197 -57/0.45 254 265
Pt(llO) 0.1 MHCI0 4 146/0.085 -38/0.34 184 185
0.5 MH 2S0 4 143 -64/0.34 207 207

Q" charge density displaced at 0.10 Vduring the potentiostatic adsorption of CO; Q2, charge density displaced by CO at
£2; Q~(I-2), charge density integrated under the Yoltammogram between 0.10 and £2.
Small Single-Crystal Electrodes 467

charge density [27,28]. This magnitude was defined as the The remark at the end of the preceding section
quantity ofelectricity to be supplied to the electrode when acquires some importance when we determine the value
its surface is increased by one unit maintaining constant ofthe PZTC: It is not necessary to perform the charge dis-
both the solution composition and the electrode placement experiment in the whole range of potentials.
potential. If we analyze the displacement experiment, It is sufficient to obtain the value of the displaced charge
we realize that the observed process is, in an approximate at a single potential and refer the integrated voltammetric
way, contrary to that involved in this definition. We begin profile to this value, as follows:
with a Pt surface having a certain total charge density at
the displacement potential, QPt, and we finish with a Q = E lil *
-dE - Qdis(E ) (5)
surface, fully blocked by adsorbed CO with a negligible JE' v
total charge, Qeo, as derived from the featureless
where Q is the total charge,} is the voltammetric current, v
voltammetric profile that characterizes the electrode fully
is the sweep rate, and Qdis(E*) is the charge displaced at
blocked by Co. The quantitative agreement between the
E*. The PZTC can be determined as the potential at
values for the displaced charges at different potentials
which Q vanishes. This minimizes the number of exper-
and the voltammetric charge density values gives support
iments required to determine the PZTC.
to this interpretation of the charge density measured in
the displacement experiments, which would be given by
IV. OBTAINING COVERAGES FROM
QD = Qeo - QPt~ - QPt (4)
COULOMETRY OF STRIPPING
In other words, the process that takes place during the PROCESSES
charge displacement with CO can be considered as being One of the most important consequences of the charge
equivalent to a decrease ofthe platinum surface in contact displacement experiments is the appearance ofan objec-
with the blank solution to a negligible value. As a con- tive and unambiguous way of accounting for the cor-
sequence, the potential at which the displaced charge is rections to be made to determine coverages from
zero would be identified as the potential of zero total coulometry. These charge corrections may be called, in
charge (PZTC). This is a relevant value whose knowledge a general way, double-layer contributions because they
is of capital importance in the understanding of the are directly related to the charge required to generate the
behavior of different surface reactions, as shown in the double layer of the clean electrode.
following. Table 2 reports some selected values of this Even if the stoichiometry of a redox process involving
magnitude. the stripping of a molecule is known, we are not capable
of singling out the charge due to this desorption process
Table 2 Values ofthe Potential of ZeroTotal Charge for Differ-
unless other contributions after the stripping process,
ent Platinum and Rhodium Electrodes in Contact with Several faradaic and non-faradaic, are evaluated. This estimation
Electrolyte Solutions is facilitated by the knowledge of the displaced charge at
a given potential and especially by the knowledge of the
Potential ofzero total charge value of the PZTC. Let us first pay attention to a
(VRHE)
much-studied case, that of the stripping of CO adsorbed
on platinum single-crystal electrodes [15,16].
Metal Electrolyte fcc(lll) fcc(lOO) fcc(llO)
The CO adlayer may be easily generated by dosing CO
Platinum0.1 MHClO 4 0.34 0.43 0.23 in an acidic working solution, either at controlled poten-
0.5 M H 2SO 4 0.32 0.38 0.15 tial or at open circuit. The excess ofCO eventually present
1 MHClO 4+ 0.32 0.36 in solution after dosing may be easily eliminated by
0.1 M NaC2H302 means of Ar bubbling. If the dosing time is long enough,
0.1 MHCI0 4+ 0.31 0.34 the metal surface becomes fully blocked and only small
0.01 M H2C204
currents are recorded in the low potential range of the
0.1 MHClO4+ 0.28 0.28
voltammetric scan (below 0.6 V). If the positive-going
0.01 MNaCl
0.1 MHCI0 4+ 0.18 0.21 scan is allowed to reach a higher potential (e.g., 1.00 V),
0.01 MKBr an oxidation peak is observed whose potential and shape
Rhodium 0.5 MH 2S0 4 0.14 0.14 0.10 depend on the metal and, for a given metal, on the surface
structure ofthe electrode (i.e., the CO oxidation is a struc-
fcc, face centered cubic lattice. ture sensitive reaction). In this process, CO molecules
468 Climent et aI.

commonly oxidize to CO 2 in a single sweep excursion.
The CO 2 molecules are not adsorbed during the time-
scale required to record the voltammetric profile that
follows the desorption scan. Consequently, a profile
virtually equal to that recorded before the CO dosing is
observed. This confirms that the initial and final states
of the surface are the same as also the cleanliness
throughout the whole experiment.
As a representative example, the CO stripping from a
fully blocked Pt(lll) electrode was recorded in an exper-
iment carried out in 0.5 M H2S04 as supporting electro-
lyte (Fig. 2C). The upper potential limit is high enough
to completely oxidize the adsorbed layer to CO 2 in a
single positive-going scan (curve c) but low enough to
ensure the stability ofthe platinum surface atoms. In fact,
the initial voltammetric profile of the electrode, as
recorded before CO adsorption, could be fully recovered
after the stripping of the adlayer (curve d).
The surface reaction taking place during the oxidative
stripping of CO may be formulated in a general way as
Pt(lll) - CO + H 20 --7 Pt(lll) + CO2 + 2H+ +2e
pte Ill) + A- --7 pte Ill) - A +e
It maybe stated that jointly with the CO stripping pro-
cess, the Pt(ll!) sites are also recovered and undergo a fast
double-layer regeneration [reaction (7)]. This recovery
implies a charge contribution due to anion adsorption,
given that the CO stripping takes place at potentials
higher than the PZTC. Thus, we can write
Qeo = Qpeak - QOL(E+)
where QOL(E+) is the total charge present on the Pt(lll)
electrode surface at the upper limit ofthe sweep E+, which
usually corresponds to the end of the stripping peak. It
is evaluated by integrating the voltammetric current
between the PZTC as lower limit and E+. Thus, the
Qpeak should be diminished by a charge given by
E+ .
QodE+) = J LdE
pZTe v
(9)
In experiments as those reported in Fig. 2, usual values
are Qpeak=437 /lC cm- 2 and QDL(E+)=129 /lC cm- 2,
which is a significant correction. The Qeo charges are
obtained by applying the procedure described above,
and the values of the CO coverage, Beo , may be deter-
mined as
Beo = Qeo (10)
2QPt(l 11)
where QPt(IIl)=243 /lC cm- 2 is the surface atomic den-
sity ofPt(ll!) expressed in electrical units. Defined in this
way, this coverage will give the number of CO molecules
adsorbed per platinum surface atom. The coverage value
determined by coulometry, Beo = 0.64, coincides well
with that determined by means of other more sophisti-
cated techniques. This procedure can be applied to other
(6) surfaces. Coverage results for different electrodes are
given in Table 3.
The characterization of nitric oxide adlayers is
(7)
another good example of the importance of charge cor-
rections and shows the fruitful coupling between electro-
chemical and in situ FTIR spectroscopic experiments.
Stable nitric oxide layer can be easily generated by
dipping a platinum group metal electrode at open circuit
in either a NO-saturated or an acidic nitrite solution.
The adlayer is stable in a potential range well above the
hydrogen adsorption/desorption region and its stripping
(8) can be properly achieved by reduction.
As a typical example ofvoltammetric curves obtained
for NO adlayers, those corresponding to Pt(lOO) elec-
trodes in 0.1 M perchloric acid are shown in Fig. 3. The
NO covered electrode shows a featureless low current
region between 0.5 and 0.9 V This proves the blockage

Table 3 CO Coverage Values and Related Magnitudes for Several Electrodes in Contact with a H 2 S0 4 Solution

Electrode E+ (VRHE) Qpeak (J.lC cm- 2) QOL (J.lC cm- 2 ) Qeo (J.lC cm- 2) BeG
Pt(lll) 1.00 437 129 308 0.64
Pt(IOO) 0.90 460 117 343 0.82
Pt(1I0) 0.90 357 116 241 0.82
Rh(IOO) 0.80 590 247 343 0.77
Rh(1lO) 1.00 885 568 317 1.02

E+, positive potential limit in the integration ofthe CO stripping peak, Qpeab charge density integrated under this peak, QDL,
charge correction for the raw stripping charge, associated with the reestablishment ofthe double layer after the CO stripping,
Qeo, corrected faradaic charge for the desorption of CO, IICO, CO coverage in CO molecules per platinum surface atom.
Small Single-Crystal Electrodes
E/V RHE
-100
1460
I ~=0.2
%
R.
-200
x5
1611
b uct formed from the NO adlayer at 0.10 V Thus, the
2200 2000 1800 1600 1400 1200
Wavenumbers!em"
Figure 3 Voltammetric profiles obtained after the formation
of a saturated NO adlayer on a Pt(100) surface. Test electrolyte:
0.1 M HCI0 4 . Curve a: cyclic voltammogram between 0.5 and
0.87 V (50 mV S-I). Curve b: reduction peak corresponding to
the stripping of the adlayer (10 mV S-I). Curve c: recovery of
the adsorption capability of the Pt(100) substrate (50 mV s-I).
Inset: Potential difference spectrum corresponding to a satu-
rated NO adlayer on a Pt(lOO) surface in 0.1 M HCI04 solution.
Sample potential, 0.50 V. Reference potential, 0.1 V. One
hundred interferograms were collected at each potential.
of the electrode surface for the adsorption/desorption
processes characteristic of a clean Pt(lOO) surface in the
supporting electrolyte solution. From the stability of this
voltammetric profile upon successive cycles, it can be
stated that neither the surface coverage nor the chemical
nature of the adsorbate change in this potential region.
When the potential excursion is extended to potentials
lower than 0.40 V, a marked reduction peak appears at
0.26 V The voltammogram obtained in the subsequent
cycle fits quite well with that recorded before the forma-
469
tion of the adlayer, provided that the reductive stripping
was made at a low enough sweep rate (10 mV S-I). This
behavior proves the recovery of the clean and well-
ordered Pt(lOO) electrode surface.
To obtain the absolute coverage ofthe NO adlayer, the
stoichiometry for the surface reaction needs to be known.
Essential information ofthe nature ofboth the adsorbate
and the reduction product in solution may be derived
from the potential-difference spectrum reported in
the inset in Fig. 3. This spectrum originates from a
single-beam reflectance spectra collected within the
stability limits of the adlayer (0.50 V) that was referred
to that collected once the adlayer was stripped at 0.10 V
In this case a negative-going band is observed at
1621 cm- 1, the typical frequency region for the N-O
stretching mode of nitrosyl compounds [29]. The
observed band can be thus ascribed to adsorbed NO at
the sample potential. This assignment is consistent with
the absence of this feature in the spectra obtained with
s-polarized light.
The spectrum reported in Fig. 3 also shows a
positive-going band at 1460 cm- I . This frequency value
fits with that of the 6N-H mode of dissolved ammonium
[29], which can be identified as the main reduction prod-
stripping ofthe adlayer could correspond to
Pt(1 00) - NO + 6H++ 5e --+ Pt(1 00) + NHt + H20 (11)
which implies a net transfer offive electrons per adsorbed
NO molecule.
To obtain the correct value ofthe NO stripping charge
from the reduction peak shown in Fig. 3, a double-layer
correction should be taken into account, as in the case
of Co. The only difference is that we are dealing with a
reduction process that should be corrected with a
double-layer contribution measured at the lower limit of
the sweep:
(12)
In this way, if the charge contribution positive to the
PZTC should be taken into account for oxidation pro-
cesses, the reverse is true for reduction processes: The
rough stripping reduction charge under the peak needs
to be corrected by the charge measured in the
voltammetric profile for potentials negative to the PZTC.
This correction is equivalent to considering that the
Pt(lOO) electrode is covered by adsorbed hydrogen at the
lower potential limit of the sweep:
Pt(100) + H+ + e ~ Pt(100) - H (13)
470 Climent et al.

In this case, the procedure for calculating the NO
coverage makes use of the expression:
QNO
8NO = - - -
5 QPt(lOO)
That is the same as in the case of CO, taking into
account that the substrate is now Pt(WO), for which
2
QPI(lOO) amounts to 209 /i. C cm- , and the number of
transferred electrons per reduced NO molecule is
five. The charge under the reduction peak amounts
to 700 /i.C cm- 2 and the double-layer correction is
196 /i.C cm- 2 . The coverage obtained by coulometry,
0.48, agrees well with that obtained under ultrahigh vac-
uum (UHV) conditions, where infrared adsorbate bands
at 1640 cm- 1 have also been described [30].
In the same way as for Pt(WO), stable NO adlayers may
be obtained and characterized on several platinum and
rhodium surfaces [31]. The significant results are
summarized in Table 4 with a comparison with the corre-
sponding data obtained under UHV conditions. In most
cases, NO coverages and vibrational properties are
similar, suggesting that the adlayer is similar in both
environments.
v. ANION ADSORPTION
In the preceding section the application ofcoulometry to
obtain surface coverages has been described. The cases
of stripping of CO and NO adsorbates have served to
illustrate the procedure to be followed. In both cases a
quantitatively important double-layer correction should
be considered in addition to the charge due to the surface
(14) reaction. In this section we deal with the study of another
aspect, that corresponding to anion adsorption [32,33],
focusing first on pte Ill) electrodes. As was said in the case
of Pt(lll), the most straightforward interpretation for
the reduction transient observed at potentials positive to
the unusual states consists in ascribing this reduction
charge to induced desorption of anions. Anion adsorp-
tion on pte Ill) is pointed out voltammetrically by the shift
of the unusual states toward lower potentials. This is
clearly observed in Fig. I when (bi)sulfate ions are in sol-
ution and in the example presented in Fig. 4, which
represents to a Pt(lll) electrode in a 0.1 M
HCI0 4 + 10- 2 M KBr solution. As for the CO and NO
adlayers, we need to know the number of electrons
involved per adspecies to calculate the anion coverage
from the charge under the unusual states. This number
has been called charge transfer coefficient and is defined
as the difference between the actual faradaic charge
number for the adsorbate and the charge number for the
reactant ion being adsorbed [34]. The knowledge of this
coefficient is also required in the case of hydrogen,
although the value is obvious in this case. If the charge
transfer coefficient may be established by means of any
experiment, then the displaced charge may be directly
correlated to the anion coverage.

Table 4 Spectroelectrochemical and UHV Data Concerning the NO Adlayers Formed

at the Metal- Electrolyte and Metal- Vacuum Interfaces

Spectroelectrochemical data UHVdata

V(NO) V(NO)
8(NO) (em-I) Structure G(NO) (em-I)

Pt(lOO) 0.51 1630 c(4x2) 0.5 1640

Disordered 0.73 1680
Pt(lll) 0.4-0.5 1680,1420 0.12 1715,1495
p(2x2) 0.25 1725
p(2x2) 0.23-0.54
Saturated 1710
Pt(llO) 0.46 1750,1580 - Saturated 1760,1610
Rh(100) 0.8-1.0 1680 Disordered 0.65 1633
Disordered 0.65
Rh(lll) 0.48 1810,1600 c(4x2) 0.5 1595
(2x2) 0.75 1830,1515
Disordered Saturated 1635
Rh(llO) 1.00 - l.l
Saturated 1710

Source: From Ref. 31 and references cited therein.

Small Single-Crystal Electrodes
100
~ A close-packed bromine adlayer has been observed by
8()
<:::::L.
-
1.00
.-' E/V RHE
-10
Figure 4 Voltammogram for a Pt(lll) electrode in contact
with a om M KBr + 0.1 M HCI04 solution. Sweep rate,
50 mV S-I.
We focus now on a particular case that can exemplifY
the procedure followed in the study of anion adsorption.
The first step must be the evaluation of the charge
number of the adsorbate. In this respect, it has been
stated that both the stable adlayers formed both by con-
tact of the electrode surface with a solution containing
the anion (1-, Be) and by exposure to neutral molecule
vapors (12, Br2) have the same electrochemical pro-
perties. Therefore, it seems reasonable to accept that
both adlayers are composed of the same halogen
species. Given that the adlayer formed from the Br2
vapors is most likely composed of neutral bromine
atoms, we can accept that neutral bromine atoms are
also generated by Be adsorption. Then the displace-
ment reaction is given by
Ptn - Br + CO + e ~ Ptm - CO + Br-
471
It is interesting to note that in this reaction (and also in
those previously shown), the number of Pt atoms linked
to the anion, as a mean value, is not necessarily the same
as those required by co. In this case, the charge density
displaced from Pt(lll) and Pt(lOO) amounts to -105
pC cm- 2, a value that is compatible with the formation
of a compact bromine adlayer on both substrate planes.
This corresponds to bromine coverages of0.44 on Pt(lll)
and 0.5 on Pt(lOO). Once we have exploited the electro-
chemical measurements to obtain a Br coverage value, it
is interesting to contrast this result with those given by
other techniques, particularly STM.
STM on Pt(IlI) substrates in some cases. The distance
between bromine atoms in the close-packed adlayer was
found to be 0.37 nm, very close to van der Waals diameter
of bromine (0.39 nm [35]). It is worth noting that the
interpretation of complex STM images is facilitated by
the knowledge ofthe bromine coverage from the electro-
chemical measurements. This makes it possible to
analyze images arising from different coincidence struc-
tures between the substrate and the close-packed bromine
adlayer that are locally presented on the surface. As an
example, Fig. 5 shows STM images ofa rectangular array
of bromine atoms on a Pt(IlI) substrate. The distances
measured along the rows (from upper left to bottom right),
0.84 nm, are equivalent to three platinum diameters
(0.278 nm), but in the normal direction the distances
are shorter (0.67 nm) and correspond to 3(~3)/2 Pt
diameters. Ifthese bromine atoms were the only ones for-
ming the adlayer, the resulting bromine coverage would
be only 1/9 (Br/Pt). When cross-section information is
analyzed, it is evidenced that the observed image is simply
a distortion of a (3 x 3)-4Br adlattice and corresponds
to a bromine coverage of 4/9 = 0.44, in agreement with
the displaced charge density values. In the case ofPt(lOO)
substrates, a bromine adlayer was found having the struc-
ture (3 x 4)-6Br, with a coverage of 0.5. In this case, the
fact ofhaving electrochemical data on the bromine cover-
age was also important.
This type of analysis has led to the discovery of other
structures on Pt(lll) and Pt(lOO) substrates. The results
are shown in Table 5, which includes UHV results for the
sake of comparison. We can conclude that the infor-
mation derived from the displaced charges will be very
useful in improving the study of STM images.
VI. ADSORPTION OFANIONLIKE MOLECULES
A somewhat different situation arises in the case of
reversible adsorption of neutral molecules [36]. These
(15) molecules are desorbed in the lower potential region
472 Climent et al.

voltammetric profile is clearly greater than that recorded

Figure 5 Atomic resolution constant height STM image of a
7.8 x 7.8 nm domain of a Pt(lll)-(3 x 3(,;'3)/2)rectangular Br
adlayer.
and their surface excess increases at the same rate as the
electrode potential, reaching a saturation coverage after
which the surface excess is maintained nearly constant.
A typical situation is obtained in the case of urea. The
voltammogram reported in Fig. 6 corresponds to a
Pt(100) electrode in a 0.1 M perchloric acid solution con-
taining 10- 3 M urea (curve a). The modification of the
in the absence of urea: The broad peaks characteristic of
the voltammetric profile of the PtO 00) electrode in per-
chloric acid solution become sharper and shift to lower
potentials. This modification indicates the adsorption of
the molecule on the surface. Radiotracer experiments
[37] demonstrate that urea adsorption begins at
potentials slightly lower than those ofthe oxidation peak
in Fig. 6, reaching a nearly constant coverage at more
positive potentials. A charge density of 310 pC cm~2 is
obtained from the integration of the voltammetric cur-
rent density between 0.1 and 0.45 V This value is signifi-
cantly higher than the charge corresponding to the
adsorption/desorption of a hydrogen monolayer on the
Pt(lOO) (1 x 1) surface (209 pC cm- 2). Thus, there must
be an additional process that accounts for the excess of
charge density. This process should be related to the
adsorption of urea.
As in the cases reported above, the CO displacement
technique may be used to discriminate between the differ-
ent contributions to the voltammetric current. In the pre-
sent case, +190 pC cm- 2 are displaced at 0.10 V, a value
similar to that measured in the urea free solution. This
suggests that at lower potentials, the hydrogen adlayer
remains the same irrespective of the presence of urea in
solution. The amount of charge density displaced at
0.45 V, when the urea adlayer is practically completed
equal -101 pC cm- 2. This charge gives us a relationship
between the charge transfer coefficient and the urea
coverage. Radiotracer experiments have shown a satu-
ration coverage of 0.25 in the case ofurea on Pt(100) [37].
This value agrees with that deduced from ex situ Auger
experiments [37] and also with the e(2 x 4) structure

Table 5 Bromine Adlayer Structures on Pt(lll) and Pt(WO) Surfacesa

Surface Structure Coverage (Br/Pt) Dosage Technique
(3x3)-4Br 0.44 (ideal coverage) Br2 (UHV) LEED
0.42-0.48 aq. Br- LEED-AES
0.44 (total Br) HBr(UHV) LEED
0.44 In situ STM
(3x3( V3)/2)rect 0.44 Br2 (air) STM
Pt(lll) 0.50 Br2 (air) STM
C ~5)
3
2
Incommensurate
~ 0.46 In situ SXRS
Hexagonal close packed
c(2v"2 x v"2)-( Br+HBr) 0.5 (total Br) HBr (UHV) LEED
Pt(lOO) (3x4)-6 Br 0.5 Br2 (air) STM
(3 x3)-4 Br 0.44 Br2 (air) STM

LEED. low-energy electron diffraction; AES, auger electron spectroscopy: SXRS, surface x-ray scattering.
Source: From Refs. 32 and 33 and references cited therein.
Small Single-Crystal Electrodes 473

200 0.25 V
15

150
a 0.26V
10

~ .... '"
100

b 0.27 V
5
50

";l I:) 0.30V

S 0 0
<.) ----
1=
(1
<t:: ('l
:::1. S
.----
....., -50 N
-5 0.50V

-100
-10
0.90V
-150

-15

0.1 0.2 0.3 0.4 0.5

-200
EN (vs RHE)
Figure 6 Curve a: cyclic voltammogram corresponding to a
Pt(100) electrode in a 10- 3 M urea + 0.1 M HCI0 4 solution;
curves band c: integrated charge density under the
voltammogram for the positive-going (b) and negative-going
(c) sweeps. Sweep rate, I mV s-I. (See text for details).
determined by low-energy electron diffraction [37,38] and
points to the stability of the adlayer. If these results are
taken into account, we deduce that two electrons per urea
molecule must be transferred during the adsorption
process.
The question ofthe potential at which urea adsorption
starts can now be addressed. This can be done in a first
approximation by using the voltammetric and charge dis-
placement data reported above to determining the PZTC
in the urea-containing solution. Curves band c in Fig. 6
correspond to the plot ofthe total charge density as afunc-
tion of the potential. This charge can be measured from
the integration of the positive- (curve b) and negative-
going (curve c) sweeps ofthe cyclic voltammogram, using
Eq. (5).
To gain more information about the urea adlayer,
FTIR experiments in deuterated water were carried out
[36]. The use ofDzO instead ofHzO has two advantages:
elimination ofthe interference at 1650 cm -z, which shifts
I~~ =0.2%
1702
2000 1500
1
Wavenumbers/crri
Figure 7 In situ FTIR spectra obtained at different sample
potentials (indicated alongside) for a Pt(100) electrode surface
in a 10- 3 M urea + 0.1 M DCI0 4 solution in Dzo. Reference
potential, 0.1 V. One hundred interferograms were collected at
each potential.
to 1250 cm- I , leading to a better definition ofthe adsorb-
ate band region. Moreover, isotopic substitution may give
additional information. Figure 7 shows a set of spectra
collected at different potentials between 0.20 and 1.0 V
that were referred at 0.10 V. All these spectra show a
negative-going band at around 1700 cm- 1, which corre-
sponds to the C-O stretching of adsorbed urea [36].
Moreover, two positive bands are observed at 1500 and
1609 cm- I . These bands, which are also observed with
s-polarized light, can be assigned to the asymmetric
C-N stretching and to the CO stretching of urea mol-
ecules in solution [36], respectively. Note that all the
observed bands appear for an electrode potential of
0.26 V, this fact being consistent with the PZTC value
found from the electrochemical data. In addition, the
intensity of the positive-going bands in the spectra
taken with s-polarized radiation [36], which are
474
proportional to the amount ofadsorbed urea, agrees also
with the plot of the Q values at potentials higher than
0.26 V (Fig. 6).
To relate the frequency of the negative band in Fig. 7 to
the bonding geometry of adsorbed urea, it is advisable to
make a comparison with the values obtained for the
c-o stretching band of well-characterized metallic
complexes having urea as a ligand to the central metallic
atom [29]. Two possible arrangements of the urea mol-
ecule around a cation have been reported: either linked
through one of the nitrogen atoms or bonding through
the oxygen of the carbonyl group. The different modes of
bonding of urea to the metal atom change the character-
istic spectrum of adsorbed urea in different ways: When
urea is bonded through the nitrogen atoms, an increase
of the CO frequency and a decrease of the asymmetric
CN stretching are observed with respect to their typical
frequencies in the free urea molecule, the opposite being
true when urea is bonded through the oxygen atom. As
can be stated from the available data, the adsorption of
urea on Pt(100) suggests that bonding through the nitro-
gen atoms is most likely. Moreover, the intensity of the
CO stretching band is relatively high, thus suggesting that
the corresponding band is perpendicular to the Pt(100)
substrate (this wnfiguration implies a strong dipole
change orthogonal to the surface). The absence of a band
corresponding to the asymmetric stretching of C-N
bond in the adsorbed urea indicates that the adsorbed
urea molecules are bonded to the electrode surface
through their two nitrogen atoms. All these spectroscopic
data are consistent with the transfer of two electrons per
adsorbed urea molecule. This process could be
schematized as follows
2Pt(100) + H2N -CO -NH2-+
Pt(100) - HN -CO - NH - Pt(l 00) + 2H+ + 2e
(16)
If this is so, the adsorption of urea would imply the
cleavage of chemical bonds and the formation of a bond
with the surface sites, which would agree with the lower
reversibility observed in the voltammogram. The differ-
ence with the proceeding case is related to the loss of
hydronium ions as a consequence of the adsorption of
the molecule.
The loss of hydrogen atoms upon urea adsorption is
still an open question [39]. It is worth noting that the pro-
posed reaction (16) is consistent with the shape of the
spectra obtained during urea adsorption in normal water
[36]. In this case the urea adsorbate band overlaps with
an intensepositivebandat1650 cm- 1 due to the OH bend-
ing mode ofuncompensated water. This loss ofwater into
Climent et al.
the thin layer is paralleledwith the development ofa strong
adsorption band at 1100 cm- 1 related to the migration of
perchlorate anions in the thin layer. These observations
point toward a strong pH change in the thin layer upon
urea adsorption, suggesting a deprotonation ofurea mol-
ecules as a consequence of their adsorption. This agrees
with the proposed reaction scheme for urea adsorption.
ACKNOWLEDGMENTS
V Climent thanks the Conselleria d'Educaci6 i Ciencia
de la Generalitat Valenciana for the award of a doctoral
grant. Financial support by DGICYT through Contract
PH 96-0409 is gratefully acknowledged.
REFERENCES
I. 1 Clavilier, R Faure, G Guinet, R Durand. 1 Electroanal
Chern 107:205, 1980.
2. A Hamelin. In: BE Conway, RE White, 10'M Bockris,eds
Modern Aspects of Electrochemistry.Vol. 16. New York:
Plenum Press. 1985.
3. 1 Clavilier, M Wasberg, M Petit, LH Klein. 1 Electroanal
Chern 374:123, 1994.
4. 1 Clavilier, K EI Achi, A Rodes. Chern Phys 141:1,1990.
5. A Rodes, K EI Achi, MA Zamakhchari, J Clavilier. 1
Electroanal Chern 284:245,1990.
6. 1 Clavilier, JM Feliu, A Fernandez-Vega, A Aldaz. 1
Electroanal Chern 269:175, 1989.
7. R Gomez, 1 Clavilier. 1 Electroanal Chern 354:189, 1993.
8. GA Attard, R Price. Surf Sci 335:63, 1995.
9. NM Markovic, BN Grgur, CA Lucas, PN Ross. Surf Sci
384:L805,1997.
10. 1 Clavilier. 1 Electroanal Chern 107:211, 1980.
11. BE Conway, H Angerstein-Kozlowska. WBA Sharp Anal
Chern 45:1331,1973.
12. DA Scherson, DM Kolb. 1EJectroanal Chern 176:353,1984.
13. FT Wagner, PN Ross. 1 Electroanal Chern 250:301, 1988.
14. PW Faguy, NM Markovic, RR Adzic, CA Fierro, EYeager.
1 Electroanal Chern 289:245, 1990.
15. Ml Weaver, SoC Chang, L-WH Leung, X liang, M Rubel,
M Szklarczyk, D Zurawski, A Wieckowski. J Electroanal
Chern 327:247, 1992.
16. 1M Orts, A Fermindez-Vega, 1M Feliu, A Aldaz, 1
Clavilier. 1 Electroanal Chern 327:2611992.
17. J Clavilier, R Albalat, R Gomez, 1M Orts, 1M Feliu, A
Aldaz. 1 Electroanal Chern 330:489, 1992.
18. 1 Clavilier, D Armand, SG Sun, M Petit. 1 Electroanal
Chern 205:267, 1986.
19. 1M Feliu 1M Orts, R Gomez, A Aldaz, 1 Clavilier. 1
Electroanal Chern 372:265, 1994.
20. 1 Clavilier, 1M Orts, R Gomez, 1M Feliu, A Aldaz. In:BE
Conway, G lerkiewicz, eds. Electrochemistry and
Materials Science of cathodic hydrogen absorption and
adsorption. Pennington, Nl:The Electrochemical Society,
1994, pp. 167-183.
Small Single-Crystal Electrodes 475

21. J Clavilier, R Albalat, R Gomez, JM arts, JM Feliu. J 30. P Gardner, M Tiishaus, RM Martin, AM Bradshaw. Surf
Electroanal Chern 360:325, 1993. Sci 240:112, 1990.
22. L Palaikis, D Zurawski, M Hourani, A Wieckowski. Surf 31. A Rodes, R Gomez, JM Perez, JM Feliu, A Aldaz. Elec-
Sci 199:183, 1988. trochim Acta 41:729,1996 and references therein.
23. BC Schardt, S-LYan, F Rivaldi. Science 243:1050,1989.
32. JM arts, R Gomez, JM Feliu, A Aldaz, J Clavilier. J Phys
24. JL Stickney, SD Rosasco, GN Salaita, AT Hubbard.
Chern 100:2334, 1996.
Langmuir 1:66, 1985.
25. E Herrero, JM Feliu, A Wieckowski, J Clavilier. Surf Sci 33. JM arts, R Gomez, JM Feliu, A Aldaz, J Clavilier.
325:131,1995. Langmuir 13:3016,1997.
26. JM arts, R Gomez, JM Feliu, A Aldaz, J Clavilier. Elec- 34. JW Schultze, FD Koppitz. Electrochim Acta 21:327,1976.
trochim Acta 39:1519, 1994. 35. RG Jones. Prog Surf Sci 27:25, 1988.
27. V Climent, R Gomez, JM arts, A Aldaz, JM Feliu. In:C 36. V Climent, A Rodes, JM arts, JM Feliu, JM Perez, A
Korzeniewski, BE Conway, eds. The Electrochemical Aldaz. Langmuir 13:2380, 1997.
Double Layer. Pennington, NJ: The Electrochemical
37. M Gamboa-Aldeco, P Mrozek, CK Rhee, AWieckowski,
Society, 1997, pp. 222-237.
P A Rikvold, Q Wang. Surf Sci Lett 297:Ll35, 1993.
28. AN Frumkin, OA Petrii. Electrochim Acta 20:347, 1975.
29. K Nakamoto. Infrared and Raman Spectra of Inorganic 38. CK Rhee. J Electrochem Soc 139:13C, 1992.
and Coordination Compounds. New York: John Wiley & 39. ACSBezerra, ELde Sa, FCNart. J Phys Chern B101:6443,
Sons, 1986. 1997.
27
Radiotracer Studies of Adsorption/Sorption Phenomena at
Electrode Surfaces
Gyorgy Honinyi
Hungarian Academy ofSciences, Budapest, Hungary
ABSTRACT
Recent developments in the application of radiotracer
methods to the study of sorption processes occurring
at electrodes are surveyed. Various versions of the
experimental technique are presented, and their theoreti-
cal background is analyzed. The applicability of the dif-
ferent methods is shown through illustrative examples
in the case of polycrystalline, well-defined surfaces, and
polymer film electrodes. It is demonstrated that the radio-
tracer method is a useful tool to investigate specific inter-
actions at electrode surfaces.
I. INTRODUCTION
Of all the in situ techniques used to obtain information
about the sorption phenomena at electrode surfaces, the
radiotracer technique was the first direct method fur-
nishing reliable data on the extent of adsorption of a
specific preselected species. Generally, in situ radiotracer
methods provide direct information on adsorption/
accumulation processes on a great a variety ofelectrodes
under various experimental conditions.
The Joliot method, reported in 1930, is considered a
landmark in the application of radiochemical methods
in electrochemistry. The 1950s and 1960s saw the begin-
ning of a remarkable development in this field indicated
by the simultaneous formation of working groups
in Moscow (in Frumkin's Institute, Balashova and
477
Kazarinov; Karpov Institute, Kolotyrkin and Losev),
Leipzig and Dresden (Schwabe and coworkers), and the
United States (Bockris and coworkers).
Since this beginning, further centers were formed in
Hungary (Honl.nyi and coworkers in Budapest; Varga
and Kolics in Veszprem), Poland (Sobkowski, Zelenay,
Franaszczuk, Szklarczyk, and coworkers in Warsaw),
the United States (Wieckowski and coworkers in
Urbana), and France (Marcus and coworkers).
The application of radiochemical methods for the
study of the electrode-solution interface extends to
a wide range of fundamental phenomena belonging
to various more or less interrelated branches of
electrochemistry. The main branches coming into con-
sideration are as follows:
1. Study of adsorption electrosorption phenomena
occurring on the surface ofelectrodes;
2. Investigation ofthe role ofelectrosorption in electro-
catalysis;
3. Study of the deposition and dissolution of metals;
4. Investigation ofcorrosion processes;
5. Study ofthe formation ofsurface layers, films on elec-
trodes (for instance, polymer films), and investi-
gation ofmigration processes in these films;
6. Study of the dynamics of electrosorption and elec-
trode processes under steady state and equilibrium
conditions (exchange and mobility of surface
species);
7. Coupling of electroanalytical and radiochemical
methods (for instance, radiopolarography).
478 Horanyi

Although the radiotracer methods offer a simple way Table 1 Research Groups Involved in Radiotracer Electro-
to approach the problems enlisted above, their appli- sorption Studies
cation did not become general practice in the electro- Groups Main fields
chemical laboratories as stated by Bockris in 1993 [1]:
In spite ofconsiderable Russian and Hungarian work, French
the radiotracer method is lamentably underused in elec- P. Marcus A,e
trochemistry, perhaps because of alleged limitations in Hungarian
Budapest
respect to available ([3 emitting) isotopes.
G. Honinyi B,e,D
There are, however, other perhaps more important
Veszprem
points that could playa role in shunning the application K.Varga, A. Kolics A,B,e
of tracer methods. Some of these points are as follows: Lithuanian B
1. Researcher's exaggerated fear of any nuclear D. Poskus
Polish A,B
radiation.
1. Sobkowski, P. Zelenay
2. Special safety requirements for the treatment of
Russian B,D
radioactive materials connected with the continuous V. E. Kazarinov,V. N. Andreev
control ofcontamination, including the intervention United States
ofvarious authorities. Texas A,B,e,E
3. As a consequence, a separate laboratory is required rOM Bockris
for the radiotracer studies. Urbana A,B,e,E
4. A special radiochemical training of the laboratory A.Wieckowski
staff is required to comply with the points raised
A, adsorption on single crystal surfaces: B. adsorption on poly-
above.
crystalline surfaces; C, corrosion and surface layers; D. polymer film
Because of these problems worldwide, less than and other modified electrodes; E, radiotracer methods in conjunction
with other in situ and ex situ methods.
10 laboratories are dealing permanently with radio-
tracer adsorption/sorption studies in the field of
electrochemistry. These laboratories and the field of their other methods answers these questions, furnishing direct
activities are listed in Table 1. information on the extent ofadsorption oflabeled species
The radiochemical electrosorption studies carried out under various experimental conditions.
in these laboratories have been reviewed periodically, The nature (metals, alloys, oxides. modified elec-
and several articles covering important subfields trodes, etc.) and the surface structure (polycrystalline or
appeared during the last 2-3 years [2-12]. single crystal, smooth or rough surfaces) of the electrode
Considering this situation, the present survey is to be studied are important factors determining the
restricted to the fundamental principles of the method approach to the electrosorption phenomena and the
and their developments during the last years, and some radiotracer methods used for their study. It is evident that
characteristic new results are presented, avoiding the the kind of labeling of adsorbing (reacting) species
description of the technical details available in the depends on the composition of the molecule and on the
literature. available isotopes for labeling. Table 2 shows a survey on
some representative examples reported in the last 2 years.

II. GENERAL PROBLEMS

III. EXPERIMENTALTECHNIQUE
The electrochemical behavior and properties ofadsorbed
The in situ experimental techniques used by various
(electrosorbed) species playa central role in the electrode
authors are described in the relevant literature (papers
processes and in the electrochemical electrocatalytic
and reviews) in detail [2-36]. The methods can be divided
transformations. Therefore, electrosorption studies
into various groups.
should answer the following fundamental questions:
How does the nature and surface structure of the elec-
A. Thin Foil and Thin Gap Methods
trode influence the sorption ofa given species? How does
the nature and structure of adsorbing species influence The main problem ofthe in situ radiotracer study of elec-
the behavior and the state of adsorbed species at a given trosorption phenomena originates from the very nature
electrode. The use of radiotracers in conjunction with of the method because the radiation measured consists
Radiotracer Studies 479

Table 2 Examples for Radiotracer Studies Reported in the Last 2 Years

Isotope Molecule Application References
35S S20~- Accumulation on stainless steel I3
HS01- Sorption on polycrystalline gold 14
HS0 3 Low carbon steel 15
HS0 4 Sorption on stainless steel 16
Sorption in polymer films 17
Adsorption on rhodized electrode 18
Induced adsorption by Cu adatoms on Rh 19
Study of adsorption on Rh in conjunction 20
with EQCM measurements
Adsorption on Cu and Bi adlayers on Pt 21
Induced adsorption by Zn adatoms on Pt 22
Adsorption on Cu crystal faces 30
Accumulation on stainless steel and Al 33
surfaces
36Cl Cl- Adsorption on gold 23
Sorption in polimerfilm 17
Adsorption on Rh electrode 18
Induced adsorption by Cu adatoms on Rh 19
Adsorption on Cu and Bi adlayers on Pt 21
Sorption on Al and Al alloys 29
32p H 2P0 4 Sorption in polymer film 17
Adsorption on rhodized electrodes 18
Accumulation on stainless steel 24
57CO Co 2+ Sorption on gold 25
14C Aniline Polyaniline degradation 32
CN- Sorption on gold 27,28
204TI Tl+ Sorption on gold 28
UPD on Ag and Cu electrodes 31,34
1iOffiAg Ag+ UPD on polycrystalline gold 26

EQCM, electrochemical quartz crystal microbalance; UPD, underpotential deposition.

of two main parts. The first one is that coming from the 1. Thin-Foil Method
solution phase or from the solution layer contacting the
In the case of the thin-foil method, the detector "sees"
electrode. The second radiation component is the
simultaneously both components ofthe radiation coming
radiation coming from the adsorption layer of interest
through a thin foil (metal or metal [gold] plated plastic
for the measurement of adsorption.
film) forming the bottom of the cell. The adsorbent is
The elaboration of a technique for the radiotracer
either the foil itselfor a thin deposited layer on the bottom
adsorption measurements is equal to the search of the
of the cell serving as a mechanical support and electric
optimal conditions for the minimalization of the role of
conductor (if the foil is metal plated).
the radiation coming from the solution background.
The situation can be visualized by reviewing Scheme 1.
The usual classification of the various methods follows
this pattern, i.e., how these requirements are fulfilled.
According to this principle, the methods can be divided
in two main groups: the radiation ofsolution background solution
is governed and minimized by self-absorption of the t:::==I==i==:::1 - adsorbed layer
radiation (thin foil method) and the background I. I.

~
radiation intensity is minimized by mechanical means
(thin gap method). The most important and widely used
representative of the first approach is the so-called foil
method. Schemel
480
B c
Figure 1 Representative of the cells characteristic for thin-
foil method. A, central compartment; B, auxiliary electrode;
C, reference electrode; D, main electrode, E, scintillation
counter. (From Ref. 5.)
The radiation measured is IT = Is + Ia (where Is and I a
are the intensities of the radiation coming from the sol-
ution phase and from the adsorbed layer, respectively).
Using isotopes emitting soft J1-radiation (radiations
characterized by high mass absorption coefficient, /l)
e 4 C, 35 S, and 36Cl), the self-absorption of the radiation
in the solution phase is so high that the thickness of the
solution layer effective in the measured solution back-
ground radiation is very low. (Similar phenomena could
be observed for isotopes emitting low energy x-ray).
Various technical versions of this method were
elaborated. For the details of the technical description,
we refer to the literature [3-7). A typical representative
ofthis type ofcells is shown in Fig. 1. These versions found
their applications mostly in the study of adsorption
phenomena on rough surfaces with high real surface area
using isotopes emitting J1-radiation.
It is an important question how to get surface concen-
tration data from radiation intensity measurements. The
procedure depends on the accuracy required. In the
review papers cited [4-10), a detailed information and
analysis can be found concerning these problems.
Honinyi
2. Thin-Layer or Gap Method
In cases where the radiation coming from the solution
background would be too high in comparison with that
originating from the adsorbed layer (smooth surfaces,
)i-radiation), some kind of mechanical means should be
applied to reduce the role of the background radiation.
The terms used for the denotation ofthese techniques
went through some changes during the last two decades
[see Refs. 2-7). In the following we try to use the terms
suggested recently.
The mechanical control of the background radiation
can be achieved by two different ways: fixed rigid
reduction of solution layer thickness (classic thin-layer
or gap method) and flexible mechanical or temporary
reduction of the thickness of the solution layer
(electrode-lowering technique). In the case of the first
version, specially designed cells are used [1,2) where only
a very thin solution layer flows between the electrode
and the detector as shown by Scheme 2.
This method is not used very often because it has sev-
eral drawbacks, for instance, complexity ofthe equipment
(a pump for solution circulation), the problem ofthe exact
knowledge of electrochemical parameters due to the
presence of a thin solution layer separating the auxiliary
and reference electrodes from the main electrode, etc.
All these problems are avoided by the application
of a flexible version, the so-called electrode-lowering
technique. In the case of this technique, the solution gap
between the electrode and detector is minimized tempor-
arily only for the time of the measurement of the
adsorption. The electrode is positioned in two positions
as shown by Scheme 3.
In the "lifted up" position, the attainment of the
adsorption and the electrochemical equilibrium (or
steady state) proceeds without any disturbance, and
the detector measures only the solution background
radiation. In the "pressed down" position, the intensity
measured comes from the species adsorbed on the elec-
trode surface and from the solution layer present in the
gap between the bottom of the cell and the electrode.
Detector
~ U ~IUtiOn
I I flow
electrode
Scheme 2
Radiotracer Studies 481

bottom of
the cell
gap

Electrode in lifted up Electrode pressed down to

position the bottom of the cell

Scheme 3

The thickness ofthis gap depends on the mechanical state

of the electrode surface, the stability of the bottom of the
cell, etc.
In the first version of this method, elaborated by
Kazarinov [37,38], the bottom ofthe cell was a plastic foil,
i.e., a mater ial with not too high mechanical stability.This
drawback was eliminated by Krauskopf et al. [39] using
a glass-scintillator embedded in a ceramic disc forming
the bottom of the cell. Because of this construction, the
gap thickness attained in the pressed down position of To pwr

the electrode could be about 1-2 x 10- 4 cm, i.e., one A

order of magnitude lower thickness is realized for the
fi-radiation of 14C than that determined by its self- @
absorption in the case of the foil method. The cell
elaborated by Wieckowski is shown in Fig. 2.
A detailed analysis of the calculation of surface con-
centrations from radiation intensities are available
[5-7,9]. Similar reduction of the gap thickness was
reported by Poskus and Agafonovas [27] by pressing the
plastic foil against the electrode.

B. Direct and Indirect Methods

As to the role of the labeled species in the radiotracer

study of adsorption phenomena, two different versions
of the method may be distinguished. The first one, pre-
sented above, is the direct method. In this case the species
to be studied is labeled and the radiation measured gives
direct information on the adsorption of this species.
However, this method cannot be used in several cases B
due to the technical restrictions connected with the very
nature of the radiotracer method. (Limitations in the
available concentration range; there is no possibility of Figure 2 Diagram of the cell elaborated by Krauskopf et al.
[39]. (A) Diagram of the electrode in the raised position for
distinguishing between the adsorption of the labeled
adsorption (left) and the "squeezed" position for adsorbate
compound studied and that ofa product formed from it; measurement (right). (B) Diagram oftheTeflon cell: 1, platinum
the number ofcommercially easily available labeled com- electrode; 2, glass scintillator; 3, Macor ceramic disc cell
pounds is restricted.) bottom; 4, Teflon O-ring; 5, flexible elbow (see insert); 6, cel1
Considering all these problems the use ofthe so-called ports (six); 7, light pipe; 8, stainless steel sphere; 9, concave
indirect radiotracer methods was suggested [11,40,41]. Teflon spacer; 10, platinum wire for electrical contact; 11, lock
Instead of labeling the species to be studied, another nut.
482 Horiinyi

A) Based on competitive adsorption

A~A

B.~
_
a
B.a
> Competition
~ A a + B·a

~
Indtcator species
~
How the adsorption of It changes
with parameters influencing the adsorption of A
B) Based on induced adsorption

A~ Aa 1
Conclusions

Adsorption of A induces the

adsorption of a labelled
species (B.)

Aa + B:01 ~ [A a B·J a
Scheme 4

adequately chosen labeled species (indicator species) is
added to the system and the adsorption of this com-
ponent is followed by the usual radiotracer measur-
ing technique. Evidently, the sorption of the indicator
species should be in relation with that of the species
to be studied. The nature of this link could be different
in different systems. For instance, in some cases the com-
petitive adsorption with the labeled species and in other
cases induced adsorption of the labeled species may fur-
nish information about the adsorption behavior ofa given
molecule. The principle of the study of those two cases is
reflected by reviewing Scheme 4.
C. Methods Based on the Study of Primary
and/or Secondary Radiation
Distinction should be made among the methods accord-
ing to the radiation measured: measurement of the pri-
mary radiation emitted by the radiation source used
(~ and y-radiation emitted by the isotope used for
labeling) and measurement of a secondary radiation
(backscattered p-radiation, x-radiation induced by p-
particles, electrons produced by y- and x-ray). Methods
based on the measurement ofprimary radiation were dis-
cussed in the previous sections. In the following, the role
ofsecondary radiations in the measurements is analyzed.
1. Secondary Effects Induced by p- -Radiation
The application of secondary effects induced by
p- -radiation in electrochemical systems was suggested
quite recently [42-45] due to the very fact that most of
the isotopes used for radiotracer adsorption studies are
p emitters. On the other hand, it is well known from the
literature that the interaction of p-radiation (its
absorption) with an absorbent is accompanied by two
processes: backscattering and the induction of
x-radiation involving the so-called Bremsstrahlung.
(aJ Coupled Radiochemical and Electrochemical
Method Based on p- Backscattering. The back-
scattering of p--radiation is a well-known and widely
studied phenomenon in the field of nuclear physics and
chemistry. p-Backscattering serves as a basis for various
analytical methods, and this phenomenon is often used
to measure the thickness ofthin layers formed on various
surfaces. In some cases, changes in layer composition
can be determined by measuring the intensity ofthe back-
scattered radiation.
Recently it was shown [42-44] that, under appropri-
ately chosen experimental conditions, p-backscattering
can be used to follow the electrochemical formation or
dissolution of thin metal layers in a cell developed for
radiotracer adsorption studies by thin-foil technique.
Two arrangements ofthe p- source can be considered:
internal and external. In the case of an internal source,
the electrode surface or a layer deposited on it is the
source of the p- -radiation and the backscattering by a
layer formed on this surface is measured. A schematic
representation ofthis arrangement is shown in Scheme 5.
In this case the measured radiation intensity consists
of the intensity / of the direct radiation and the intensity
h of the backscattered radiation:
h=/+h
Radiotracer Studies
~ ----+ deposited layer (scatterer)
~ ----+ radiation source (support)
~detector
SchemeS
In the case of an external source, the situation is quite
different, and there are several options depending on the
position of the source. For instance, two possible
arrangements of the f3 source could be as follows (see
Scheme 6).
In this case the measured radiation intensity consists
of the intensity JS of the radiation backscattered by the
support and the \ncrease /!"h in the intensity of back-
scattered radiation caused by the layer formed on the
support:
However, the role of direct radiation cannot be com-
pletely excluded, and thus a third term should appear in
this equation.
(b) Method Based on the Study of x-Radiation
-Bremsstrahlung-Induced by f3- -Particles. Funda-
mentally, two types of induced radiation should be dis-
tinguished: radiation with continuous energy spectrum
up to the Emax value of f3-radiation, the so-called
Bremsstrahlung, and Characteristic x-radiation with a
well-defined energy spectrum.
The method based on the fact that the value of absorp-
tion coefficient of the resultant x-radiation in materials
is significantly lower than that of the original f3--
radiation. Measuring the x-radiation, some problems
(The external source is indicated by b.)
Scheme 6
483
connected with certain in situ radiotracer methods (see,
for instance, the foil method), the necessity of the use of
very thin layers, can be eliminated [45].
With this method, some problems connected with the
study of species labeled with isotopes emitting very soft
f3- -radiation can be solved as well.
2. Role of Electrons Induced by y- (or x-) Radiation
In the case ofthe application oftracers (isotopes) emitting
simultaneously f3- and y-radiation, it is ofinterest to study
how the electrons induced by photons contribute to the
measurement of f3-radiation. It is a well-known fact
that during the energy loss of y-radiation in the surround-
ing matter, electrons are emitted. Thus in the case of
simultaneous emission of f3- and y-radiation, the meas-
urement of "pure" f3-radiation cannot be achieved
because the interference with electrons induced by y
(or/and x-) radiation cannot be avoided.
The role ofsecondary electrons in the radiation meas-
urement has been discussed in Refs. 46 and 47. In Ref 47,
the problems connected with the use 0 f 1251 Isotope
. r
lor
labeling [36] were analyzed, showing that the confusion
of secondary effects with the primary one could lead to
significant problems in the evaluation of experimental
data.
D. Role of the State of the Electrode Surface
1. Polycrystalline Surfaces
For a long period the adsorption phenomena have been
studied only at polycrystalline surfaces. Both smooth
and rough surfaces with high real surface area were con-
sidered, using preferably the electrode-lowering tech-
nique in the former and the foil method in the latter
cases. [4,5,37,38]. The method elaborated by Krauskopf
et al. [39] offers a very advantageous technique for
the study of polycrystalline smooth surfaces (and
well-defined surfaces; see later).
For a long period, platinized platinum electrode has
been in the foreground of the studies using an electrode
with high real surface area. During the last decade the
investigations were extended to other metals using
copperized [48-50], silverized [51,52], nickelized [53],
rhodized [18,19,54,55], and aurized [49,56] electrodes
with high real surface area (roughness factor values
above 20). This extension of adsorption studies involves
the elaboration of methods for the preparation of the
electrodes and measuring of the roughness factors.
2. Well-Defined Surfaces
The investigation of electrosorption phenomena at
morphologically uniform and ordered single-crystal,
i.e. well-defined, electrodes is a new development since
484
the end of the 1980s [5-7,39]. The version of elec-
trode-lowering technique elaborated by Wieckowski
and colleagues was created to this end [5-7, 39] in
conjunction with methods for manipulation, with
single-crystal surfaces and ordering ofdisordered crystal
faces. It is evident that the methods gives excellent results
for polycrystalline smooth electrodes as well.
3. Powdered Electrodes
In some cases, for instance, in the case of the study ofthe
sorption ofvarious ions onto the layer ofcorrosion prod-
ucts adhered to the surface of the corroding metals, a
special version of the foil method, the sprinkling of the
powdered metal on the bottom of the cell, could be a
useful technique [57]. A series of papers [57-60] were
published presenting results obtained with stainless steel
samples used as construction material in nuclear
reactors.
4. Polymer Film Electrodes
A great variety of methods has been used for the investi-
gation of polymer film electrodes and one of them is the
radiotracer method [61 ~ 74] that enables us to obtain in-
formation on the ionic charge transport in electroactive
polymer films labeling co- and/or counter ions and on
the formation and destruction of the films labeling the
monomers. The main problems were [67] embedding of
electrolytes during the formation of polymer films, study
of the motion of counter- and co-ions in the course
of electrochemical measurements, and study of the
exchange processes. For a more detailed discussion of
the problems mentioned above, we refer the reader to
Ref 75.
IV. ILLUSTRATIVE EXAMPLES FOR
APPLICATIONS
A. General Remarks
The radiochemical methods can be used to answer a great
variety ofquestions appearing in the course ofthe investi-
gation ofelectrochemical systems.
1. Questions Connected with the Dynamic Behavior
of the Adsorption
The radiotracer technique is extremely suitable to answer
questions connected with the presence or absence of a
given species on the electrode surface or to those con-
cerning the mobility or immobility of adsorbed species,
i.e., to make a distinction between reversible and irrevers-
ible adsorption. Thus, simple radiochemical experiments
playa very important role in answering fundamental
questions. Some examples are discussed briefly.
Horanyi
(a) Problem of Co-Adsorption or Induced
Adsorption. It is an important question whether the
electrosorption of species in a g~ven system is accom-
panied with the simultaneous adsorption of other mol-
ecules or not. Radiotracer method offers a unique
possibility of answering this question by labeling the
species considered as possible partners in co-adsorption.
The important, and today widely known, fact that the
underpotential deposition ofmetals is accompanied very
often by the co-adsorption (induced adsorption of
anions) was demonstrated first by the radiotracer tech-
nique labeling the anions [3].
(b) Reversibility ofthe Adsorption. The reversibility of
adsorption implies that the desorption of adsorbed
species takes place with a measurable rate. The rate of
the desorption can be easily estimated by the exchange
of adsorbed labeled species with nonlabeled ones added
to the solution phase or vice versa. In the case of
irreversibility of the adsorption, the absence of any
exchange clearly demonstrates the situation.
2. Determination of Simple Relationships
In the study of electrosorption processes, the main
relationships to be determined are potential and concen-
tration dependence of the adsorption and determination
of adsorption isotherms and the relationship between
the rate ofelectrode processes and the apparent coverage
of reacting species. In most cases radiotracer methods
furnish reliable direct data for the determination of
isotherms and adsorption vs. potential relationships.
In some cases the sensitivity of the method could be
very high depending on the specific activity of the iso-
topes used. It is important that for the calculation of
the adsorption values, no specific assumptions are
required and the separation of the signal coming from
the adsorbed layer from that coming from the solution
phase is relatively easy in comparison with other
techniques.
The radiotracer method determines directly the cover-
age vs. current or potential relationship under steady state
conditions (potentiostatic or galvanostatic) in the course
of electrode processes even in the absence of adsorption
equilibrium with respect to the reacting species, i.e.,
without the knowledge of the adsorption isotherms [3].
3. Study of Specific Interactions
The radiotracer technique offers a unique possibility of
demonstrating the occurrence of the specific adsorption
ofan ion by labeling it and studying its adsorption in the
presence of a great excess of other ions and electrolytes
(supporting electrolyte). For these studies, at least a differ-
ence ofone to two orders of magnitude in concentrations
--
Radiotracer Studies 485
1
should be considered. Under such conditions it is evident
that in the case of nonspecific adsorption due to the ....
coulombic interactions, no significant adsorption of the 'e
u
labeled species, present in low concentration, could be '0
e

1 observed. In contrast to this, the observation of a

measurable adsorption can be considered as a proof of 2
12 w
........

~
l.,

I
the occurrence of the specific adsorption. 8 "'l
"'~
For instance. ifin the presence ofl mol dm- 3 HCI0 4 '0
supporting electrolyte and 1x I0- 4 mol dm -335 S-labeled 4 ~

fl H 2S0 4 , a measurable increase in the count rate (that cor-

responds to the adsorption of the labeled species on the (a) -400 -200 o 200 400 600 E/mV
electrode) can be observed, and there could be no doubt
that a specific adsorption took place. Thus, the potential
and concentration dependence of this specific adsorp- .,
tion can be systematically measured; however. it should i=
be taken into consideration that these relationships 10

reflect the results of adsorption competition with other

species present in the system.
'x 5

'X.' >$, •• x',

B. Anion Adsorption "x.·x '
X.
The radiotracer studies of anion adsorption can be O+------<-"'-"-~--_--~--'--,--~----J

divided into two groups interrelated to each other: (b) 0 200 400 600
adsorption on "bare" or "clean" surfaces and adsorption E/mV

and sorption on modified surfaces by adatoms, organic

molecules. polymer films, etc. The most important
among the latter processes is the induced or co-
adsorption ofanions caused by the underpotential depo-
sition of metal adatoms on a foreign metal support. A
special and interesting representative of co-adsorption
is the co-adsorption ofanions and hydrogen on platinum
metal electrodes. The anion adsorption on poly-
crystalline (rough) and well-defined surfaces is discussed
separately.
1. Polycrystalline and Rough Surfaces
During the last 15 years as an extension ofthe work with Pt
(platinized and smooth) electrodes [11,12,36,76-80], the
potential (and partly the concentration) dependence of
the adsorption of Cl-, HS0 4 (SO~-), and in some cases
H2P04 ions was studied at Cu [48,49,81], Ag [51,52], Ni
[53], and Ru [82]. Rh [18,54,55,82-84] and Au [49,56] elec-
trodes (smooth and with high real surface area) were
studied in the presence of a great excess of HCl0 4
supporting electrolyte, i.e., the specific adsorption of
these ions.
The main general conclusions are as follows. First, the
potential dependence ofthe adsorption the rvs. E curves
has one or more inflexion points, thus the corresponding
dr/dE vs. E curves contain one or more peaks. Some
typical r vs. E and dr/dE vs. E relationships are shown
in Fig. 3. Second, potentials where the dissolution of the
Figure 3 (a) Potential dependence of the adsorption (r) of
CI- ions on copperized (1) and platinized electrodes (2) and
the corresponding.1r1 M-E curves (1' and 2') in I mol dm- 3
HCI04. (From Ref. 48.) (b) Potential dependence ofthe adsorp-
tion (r) ofCO~- (5xlO- 4 mol dm- 3 Na2C03 in 0.5 mol dm- 3
NaCI0 4, pH ;:;; 9) ions and the corresponding.1r/ M curve.
metals (Ag, Cu, Ni) and/or the formation of oxide layer
(Rh, Ru, Au) starts, the anion adsorption attains a high
level, i.e., the metal surface is covered by adsorbed anions
preceding the oxidation processes.
Enhancement ofthe adsorption oflabeled HS0 4, CI-,
and H2P04 induced by the formation of adatoms Cu,
Cd, and Ag adatoms on Au, Pt, and Rh electrodes was
studied extensively to get better insight in the overall pro-
cesses occurring in the course ofthe formation of adatom
layers [11,12]. The characteristic features of enhanced
anion adsorption induced by adatoms are shown in Fig.
4. Although the adsorption of Cl-, HS0 4, and H2P04
ions is a more or less reversible process depending on
the nature of the electrode studied, there are anion
adsorption processes that should be considered as strong
chemisorption. This type of behavior was found in the
case ofthe adsorption ofCN- ions on platinum and gold
electrodes [85] and for S2- and HS- ions on platinum [86]
and silver electrodes [52].
486 Horanyi

on adsorption ofHS0 4 (SO~-) ions obtained on Pt(lOO),

Pt(lll), Pt(llO) and Pt(poly) electrodes [9,10,87,88]
':"~ 0.75
~---'Z. clearly demonstrates that the adsorption of sulfate
-e anion on the Pt(hkl) electrodes is strongly surface
E \
"'\
t:: 0.5 ,-\
. structure specific. It follows from the analysis of the

\
-o_ _ o ~
<:>
,/
~ adsorption data that the extent of adsorption (r) vs.
,,'4
0.25
\ \ ,/
,,
, potential plot obtained for the polycrystalline platinum
electrode is a result of a cumulative adsorption of sulfate

(a)
,
-400
\ 400
~
r-a- ~ ~ T
800
T
1200 E/rril
on the single crystal facets lll, 100, and 110 of the poly-
crystalline surface; however, the contribution from
ordered 110 plane to the overall behavior is quite small.
1.5
A comparison of the adsorption of HS0 4 at ordered
Pt(lll), disordered Pt(lll), and polycrystalline platinum
is shown in Fig. 5. An excellent agreement was found for
":'e
the adsorption ofsulfate ions on Au(lll) between the data
'" l~-~ obtained by radiotracers and chronocoulometry [89].
~ "+~ //., Another interesting comparison was made between the
adsorption behaviorofHS04 ions on Pt(lll) and Rh(lll)
~//
!:
o
- 0.5 surfaces.
The extensive and comparative studies ofthe enhance-
.,p'-
ment of HS0 4 adsorption caused by the underpotential
oI 0 0
0
•
deposition of metal ions (Cd2+ Cu2+, Ag+) on PtOll)
i i
o i and polycrystalline Pt surfaces should be mentioned
200 400 600
(b) [80,90].
E/mV

Figure 4 (a) Effect of the underpotential deposition of Cd 2+ C. Cation Adsorption

(I), Cu2+ (2), and Ag+ (3) on the potential dependence of the
Disregarding the underpotential deposition of metal
adsorption of HS04' ions. Curve 4 (- - -) corresponds to the
potential dependence without any addition: CH,SO, = cations, relatively less attention was paid to the cation
4 X 10-4 mol dm- 3 , CMe = 8 X 10-4 mol dm- 3 . (From Ref. adsorption in direct radiotracer studies, at least during
56.) (b) Potential dependence ofthe adsorption oflabeled sulfate the last 10 years. However, radiotracer methods proved
species (c=2.5xlO- 4 mol dm- 3) in the presence of to be an ideal tool for the study of cation adsorption
I x 10- 1 mol dm- 3 HCI0 4 supporting electrolyte in the induced by the adsorption of some anions and organic
absence of Zn2+ ions (dotted line), in the presence of species [91]. The unexpected potential dependence of
5xlO-4 mol dm- 3 Zn 2 + ions (full line). the adsorption of labeled Ca 2+ ions on Pt and Au elec-
trodes in alkaline medium was explained by the assump-
tion that this behavior should be ascribed to the
More or less strongly adsorbed anions induce cation
electrosorption of OH- ions, i.e., the observed r vs. E
adsorption. This problem is discussed in connection with
relationship reflects that of OH- adsorption that induce
cation adsorption.
the cation adsorption
CN- ion was chosen as a model species for the study of
2. Well-Defined Surfaces the induced adsorption of labeled Ca2+ ions [85,92].
As mentioned previously, the field of radiochemistry of It was shown [85] that the strong chemisorption of
well-defined surfaces was opened by Wieckowski. Most CN- ions results in a significant increase of the Ca 2+
achievements on this field are connected with the investi- adsorption in alkaline medium, leading to a potential
gation of HS0 4 (SO~-) adsorption on various crystal dependence of 45Ca-labeled Ca2+ adsorption that is
faces of Pt, Rh, and Au and on the same surfaces after characteristic for the potential dependence ofthe adsorp-
underpotential deposition of adatoms (formation of an tion of CN- ions. This result confirms the assumption
ultrathin layer). that the unexpected potential dependence of alkaline
These works were reviewed during the last 2 years in earth metal ions (increasing adsorption with increasing
several publications [5-10]; thus, only some of them potential) in alkaline medium is a consequence of their
should be mentioned here. The comparison of the results induced adsorption via adsorbed OH- species.
Radiotracer Studies 487

.--------,------,------,-----r- D. Adsorption of Organic Species

(a)
In all adsorption studies, one ofthe most important ques-
tions pertaining to the treatment ofthe experimental data
is the existence of the adsorption equilibrium, i.e.,
whether it can be assumed that the adsorption process is
reversible or not. The mobility of labeled species
6
adsorbed on the surface of the electrode can be easily
detected by their exchange with nonlabeled molecules
added to the solution phase.
This type ofexperiment was carried out several times
with various organic species adsorbed on noble metal
N (b) (first of all platinum) electrodes, and it was found that
ORDERED
IE C HS0 4" =4x10- 4 M due to a very low mobility of adsorbed species, observed
very often, the assumption of adsorption equilibrium in
u 12
x most cases is very questionable. Considering this pro-
III
blem, the adsorption behavior of organic species was
c: divided into two categories according to the mobility of
o
.:.::::. their adsorbed molecules probed by the rate of exchange

-
I")

I
o.-
6 between labeled adsorbed and unlabeled dissolved
species [3,95].
The first group is characterized by significant mobility
x of the adsorbed molecules. It includes some saturated
L.
carboxylic acids (no formic acid), urea, etc. The second
group is characterized by the practical immobility of
(e) adsorbed species and it contains aromatic compounds,
unsaturated compounds, alcohols, acetone, methanol,
formaldehyde, formic acid, etc. [3]. Figure 6 reflects the
ORDERED
significant difference in the adsorption behavior of the
6 unsaturated maleic acid and the saturated succinic acid.
Despite the evidence calling attention to a very cautious

-0.2 0.0 0.2

POTENTIAL/V (Agi Agel)
0.4 0.6
3 I~X-X-X~ ___

j/
Figure 5 Potential dependence of bisulfate adsorption on
ordered Pt(lll), disordered Pt(lll), and polycrystalline plati-
num at three bulk concentrations of (bi)sulfate. (From Ref. 87.)

The results ofexperiments carried out in acid medium

in the presence ofCI-, H2P04' and HS0 4 (SO~-) anions
studying the adsorption of 45Ca-Iabeled Ca2+ ions con-
firmed the assumption that cation adsorption induced o+---r=:==------r--~---.--~--.--~--
by the specific adsorption of anions is a general feature o 200 400 600
[93]. E/mV
Another interesting feature is the enhancement of the
sorption oflabeled Ca2+ ions by -S03H and -COOH Figure 6 Potential dependence of the adsorption of labeled
groups anchored to the surface of a platinum electrode maleic (I) and succinic (2) acids at c = 10- 4 mol dm- 3 concen-
via strongly chemisorbed organic species [94]. tration of the labeled species in I mol dm- 3 HCI0 4 solution.
488
treatment of adsorption data in terms of adsorption
isotherms, there are attempts in the literature to do so
without any distinction. A recent very interesting con-
frontation ofviews in the literature [96,97] enlightens this
situation very clearly concerning the equilibrium treat-
ment of the adsorption of some organic species. To avoid
ambiguities, it is a fundamental task, before treating the
adsorption phenomena in terms ofequilibrium, to study
the mobility of the adsorbed species to furnish reliable
information concerning the reversibility (or irreversi-
bility) of the adsorption. The radiotracer technique,
as mentioned, offers the simplest way to fulfill this
requirement, and the results of such studies should be
taken into consideration in the case of any effort aiming
at the interpretation of the apparent concentration and
potential dependence of adsorption.
The investigation of the electrosorption and
electrooxidation of CH 30H and the possible
intermediates of its oxidation, HCHO, HCOOH, and
CO, have been a central task for fuel cell-oriented
electrocatalytic research for several decades. The field
was reviewed several times during the last years [98,99]
involving the results of the relevant radiotracer studies.
In the second half of the 1980s and in the 1990s,
spectroscopic methods came into the foreground of these
studies, and thus today investigations based on the appli-
cation of radiotracer techniques are very sporadic [100]
in comparison with the previous years. As a new
development, the studies on the adsorption ofurea should
be mentioned. Wieckowski and colleagues reported
a complete experimental and theoretical description
of urea adsorption on Pt(lOO) using voltammetry,
radiochemistry, low-energy electron diffraction, and
quantitative Auger-electron spectroscopy [101,102].
The radiotracer study of the adsorption behavior of
saturated aliphatic mono- and dicarboxylic acids at plati-
num electrodes has been the subject of several studies
[3-5]. Adsorption of acetic acid, being a representative
ofthe reversible adsorption oforganic species, remained
in the focus ofinterest during the last years. An exhaustive
analysis of the structural aspects of the adsorption of
acetic acid was given by Corrigan et al. [103]. In this
analysis, it was shown how the direct quantitative
radiochemical information on adsorbate concentration
can be used in conjunction with data obtained from
infrared spectroscopy to provide an exhausted surface
analysis of adsorbate in the solid-liquid interface. On
one hand, the radiotracer measurements provide a valu-
able check on the interpretation of the spectral data; on
the other, the spectral information reveals the nature of
the surface coordination and orientation of the adsorbed
species.
Honinyi
A survey on the results obtained from a radiotracer
study of the adsorption ofaliphatic primary amino com-
pounds at platinum electrodes can be found in a recent
review [104]. The investigation of the adsorption of aro-
matic compounds on noble metal electrodes was one of
the earliest studies carried out by radiotracer techniques
in the 1960s [3-5]. Adsorption of benzene, benzene
sulphonic acid, phenol, benzoic acid, and other
derivatives on platinum was studied during the last
decades [3-5]. Such studies are continuing using, for
instance, benzoic acid as a model compound.
Adsorption of 14C-labeled benzoic acid on a poly-
crystalline gold and copper electrodes was studied by
Zelenay and colleagues [105,106]. It was found that a
strong adsorption occurs in a wide potential range;
however, the exchange of adsorbed labeled molecules
with nonlabeled species added to the solution phase
attests the occurrence of dynamic equilibrium between
the adsorbed and solution species. On the basis of
adsorption data and model calculations, conclusions
were drawn concerning the orientation of the molecules
in the adsorbed state.
V. RADIOTRACER STUDY OF THE BEHAVIOR
OF POLYMER FILM ELECTRODES
Thevarious applications ofradiotracer techniques for the
study of the behavior of some polymer film electrodes
are summarized [67,75]. Results obtained from the study
of the sorption of labeled co- and/or counter-ions
in the course of the redox transformations of poly/
vinyl ferrocene, tetracyanoquinodimethane polyester,
polypyrrole, and polyaniline (PANI) films are reported.
Similar studies with poly(o-phenylenediamine (PPD)
films were carried out recently [17,107]. For instance, in
the latter case, the sorption of H2POi, HSOi, and CI-
ions in PPD film was studied and compared by the radio-
tracer technique using 35S, 32p, and 36Cl isotopes for
labeling. It was found that the anion sorption in both
oxidized and reduced films depends on pH, i.e., on the
protonation of the film; however, the protonation and
anion sorption is not an essential condition for the occur-
rence of the redox process.
Results furnished by differential volt-radiometric
measurements advocate in the favor of the assumption
that the reduction of film results in the formation of three
or four types ofcenter with different behavior with respect
to the protonation and anion sorption. It was demon-
strated that PPD films are very selective for the sorption
of HSOi (SO~-) ions in the presence of a great excess of
other anions.
Radiotracer Studies
An interesting example is when the formation and the
state ofthe film is studied labeling the monomer forming
the film. This procedure was followed in the case ofPANI
films using J4C-Iabeled aniline for the preparation
(electrochemical polymerization) of the film.
By labeling the monomer the following information
can be obtained: correlation between the amount of
monomer involved in the film and the charge involved in
the corresponding redox transformations; the charge
involved in the formation of the film; and changes in the
stability of the film, the possible overoxidation and
decomposition of the film.
VI. CORROSION PROCESSES
Today, radiochemical methods are widely applied in
corrosion-oriented research aiming at the clarification
of the role of the adsorption of various ions (HS0 4,
Cl-, S20~- etc.) in the corrosion processes
[16,29,57-60,108-113]. Various stainless steels, being
important constructional materials, are in the center of
the interest. The time, potential, and concentration
dependence of the accumulation of labeled adsorbing
species (for instance, anions) in the surface layer are gen-
erally studied. In most cases no simple adsorption, but
sorption, in a layer is observed. As in corroding systems,
the state of the surface could change during the radio-
tracer measurement; this fact should be taken into con-
sideration when interpreting the experimental results.
Only some illustrative examples can be mentioned
here. The dissolution behavior and the time, potential,
and concentration dependence of HS0 4/SO~- and CI-
accumulations measured by an in situ radiotracer
method on surface oxide layers of duplex stainless steels
containing various amounts of ruthenium as an additive
are presented and discussed [112]. In a series of papers
by Kolics et al. [113,114], coupled radiochemical,
electrochemical, and ultrahigh vacuum techniques were
applied for study of chloride and sulfate accumulation
on pure aluminum and Al 2024 alloy surfaces during
anodic and cathodic polarization under different pH
conditions in 0.1 M NaCI0 4. A comparative study [114]
of chloride accumulation on stainless steel, aluminum,
and gold electrodes was carried out. The data were dis-
cussed in terms ofthe role ofoxide chemistry and anionic
adsorption properties.
VII. SUMMARY
The application of radiotracer methods to the study of
adsorption processes occurring at the solution-
electrode interface is surveyed. The main trends in the
489
research and the various verSlOns of the experi-
mental technique are schematically presented. It is
demonstrated that the radiochemical methods can be
used to answer a great variety of questions appearing in
the course ofthe investigation ofelectrochemical systems.
ACKNOWLEDGMENT
Financial support from Hungarian Science Foundation
(GrantsTl4446 and 023056) is acknowledged.
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28
Structure and Reactivity of Rhodium and Rhodium-Based
Alloys
Ken-ichi Tanaka
Saitama Institute of Technology, Saitama, Japan
Akira Sasahara
The Kanagawa Academy ofScience and Technology Foundation, Kawasaki, Japan
ABSTRACT
Recent developments in electrochemistry of Rh(lll),
Rh(lDD), and Rh(llD) electrodes are reviewed, where the
characteristics of the cyclic voltammogram of these
surfaces in acidic solutions are discussed in relation to
the adsorption of anions depending on the electrode
potentials. Characteristic cyclic voltammogram is a good
monitor of Rh on the bimetallic surfaces, which is a
highly sensitive tool to detect the compositional change
of bimetallic surfaces. The role of Rh for the prominent
catalytic activity of Pt-Rh bimetallic catalyst for the
reaction of NO + H 2 is discussed by diagnosing the
bimetallic catalyst surfaces before and after the catalysis.
I. INTRODUCTION
SinceWill [1] represented the characteristic potential cur-
rent curves for the pte100), Pt(lIO), and Pt(lll) electrodes
in 1965, electrochemical studies of noble metal
single-crystal electrodes started.
After that, one important development was given
by Clavilier et al. [2], who showed a simple method to
get a Pt single-crystal electrode in the atmospheric
circumstances. That is, a single-crystal bead that is
formed at the end of a polycrystalline wire by melting
in hydrogen-oxygen flame is quenched in superpure
water. Development of this flame-melting method has
explosively promoted the electrochemical experiments
493
using single-crystal surfaces. To prevent the contami-
nation from the air during sample transfer from the
superpure water vessel into a cell for the electrochemical
experiment, the electrode surface was covered with
a droplet of superpure water. The low-index Pt
single-crystal surfaces obtained by this method give the
characteristic voltammograms reflecting the adsorption
and desorption of hydrogen at the potential below the
double-layer region [2-7].
On the other hand, electrochemical studies by using
single-crystal surface prepared in an ultrahigh vacuum
(DRV) chamber were started at the end of 1970s. In this
procedure, a liquid cell for the electrochemical exper-
iment is directly connected to the URV chamber
(EC-DRV) [3,8,9] so that the electrode surface can be
characterized before and after the electrochemical exper-
iments in the URV chamber by low-energy electron
diffraction (LEED), Auger-electron spectroscopy (AES),
and x-ray photoelectron spectroscopy (XPS). One advan-
tage of the DRV-electrochemical experiment is to pre-
vent the electrode surface from the contamination in the
sample transference and during the electrochemical
experiments. By this method, the electrochemical exper-
iments are now possible on any single-crystal metal sur-
face that can be handled in the DRV chamber.
Compared with the Pt single-crystal surfaces, only a
limited number of electrochemical experiments have
been reported for the low index Rh single-crystal
494 Tanaka and Sasahara

ution and a typical voltammogram (dashed line) for a

CO stripped Rh(lll) surface measured in 0.1 M NaCI0 4
solution [16]. The validity of this iodine coating method

I50~
was verified by coincidence of the voltammogram with
that obtained in the EC-UHV experiment [17]. As
described later, the scanning tunneling microscopy
(STM) image (see Fig. 7) of the CO stripped Rh(lll) sur-
face proves the formation ofa (I xl) Rh(lll) surface in
a 0.5-M NaCl0 4 solution. Clavilier et al. [18] also studied
an Rh(lll) electrode prepared by his bead method, but
the STM image of this Rh( Ill) electrode surface showed
a(2 x 2) periodicity, which is similar to thep(2 x 2) struc-
ture of oxygen-covered Rh(lll) observed in the UHV
chamber. It should be pointed outthatthe R h(lll) surface

0 /~,
~
/ '
;-~

' \ '\
_' ....
. .,.., .-.,.. ..... --- ... -~ .........".. .. _.... '
1_
~ ,
,''''-
'~ ~
\I ,I V method for the Rh single-crystal electrode experiments.
I ,
,
, I
I curve for the adsorption and desorption of hydrogen [19],
I I
I :
, I
H ions adsorb on Rh(lll) and Rh(lOO) [21,22] electrode
V surfaces, which is in contrast to very weak adsorption of
-0.2 o 0.2 0.4
EN vs seE
Figure 1 Cyclic voltammogram for ordered Rh( Ill) crystal in
0.1 M HCI0 4 at 50 mV S-I. Solid trace, electrooxidation of
irreversibly adsorbed CO, preadsorbed at -0.25 V (SCE).
Dashed trace, a typical voltammogram of CO removed surface
after 10 cycles between -0.25 and +0.55 V. (From Ref. 16.).
surfaces. One reason is the difficulty for getting clean Rh
single-crystal electrode by Clavilier's flame method,
because Rh is oxidized in the sample transportation. In
regard to this difficult problem of Rh electrode, signifi-
cant progress has been made on an Rh(lll) single-crystal
electrode by Wieckowski and colleagues [10-13]. In
their experiments, the Rh(lll) electrode prepared by
Clavilier's flame method was coated with iodine to pre-
vent the oxidation of the Rh surface [11-16]. The iodine
adsorbed on Rh single crystal is readily replaced with
adsorbed CO molecules in the electrolyte solution by
bubbling CO and then a clean Rh(lll) surface is obtained
by removing the adsorbed CO molecules by a potential
sweep. Figure I shows a voltammogram (50 mYls) for
the electrochemical oxidation of irreversibly adsorbed
CO on an Rh(lll) electrode surface in 0.1 M HCI0 4 sol-
exposed to water vapor in a UHV chamber also gives a
p(2 x 2) LEED pattern at room temperature. Taking
these facts into account, we can confidently conclude that
clean Rh(lll) surface is obtainable by cyclic potential
sweep in solution [17] and that one can use the flame-bead
Rh(111) electrode gives an asymmetric voltammogram
which is quite different from that of Pt(lll) electrode. It
has been shown that not only SO~- ions [20] but also CIO;
ClO; ions on the Pt electrode surface [23]. Therefore, the
electrochemical reactions on the Rh electrode are influ-
enced by the anions in the solution.
In this chapter, recent electrochemical studies of Rh
single-crystal electrodes and of PtiRh bimetallic
surfaces prepared on Pt or Rh single-crystal surfaces
are reviewed. By comparing the voltammogram of the
low index single-crystal electrodes ofPt and Rh with that
of PtiRh bimetallic electrodes, we can diagnose the
PtiRh bimetallic and Pt-Rh-alloy electrode surfaces.
Pt-Rh bimetallic catalyst is well known as one ofthe most
important catalyst for the environmental protection that
has been developed for cleaning the automotive exhaust
gas. A small amountofRh metal is indispensable for this
prominent catalyst, but the roles of Rh atoms are not
clear. To gain an insight into the structure and the compo-
sition ofactive Pt-Rh bimetallic catalyst, electrochemical
diagnosis of the active PtiRh bimetallic surfaces is quite
an interesting subject. It is well known that the cyclic
voltammogram is sensitive to the structure and compo-
sition ofthe electrode surface. Therefore, electrochemical
diagnosis of the catalyst surface is an interesting tool to
know the compositional and/or the structural change of
the catalyst surface. From this point ofview, the cyclic vol-
tammetry of the PtiRh bimetallic surfaces used as the
catalyst for NO reduction reaction was studied.
Rhodium and Rhodium-Based Alloys 495

II. EXPERIMENTAL PROCEDURE

Electrochemistry on single-crystal surfaces has evolved

high - pressure cell
with two important technical developments; one is a con-
ventional method for the preparation of single-crystal
metal electrodes from a polycrystalline wire by flame
melting and the other is the combination with surface
science (EC-UHV), especially the development of the
electrochemical STM system (EC-STM). Based on these
developments, insight is gained of the electrochemical
processes in atomic level detail. In this review, application
of an EC-UHV system to Rh and Pt single-crystal
electrodes, as well as to the PtiRh bimetallic surfaces, will
be shown, where the bimetallic surfaces were prepared
electrochemical glass cell
by electrochemical deposition of Pt on Rh single-crystal
surface, and vice versa. The electrochemical diagnosis ,
ofthe bimetallic catalyst surfaces was also carried out in high pressure cell ---:----
, UHV chamber
the EC-UHV system.
Figure 2 shows the EC-UHV system used in these ring - shaped Teflon gasket _
experiments, which is composed of a main UHV
chamber equipped with LEED, XPS, and a small volume
high pressure cell. Described briefly here is the procedure
of the electrochemical experiment performed by this
EC-UHV system. Electrochemical experiments and the
catalytic reaction are carried out in the high pressure cell
conic· shaped sample holder
that is directly attached to the main chamber through a
gate valve. When catalytic reaction or electrochemical
experiment is performed in the high pressure cell, the
conic shape sample holder head is pressed to the Teflon
gasket at the gate ofthe high-pressure cell to make airtight potentio I galvanostat
contact. By this method, the UHV chamber is perfectly
reference electrode
separated from the high pressure cell. A clean surface
was prepared by repeated sputtering with Ar+ ion and Figure 2 An EC-UHV system combined a UHV chamber
annealing at rather high temperatures in the high pressure with a high pressure cell, and conical shaped sample holder
head separating the UHV chamber from the electrochemical
cell. The sputtered Pt and Rh surfaces were annealed at
system.
1300 and 1000 K, respectively. The sample surface can
be characterized in the UHV chamber by XPS and
LEED. Electrochemical studies ofsingle-crystal surfaces attained. When the electrochemical deposition is
are performed in the small high pressure cell filled with accomplished, HSOi and ofCI- ions on the Rh disk elec-
one atmospheric pressure ofhighly pure Ar gas. The cata- trode are washed by replacing the solution with pure
lytic reaction is performed in the high pressure cell by water [3]. The water vapor in the high pressure cell was
raising the temperature in a flow of a mixture of reactant trapped by cooling with liquid nitrogen and then the
gases. sample disk was pulled back to the UHV chamber for
A quartz cell filled with a solution of 0.05 M analysis by LEED and XPS. It was confirmed that the
H2S04+3.0 x 10- 5 M PtCI~- (in the case of Rh depo- sample surface washed with ultrapure water in highly
sition on Pt surface, H2S04 + 5.0 X 10- 5 M RhCI 3) is pure Ar gas was free from the contamination of electro-
lifted up in one atmospheric pressure of Ar, and one side lytes by XPS. The thickness of the deposited metal over-
of the Rh single-crystal disk makes a meniscus contact layer was evaluated by measuring the intensity ratio of
with the solution [24]. After the meniscus contact of the XPS peaks for Rh 3d / 5/ 2 and Pt4f/7/2 [25].
crystal surface, a cyclic potential sweep is applied to the Catalytic activity ofthe bimetallic surface prepared by
sample while monitoring the voltammogram (50 mYls). the electrochemical deposition was studied in the high
By this procedure, a controlled deposition of Pt is pressure cell. The single-crystal disk was heated in a flow
496 Tanaka and Sasahara

ofamixtureof5.8 x 10-9 Torr of NO and 1.6 X 10-8 Torr reversibility of the corresponding oxidation and
of H 2 by raising the temperature by a rate of I K/s, and reduction reactions. The butterfly peaks at ca. 0.42 V
the partial pressure of N2 formed by catalytic reaction (in Fig. 3 the peak is at ca. 0.4 but the value of 0.42 V
ofNO + H 2 ---+ N 2 + H 20 is monitored by a quadrupole is used in Ref. 17) reflect the formation and reduction
mass analyzer. of adsorbed oxygen or oxidized layer on the Rh surface.
An interesting fact is that the first run of the cyclic
voltammogram (dotted line) is quite different from the
III. Rh(111) SURFACE stationary voltammogram (solid line) obtained after
As mentioned in the Introduction, one interesting several cycles. The difference in current of these two
characteristic of Rh electrode is the adsorption of anions voltammograms was 280 /lC cm- 2 in a potential range
because this adsorption on Rh surface is stronger than between -0.2 and -0.1 V This value corresponds to
that on Pt electrode. Hourani et a1. [17] studied by using one-electron reduction reaction of one monolayer or
the EC-UHV system the adsorption of HSO; and CIO; two-electron reduction reaction of one-half monolayer
anions on Rh(lll) surface. An Rh(lll) electrode surface of the oxygen or the hydroxide species formed on the
characterized by ex situ LEED was applied to a cyclic surface by adsorption of water. In fact, when a clean
voltammetry in a O.1-M HCI0 4 solution, and a Rh(lll) electrode was exposed to Ar gas-containing
voltammogram such as shown in Fig. 3 was obtained. It water vapor, the LEED pattern changed from the
was proved that the steady-state voltammogram became p(1 x I) to the p(2 x 2) pattern. This LEED pattern
almost equal to that shown in Fig. 1. change does not mean the reconstruction of the Rh(lll)
The current for the adsorption and desorption of surface, because the intensity of the integral LEED
hydrogen on the Rh(lll) electrode shows no symmetric spots changes little and no noticeable increase occurs
voltammogram curves, which indicates rather poor on the background scattering after exposing the surface
to water vapor. Based on these facts, it is deduced that
a clean p(l x I) Rh(lll) electrode surface can be pre-
-0.2 0.0 0.2 0.4 pared by repeating cyclic potential sweep in a O.1-M
HCI0 4 solution.
It was also shown that the Rh(lll) electrode surface
emersed from a HCI0 4 solution at 0.44 V reversible
w hydrogen electrode, (RHE) increased the AES signal
~ of oxygen. Therefore, the symmetric butterfly peaks at
W a potential of 0.42 V are attributable to the formation
~
~ of oxygen or hydroxide species from H20 molecules
~ 01 f • ; and their reduction on the Rh(lll) electrode [17]. Wan
~ et a1. [26] studied the Rh(lll) electrode surface in the
o butterfly potential range by using the STM. They
~ observed a hexagonal STM image in a O.l-M HCI04
~ solution that was independent of the tunneling current
Z from 10 to 50 nA, but no structure as for p(2 x 2) oxy-
W
~ gen adsorption [17] was observed. They explained that
~
~
o
}OOi1A the discrepancy between the p(2 x 2) LEED pattern
and the (l x I) STM image might be caused by a dis-
turbance induced by the STM tip.
Tounderstand the cyclic voltammogram as the chemi-
cal reaction taking place at the solution-electrode inter-
-0.2 0.0 0.2 0.4 face, it is indispensable to make clear the adsorption of
anions and/or cations on the electrode. So far, H 2S0 4 is
POTENTIAL, VOLT vs Ag/AgCI commonly used as a suitable electrolyte because of its
Figure 3 Cyclic voltammograms ofRh(lll) in a 0.1-M HC104 high purity and high stability, but HClO; ion undergoes
solution. The first scan starts along the dotted line from the rest decomposition, forming chloride anion. Therefore,
potential. The second cycle is represented by a dashed line, and adsorption of HSO; or SO~- anions on the electrode is
the steady-state voltammogram is shown as the solid line. Poten- especially important to understand the electrode pro-
tial scan rate, 50 mV S-I. (From Ref. 17.) cesses in H 2S04 solution.
Rhodium and Rhodium-Based Alloys 497

(A) (B)
(a)
o
o

...
c:
(])
~
~
:::J
(b) ...
c:
(])
(b)

0 ~
~
0
80

I 100 f.IA

-0.2 0.0 0.2 0.4 0.6

Potential N (Ag/AgCI)
-0.2 0.0 0.2 0.4 0.6
Potential N (Ag/AgCI)
Figure 4 Cyclic voltammetry of (a) Pt(lll) and (b) Rh(lll). (A) in 0.1 M HCI04 and (B) in 0.1 M HCI0 4 + I mM H 2 S0 4 solution.
Potential scan rate, 50 mV S-I. (From Ref. 19.)

The voltammograms ofPt(Ill) and Rh( Ill) electrodes
in O.1-M HCI0 4 solution are dramatically influenced by
adding 1 mM of H 2 S0 4 as shown in Fig. 4. By using a
radiochemical assay technique, Zelenay and Wieckowski
[19] showed that bisulfate (HSO;j) ions are adsorbed
on the Pt(lll) electrode at 0 V (Ag/AgCl). In their
experiment, the electrode surface was tightly contacted
with the scintillation counter to minimize the count of
the radioactive species from the bulk solution. When the
contact gap between the sample electrode and the
scintillation counter becomes 1~2 !tm, the radioactive
species adsorbed on the electrode surface are sensitively
detected by the scintillation counter. By this method, it
was shown that no adsorption of bisulfate ions occurs
on the Rh(lll) electrode surface below -0.2 V (Ag/AgCl)
but that the maximum adsorption of bisulfate (HSOi)
ions is attained in a narrow potential range at higher than
-0.2 V From this experiment, it was concluded that the
Rh(lll) electrode is perfectly covered with bisulfate ions
at about -0.16 V (Ag/AgCl) in a H 2 S04 solution. When
an Rh(lll) electrode keeps at a potential of 0.30 V
(Ag/AgCl) in a solution oflO- 3 M oflabeled H 2S0 4 and
10- 1 M of unlabeled H 2S0 4, the counting rate of radio-
active HSOi anions adsorbed on the Rh(lll) surface
gradually decreased with time. From these results,
Zelenay and Wieckowski concluded that the adsorbed
498 Tanaka and Sasahara

bisulfate anions on Rh(l11) undergo rapid exchange with ,

~'V
the anionic precursors in solution at 0.3 V The threshold
potential for the adsorption of HS0 4 anion was studied
on polycrystalline Au, Rh, Pt and Pt(l11), and Rh(l11)
electrode surfaces in a solution of 0.1 M HCl04 + 5
0.1 mM H 2S0 4, and it was shown that the threshold
potential for the adsorption of HS0 4 relate to neither
the zero charge potential nor the work function of the 4
electrode. More recently, Sung et al. [27] showed that a
Rh(lll) surface emersed from a clean H2S04 solution to
UHV gives a stable LEED pattern of (y"3 x y"3)R30° 3
attributable to 0.33 monolayer (ML) adsorption ofHS0 4 E
ion confirmed by a quantitative analysis of the AES -E
spectrum, and the coverage ofHS0 4 is retained between 2 >-
-0.10 and +0.50 V (Ag/AgCI). Surprisingly, a Rh(lll)
surface emersed from a mixed solution of 0.1 M per-
chloric acid and 3 or 5 mM H 2S04 adsorbed 0.24 ML 1
of HS0 4 ion, which was apparently lower than 0.32 ML
adsorption when perchloric acid was absent. Based on
these results, they concluded that the adsorption of per- 0
chlorate ions on Rh(lll) surface is strong enough to com- I I I I
pete with bisulfate ions, and they cited that this fact is 5 4 3 2 1 0
consistent with the in situ radioactivity in the (a) X/nm
radiochemical experiment, although the shape of cyclic
voltammograms are quite similar in the two solutions.
It should be pointed out that the in situ STM image of

~
Rh(l11) surface observed by Wan et al. [20] in 0.5 M
H2S04 solution did not give the (y"3 x y"3)R30° struc-
ture as expected from the LEED pattern of the emersed
Rh(l11) surface from a 50-mM H 2S04 at 0.33 V but was
a (y"3 x y"7) structure shown in Fig. 5. The (y"3 x y"7)
structure is composed of the two rows rotating a 30 ± 2°
to the substrate Rh lattice. Both the bright and the dark
spots have a distance of a y"3aRh lattice constant. This
(y"3 x y"7) structure is very similar to the (y"3 x y"7)
structure observed on Au(lll) surface in H 2S04 solution
o~· ee:
by Magnussen et al. [28J and Edens et al. [29]. (b) Rh SOiorHSO.j
In the case of (y"3 x y"7) structure on the Au(l11)
surface, adsorption of HS0 4 ion was evaluated to be Figure 5 (a)STM topviewof5 x5 nm 2 areaofsulfateadlayer
0.20 ML by Shi et al. [30]. Therefore, Edens et al. [29] on Rh(lll) at 0.5 V. Tunneling current 20 nA. Scanning rate
81.4 Hz (the constant-height mode). (b) Illustrative adlayer
proposed a composite adlayer composed of bisulfate
structure on Rh(lll) surface. Coadsorption of sulfate and
anions and hydronium cations for the (y"3 x y"7)Au(111)
hydrogen-bonded water chains, and side view of the
surface. It is quite interesting that the position ofthe dark hydrogen-bonded water chain along the )3 direction. (From
spots with respect to the bright spots in the STM image Ref. 20.)
shown in Fig. 5 moves depending on the tunneling
current, bias voltage, and the data acquisition mode,
where the STM image was obtained in a potential range three-fold hollow sites give the bright spots and the
between 0.15 and 0.675 V (RHE). Taking account of the hydrogen bonded water molecules correspond to the dark
(y"3 x y"7) adlayer on Au(1ll) surface and the character- spots, respectively. In this model, the water molecules in
istics (y"3 x y"7) structure of Rh(l11) surface, Wan et al. the first layer are directly bonded with Rh atoms via the
proposed a structural model for the (y"3 x y"7) Rh(l11) oxygen lone pair and the water molecules in the second
surface, where the bisulfate anions positioned at the layer make a network structure with the water molecules
Rhodium and Rhodium-Based Alloys 499

in the first layer via the hydrogen bond. The characteristic ~2044

change ofthe dark spot ofthe STM images with tunneling

current and/or bias voltage in the constant current or EN
0.39
constant height mode was explained by this rather flexible
network structure of H 20 molecules containing 0.2 ML
of bisulfate anions.
On the other hand, Thomas et al. [31] applied quanti-
0.32
I1X10
·3
a.v.

tative Auger analysis and deduced a maximum coverage 0.25

for (bi)sulfate anion to be 1/3 monolayer on Rh(lll) and
0.18
Pt(lll), and 1/5 monolayer on Au(lll). The ex situ LEED
ofthe Rh(lll) surface with adsorbed bisulfate anions gave 0.11
a (,J3 x ,J3)R30° pattern, which is in agreement with
1/3 monolayer of bisulfate anions.
Core-level electron energy loss spectroscopy of the
S2p electron was measured by taking out the Pt(lll)
and Rh(lll) electrodes from the solution at 0.44 and
0.12 V (Ag/AgCl), respectively. By using a mono-
chromatic primary electron beam, the energy loss of
the incident electron by the excitation of the core level
electrons of the target atoms above the Fermi level
was measured. It was found that the energy loss by
the excitation of S2p electrons of absorbed HSOi
anion on the Pt(lll) and Rh(lll) electrodes was lower
than that measured for a Na 2S04 thin film reported
in the reference. This fact suggests that the sulfur atom
of adsorbed HSOi anion on Pt and Rh electrodes has
higher electron density compared with that of Na2S04
film. From this fact, Thomas et al. deduced that the
2100 2000 1900 1800
adsorbed HSOi anion takes large back donation of
lI/em-'
electrons from Pt and Rh electrodes.
Figure 6 Infrared absorbance spectra in the 1750- to
This result is consistent with that of Zelenay and
2l50-cm- 1 region for adsorbed CO or Rh(lll) in CO-saturated
Wieckowski [19], in which they deduced a chemical
0.1 M NaC104, obtained during potential sweep at 1 mV S-1
interaction of HSOi with the Rh electrode. If the from -0.4 V (SCE). (From Ref. 16.)
adsorption ofHSOi anion is caused by a chemical inter-
action with the electrode surface, the adsorption of
anions, either HSOi or SOi 2, should depend on the shape of the cyclic voltammogram on Rh single-crystal
chemical interaction with the surface. In fact, SO~­ electrodes compared with the symmetric voltammogram
anion is predominant on the Au(lll) electrode surface, on Pt electrodes.
but HSOi anion is the main anion adsorbed on the One important electrochemistry study on the Rh(lll)
Pt(lll) and Rh(lll) surfaces. The electronic configur- electrode surface was performed by Yau et al. [16]. They
ation of Pt, Rh, and Au atoms is expressed by 5d9 6s l , measured irreversibly adsorbed CO on Rh(lll) by infra-
4d 8s l , and 5d IOsl, respectively. The interaction ofHSOi red reflection absorption spectroscopy (lRAS) in a
or SOi 2 anions with the d-band holes of Pt and Rh CO-saturated O.l-M NaCl0 4 solution and found a
surfaces might be an origin of chemical interaction of remarkable potential dependent shift for the CO stretch-
sulfate or bisulfate anions with the Pt(lll) and Rh(lll) ing frequency in a potential range from -0.4 to 0.39 V
surfaces and they are stabilized by interacting with water saturated calomel electrode (SCE) as shown in Fig. 6.This
molecules. phenomenon has been explained by altering of the ad-
The adsorption of HSOi anions on Rh(lll) surface sorption sites for CO molecules with electrode potential.
deduced by the ex situ LEED and the EC-STM is still a At potentials lower than -0.23 V (SCE), a strong absorp-
controversial problem, but we could say that the interac- tion band and a relatively weak band appeared at
tion ofHSOi anion with the Rh electrode is stronger than 1885-1900 cm- l and at 2010--2020 cm- l , respectively.
that with the Pt electrode as evidenced by the asymmetric These bands are attributable to the adsorption of CO on
500 Tanaka and Sasahara

(a)
(b)

(c)

Figure 7 (a) In situ atomic-resolution STM image ofRh(lll) acquired in CO-containing 0.1 M NaC104 at 0.5 V (SCE). Tip-surface
bias, -17.7 mY; setpointcurrent, 15 nA. (b) A zoom-in STM image (25 x 25 A2 ) ofthe Rh(111)-(2 x 2)-3CO structure. Tip-surface bias
voltage, 1.8 mY; setpoint current, 45 nA in CO-saturated 0.1 M NaC104 at -0.1 V (SCE). (c) STM image of the Rh(lIl)-(3 x../3
rect)-4CO structure (25 x 25 A2). Tip-surface bias voltage, 166 mY; setpoint current, 9 nA in CO-saturated 0.1 M NaC10 4 at -0.3 V
(SCE).
Rhodium and Rhodium-Based Alloys
(d)
Figure 7 Continued. (d) Proposed ball models for (d-l)(2 x 2)-3CO adlayer, (d-2)(3 x ,)3 rect)-4COadlayer. The top-layer Rh atoms
are depicted as the larger circles, with smaller circles representing position of individual CO molecules. (From Ref. 16.)
the asymmetric twofold sites (bridged CO) and on the
atop sites (linear CO). Interestingly, the absorption
spectrum is markedly changed at the potential between
ca. -0.2 and -0.1 V, that is, the adsorption on the atop sites
giving the band at 2030-2045 cm- I becomes major.
Figure 7a shows a typical STM image for a (l xl)
Rh(lll) surface obtained by removing adsorbed CO at
ca. 0.5-0.6 V by electrooxidation in 0.5 M NaCI0 4
solution. In a CO-saturated solution, the in situ STM gave
two types ofdifferent STM images depending on the elec-
trode potentials as shown in Fig. 7b and c. It should be
pointed out that the spots in the STM image reflect the
adsorbed CO molecules instead of Rh atoms. This fact
is interesting because CO molecules adsorbed on the
metal surface are hardly discernible at room temperature
by STM in DHV except when coadsorbed with other
molecules. Taking this fact into account, water molecules
adsorbed or oriented over the Rh(lll) electrode surface
might play an important role for immobilizing the
adsorbed CO on the surface. Figure 7b shows an in situ
STM image for the CO molecules adsorbed on the
Rh(lll) electrode surface keeping at -0.1 V (SCE) in a
CO-saturated O.1-M NaCI0 4 solution, where the three
nonequivalent spots are discernible. The image is that of
501
d-2
a (2 x 2) structure described in Fig. 7d-l (a coverage of
0.75 ML). By referring to the IRAS in Fig. 6, the bright
spots (2/3) reflect the CO molecules adsorbed on the atop
sites and the faint spots (l /3) correspond to the CO mol-
ecules adsorbed on the bridge sites, which is consistent
with a (2 x 2) structure of adsorbed CO on Rh(lll) in
DHV [32] and adsorption of CO on a Rh(lll) electrode
in 0.1 M HCI0 4 solution at ca. 0.1 V (SCE) [16]. The
STM image markedly altered when the electrode poten-
tial keeps at more negative electrode potential of -OJ V,
as shown in Fig. 7c, which was assigned as a (3 x J3
rect)-4CO structure. The IRAS at -0.3 V in Fig. 6
suggests that the spots involve the CO molecules bonding
at the bridge sites and at the atop sites on Rh(lll) such
as shown by the model in Fig. 7d-2 shows.
This experiment suggests an advantage of the combi-
nation of the STM and the spectroscopy such as IRAS
to gain insight of the electrode chemistry.
IV. Rh(100) SURFACE
Figure 8 shows a cyclic voltammogram of an Rh(lOO)
surface obtained in a 0.05-M H2S04 solution in highly
pure argon atmosphere [33]. In this experiment, it was
502 Tanaka and Sasahara

the 1 x 1 adsorption of H atoms on an Rh(100) surface

at 95 K where the fourfold hollow sites are deduced
80 for the adsorption of H atom by the electron energy
loss spectroscopy [34].
It is known that the voltammogram of the Rh(100)
electrode in 0.1 M HF and in 0.1 M HCI0 4 solution is
influenced by adding small amounts of H2S04 as
shown in Fig. 9a, 0.1 M HF; b, 0.1 M HF + 1 mM
H2S04; and c, 0.1 M HCI0 4 + 1 mM H 2S04, respect-
40 ively [21]. It is clear that the voltammogram in an HF
solution and in an HCl0 4 solution approaches to that

-«
::l
in an H2S04 solution (Fig. 8) by adding a small amount
of H2S04. These phenomena are explained by the
adsorption of SO~- and/or HSO; anions on the
Rh(lOO) electrode.
Taking account of rather strong interaction of anions,
:::-
c::
0 if CIO; anion would decompose on the Rh electrode,
the vohammogram will be influenced by the anions pro-
Q) duced by the decomposition. From this view point, the
~
~ reduction of perchlorate anion on the Rh(lOO) electrode
::::J surface was scrutinized by Rhee et al. [21]. The cyclic
0 voltammogram of Rh(100) measured in a O.1-M HCI04
solution gives two peaks for hydrogen adsorption as
shown in Fig. 10. On the other hand, it was found that
-40 the cyclic vohammogram for the Rh(100) surface
measured in a O.1-M HCI0 4 solution undergoes remark-
able change upon keeping the Rh(lOO) electrode at the
following potentials for 60 s: at the threshold for
hydrogen evolution, within H+ +e ~ H region, and the
beginning of the double-layer region, respectively. The
result is shown in Fig. lla, where the oxidation current
-80 peak for the hydrogen desorption at -0.03 V is similar
to that in HF solution (Fig. 9a) and a tiny new reduction
current peak appeared at -0.08 V (Ag/AgCl). The
experiments in a O.1-M HCI0 4 solution shown in Fig.
Potential ( V vs SeE) l1a-c were performed at potentials lower than the for-
mation of surface oxide that is formed at 0.2 V in an
Figure 8 Cyclic voltammogram of a clean Rh(IOO) surface in
HF solution (Fig. 9a). Adsorbed chloride anion on the
0.05 M H 2 S0 4 electrolyte solution (steady state). Scan rate,
Rh(100) electrode can be removed by holding the elec-
50 mV S-I. (From Ref. 29.)
trode potential at the threshold potential for the
hydrogen evolution (-0.225 V) for a time. Based on
these results, they concluded that the tiny peak at
-0.08 V in Fig. lla is attributable to the reduction cur-
confirmed that the pO x 1) LEED pattern does not rent of perchlorate anions forming chloride anions on
change before and after the electrochemical experiment the Rh electrode. Figure lIe shows that the hydrogen
and the XPS shows no contamination on the surface. adsorption peak at -0.13 V is suppressed by the adsorp-
The cyclic vohammogram has sharp hydrogen adsorp- tion of CI- anions formed by the reduction of perchlor-
tion and desorption peaks at -0.26 and -0.19 V and ate anion but that the hydrogen adsorption peak at
the current for the hatched area was about -0.02 V is markedly enhanced because CI- anions are
237 f.1C cm- 2. This current is close to 222 f.1C cm- 2 cal- desorbed at this potential. In fact, the voltammogram
culated for one hydrogen atom per each surface Rh of the Rh(lOO) surface in a 0.1 HF solution gives an
atom assuming a flat surface, which is consistent to additional peak at ca. -0.22 V upon adding 10- 6 M of
Rhodium and Rhodium-Based Alloys 503

(a)
I25~A
110 !!A
o

1- 0
Z
I25~A
w
a:
a:
::>
(b) u

o
to-
Z
W
a:
a:
::>
u
-0.4 -0.2 0 0.2 0.4
POTENTIAL / V (Ag/AgCI)
(c)
I25~A Figure 10 CyclicvoltammogramofRh(lOO) in 0.1 M HCI0 4.
Potential scan rate, 50 mV S-I. (From Ref. 21.)

NaCl to the solution. The original peak is the adsorption

of hydrogen on a clean area of Rh(IOO), and the new
peak is the adsorption of hydrogen after desorption of
Cl- anions. Based on these results, they deduced that
the peak at -0.2 V in the voltammogram of the Rh(IOO)
electrode in HCl0 4 solution is attributable to the
adsorption of hydrogen concomitant with desorption
of Cl- ions. Another peak at more positive potential is
-0.4 -0.2 0 0.2 0.4 due to the adsorption of hydrogen on a clean area of
POTENTIALN(Ag/AgCI) the Rh(IOO) surface in the HCl0 4 solution, where the
Cl- anions are formed by the reduction of ClO; on
Rh(IOO). It should be pointed out that no adsorption of
Figure 9 Cyclic voltammograms of Rh(lOO) in (a) 0.1 M HF, perchlorate anion occurs on the Pt electrode at
(b) 0.1 M HF + I mM H 2S0 4 and (c) 0.1 M HCI0 4 + 1 mM potentials below 0.5 V normal hydrogen electrode
H2S04. Potential scan rate, 50 mV s-l. (From Ref. 21.) (NHE) in 0.1 M HCl0 4 solution [23].
504 Tanaka and Sasahara

I10~A I10~A I10~A

(a) (b) (c)

o
I- ,-"
Z
W
,
~;1

I
a: !\ I
a: 'I', :
:::> tI
()
I,
"
~ ~

-0.4 -0.2 o -0.4 -0.2 o -0.4 -0.2 o

POTENTIALN (Ag/AgCI)
Figure 11 Cyclicvoltammograms ofRh(lOO) in 0.1 MHCI0 4 after scanning interruptions for 60 s at (a) -0.225 V, (b) -0.161 V, and
(c) 0.040 V. Steady-state voltammograms are indicated by dashed lines. Potential scan rate, 50 mV S-I. (From Ref. 21.)

V. Rh(110) SURFACE the peaks for the adsorption and desorption of

Compared with the electrochemical studies ofthe Rh(lll)
and Rh(lOO) surfaces, only a limited number of studies
have been done on the Rh(llO) surface. Figure 12 shows
a cyclic voltammogram ofa p(1 x 1) Rh(llO) surface in a
0.05-M H 2S04 solution, where the p(l x 1) Rh(llO) sur-
face was prepared in the DHV system [35]. The peak area
at -0.21 V (SCE) corresponds to about 161 /lC cm- 2,
which is almost equal to the calculated value of
157 /lC cm- 2 by assuming one hydrogen atom per each
Rh atom on the p(l x 1) Rh(llO) surface.
Figure 12 shows a voltammogram obtained in
0.05 M H2S04 solution, which is quite similar to the
voltammogram of Rh(l10) measured in a 0.5-M H 2S04
solution by Gomez et al. [36]. In their voltammogram,
hydrogen appear at -0.17 V (SCE), which are more
sharp compared with corresponding peaks at -0.21 V
in the 0.05-M H 2S04 solution shown in Fig. 12. The
quality of the two Rh(llO) surfaces might be respon-
sible for this discrepancy, that is, the voltammogram
in Fig. 12 was obtained by using a disk cut from a large
single-crystal rod, but the crystal used by Gomez et
al. was made by the flame-melting method. This fact
suggests that the voltammogram is sensitive to the
crystallographic surface structure and to the local
structure or perfectness of the surface. This fact
prompts us to apply the voltammogram measurement
to diagnose the structural and the compositional
changes of the surface by the catalytic reactions as dis-
cussed in the next section.
Rhodium and Rhodium-Based Alloys 505

80 80

40
-«
::i
40

--
c: 0
.-.
«
-.....
::i
Q)
~
~
:J
()
c:: 0
Q)
-40 '-
'-
:)
U

-80 -40

Potential ( V vs SeE)
Figure 12 Cyclic voltammogram ofa clean Rh(ll0) surface in
0.05 M H 2 S0 4 electrolyte solution (steady state). Potential scan
rate, 50 mV S~I. (From Ref. 31.)
-80

VI. BIMETALLIC SURFACES OF Pt/Rh(100),

Rh/Pt(100), Pt/Rh(110), AND Rh/Pt(110)
Pt-Rh bimetallic catalyst is known by the name of
"three-way catalyst" for environmental protection and
has been developed for removing NOx, CO, and
hydrocarbons from automotive exhaust gas. However,
the role ofRh atoms in this prominent bimetallic catalyst
is an unsolved question. To shed light on the role of Rh,
the reaction of NO with H2 has been precisely studied
on the Pt-Rh(lOO) alloy surface [37-39] and on a series
of bimetallic model surfaces such as Rh/Pt(lOO) [24],
Pt/Rh(lOO) [40-42], Rh/Pt(llO) [43], and Pt/Rh(llO)
[35], where the bimetallic surfaces were prepared by elec-
trochemical deposition in an EC-UHV system.
The voltammogram of an Rh(lOO) surface changes
sensitively with deposition of Pt as shown in Fig. 13 [33],
where the peak attributable to the Rh surface at ca.
Potential ( V vs SCE )
Figure 13 Cyclic voltammograms of Rh(100) electrode
changing with increasing the deposition of Pt in 0.05 M
H 2 S0 4 + 5 X 10- 5 M PtC1 4 solution. The 5th to 12th cycles are
shown. Potential scan rate, 50 mV S-I. (From Ref. 29.)
-0.25 V (SCE) becomes smaller with increasing depo-
sition of Pt and a new shoulder concomitantly appears
at around -0.2 V By monitoring the voltammogram,
one can control the deposition of Pt on the Rh(lOO)
surface. When a desired amount of Rh is deposited on
the Rh(lOO) surface, the Pt/Rh(lOO) bimetallic surface
is washed with pure water and then it is pulled back to
the UHV chamber to characterize the surface with the
XPS and LEED.
506 Tanaka and Sasahara

As prepared, the Pt/Rh(lOO) surface showed a

p(l x 1) LEED pattern with high background intensity.
However, when the Pt/Rh(lOO) surface is heated in O 2, 80
the surface undergoes dramatic change. The XPS peak
ratio of the Rh 3d / 5/ 2/Pt4f/7/2 is markedly increased at
600 K and a clear p(3 x 1) LEED pattern appears. It
should be pointed out that this p(3 x I) pattern is anal-
ogous to the p(3 x I) LEED pattern observed on the
Pt-Rh(IOO) alloy and Rh/Pt(IOO) surfaces when they
are heated in O 2 at 400-500 K [24,39]. Taking account 40
-«
the fact that the Pt-Rh alloy surface is hardly in equilib-
rium in vacuum at temperatures lower than ca. 900 K
[44], the observed reconstruction is a kind of chemical
restructuring. That is, the bulk diffusion of Pt and/or
Rh atom is very slow at temperatures lower than 900 K, ::i
but a selective reaction of Rh atoms with oxygen
dramatically promotes the segregation of Rh atoms
from the second layer and/or deeper onto the topmost
:::-
c
0
layer of the surface. On the other hand, when the bimet- Q)
~
allic surfaces of Pt/Rh(IOO) and Pt/Rh(llO) are heated ~

in O 2 or NO, the XPS peak ratio of Rh3d/5/2/Pt4f/7/2 is ::J

rapidly increased even at ca. 600 K and a clear p(3 x I) 0
LEED pattern appears. That is, a chemical segregation
of Rh atoms occurs by reacting with oxygen on these
surfaces. The most important fact is that the catalytic -40
activity for the reaction of NO + H2 is dramatically
enhanced by this surface restructuring. That is, the for-
mation of Rh-enriched p(3 x 1) Pt/Rh(IOO) surface
brings about a prominent catalytic activity for this
reaction [33,41,42]. Such a remarkable enhancement of
the catalytic activity was observed not only on the
Pt/Rh(lOO) but also on the Rh/Pt(IOO) surface, and -80
Pt-Rh(lOO) alloy surfaces when the p(3 x I) structure
was formed on these surfaces by treating with oxygen.
Another interesting feature of this Rh-enriched p(3 x I)
Pt/Rh(lOO) surface is the reversibility in the redox Potential ( V vs. SeE)
reaction of the surface, that is, the p(3 x 1)~ p(l xl)
Figure 14 Cyclic voltammogram of p(3 xl) PtlRh(lOO) sur-
conversion takes place rapidly at room temperature by
face obtained by annealing in 02 (1 X 10- 7 Torr) at 600 K for
exposing to H2 and O 2 [40].
20 min measured in 0.05 M H 2 S0 4. Potential scan rate.
Therefore, the voltammogram of the p(3 x I) 50 mV S-I. (From Ref. 29.)
Pt/Rh(IOO) surface, which is active for the reaction of
NO + H2, is very interesting. Figure 14 shows the
voltammogram for a p(3 x I) Pt/Rh(lOO) surface. It is
very interesting that the voltammogram of the p(3 x I)
Pt/Rh(lOO) surface is very similar to that of the Rh(IOO) retained on the emersed Pt/Rh(IOO) surface after the
surface shown in Fig. 8 except the current curve at the cyclic voltammogram. In addition, it was confirmed that
oxidation region. It is worthy of note that the p(3 x I) the p(l x I) Pt/Rh(lOO) surface prepared by exposing to
structure is retained on the emersed Pt/Rh(IOO) surface H2 in the UHV chamber, thep(3 x I) Pt/Rh(lOO) surface,
at a potential of -0.3 V. As it was mentioned above, the and Rh(lOO) surface gave very similar voltammograms
p(3 x 1) Pt/Rh(lOO) surface is readily reduced by H2 at in H2S04 solution. Taking these facts into account,
room temperature and the p(l xl) surface is established. the p(l xl) Rh/Pt(lOO) formed during the cyclic
Therefore, it is curious that the p(3 x I) structure is voltammogram is perhaps converted into the p(3 x 1)
Rhodium and Rhodium-Based Alloys
0.5
A~
o The promoting effect ofRh atoms is more dramatic on
~ the Pt(llO) surface. The Pt(llO) surface is almost inactive
....
oz A
l rJ'•
• for the reaction of NO + H 2 --+ N2+H20, but deposition
-
A •
A .0
C\l AA :0
Z A • 0
A ·0
AA "0
, .·0
tJ; ·0
•• 0 p(3 x I) PtlRh(lOO) and the p(3 x I) Rh/Pt(lOO) surfaces
200 300 400 500 600 700 800
Temperature (K)
Figure 15 Temperature-programmed reaction on (open
circle) Rh(lOO) clean surface, (solid circle) p(l x I) Pt/Rh(lOO)
surface annealed in vacuum at 1000 K, (open triangles)p(3 x I)
Pt/Rh(lOO) surface. (From Ref. 38.)
structure by the adsorption of H20 molecules. If this is
the case, the p(3 x 1) surface would be observed even if
the surface is emersed at -0.3 V
On the other hand, the dissolution ofRh was observed
on a Pt-Rh alloy thin film when a cyclic potential sweep
was applied up to the oxidative region in a H2S04 solution
[45]. In conformity with this fact, the Rh-enriched
p(3 xl) PtlRh(lOO) surface dissolves little Rh during
the voltammetric experiments, which was confirmed by
a small decrease of the XPS Rh3d/5/2/Pt4f/7/2 ratio after
the electrochemical experiment [33].
The PtiRh bimetallic single-crystal surfaces prepared
by electrochemical deposition were subjected to the cata-
lytic reaction ofNO + H 2 --+ N 2 + H 20 in the high press-
ure cell. Figure IS shows the temperature programmed
reaction (TPR) on the Rh(lOO) and the PtlRh(lOO)
surfaces performed by raising the temperature in a flow
ofNO + H 2 mixture by a rate of! K/s.When the catalytic
reaction of NO + H 2 --+ N2 + H 20 proceeds, the partial
pressure ofN2 will increase proportional to the reaction
rate. It is known that the N2 pressure starts to increase at
about 600 K on the Rh(lOO) surface. The PtlRh(lOO)
bimetallic surface was prepared by electrochemical
deposition ofPt and annealing in UHVat 1000 K, which
gave a p(l xl) Pt/Rh(lOO) surface. This p(l x I) Pt/
Rh(lOO) surface showed an activity being slightly higher
than that of Rh(lOO) and the N 2 partial pressure started
507
to increase at ca. 500 K. In contrast to the Rh(lOO) and
the annealed p(l xl) PtlRh(lOO) surfaces, the p(3 x 1)
PtlRh(lOO) surface prepared by treating with O 2 showed
remarkable catalytic activity and the N2 formation
started at about 370 K [41,42].
ofa submonolayer ofRh dramatically enhances the cata-
lytic activity of the Pt(llO) surface for the reaction of
NO + H2. An interesting fact is that the catalytic activity
of the Rh/Pt(llO) surface is almost equal to that of the
[33,41-43]. These results strongly suggest that the acti-
vated PtiRh bimetallic surfaces are constructed by a
common local structure composed of Rh and Pt atoms,
which is constructed by the adsorption of O 2 or in the
catalysis of NO + H2. Therefore, we could conclude that
dissociation of NO may occur on the activated
PtlRh(lOO) surface and that the Rh atoms on the acti-
vated Rh/Pt(lOO) surface are entirely different from that
of the Rh(lOO) single-crystal surface.
By the same way as the PtlRh(lOO) surface was pre-
pared, Rh/Pt(lOO) bimetallic surface was prepared by
electrochemical deposition of Rh atoms on a Pt(lOO)
electrode surface in a H2S04 + RhCI 3 electrolyte
solution. The amount of deposited Rh on the surface
was adjusted by repeating a cyclic potential sweep
between -0.3 and 0.2 V (SCE).When an Rh/Pt(lOO) sur-
face with 0.8 ML of Rh was heated in 02, the surface
structure was readily changed to the p(3 x 1) structure at
400 K, which is about 200 K lower than the temperature
(600 K) at which the p(3 x 1) structure is formed on the
PtlRh(lOO) surface.
The cyclic voltammogram of this p(3 x I) Rh/Pt(lOO)
surface was measured in an H2S04 solution. Inter-
estingly, the shape of the cyclic voltammogram of this
Rh-deposited Pt(lOO) surface is quite different from that
of the p(3 xl) PtlRh(lOO) and of the Rh(lOO) or Pt(lOO)
surface [33,43] as shown in Fig 16, where a couple of
reversible current peaks attributable to the adsorption
and desorption of hydrogen appear at -0.18 V (SCE).
The reversibility for the adsorption and desorption of
hydrogen on the PtlRh(lOO) contrasts to that on Rh(lOO)
surface. This fact reveals that submonolayer Rh atoms
deposited on the Pt(lOO) surface are quite different from
those on the Rh(lOO) surface.
As it was mentioned above, the p(3 x 1) Rh/Pt(lOO)
surface undergoes a reversible change of the p(3 x 1) *+
p(l x 1) by exposing to H2 or O 2 at room temperature
[24]. The Pt-Rh(lOO) alloy and PtlRh(lOO) surfaces
undergo similar reversible change of the p(3 x I) *+
508
120
80
f
~
40 f
« a ratio of Rh/Pt = 112, where an (Rh-O) chain is
::l. r
-- 0
'E
...::::l~
()
-40 r layer. The third layer and deeper are almost the bulk com-
I 1000 K [44]. If this is the case, we could expect that the
-80
-120
I •
Potential ( V vs SeE)
Figure 16 Cyclic voltammogram of a p(3 x I) Rh/Pt(lOO)
surface (BRh = 0.8) measured in 0.05 M H 2S04. Potential scan
rate, 50 mV S-I. (From Ref. 39.)
p(1 x I) reconstruction. Such unique p(3 x 1) structure
was first found on the Pt-Rh(lOO) alloy surface when it
was heated in 02 or NO [37-39]. The atomic structures
ofthe p(3 x 1) and p(1 x 1) Pt-Rh(lOO) alloy surfaces were
recently studied by the STM [46].
Through these experiments, an important role of Rh
becomes clear, that is, a common local structure is con-
structed on the surface by reacting Rh atoms with oxygen,
and the local structure on the surface gives an ordered
arrangement of Rh and Pt atoms on 100 surface, which
is the p(3 x 1) structure formed on the Rh/Pt(100),
Pt/Rh(100), and Pt-Rh(lOO) alloy surfaces [24,37-42].
Such a common local structure of the sites is responsible
for the prominent catalytic activity of the Pt/Rh bimet-
allic and Pt-Rh alloy surfaces for the reaction of
NO+H 2 .
The cyclic voltammograms ofthe p(3 x 1) Pt/Rh(100)
and the p(3 xl) Rh/Pt(lOO) surfaces were measured in
H 2S04 solution. The electrochemical diagnosis of the
p(3 x 1) Pt/Rh(lOO) and Rh/Pt(lOO) surfaces suggest a
Tanaka and Sasahara
little discrepancy to the model of the p(3 x 1) Pt-Rh(lOO)
alloy surface proposed from the STM image shown in Fig.
17a [46]. ThePtand Rhatoms assigned in the STM image
are perhaps the reverse because as it was mentioned
above the voltammogram of the p(3 x 1) Pt IRh(lOO) sur-
face (Fig. 14) is rather similar to that of Rh(lOO) (Fig. 8).
In addition, the surface composition of the p(3 x 1)
Rh/Pt(lOO) and the p(3 x 1) Pt/Rh(100) bimetallic
surfaces might be composed of more Rh atoms than Pt
on the topmost layer. The STM model proposed for the
p(3 x 1) Pt-Rh(lOO) surface, however, is composed of
sandwiched between the two Pt-rows along the [001]
direction as shown in Fig. 17a. The Pto.2sRho.7s(100) alloy
surface annealed at ca. 1000 K is composed of a
Pt-enriched topmost layer and a Pt-depleted second
position [47]. This fact may suggest that the top two layers
are in a local thermodynamical equilibration at around
maximum fraction of the Pt atoms in the topmost layer
ofthePto.2sRho.7s(lOO) surface will be 50%. This is clearly
different from the model proposed for the STM image
that is composed of a 2/3 monolayer of Pt atoms. It is
unlikely that a large amount of Pt atoms is segregated
from the bulk of deeper than third layer in O2 at 600 K,
because Rh atoms prefer to segregate by reacting with
O 2.Therefore, the Rh and Pt atoms in the previous atomic
model are perhaps opposite, that is, one Pt-row is
interposed between the two (Rh-O) chains as shown in
Fig.17b. This new model is quite consistent with the quan-
titative analysis of the composition of Pt-Rh(lOO) alloy
surface and the voltammetric feature of the p(3 x 1)
Pt/Rh(lOO) and Rh/Pt(100) bimetallic surfaces.
It is worthy of note that the p(3 x 1) and p(l xl)
Rh/Pt(lOO) bimetallic surfaces have quite similar cyclic
voltammograms as shown in Fig. 16 and 18a, but these
are undoubtedly different from the p(3 x 1) Pt/Rh(lOO)
surface shown in Fig. 14. In addition, the p(3 xl)
Rh/Pt(100) surface is readily changed to the p(1 xl)
structure by immersing the surface in an H 2 S0 4 solution
at -0.3 V (SCE), whereas the p(3 x 1) structure of the
Pt/Rh(lOO) surface is retained after the cyclic
voltammogram experiment. The voltammograms of an
Rh-segregated Pt/Rh(lOO) surface and an Rh-deposited
Pt(lOO) surface are distinctive in the hydrogen adsorption
and desorption range. The voltammograms for the
p(3 x 1) Rh/Pt(lOO) surfaces with different amount of
Rh, 0.8, 0.4, and 0.3 ML, are shown in Fig. 18a-c. A large
peak is commonly observed at -0.18 V (SCE) in an
H 2S0 4 solution, which is observed neither on Pt(lOO)
nor on Rh(lOO) surface and also not on the Pt/Rh(lOO)
Rhodium and Rhodium-Based Alloys 509

(a) (b)

eo o substrate Pt
Figure 17 The structural model for a p(3 x 1)-O/Pt-Rh(IOO) surface. (a) Previously proposed model [42); (b) a new model proposed
from the cyclic voltammograms.

120 (a) 120 (b) 120 (c)

80 80 80

.,J 40 40
40

~
< <
::l. ::l.
<
::i 0
E E 0
C 0
~
:;
u
-0.2/0.2 ~
:5
u
-40
-03 ~
:5
U
·40
0.2

·40

'" ·80 -80

-80

-120 -120
Potential ( V vs SCE ) Potential ( V vs SCE )
·120
Potential ( V vs SeE)
Figure 18 Cyclic voltammograms of a p(l x I) Rh/Pt(IOO) surfaces with various Rh loadings measured in 0.05 M H 2S0 4 : (a)
BRh = 0.8, (b) BRh = 0.4, (c) ORh = 0.3. Potential scan rate, 50 mY s -1. (From Ref. 39.)

surface. The voltammogram of a clean p(5 x 20) Pt(lOO) Therefore, the tiny peaks appearing at -0.02 V and
surface gives tiny peaks at -0.05 and + 0.06 V This fact + 0.02 Von the Rh/Pt(lOO) surface may reflect the Rh
indicates that the reconstructed p(5 x 20) structure of free area of the Pt(lOO) surface. The characteristic large
the Pt(lOO) surface is retained at this potential [48]. peak commonly at -0.18 V observed on the p(3 x 1)
510 Tanaka and Sa sahara

80

~~
0.5 00 A PocxxP<P
40 o 00 AA ••
0
~ o A ••
c( .... A •
::t

- .. ..
o A •

---- 0
Z .. ......
t:
......
Q)
0
0 0.2
Z
C\I
..
0 ·"
~....
..
.•
.
..
:::J
() 'iA ....... • ••
-.....".
-40

200 300 400 500 600 700 800

-80
Temperature (K)
Potential (V vs SeE)
Figure 20 Temperature-programmed reaction on (solid
Figure 19 Cyclic voltammogram of aPt-deposited Rh(100) circle) Rh(llO) clean surface, (solid triangles) p(l x I)
surface in 0.05 M H 2S04. Potential scan rate, 50 mV S-I. (From PtlRh(llO) surface annealed in vacuum at 1000 K, (open
Ref. 3\.) circles) Rh-O/PtlRh(llO) surface prepared by annealing in O2
(10- 7 Torr) at 760 K. (From Ref. 3\.)

Rh/Pt(lOO) surfaces is attributable to the active sites
involving Rh and Pt atoms on the Pt(lOO) surface. The
p(l x 1) surface obtained by reducing the p(3 x 1)
Rh/Pt(lOO) surface with Hz at room temperature gives
the same characteristic large peak at -0.18 V. This fact
suggests that the local arrangement of the Rh and the Pt
atoms on the p(3 xl) Rh/Pt(100) surface is retained on
the p(l x 1) surface after the reduction with hydrogen.
Figure 19 shows a cyclic voltammogram of a
Pt-deposited Rh(llO) surface in a 0.5-M H zS04 sol-
ution [35], where 0.9 ML of Pt was deposited on a
Rh(llO) surface from a KzPtCl z + H zS0 4 solution. A
new oxidation and reduction humps appear at -0.15 V
(SCE) symmetrically, and the total charge for the
hydrogen desorption peak is 159 /lC cm- z. On the
other hand, when a Pto.7Rho.3 alloy thin film was
subjected to a cyclic potential sweep in a range of
0-1.2 V (RHE) in a 1-M H zS04 solution, a new peak
attributable to Pt appears at 0.12 V positive side, which
may indicate an electrochemical dissolution of Rh
atoms from the surface [45]. Taking this fact into
account, the shoulder at -0.15 V (SCE) may be attribu-
table to the Pt layer formed on the Rh(llO) surface.
The LEED pattern of this Pt-deposited Rh(l1O) surface
gave a p(1 xl) LEED pattern with high background
intensity, which suggests less ordered deposition of Pt
atoms on the Rh(llO) surface.
As it was mentioned, when a PtozsRho.7s(l00) alloy
surface is annealed at 1000 K in vacuum, aPt-enriched
surface is formed with the formation of the Pt-depleted
second layer (Rh-enriched layer).When this Pt-enriched
Pto.zsRho.7s(100) alloy surface is exposed to Oz or NO,
Rh atoms are segregated from the second layer onto the
topmost layer even at 450 K, and a clear p(3 x 1) LEED
pattern appears [38,39].
Similar extraction of Rh by oxygen occurs on a
Pt/Rh(llO) bimetallic surface (2.0 ML of Pt). The
Rh3d/s/z/Pt4f/7/z XPS peak ratio changes little by
annealing in vacuum at 760 K but is gradually increased
by heating in 1 x 10- 7 Torr Oz at 760 K, and a e(2 x 4)
LEED pattern appears [35]. That is, the Rh atoms are
extracted onto the topmost layer by reacting with oxygen
at 760 K.
The Pt/Rh(l10) surface activated by heating in Oz
gives very high catalytic activity for the NO + Hz reaction
as shown in Fig. 20, where the Rh atoms are extracted
on the surface. The catalytic activity of this Pt/Rh(l1O)
surface is almost equal to that of the Rh segregated
Pt-Rh(lOO) alloy and Pt/Rh(100) surfaces activated by
heating in oxygen, where the Rh atoms are segregated
on the surface. Consequently, the formation of
Rh-enriched overlayer on the Pt/Rh(llO) surface is
responsible for the prominent catalytic activity of the
Pt/Rh(l1O) surface for the reaction of NO + Hz. In fact,
Rhodium and Rhodium-Based Alloys
80E <al 80
~rl~"V
-0.22 V
!r·
1SV
40
40
« «
::I. ::I.
E 0 E 0
~
::J
~ a new peak at -0.22 V (SCE) as shown in Fig. 21b. This
::J
0 ()
-40 -40
sweep rate: sweep rate:
-80 50 mV Isec. -80 50 mV Isec.
Potential ( V vs SCE ) Potential ( V vs SCE )
Figure 21 Electrochemical diagnosis of the Pt/Rh(llO) sur-
face ((1Pt = 0.9) carried out in 0.05 M H 2 S0 4 . (a) Pt/Rh(llO)
heated to 760 Kin vacuum; (b) Pt/Rh(llO) after theTPR exper-
iment in a flow of NO and H 2 to 760 K. Potential scan rate,
50 mV S-I. (From Ref. 31.)
when the active Pt/Rh(llO) surface (Rh segregated
surface) is annealed in vacuum at 1000 K, the Pt atoms
on the surface are diffused into the bulk and the
Rh3d/5/2/Pt4fj7j2 ratio of the XPS peaks is increased,
and the catalytic activity is concomitantly suppressed.
This fact suggests that the active sites made by Pt and
Rh atoms are decomposed by diffusing Pt atoms from
the surface into the Rh(llO) bulk.
Based on these facts, we could say that the Pt-Rh
three-way catalyst is activated by reacting Rh atoms with
O 2and/or NO during catalysis, which forms specific sites
composed of Pt and Rh. When a deposited Pt/Rh(llO)
surface of 0.9 ML of Rh was heated in UHV up to 760 K
at a rate of 1 K/s, no clear LEED pattern appeared and
the Rh3d/5/2/Pt4f/7/2 XPS peak ratio changed little by
photoelectron spectroscopy [49]. The Pt/Rh(llO) surface
used for the NO + H 2 reaction was diagnosed by
measuring the cylic voltammograms before and after
the NO + H 2 reaction. The cyclic voltammogram was
sensitively changed by annealing the Pt/Rh(llO) surface
invacuum, and a new peak appeared at ca. -0.15 V (SCE)
after the annealing of the Pt/Rh(llO) surface in vacuum
as shown in Fig. 21a. If we compare the cyclic
voltammogram of this annealed Pt/Rh(llO) surface to
that of the Rh(llO) surface, the new peak at -0.15 V
(SCE) for the annealed Pt/Rh(llO) surface (760 K) may
be attributable to the Pt atoms arrayed over the Rh(llO)
surface. The voltammogram curve for the hydrogen
adsorption and desorption current changed little before
511
(b)
and after the annealing in vacuum, but a slight decrease
of the current to 150 flC cm- 2 was observed after the
annealing at 760 K.
When this vacuum-annealed Pt/Rh(llO) surface was
heated up in a flow of a mixture of NO + H 2 at a rate of
1 K/s (the TPR experiment), the Rh3d/5/2/Pt4fj7j2 XPS
peak ratio changed little. However, the voltammogram
of the Pt/Rh(llO) surface after theTPR experiment gave
fact indicates that the topmost layer ofthe Pt/Rh(llO) sur-
face may change its structure by reacting Rh atoms with
oxygen in a mixture of NO + H 2. This restructuring is
essentially different from the surface annealed at 760 K
in vacuum. That is, the cyclic voltammogram sensitively
reflects the change of the topmost layer that is brought
about during the TPR. It is worthy of note that the new
peak at -0.22 V (SCE) has a symmetric current curve,
which indicates a reversible oxidation and reduction pro-
cess on the Pt/Rh(llO) surface, which is a remarkable
contrast to the corresponding process on the Rh(lll),
Rh(lOO), and Rh(llO) surfaces. Similarly good
reversibility was observed for the voltammograms of the
Rh/Pt(lOO) and Rh/Pt(llO) electrodes [43], where the
redox peaks attributable to the Rh atoms or layer show a
symmetric curve. From these results, we conclude that
the Rh atoms deposited on the Pt layer are different in
their redox properties from the single-crystal surface of
Rh. An important role of Rh atoms for the prominent
catalytic activity of the Pt/Rh bimetallic surfaces is the
construction ofsuch active sites on the surface by combin-
ing with Pt atoms.
VII. CONCLUSION
Rh single-crystal electrodes give characteristic
voltammograms depending on the crystallographic
planes, which is similar to the Pt electrodes. Voltammetry
ofthe Rh electrodes is more sensitively changed by anions
compared with Pt single-crystal electrodes. The volt-
ammogram shape for the hydrogen adsorption and
desorption current is asymmetric on the Rh electrode
but is symmetric on the Rh deposited pte I 00) and Pt(ll 0)
electrodes, and on the Pt deposited Rh(lOO) electrode.
Pt-Rh(lOO) alloy and Rh/Pt(lOO) and Pt/Rh(lOO)
bimetallic surfaces prepared by the electrochemical
deposition of Rh or Pt show a common LEED pattern
of the p(3 x 1) structure when these surfaces are heated
in O 2 or NO. Interestingly, the p(3 x 1) reconstructed
surfaces have almost equal high catalytic activity for
the reaction of NO with H 2. The voltammogram of
the p(3 x 1) Pt/Rh(lOO) surface is similar to that of
the Rh(lOO) electrode but is different from the
512
voltammogram ofthe p(3 x 1) Rh/Pt(lOO) surface. It was
found that the p(3 x 1) PtlRh(lOO) surface retains the
p(3 x 1) structure after a cyclic voltammogram exper-
iment but that the p(3 x 1) structure of the Rh/Pt(lOO)
surface is readily lifted merely by contacting with a
solution. Delicate changes induced on the PtiRh bimet-
allic surfaces during catalysis and/or in the adsorption,
even though difficult to detect by XPS and LEED, can
be detected by measuring the voltammogram, which
may reveal that the voltammogram is an interesting new
tool for diagnosing the surface by combining with the
STM, ultraviolet photoelectron spectroscopy (UPS),
and other surface-sensitive techniques.
REFERENCES
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29
Spectroelectrochemistry of Monolayer and Submonolayer
Films Using an Electroactive Integrated Optical Waveguide
Darren Dunphy, Sergio Mendes, S. Scott Saavedra, and Neal R. Armstrong
University ofArizona, Tucson, Arizona
I. INTRODUCTION
Spectroelectrochemistry has proven to be a very powerful
technique for the study of redox processes in terms of its
ability to provide optical data that is complementary in
nature to standard current or potential measurements
[I,2]. Absorbance spectroelectrochemistry suffers from
the disadvantage ofpoor sensitivity, however, limiting its
use in the characterization of thin (monolayer) films.
Recently, spectroelectrochemistry has been performed
at the surface of an integrated optical waveguide (lOW)
to allow for the ultrasensitive characterization of redox
behavior in thin film materials at monolayer surface
coverage or less [3-5]. This review focuses on the develop-
ment and use of the electroactive integrated optical
waveguide (the EA-IOW), a multilayer, step-index,
single-mode lOW that possesses a transparent metal
oxide film as the top layer that functions as a working elec-
trode [5]. With the EA-IOW, changes in absorbance at
the surface of this electrode can be monitored with a
sensitivity ofup to 4000 times that of a single-pass trans-
mission spectroelectrochemical experiment.
Spectroelectrochemistry was originally conceived as a
means to monitor solution electrochemical processes
through absorbance changes in the visible spectral
region, occurring within the diffusion layer thickness
adjacent to optically transparent electrodes [I]. The
power of this approach in monitoring electrochemical
processes was readily apparent, because spectro-
electrochemical techniques offer the possibility of
513
obtaining data regarding redox processes in the
absence of background current due to nonfaradaic
charging and/or electroactive impurities [1,2]. Also,
through the choice of an appropriate wavelength,
spectroelectrochemistry can add a dimension of
selectivity to an electrochemical measurement. Due
in part to these features, conventional transmis-
sion spectroelectrochemistry in the visible wavelength
regime has now proliferated widely as a means to
spectroscopically characterize redox processes of diverse
materials, ranging from electron transfer proteins [6],
to electroactive polymers [7], electrochromic organic
and inorganic thin films [8], and a host of organic
radical-producing processes [1,2]. The application of
spectroelectrochemistry to ultrathin films, however, has
been limited due to poor absorbance sensitivity in a stan-
dard transmission experiment.
The drive to improve the sensitivity of conventional
spectroelectrochemistry began with the introduction of
an attenuated total reflection (ATR) geometry for the
optically transparent electrode [1,2]. The sensitivity ofthe
ATR format was improved through the use of multiple
internal reflection elements but was limited to an increase
in sensitivity ofca. 10, compared with a single-pass trans-
mission experiment. Additional sensitivity increases were
not realized until the late 1980s, with the combination of
integrated optics and spectroelectrochemistry in a
gradient-index lOW overcoated with a doped tin oxide
electrode [3,4]. The EA-law, due to its step-index design,
represents a significant increase in absorbance sensitivity
514
when compared with this earlier gradient-index
waveguide. We discuss here the construction of the
EA-IO\Y, its properties as an integrated opticalwaveguide,
and the interfacing of this technology to electrochemical
cells. The use of the EA-IOW in spectroelectrochemistry
is demonstrated through the monitoring of absorb-
ance changes occurring during the reduction of
surface-adsorbed methylene blue, an electroactive dye
molecule, at low surface coverages (4% of a full
monolayer). Methylene blue will also serve as a model sys-
tem to demonstrate the feasibility ofusing the EA-lOW to
measure shifts in the averagemolecularorientation during
electrochemical events in films adsorbed to the EA-IOW
using absorbance linear dichroism. Finally, the reduction
of an electrostatically adsorbed cytochrome c film and
the oxidation of phthalocyanine aggregates at sub-
monolayer coverage will serve to illustrate how the
EA-IOW can be applied to facilitate the characterization
ofmolecular systems ofcurrent interest.
II. DEVELOPMENT OF lOW
SPECTROELECTROCHEMISTRY
In internal reflection spectroelectrochemistry (IRS), a
reflected beam is incident on a semitransparent
glass- metal oxide thin-film electrode (e.g., indium-tin
oxide [ITO] or antimony or fluorine-dope tin oxide) or a
glass- metal thin film at an angle greater than the critical
angle for total internal reflection [1]. An exponentially
decaying evanescent field is formed that extends beyond
the IRS element surface (the metal oxide-solution
interface) to a depth of ca. one wavelength. The
penetration depth, b, defined as the distance at which
the electric field decays to 1Ie of its value at the sub-
strate-solution interface, is a function of the refractive
index of the substrate and the metal oxide thin film,
the refractive index of the solution, the wavelength of
light, and the reflection angle. In practice, for IRS at a
transparent semiconductor film such as Sn02, the
penetration depth varies between ca. 100 and 200 nm.
The absorbance sensitivity of IRS for a single reflection
can be described through the use of the Beer's law
analogue:
A = Neff(sbC) (1)
where sand C have their usual meanings, b is defined as
before, Neff is a sensitivity factor dependent on the optical
constants of both the electrode and solution, the incident
reflection angle, and the wavelength and polarization of
the light [I]. Experimentally, Neff has been found to vary
between ca. 3 (for agold electrode) to ca. 15 (fora tin oxide
electrode) [1]. Although this is a significant increase in
Dunphy et aI.
(a)
(b)
# #
(c)
#
11\ #
Figure 1 Principle ofIOW spectroscopy. As the thickness ofa
multiple-internal reflection element is decreased (from a to b),
the number ofreflections, and hence the absorbance sensitivity,
is increased. Eventually, as the thickness is reduced to less than
ca. 10 j1m, discrete reflections are no longer present, and the
evanescent field extends the entire length of the waveguide
(waveguide structure c). In this thickness region, the IRE is in
the integrated optical waveguide (lOW) regime.
sensitivity to changes in the absorbance occurring near
the electrode-solution interface, as compared with a
standard single-pass transmission experiment, the
measured changes in light intensity are still very small.
Improved sensitivity can be gained by using a
multiple-internal reflection geometry (as illustrated in
Fig. la); Neff is then multiplied by a factor equal to the
number of reflections. Sensitivity can be further
maximized by increasing the number of reflections,
either by lengthening the internal reflection element or,
as illustrated in Fig. 1b, by decreasing the element
thickness. Because the number of reflections is inversely
proportional to the thickness of the multiple internal
reflection element for a given reflection angle, the
sensitivity is also inversely proportional to this thickness.
After the thickness is decreased to less than ca. 10 j1m,
discrete waveguide modes are observed; only certain
angles of incoupled light produce a bound mode in the
internal reflection element. Individual reflections at this
point disappear, and the evanescent field extends the
entire length ofthe waveguide structure. In this thickness
regime, the internal reflection element is known as an
lOW [9,10].
Electroactive Integrated Optical Waveguide
The combination of spectroelectrochemistry with
lOW spectroscopy was first reported in 1989 by Hoh and
Fujishima [3,4], who used gradient-index lOWs con-
structed through an ion-diffusion process in which a glass
slide is immersed into a KN03 melt. A thin (ca. 100 nm)
antimony-doped tin oxide layer was then applied over
this waveguide to serve as the electrode. The sensitivity
factor, Neff, as measured through the reduction ofmethyl-
ene blue at the tin oxide surface, was reported to be 30-40
for a multimode structure (ca. 8 ,um thick) and ca. 150
for a 2-,um single-mode waveguide with an interaction
length of 3.3 cm between the input and output gratings
[4].
Although a gradient-index lOW represents a signifi-
cant improvement in sensitivity over that obtained with
a multiple internal reflection element, it was apparent
to us that this figure could be increased further through
the use of a step-index lOW design. In general, a
gradient-index lOW is not as sensitive as a step-
index-lOW, because a smaller percentage of the electric
field is present at the lOW-superstrate interface in a
gradient index IOWas compared with a step-index lOW
[11]. The following discussion is concerned only with a
step-index design, the EA-IOW, which demonstrates an
Neff of ca. 400 and is up to a factor of 4000 times more
sensitive than a single-pass transmission experiment in
the detection of absorbance changes in thin (monolayer)
films adsorbed to or deposited on the ITO surface [5].
Other step-index electroactive waveguide designs have
appeared in the literature but have been primarily devel-
oped for use in chemical sensing and not for
spectroelectrochemistry per se and thus will not be
covered here [12].
III. DESCRIPTION AND PROPERTIES OF THE
EA-IOW
The multilayer structure of the EA-IOW is illustrated in
Fig. 2, along with layer thicknesses and refractive
indexes. It is assumed that the refractive index profile is
constant across each layer; there is evidence, however,
that ITO can possess a refractive index gradient [13].
The precision to which the refractive index profile is
known is a fundamental limitation of all thin-film
optical methodologies. By proper choice of EA-IOW
design parameters, however, the effect of any refractive
index gradient on experimental quantities such as
absorbance sensitivity can be minimized [14]. The
substrate is composed of a soda lime glass microscope
slide into which diffraction gratings have been etched
to form integral waveguide couplers [15]. The diffraction
gratings are first produced in spin-on photoresist
515
Light In Light Out
Figure 2 Structure of the electroactive integrated optical
waveguide (the EA-lOW), along with thicknesses (not to scale)
and refractive indices ofeach layer.
through a holographic exposure process; they are then
etched into the substrate using an ion-milling process.
Although prism coupling could also be used to bring
light into the law, grating coupling offers the advan-
tages of increased experimental simplicity, especially
for spectroelectrochemistry, and improved waveguide
durability. The grating period can be designed to yield
an experimentally convenient coupling angle, and the
distance between the input and output couplers can be
chosen to control absorbance sensitivity.
The three layers of the EA-IOWare then deposited
onto the substrate with RF sputtering. Corning 7059, a
barium borosilicate glass, forms the primary wave-
guiding layer. The second layer, composed of Si0 2, has
two purposes: It forms a barrier to ion diffusion between
the ITO and 7059 layers during annealingofthe EA-IOW
[16] and it also serves as an optical "buffer" layer to con-
trol the amount of bound light present in the ITO thin
film, relative to that bound in the 7059 glass layer.
Although ITO is known as a transparent conductor, it
possesses a significant optical absorptivity when com-
pared with other materials such as borosilicate glass or
silica, which can lead to unacceptable waveguioe loss.
Furthermore, because ITO has a high refractive index,
the modal profile can be unduly concentrated in the ITO
layer, further exacerbating waveguide loss. The silica buf-
fer layer helps to mitigate these problems and is essential
to the operation of the EA-IOW The top layer, applied
over the Si02, is the actual ITO electrode. At a thickness
of 50 nm, the resistivity of the ITO film is ca.
700-800 n; D. The thickness of this layer is chosen as a
compromise between electrical conductivity and optical
516
TE
N
W
>.
o!
TM
- II .........
N
x
W
N
+
N
W
0' '--====""'Il",,,I."'II·l.i.Nb,. """',,,,'
-1500 -1000 -500 0 500 1000 1500
z-coordinate, nm
Figure 3 The light intensity as a function of z-position in the
EA-IOW, for bothTE and TM polarization. Thex-axis is defined
relative to the EA-IOW-substrate interface. The y-axis is
proportional to light power; the area under each curve is
normalized to allow direct comparison ofintensity as a function
of position between the TE and TM modes. The layers of the
EA-IOWare labeled as A, Corning 7059; B, Si0 2 ; and C. ITO.
loss in the EA-IOW (as discussed above). Another factor
that is strongly affected by ITO thickness is absorbance
sensitivity (yide infra).
Although in principle a ray-optics model could be
used to describe a multilayer waveguide structure such
as the EA-IOW, a full wave description is used here, where
the optical properties are calculated through numerical
methods starting with Maxwell's equations [17,18]. There
is substantially greater flexibility with this model when
compared with the ray-optics approximation. It must be
stressed, however, that the full wave model and ray-optics
approximation yield equivalent results for lOWs with
low optical losses [19].The mode structure oftheEA-IOW
as a function of position in the waveguide, calculated
through numerical methods, is shown in Fig. 3 for
transverse electric polarization (top) and for transverse
magnetic polarization (bottom) [17]. Figure 4 defines
the two polarizations in relation to the waveguide surface,
along with the Cartesian coordinate system. In transverse
electric (TE) polarization, the electric field vector of the
light lies in the plane of the waveguide, perpendicular to
the direction of light propagation. For transverse
magnetic (TM) polarization, the electric field vector is
primarily perpendicular to the waveguide surface, with
a small (approximately 10% for the structure in Fig. 2)
component in the direction of propagation. The y-axis
Dunphy et aI.
z
!Lx
Figure 4 TE and TM polarizations defined with respect to the
waveguide surface, the surface normal (dashed line), and the
direction of propagation (heavy arrow). The coordinate system
is depicted as an inset.
for each panel in Fig. 3 is proportional to light power;
the area under each curve is normalized to allow for direct
comparison between the TE and TM modes. Both the
TE and TM modes exhibit the exponentially decaying
evanescent field, extending beyond the ITO surface into
the superstrate to a distance of ca. 100 nm, which is the
source of the high selectivity toward absorbance by
surface-adsorbed layers. ForTM polarization at 633 nm,
the EA-IOW is as sensitive to superstrate absorbance as
a single-pass transmission experiment with a pathlength
of 0.14 mm (determined through absorbance measure-
ments of a dye-labeled dextran that interacted only
weakly with the ITO surface) [5]. Because ofthe high field
intensity at the waveguide-superstrate interface,
however, and the high equivalent molar concentration
of chromophores in thin films, even at low surface
coverages, the EA-IOW is very sensitive to light
absorbance by monolayer and submonolayer films. For
the TE mode, the EA-IOW (with an 8-mm separation
between the input and output gratings) is ca. 4000 times
more sensitive than a standard single-pass transmission
experiment. The differences in properties between the
TE and TM modes can be largely explained by the
presence of the ITO layer. The percentage of total light
intensity in the ITO layer for theTM mode is significantly
less than in the TE mode; for this reason, the inherent
optical loss of the EA-IOW is substantially lower forTM
polarized light than TE polarized light (a factor of more
than 10 at 633 nm). There is a trade-off between loss and
sensitivity, however, that can be seen as a difference in
electric field intensity at the EA-IOW-superstrate inter-
face; at 633 nm, the TE mode is ca. four times more
sensitive than theTM mode to adlayer light absorbance.
Electroactive Integrated Optical Waveguide
::l 10
-TED (a)
.3 """" TM o
••••• TE,
~
o ··~,7,~:"·":~'~
•• ,»
;:;: ,,,.,. "."'
w 0.1
.~ .... , ."l-> ,.,l'
Cii
~0.01
.. , ,."
20 40 60
o 20 40 60
ITO Thickness, nm
Figure 5 The EA-IOW loss (a) and absorbance sensitivity (b),
at 633 nm, as a function of ITO thickness, defined relative to
the values for the TEo mode at an ITO thickness of 50 nm. For
the relative EA-IOW loss, the ITO layer was assigned a small
(0.01) value for the imaginary portion of the refractive index;
for calculating the relative sensitivity, a thin (l.0 nm) weakly
adsorbing adlayer (k = 0.01), with a refractive index of lA, was
added to the EA-IOW structure. Other modeling parameters
are as given in Fig. 2.
The above qualities are a function of many design
parameters, such as layer thicknesses and material
refractive indices. It is not possible to address all these
factors here due to space considerations; a future publica-
tion will discuss the dependence of EA-IOW properties
on design parameters and experimental conditions [14].
It will be helpful, however, to discuss the variation in
EA-lOW loss and sensitivity as a function ofthe ITO layer
thickness as an illustration of the effects of changing the
design parameters of the EA-IOWon experimental pro-
perties. The ITO thickness was based on two factors.
First, because of its high refractive index, small changes
in the thickness of this layer can lead to large changes in
EQ-IOW characteristics. Also, because the ITO serves
as an electrode, electrical conductivity is an important
consideration, severely constraining the minimum
thickness of this layer.
Figure 5 contains the results ofmodeling the EA-IOW
loss (a) and sensitivity (b) as a function ofITO thickness.
Both the loss and sensitivity are plotted relative to the
values of these parameters for the TEo mode at 50 nm.
The data were calculated using a value of 0.01 for the
imaginary coefficient of the refractive index for either
the ITO layer (in the case of EA-IOW loss) or a thin
517
l.O-nm adlayer (in the case of EA-IOW sensitivity). The
EA-IOW loss was calculated assuming that light
, ,
.. absorbance by the ITO layer is the only loss mechanism.
This is only an approximation, as experimental evidence
suggests that light scattering by the grain structure of
the ITO is an equally important contributor to optical
losses [20].
80 100 In general, both the loss and sensitivity ofeach mode
decrease as the ITO thickness decreases over the
thickness region plotted. This is an effect of the high
.' .
.. , .. .. '
'
refractive index of the ITO relative to the rest of the
'-" EA-IOW structure; as the layer thickness is increased, a
"" ""
greater percentage of the total bound light intensity is
found in the ITO layer. This increases absorption losses
80 100 due to the ITO and intensifies the strength of the evan-
escent field at the EA-IOW-superstrate interface,
improving the sensitivity. The magnitudes of the loss and
sensitivity of the TEo mode are more sensitive to ITO
thickness changes from the TMo mode between 20 and
80 nm. This is a consequence of being close to mode
cutoff for theTE polarization; there is a second TE mode
that appears at an ITO thickness of 75 nm, whereas the
second TM mode does not appear until the ITO
thickness is over 125 nm. Both the loss and sensitivity
are ca. a factor of 10 times less for the TEl mode than the
TEo mode when compared at the same ITO thickness.
Relative to an EA-IOW design incorporating a 50-nm
[TO layer, increasing the ITO thickness and utilizing
theTE I mode could be advantageous in the reduction of
optical loss without alarge sacrifice in sensitivity. It is gen-
erally desirable, however, to work in the single-mode
regime to avoid scattering between the different modes
and maximize sensitivity. Decreasing the thickness of
either the Corning 7059 or Si0 2 1ayer has the same effect
of shifting the mode profile into the ITO [21].
The data in Fig. 5 have been calculated for 633 nm
light. At shorter wavelengths, the cutoff for the second
TE (and TM) mode is shifted to thinner ITO
thicknesses, increasing the relative differences in loss
and sensitivity between TE and TM polarization. As
an example, at 514 nm, theTE mode is ca. 10 times more
sensitive toward changes in adlayer absorbance than
theTM mode but has a loss factor that is almost a factor
of 30 times larger.
IV. SPECTROELECTROCHEMICAL
MEASUREMENTS USING THE EA-IOW
Experimentally, the EA-lOW is incorporated into a stan-
dard three-electrode Lucite cell, outfitted with ports to
allow for solutions to be routinely introduced without
affecting the optical alignment, with a design similar to
518 Dunphy et al.

~
c
0.6

0.4
- (a)
:J
?:'
f!!
}§ 0.2
.<
~O.O
~ lOOO
500 o -500
::0.6 ~ (b)
.c
.Ql
~ 0.4
Q)
Ci.
80.2
--=
:;
00.0 [
100
. [
[[
[ [
o -100 -200 -300 -400
Potential, mV vs. Ag/AgCI
Figure 6 EA-IOW outcoupled intensity as a function of
potential, at a wavelength of 633 nm, without any electroactive
species present at the surface of the ITO or in solution. (a) No
EA-IOW preconditioning; (b) EA-IOWequilibrated in 0.1 M
KCl for 2 days.
cells used for standard transmission spectro-
electrochemical measurements [1]. The in coupling
beam (chopped at I kHz) is focused onto the input
grating through the rear of the EA-IOW substrate, and
the polarization state of the beam is selected through the
use of a Fresnel rhomb prism and a sheet polarizer to
"clean up" the polarization. The outcoupled light
intensity, after spatially filtering the output beam, is
measured with a large-area photodiode. To minimize
stray light and suppress any substrate modes (internal
reflection within the glass substrate) that may be present,
the backside of the EA-IOW substrate between the two
gratings is coated with black strippable paint.
Before discussing the use of the EA-IOW to monitor
absorbance changes in an adsorbed film during a
potential scan, it is first necessary to describe the
optical background upon which these absorbance
changes are superimposed. Figure 6 illustrates the
change in outcoupled light intensity as a function of
electrode potential during a scan in which no
electroactive species are present, either in solution or
adsorbed to the EA-IOW surface. There are two
observable effects: a linear decrease in outcoupled light
intensity (Fig. 6a and b) and a nonlinear change accom-
panied by a large hysteresis during the return potential
scan (Fig. 6a). The nonlinear change in signal is
attributed to diffusion of ions from the electrolyte into
the near-surface region of the ITO overlayer during
the potential scan. The magnitude of the hysteresis is
consistent with an ion diffusion process; higher scan
rates yield a smaller hysteresis, as do electrolyte ions
with smaller diffusion coefficients. Equilibration of the
ITO in electrolyte solution over a period of ca. several
days removes any hysteresis of the optical signal
between the forward and return scans; the EA-IOW
was equilibrated in 0.1 M KCI for 2 days before the
scan in Fig. 6b, whereas in Fig. 6a there was no
pretreatment of the EA-IOW [5]. Secondary ion mass
spectrometry (SIMS) depth profiling of ITO soaked in
0.1 M KCI for 2 days shows an increase in the
potassium/tin signal ratio over time. A concurrent
[
decrease in the chloride/oxygen signal ratio suggests
-500 that charge balance during the uptake of potassium
ion is maintained by deprotonation of hydroxyl groups
inside the ITO film [22].
The linear change in outcoupled light intensity as a
function of potential is ascribed to a change in ITO
absorptivity due to an increase in the free electron con-
centration inside the ITO [23]. Changes in the real portion
ofthe refractive index for the ITO or electric double layer
at the electrode surface could also lead to a sloping optical
background, either due to perturbations in the mode pro-
file or shifts in coupling and outcoupling angles. It is
believed that both effects do occur butdo not significantly
contribute to the observed change in outcoupled intensity.
The slope of the optical background is dependent on the
wavelength oflight; at wavelengths close to those corre-
sponding to the "band gap" energy (less than 500 nm),
the outcoupled light intensity actually increases as the
potential is scanned negative due to a shift of the band
edge energies of higher energy [24]. The change in
absorptivity of the ITO as a function ofpotential has also
been observed in transmission experiments and is
proportional to the slope of the EA-IOW background
[20]. After preconditioning, the slope of the back-
ground has been found to be linear (or close to linear)
between -500 and +1200 mV Furthermore, the slope
is reproducible from experiment to experiment, un-
like the hysteresis seen in Fig. 6a. This reproducibility
makes it possible to perform quantitative EA-IOW
spectroelectrochemistry of monolayer films deposited
through the Langmuir-Blodgett (LB) technique
(because it is not possible to obtain a background after
depositing the LB film). In addition to reproducibility,
another important experimental consideration is the
time constant of the observed optical background
changes. Ultimately, the rates of these changes may limit
the ability to obtain kinetic information from EA-IOW
absorbance data. This area of EA-IOW development has
yet to be explored.

L
 Electroactive Integrated Optical Waveguide 519

v. SPECTROELECTROCHEMISTRY OF
METHYLENE BLUE
80
=- Background
(a)

The electrochemical reduction of surface-adsorbed

methylene blue (MB) was chosen as a test system for the
~60
(ii40
c
= ;;>

Signal after introduction

initial EA-IOWexperiments for several reasons. MB, a
.9120
en --------
of methylene blue

thiazine dye with the structure given as Fig. 7, is known

J to adsorb to oxide surfaces and possesses a well-defined
reversible two-electron reduction (accompanied by Q) 0.16
(,.)

addition of two protons) at -0.275 V (vs. Ag/AgCI) [5]. ffiO.12

..c
Also, MB is highly colored, with a molar absorptivity of
~0.08
7800 M- 1 cm- 1 at 633 nm but becomes colorless upon ..c
reduction to the leuco form. Finally, MB is a good candi- « 0.04
date molecule for the demonstration of the EA-IOW's 0.00 '-----L-~_ __'_~_--'---~_--'---~_ __'___~_ __'___~

utility in the measurement of the linear dichroic ratio as

o -500

a function ofpotential, a capability that makes it possible

to follow changes in electroactive film structure during
electrochemical events. Figure 8a contains the optical
response of the EA-IOWas a function of potential both
before and after the adsorption of MB from a 2.0-tIM
solution onto the ITO surface. The surface coverage of
MB at this solution concentration was determined
electrochemically to be 4% ofa close-packed monolayer
(assuming an area of 65 A2 /molecule). From the data in
Fig. 8a, the absorbance as a function ofpotential was cal-
culated and plotted in Fig. 8b. The measured absorbance
is due solely to a submonolayer ofMB adsorbed at the sur-
face of the ITO, as the concentration of solution-phase
MB is far too low to produce a measurable absorbance
(vide supra). Before reduction of the MB at ca. -250 mY,
the absorbance is proportional to the solution concen-
tration of MB, as expected for an adsorption isotherm
at low solution concentrations. Upon reduction, the
absorbance drops as the MB is reduced to
Figure 8 EA-IOW signal, at 633 nm, as measured during the
cyclic voltammetry of surface-adsorbed methylene blue (ca.
4% of a full monolayer coverage). Electrolyte, 0.1 M KCl; scan
rate 10 mVis. (a) Raw outcoupled intensity signals before and
after the introduction ofa 2.0 J.lM methylene blue solution. Each
signal is an average of three separate scans. (b) Methylene blue
absorbance as a function of potential, calculated from the data
in a.
with the change in oxidation state; colorless reduced
MB has a greater affinity for the ITO surface than the
colored prereduced MB and is concentrated on the ITO
surface at potentials negative to the reduction potential
but is not detected optically until the reoxidation of the
ME film above ca. -300 mV This proposed mechanism
is supported by the scan rate dependence of the increase

t
I
I
leucomethylene blue. The absorbance never falls com-
pletely to zero, however, suggesting that over the potential
region investigated, approximately 20% of the MB mol-
i ecules are electrochemically inactive. During the reverse
scan, the absorbance increases to a level above that before
reduction. This increase is a result ofa shift in the equilib-
rium between adsorbed and dissolved MB associated
in absorbance during the anodic scan; at higher scan
rates there is less time to collect MB at the surface, leading
to a smaller increase in absorbance. Also, it was observed
that after a period of several minutes at 0 Y, the
absorbance signal returns to the level seen previous to
the potential scan.
The measured absorbance as a function ofpotential is
directly proportional to the integral of the cyclic
voltammogram. Starting with the formalism for the i-V
curve for the cyclic voltammetry of a surface-adsorbed
electroactive species [25], an expression for the derivative
of the measured EA-IOW absorbance with respect to
potential can be derived:

dA _ nF r*eS(bo/br)exp[(nF/RT)(E - E0 1)]
dE - RT {1 + (bo/br)exp[(nF/RT)(E _ EOI)]}2
Figure 7 Structure ofthe methylene blue cation. (2)
520 Dunphy et aI.

where n, F, R, and Thave their usual meanings; r* is the g-10 [ (a)

total surface concentration of the adsorbate; e is the o
ci -5
molar absorptivity of the adsorbed species; bo/ br is a ><
measure of the relative strength of adsorption for the ~ 0
oxidized and reduced forms of the electroactive species; «
;> 5

>J
EO' is the formal potential of the redox couple, and E is "0

the applied potential. The term S is a sensitivity factor, ~

..... 10 I- I I I I • I I !

1~ (~)
analogous to pathlength is a transmission experiment, -100 -200 -300 -400 -500
that is a function of the evanescent field strength, the
thickness ofthe adsorbed layer, and the distance between
~
6
the input and output grating couplers. From Eq. (2) it is 1
...:
c
4
readily apparent that the derivative of the EA-IOW ~ 2 _ __
absorbance with respect to the potential is directly
:s
() 0 _

proportional to the faradaic current (by a factor of -2

nFA v/ is, where v is the scan rate and A is the electrode
area) without any contribution from nonfaradaic
charging and background currents. Thus, by computing
the derivative of the data in Fig. 8b, it is possible to
reconstruct the faradaic component of the cyclic
voltammogram. This is shown in Fig. 9a, along with the
current-detected cyclic voltammogram for comparison
(Fig. 9b). The amplitude difference between the cathodic
and anodic signals is due to the shift in adsorption equi-
librium addressed previously.
VI. LINEAR DICHROISM OF MB
The measured adlayer absorbance in either TE or TM
polarization is not only a function of surface coverage,
film thickness and molar absorptivity. The ratio of
absorbances obtained in TE and TM polarizations (the
linear dichroic ratio) is related to the average orientation
angle between the ensemble of absorption transition
dipoles and the surface normal [26-28]. The results of
o -100 -200 -300 -400 -500
Potential, mV vs Ag/AgCI
Figure 9 (a) Reconstructed cyclic voltammogram (from the
data plotted in Fig. 8b) and (b) current-detected cyclic
voltammogram measured simultaneously as the optical data
in Fig. 8a. The arrows indicate the positions of the cathodic
and anodic signals and the scan direction.
assignment is subject to several major assumptions,
which are addressed in the following paragraph. Before
reduction, the average orientation of the MB is ca. 58°
with respect to the z-axis, similar to the orientation deter-
mined for MB adsorbed at an Si02 interface determined
by second harmonic generation [29]. During reduction,
20
18

/~l~
16
modeling the dichroic ratio as a function ofaverage mol-
14
ecularorientation for a linear dipole at 633 nm, assuming
an infinitely narrow distribution of orientation angles, 12
are presented in Fig. 10. The orientation angle, e, is :210
defined as an inset in the figure. It is apparent from this ~8 -~
<t
-

plot that the dichroic ratio is more sensitive to molecular 6

orientation at large values of e, as discussed in Ref. 27, 4
for an ensemble of circular dipoles. Another important
2
point illustrated in Fig. 10 is that the dichroic ratio varies
between zero (when the molecular dipole is oriented O~
vertically to the surface leading to zero absorbance in 0 15 30 45 60 75 90
TE polarization) and a large number (18 for the Average e
waveguide structure shown in Fig. 2) but does not go to
infinity due to the non-zero electric field along the x-axis Figure 10 Theoretical dichroic ratio as a function of average
in TM polarization. orientation angle for a linear adsorption dipole at 633 nm. Inset:
From this theoretical data, it is possible to then assign The orientation angle for a single linear dipole is defined with
an average orientation angle to experimental results, as respect to the surface normal. The EA-IOW modeling par-
shown in Fig. 11 for the cyclic voltammetry of MB. This ameters are given in Fig. 2.
 Electroactive Integrated Optical Waveguide 521

When calculating an average orientation angle from a

4.5 60
measured linear dichroic ratio, it is assumed that the
58
~
eo angular distribution oforientation angles about the mean
4.0 iiJ is infinitely narrow. This is a significant limitation oflin-
a 56 cal
& 3.5 o
54 :::!.
ear dichroism measurements; the average orientation
angle is by itself not a measure of the relative degree of
() eo
'..ce 3.0
52
:J
§I
molecular order because a measured dichroic ratio is a
()
o' function ofnot only the average orientation angle but also
is 2.5 50 :J the distribution ofangles about this mean [27]. In general,
» as the distribution ofangles becomes wider, the measured
48 ~
2.0 CD average orientation angle increases. Surface roughness
46 can also increase the apparent average orientation angle
1.5 L---'------'_--'-~_-'-~_ _'__~ _ _'__~_.l...__...J

0.0 ~.1 ~.2 ~.3 ~A -0.5 [30]. The combination of lOW linear dichroism with
Potential vs Ag/AgCI fluorescence anisotropy in a total internal reflection
geometry partially alleviated these complications,
allowing the determination of both the mean orientation
Figure 11 Experimental dichroic ratio as a function of poten-
tial during the cyclic voltammetry of methylene blue under the
angle and the distribution of angles about the mean
conditions given in Fig. 8. The average orientation angle was in molecular films deposited on nonelectroactive
determined from the data in Fig. 10. The initial scan direction waveguide surfaces [26-28]. Because MB and related
is indicated by an arrow. molecules are fluorescent, we intend to use it in future
studies as a model system for the implementation offluor-
escence anisotropy in conjunction with linear dichroism
using the EA-IOW

the ratio ofTE absorbance toTM absorbance drops; it is

important to remember that the reduced form of MB is VII. APPLICATIONS OF THE EA-IOW
colorless and thus does not contribute to the measured
To illustrate the use of the EA-IOW in the spectro-
dichroic ratio. A plausible explanation for the measured
electrochemistry of monolayer and submonolayer
change in average orientation angle is that, on average,
films, two molecular systems currently under study
molecules with horizontal orientations are more easily
are briefly discussed. The first involves the optical
reduced than molecules with more vertical orientations.
monitoring of phthalocyanine aggregate structures at
Rearrangements of MB molecules due to a change in
submonolayer coverages during oxidation to elucidate
ITO charge during the potential scan could also produce
the role of aggregate~aggregate interactions and
a change in average orientation angle. This effect is prob-
t ably not important in this case, because this is no signifi-
cant change in dichroic ratio in the potential window
counterion diffusion on electron transfer. The goal of the
second study is to test the hypothesis that a necessary con-
dition for electron transfer between protein films and
I
r
from 0 to -0.25 V, where no electron transfer occurs but
over which there is a change in surface excess charge at
solid electrodes is a well-ordered protein film with a
favorable orientation.
the electrode-solution interface. Interaction between
adsorbed MB molecules on the ITO surface during
A. Spectroelectrochemistry of
reduction could also possibly cause the observed changes.
Phthalocyanine Aggregates
However, because the surface coverage is only 4% of a
monolayer and the MB is adsorbed as the monomer Recently, phthalocyanine molecules with good solution
species at a solution concentration of 211M (as indicated processability and the ability to form well-ordered
by the linear dependence of EA-IOW absorbance with films through the LB technique have been of interest
solution concentration), interactions between paired for applications such as chemical sensing and
MB molecules is not likely. Negative of -0.4 V, there is a molecular electronics [31,32]. Two such molecules are
second change in dichroic ratio that occurs. It is not illustrated in Fig. 12. The first is an example of a class
known if this change is the result ofa faradaic process, is of compounds known as "hairy-rod" molecules,
induced by other means, or is an artifact. During the phthalocyaninatopolysiloxane (PcPS) [31]. This polymer
anodic scan, the dichroic ratio returns to its prereduction (20-50 nm in length) consists ofperipherally substituted
value. phthalocyanine monomer units axially linked though
522 Dunphy et al.

''-@

\ I

Figure 12 Phthalocyaninatopolysiloxane (left structure) and 2,J,9,10,16,17,23-octakis((2-benzyloxy)ethoxy)phthalocyaninato

copper (right structure), along with a schematic of the columnar structure formed by both through deposition with the
Langmuir- Blodgett technique.

silicon-oxygen bonds to maintain rigidity [31]. The
flexible side chains, most commonly in a tetra-
(methoxy)-tetra-(octyloxy) substitution pattern (referred
to as Cl-C8), impart solution solubility to the rigid
core structure. LB films produced from this technique
are highly ordered, consisting of rows of parallel
PcPS columns. The second phthalocyanine,
(2,3,9,10,16,17,23 -octakis((2-benzyloxy)ethoxy)phthaloc-
yaninato)copper (abbreviated CuPcOC 2 Bz) also forms
well-ordered LB films with a similar columnar
microstructure [32]. Contrary to PcPS, however, the
high degree of ordering is not due to covalent bonding
between individual phthalocyanine rings but is an
effect of side-chain aggregation and phthalocyanine-
-phthalocyanine interactions. The electrochemical
properties ofCuPcOC2 Bz (and PcPS) appear to be highly
sensitive to this film structure in a manner that is not com-
pletely understood. One hypothesis is that in multilayer
films of CuPcOC2 Bz, the film structure is disrupted by
ion diffusion into the film during an initial oxidation pro-
cess and that this disrupted structure is further oxidized
at more positive potentials [32]. By using the EA-IOW to
follow the oxidation process at submonolayer coverages,
it becomes possible to observe the electron transfer in
the absence ofcounterion diffusion effects. Furthermore,
in mixed LB films ofCuPcOC2 Bz and methyl arachidate
(MA), where the surface coverage ratio is approximately
1 : 20, individual aggregates of the material can be
physically separated from one another, allowing the elec-
trochemical properties ofisolated domains to be studied.
 Electroactive Integrated Optical Waveguide
0.04
0.03
0.02
0.01
0.00
-0.01 L-~---,L---,---'_~-----'_~--...J.._~---'-_~----'-~
o 200 400 600 800 1000 1200
Potential, mV vs Ag/AgCI
Figure 13 Change in absorbance as a function of potential
during the oxidation ofa 5% CuPcOC 2 Bz in methyl arachidate
monolayer film, deposited on the EA-IOW from a Langmuir-
Blodgett trough. Electrolyte; 0.1 M KCl; scan rate; 10 mYls.
\ between surface-adsorbed cyt c and a solid electrode,
'"
There are two pieces ofevidence that support the exist-
ence of these isolated CuPcOC 2 Bz aggregates. First, it is
evident from isotherm data on the LB trough that the
CuPcOC 2 Bz is incorporated into the MA film and does
not lie on top of it; the surface area/molecule (after
subtraction of the contribution from MA) is ca.
140 A2 per CuPcOC 2 Bz molecule, consistent with a
"tilted-edge-on" orientation [20]. Also, the onset of
oxidation occurs at a potential less positive (+400 mY)
than that for the monomeric material, indicating that
the phthalocyanine is in an aggregated state [33]. This
onset voltage was determined from the optical data in
Fig. 13, the results of an experiment where absor-
bance changes at 633 nm, occurring in a mixed
r CuPcOC 2 Bz/MA monolayer film, were monitored as a
I! function of applied potential. These data are very similar
to that obtained for CI-C8 substituted PcPs in both sub-
monolayer and multilayer coverages [8,33]. As expected,
however, the onset potential for oxidation is ca. 200 mV
more positive for CuPcOC 2 Bz than PcPS [8,32]. This
may be due to the smaller separation distance between
phthalocyanine units in the latter material or to differ-
ences in cofacial arrangement of the phthalocyanine
rings between the two molecular architectures [34].
This similarity between the CuPcOC 2 Bz and PcPS
potential-dependent absorbance changes suggests that
CuPcOC 2 Bz exists in a "rodlike" aggregate form; this is
supported by recent imaging of CuPcOC 2Bz films by
STM [35].
The observed absorbance changes are interpreted as
arising from the movement of an absorbance band
523
through 633 nm in the potential region between +400
and +800 mY, followed by the appearance of a second
band at a higher degree of oxidation [33].
B. Spectroelectrochemistry of
Cytochrome c
Because of potential applications in biosensing and to
develop a better understanding of protein electron
transfer reactions, direct electron transfer between
adsorbed proteins and solid electrodes has been studied
extensively [36]. It has been demonstrated that facile elec-
tron transfer in these systems occurs only under very
specific conditions such as high protein purity and elec-
trode preconditioning in electrolyte [36]. Much of the
research in this field has dealt with equine cytochrome c
(cyt c), a small electron transfer protein that contains a
redox-active iron porphyrin prosthetic group. It is widely
hypothesized that for facile electron transfer to occur
the protein molecules must be oriented with the heme
pocket facing the electrode surface and the film must be
well ordered (i.e., the molecular orientation distribution
must be narrow). Presumably this favorable structure is
a result ofelectrostatic interactions between the positively
charged face of cyt c and the negative charge of the elec-
trode surface [36]. To test this model (illustrated in Fig.
14) along with examples of good and poor electron
+ +
~ ~ ,;!;.
~: + + .+
+
Potential
-......
C
Ql
~
(J Potential
Figure 14 Depiction of the hypothesized relationship
between protein film structure and ease of electron transfer (as
illustrated through cyclic voltammetry). Top: a poorly ordered
film yields poor electron transfer between the protein and the
solid electrode. Bottom: a well-ordered film, with the protein
molecules in a favorable orientation, leads to good electron
transfer.
524
transfer as measured with cyclic voltammetry, data
regarding protein average orientation and distribution
of orientations must be obtained. The number of tech-
niques that can yield quantitative information regarding
the orientation and orientation distribution are limited,
however. As noted above, an approach that has been
used to measure these properties in monolayer films of
cyt c at oxide surfaces has been the combination of
linear dichroism using integrated optical waveguide
spectroscopy and total internal reflectance fluorescence
anisotropy [27,28].
An example of the spectroelectrochemistry of a cyt c
film, as measured with the EA-IOW in TM polarization,
is given in Fig. 15. This absorptovoltammogram, and the
corresponding reconstructed voltammogram (presented
as an inset), demonstrates the feasibility of using the
EA-IOW to study electron transfer in protein films.
Implementation of the full linear dichroism experiment
is underway, starting with the redesign of the EA-IOW;
at present the optical losses for theTE mode are too high
to allow a reasonable measurement of the outcoupled
light intensity at 514.5 nm. Preliminary experiments
using an EA-IOW design with a 25-nm ITO layer have
been promising, because both the TE and TM modes at
a wavelength of 514.5 nm have detectable outcoupled
intensity [37]. This will enable the EA-IOW to be used to
measure linear dichroic ratios; when combined with flu-
orescence anisotropy data, it is anticipated that the
relationship between cyt c film structure and electron
transfer can be elucidated.
VIII. FUTURE DIRECTIONS
FurtherdevelopmentofEA-IOW technology promises to
increase the applicability ofspectroelectrochemical tech-
niques to the study of electron transfer reactions of
adsorbed molecules on semitransparent metal oxide
electrodes, such as ITO and tin oxide, at surface coverages
not amenable to standard single-pass transmission
experiments. The ability to perform spectro-
electrochemical characterization of monolayer and
submonolayer films has the potential to yield significant
insight into such current problems in electrochemistry
as the determination of the relationship between film
structure and electron transfer kinetics (as discussed in
the context ofcyt c) or the effect ofmolecular architecture
on redox processes (illustrated by the example of thin
films ofphthalocyanine polymers and aggregates). Future
applications for the EA-IOW include development of
multiresponse chemical sensors (for analytes such as
trace metal ions) where absorbance, luminescence, and
some electrochemical parameter such as current or
Dunphy et aI.
..-
Reconstrycted Cyt c Voltammogram
I,~.
U.J J. -, •
"0'
~ : . +-"'
I "
Potential
o ·200 -400 -600
Potential, mV vs Ag/AgCI
Figure 15 Spectroelectrochemistry of a monolayer cyt c film,
as measured at 543 nm with the EA-IOW Electrolyte, 10 mM
phosphate buffer, pH 7; scan rate, 10 mY,/s; TM polarization.
The EA-IOW used for this experiment had a 50-nm ITO layer,
with a 22-mm separation between the input and output grating
couplers. The purified cyt c was deposited from a 5-,uM solution.
interfacial potential can be monitored simultaneously to
produce greater "orthogonality"ofdata in response space
in comparison with standard electrochemically based
sensors such as ion-selective electrodes [12,38,39]. It is
also possible that the observed optical background
changes could be used as a means ofstudying the interac-
tion of the ITO (and other metal oxides) with electrolyte
solutions.
At present, the primary limitation to broader appli-
cation ofEA-IOW technology is that only one wavelength
may be coupled into the waveguide at a given incidence
angle. True multi-wavelength spectroelectrochemistry
would greatly facilitate the interpretation of data such as
that shown for the oxidation of phthalocyanine
aggregates (Fig. 13). Also, observation of complete
spectra could be useful in determining film structure as
in the use of the Q-band absorbance for cyt c as an
indicator ofprotein folding [40]. An achromatic coupling
system with a 200-nm bandwidth has recently been dem-
onstrated for a single-layer waveguide structure, allowing
true spectroscopy to be performed on monolayer cover-
age adsorbed films [41]. The extension of this tech-
nology to the multilayer structure of the EA-IOW is an
area of future development but will require the
further characterization of the potential- and
equilibration-dependent changes occurring in thin ITO
films.
+ Electroactive Integrated Optical Waveguide
ACKNOWLEDGMENTS
Supported in part by grants to N.R.A. and S.S.S. from the
National Science Foundation (Chemistry), the National
Institutes of Health, the Department of Energy/Pacific
Northwest National Laboratories, and by a graduate fel-
lowship to D.R.D. and faculty fellowships to N.R.A. and
S.S.S. through Associated Western Universities.
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30
Surface Science Studies of Organic Monolayer Corrosion
Inhibitors
Steven L. Bernasek
Princeton University, Princeton, New Jersey
ABSTRACT
The inhibition of corrosion in the petroleum production
industry is both economically important and technically
challenging. Organic monolayer corrosion inhibitors
have been used effectively to reduce corrosion rates of
carbon steels in production and refining environments.
These molecules typically include a heteroatom site that
attaches the molecule to the surface and a hydrocarbon
portion of the molecule that serves to form a protective
barrier. The actual mode of interaction with the surface,
thermal stability, and decomposition pathways for these
inhibitor molecules are not well understood. Surface
science methods can be used to examine the thermal
stability and decomposition pathways ofthese monolayer
inhibitors, using well-characterized model substrates
and model inhibitor molecules. A combination of
vibrational spectroscopy, thermal desorption spectro-
scopy, and electron spectroscopic methods has been
used to examine the interactions of model corrosion
inhibitor molecules with well-characterized iron sur-
faces. Alkanethiol decomposition has been studied for
a series of normal and substituted thiol molecules.
Decomposition via f3-hydride elimination limits the
thermal stability of the normal alkanethiols. Methyl
substitution at the f3-site improves thermal stability and
leads to possible oligomerization on the surface.
Oligomerization is also observed in studies of thiophene
decomposition, leading to improved corrosion inhibition
for this overlayer. Redox active inhibitors such as
polyaniline have been examined, as have phosphorous
containing inhibitors whose action may involve struc-
tural modification ofthe corroding surface. These studies
527
indicate the importance of understanding kinetic
pathways for decomposition and thermodynamic and
structural stability of the organic corrosion inhibitor
monolayer.
I. INTRODUCTION
The corrosion ofiron and steel is ofparticular concern in
the petroleum industry. The enormous capital investment
in well piping, production equipment, transport systems,
and refinery complexes makes corrosion inhibition of
paramount economic importance, whereas the aggress-
ive environment ofthe petroleum production and refining
process makes corrosion inhibition technically very
challenging. It is estimated that more than 30 billion
dollars is spent annually for corrosion related repair and
replacement in the United States [1]. As much as 10% of
this cost can be attributed to spending in the petroleum
industry. Petroleum production fluids in the well environ-
ment contain, in addition to crude oil of considerable
complexity, corrosives such as hydrogen sulfide, carbon
dioxide, elemental sulfur, polysulfides, organic acids,
chloride and other salts, and water [2]. Well pressures
can be greater than 15,000 psi at depths up to 6 km, and
temperatures up to 230°C are common. Fluid velocities
are high, with sand, drilling mud, and heavy metals
adding to the complex mix. This is indeed an aggressive
environment, and corrosion inhibition of carbon steel
and low alloy steels is quite difficult. In the refinery
environment, temperatures can be considerably higher
528
(up to 500°C), with significant concentrations oforganic
sulfur and organic acids present in the refinery stream.
Although higher alloy steels are more commonly used
in the refinery, stress corrosion cracking and
carburization failure mechanisms begin to come into
play in this case [3].
Corrosion of iron and steel in these environments
occurs by both chemical and electrochemical pathways.
In practice, corrosion inhibition in the oil well environ-
ment involves the use of corrosion inhibition "cocktails"
that are periodically injected at the wellhead to mix with
the production fluid, extending the life of the well tubing
by slowing the action of these corrosive agents. These
proprietary mixes of organic chemicals include sulfur,
nitrogen, and phosphorous-containing hydrocarbons of
various types [4]. Thiols, amines, organophosphates,
and heterocyclic molecules have all been used in this way.
These compounds are thought to act by retarding the
anodic dissolution of the steel or the cathodic evolution
of hydrogen. Organic inhibitors also are believed to form
protective barriers on the exposed metal surface [5].
Although a number of cocktails have been developed
empirically and improvements to the technology have
been made based on chemical intuition and hypotheses
about the mechanisms of action of these materials, little
molecular level information is available about the oper-
ation of these inhibitor systems. A molecular level under-
standing of the inhibitor-surface interaction and a
detailed knowledge of the inhibitor decomposition
mechanisms could lead to the design ofcorrosion inhibi-
tor systems with improved performance.
Organic corrosion inhibitors are particularly
attractive because they are postulated to bind to the iron
surface and form well-ordered monolayers. Because only
a very small amount of inhibitor is needed in this
instance, structurally organized monolayer inhibitors
are economically attractive. The study of organic thin
films has burgeoned over the last several years, in no small
part because of this possible application in corrosion
inhibition. Clearly, the synthesis and characterization of
well-ordered monolayer films of long-chain thiols on
gold surfaces [6], chlorosilanes on silicon [7], and alka-
noic acids on oxide surfaces [8] have added to research
interest in these and related materials for corrosion
inhibition applications. The construction of ordered
organic thin films on reactive metal surfaces is somewhat
different and has not yet been fully explored.
The strategy of "multifunctional inhibitor design" for
the preparation oforganic thin film inhibitors on reactive
surfaces such as iron is illustrated in Fig. 1. The inhibitor
molecule is bound to the reactive surface through an
appropriate heteroatom ligation, perhaps involving
Bernasek
~J
Hydrophobic
Head Group
R_J Overmyer-
Mechanical
Barrier
---- 1 ImerfJCial
Decomposition
Zone
o•
Surf~c~ Lig~tion H~t~ro~[Qm
T~lh~red R~dox R~~g~nl
R Polymeriz~bkSide
....... -". " Group for Crosslinking
• H~~d Group D~signed to ~ldi~t~ Chain PJcking
Int~rJc!ions and Provid~ a Robust Hydrophobic Barrier
Figure 1 Concept of multifunctional inhibitor design.
sulfur, nitrogen, or phosphorous. A long-chain hydro-
carbon or polycyclic hydrocarbon attached to the
heteroatom forms a densely packed hydrophobic
overlayer. This layer serves as a barrier to the transport
of ions and corrodant molecules to the reactive metal
surfaces. Chain -chain interactions, or cross-linking
and polymerization between molecules, can improve
the thermal stability of the overlayer and its mechanical
properties. Hydrophobic head groups can increase the
resistance of the layer to the mass transport ofcorroding
species, and the incorporation of redox active species in
the molecular layer may act to neutralize ions and slow
electrochemical corrosion pathways. This model forms
the basis for the studies ofmolecular corrosion inhibitors
described here. Particular attention is paid to the
metal- heteroatom ligation and the effect of the reactive
metal on the stability and decomposition pathways for
model inhibitor molecules.
Model studies designed to address questions of
organic overlayer stability and thermal decomposition
mechanisms of these model inhibitors are the subject
of this chapter. Ultrahigh vacuum (UHV) electron
spectroscopy and thermal desorption spectroscopy are
used to probe the detailed molecular mechanisms of
l
model inhibitor interactions with well-characterized
single-crystal iron surfaces [9]. These model studies,
which are about as far removed from the actual environ-
ment of petroleum production as is possible, do provide
l
 Organic Monolayer Corrosion Inhibitors
information of value for the design of corrosion
inhibition systems. We hope that the individual examples
to be treated here will convince the reader of the validity
of the previous statement. The examples draw heavily on
work from our own laboratory and from related studies
from other groups. After a description of the
experimental methods used in this work, the interaction
of alkylthiols with the iron surface is first discussed. This
system provides an excellent example of the use of the
knowledge of the inhibitor decomposition mechanism
to suggest a strategy for the improvement ofthe inhibitor
species. The interaction of thiophene and aniline with
the iron surface is then discussed, providing an example
of the possibility of cross-linking and surface
polymerization of the overlayer to increase inhibitor
stability. Finally, recent work that suggests that atomic
level modification of the iron surface structure occurs in
the presence of inhibitor molecules and inhibitor
decomposition products is described. These examples
serve to illustrate recent work whose goal is to develop a
molecular-level understanding of corrosion inhibitor-
surface interactions. Considerably more work remains
to be done to connect the results of these sorts of investi-
gations to the technology of corrosion inhibition,
although a start has been made.
Low Energy
Electron
Diffraction
(LEED)
High Resolution
Electron Energy
Loss ---t----I--.
Spectroscopy
(EELS)
~
\
Multichannel ~
Gas Dosers
t Figure 2 Schematic of typical multiple technique UHVelectron spectroscopy apparatus.
i
I
529
II. EXPERIMENTAL
The model studies described here were typically carried
out in DHV systems equipped with facilities for
low-energy electron diffraction (LEED), Auger electron
spectroscopy (AES), x-ray photoelectron spectroscopy
(XPS), high-resolution electron energy loss spectroscopy
(HREELS), and thermal desorption spectroscopy (TDS)
[10]. LEED and AES provide structural and com-
positional characterization of the single-crystal iron
substrate used in these investigations. XPS, a core-level
electronic spectroscopy, provides information about the
chemical environment (oxidation state) and composition
of the substrate and the adsorbed overlayer. HREELS,
and other vibrational spectroscopic methods such as
reflection-absorption infrared, can give structural infor-
mation about the adsorbed monolayer. Vibrational
spectroscopy provides molecular bonding information
that can be used to identifY adsorbed intermediates and
to sort out surface reaction pathways. TDS provides direct
information about the thermal stability of the overlayer
and is used to identifY decomposition mechanisms and
kinetic pathways for reactions at the surface. Figure 2
shows a schematic diagram ofa typical DHV system used
in these studies. The multitechnique approach is evident
Auger Electron
Spectroscopy
(AES)
Mass Spectrometer
for Thermal Desorption
530
from this diagram, because information about structure,
identity of intermediates, thermal stability, and reaction
pathway must be combined to obtain a molecular under-
standing of the model inhibitor-surface interaction.
The surface in these studies is a high purity
single-crystal sample of iron. The sample is oriented by
x-ray diffraction and then mechanically cut and polished
to expose a surface of a particular crystallographic
orientation. Crystallographic orientation affects the
reaction chemistry in subtle and not so subtle ways and
must be carefully considered in the determination of the
molecular mechanism of surface reactions. The iron
sample can be purged of bulk impurities, such as carbon
and sulfur, by annealing at 300°C in a flow of hydrogen
in a tube furnace. After mounting the sample in the
UHV chamber, surface cleaning is effected by ion
bombardment and annealing under vacuum. Adsorbate
molecules are exposed to the cleaned surface by
admission into the vacuum system through a controlled
leak. Careful control of the pressure and exposure time
determines the coverage of the molecularoverlayer.
Typical experiments are initiated by the preparation of
a clean single-crystal surface. Surface composition is
then verified by AES and surface structure by LEED.
The cleaned surface, held at low temperature (100 K), is
exposed to the adsorbate of interest. TDS spectra are
obtained by heating the surface at a linear rate (typically
10 K/sec) and recording the partial pressure of species
desorbing from the surface as a function of its
temperature. Electron spectroscopic methods are used
to identifY intermediates that may be present on the sur-
face during the decomposition and to characterize the
structure and composition of the surface after the
thermally induced reaction ofthe adsorbate. Appropriate
isotopic labeling of the adsorbate can be used to help
identifY mechanistic pathways, and to assign vibrational
spectra for the characterization of adsorbed inter-
mediates. Further experimental description of this
multitechnique approach, and details of the spectro-
scopic methods typically used are available in the litera-
ture [10-12].
III. RESULTS FROM MODEL SYSTEMS
A. Alkanethiols on Fe(100)
As already indicated, the adsorption ofalkanethiols and
the formation of stable alkanethiol overlayers on
transition metals, especially gold, has been something of
a growth industry the past several years [6,13-15]. These
well-ordered organic overlayers, or self-assembled
monolayers, have been studied in considerable detail.
Bernasek
Structural studies have been carried out using x-ray
diffraction [16], helium atom scattering [17], and
scanning probe microscopy [18] for long-chain thiols
adsorbed on gold surfaces. The stability of these
overlayers increases with increasing alkyl chain length,
with the long-chain systems essentially forming
two-dimensional crystals on the surface that serve as
barriers for electron transport in electrochemical systems
[19] and that may be effective as corrosion inhibition
agents. Until recently, very little work had been carried
out on the interaction of these sorts of molecules with
reactive surfaces such as iron. Several studies have
addressed the reactivity of methanethiol on a variety of
transition metal surfaces [20], but longer chain thiol
adsorption on reactive surfaces has been less well
explored.
When alkanethiol molecules are adsorbed on the
Fe(lOO) surface, the decomposition of the thiol occurs
around 260 K (Scheme I). Ethanethiol adsorption and
decomposition on the Fe(lOO) surface has been studied
in detail, both on the clean surface [21] and on the surface
exposed to sulfur, oxygen, and water [22]. Exposure of
the surface to the thiol results in the formation of an
adsorbed ethylthiolate identified by HREELS spectra.
The thiolate decomposes near 260 K via C-S bond
cleavage that is identified as the rate-determining step in
the decomposition. On the low coverage surface, the
C-S bond cleavage is followed by f3-hydrogen elimin-
ation to desorb ethylene. At higher initial coverages, some
ethylene reacts with adsorbed hydrogen, resulting in
ethane desorption from the surface at the same
temperature. Decomposition of the saturated ethane-
thiolate surface results in the formation of a c(2 x 2)
sulfur overlayer on the Fe(100) surface.
On gold surfaces, the increase in thiol chain length
results in an increased thermal stability for the organic
overlayer [23]. On the reactive iron surface, the expected
increase in overlayer stability due to chain-chain interac-
tions is frustrated by the low temperature f3-hydrogen
elimination pathway for thiol decomposition. Figure 3
shows the thermal desorption spectra for the adsorption
and decomposition of l-butanethiol on the Fe(100) sur-
face as a function of thiol exposure. Decomposition at
260 K to desorb I-butene, as well as n-butane at higher
initial coverages, is evident. Similar behavior was
observed for thiols ranging from ethanethiol to
l-decanethiol. Decomposition occurred at 260 K, and
desorption of the terminal olefin was observed. Comp-
lementary HREELS studies of the thiol adsorption and
decomposition on the Fe(100) surface suggested that the
reaction proceeded by low temperature S--H bond
cleavage to form the adsorbed thio1ate upon exposure of
I
II
II
II
Ip
L
 Organic Monolayer Corrosion Inhibitors 531

R-CH 2-CH 2-SH(g)

t
+ R
I >3OOK

Fe(I00)
~+ 4
CH :>
CH 2 (g)

lOOK 1 Unsaturated Surface

R
I
CH 2 R
/ I
~ ~
CH 2
CH +
I 260K ~4
S H CH (g)
2
--L-L Saturated Surface

Schemel

(a) Mass 2 (x2) (b) Mass 41 (c) Mass 43 (d) Mass 47 (x4)
Hydrogen Butene Butane Butanethiol

11
'"
tJ
'2
::s
~ m 1.0L
1 1.0L j 1.0L

1\
~

~ ~
OJ
J::
...
:0
0.6L 0.6L
j
..::. 0.6L
e:;
C

.'
~ 1\
till
u;
...
£Q)
e
...
0
0.4L
--f\ 0.4 L 0.4 L

~ J\
~ &
CI)
III 0.2L 0.2L 0.2L
~ -'"
~

~ ~ ~ 0.1 L 0.1 L 0.1 L

I I ,I I I I I I ,I ,I I I I ,I I I

o 200 400 600 800 o 200 400 600 800 o 200 400 600 800 o 200 400 600 800 1000
Temperature (K) Temperature (K) Temperature (K) Temperature (K)

Figure 3 TPD ofl-butanethiol on the Fe(IOO) surface as a function ofl-butanethiol exposure: (a) hydrogen, (b) butene, (c) butane, (d)
butanethiol.Vertica1 scale expansion factors for mass 2 and 47 are referenced to mass 41 and 43. The data shown are not corrected for
alkane fragmentation.
532
the clean surface to the thio!. This thiolate species then
reacted by j3-hydrogen elimination at around 260 K to
form the terminal olefin that desorbed readily from the
surface at this temperature.
In contrast, when methanethiol is adsorbed on the
clean Fe(IOO) surface, the decomposition products are
hydrogen and methane [24]. Again, HREELS spectra
identifY an adsorbed methylthiolate after adsorption at
100 K. In this case, however, further reaction occurs by
C-S bond cleavage to form adsorbed methyl on the
Fe(lOO) surface, which recombines with adsorbed
hydrogen to desorb as methane at 320 K, considerably
higher than the decomposition temperature ofthe longer
chain thiols on this surface. The enhanced stability of
the methanethiol on the Fe(lOO) surface can be traced to
the fact that the j3-hydrogen elimination pathway, which
controls decomposition in the longer chain thiols, is not
available for methanethio!. The thermodynamic consid-
erations, i.e., the strength of interaction between the iron
surface and the ligating sulfur atom or the strength of
the C-S bond in the thiol, are essentially the same for
the entire range ofthiols. Kinetic considerations, on the
other hand, i.e., the presence ofa j3-hydrogen elimination
pathway for the long chain thiols and not the
methanethiol, enhance the stability of the C 1 thiol on
the Fe(lOO) surface. This observation suggests that it
may be possible to design a model inhibitor molecule
appropriately substituted at the j3-position, with the pur-
pose of blocking this low temperature decomposition
pathway. If this were successful, then the chain-chain
interactions that improve the stability of longer chain
thiols on the gold surface may be used to increase the stab-
ility of appropriately substituted longer chain thiol
overlayers on iron as wel!.
This reasoning suggested the investigation of thiol
molecules methyl substituted at the j3-position. The
simplest example of this class of molecules is neo-pentyl
thiol, with all j3-hydrogens replaced by CH 3 groups.
HREELS and TPD studies ofthe adsorption ofthis mol-
ecule on the Fe(IOO) surface [25] suggest that again the
thiolate species is formed upon adsorption at low
temperature. Figure 4 shows the TPD spectra for the
decomposition of the neo-pentyl thiolate species at low
coverage and higher coverage. Hydrogen, neo-pentane,
and iso-butylene products are monitored. Hydrogen
desorbs in a broad multiple peak, beginning near 260 K
and extending to well over 500 K. The neo-pentane
product dominates at low coverage, desorbing from the
surface at around 300 K. At higher coverages, the
iso-butylene product dominates, coming off the surface
at much higher temperatures than observed for the
olefin products of the straight chain alkanethiol
Bernasek
decomposition. Clearly, methyl substitution at the
j3-position has enhanced the stability of the thiolate over-
layer by closing off a low energy kinetic pathway for the
molecular decomposition. HREELS spectra identifY
the thiolate overlayer formed at low temperatures, show
clear evidence for the C-S bond cleavage, and identifY
species present on the surface with intact C-H and
C-C bonds at temperatures well above 450 K. The pro-
posed decomposition pathway for neo-pentyl thiol is
illustrated in Scheme 2. This pathway suggests that the for-
mation of iso-butylene at 400 K results from the forma-
tion of a double bond in the adsorbed overlayer after
methyl migration to the surface. Product iso-butylene
may desorb or the double-bonded species may remain
on the surface and undergo further reaction.
The further reaction that may occur is suggested
by initial results obtained for the adsorption and
decomposition of 2,2-dimethyl-l-dodecanethiol on the
Fe(lOO) surface [26]. Hydrogens j3 to the thiol group are
replaced by methyl in this molecule, and the C IO chain is
available to provide overlayer stability by chain -chain
interactions. Thermal decomposition spectra show a
broad hydrogen desorption spectrum extending to nearly
600 K. Hydrocarbon fragments, masses IS, 29, and 43,
desorb from the surface at temperatures well above
400 K. Most intriguingly, the HREELS spectra show evi-
dence for the presence of a C=C bond on the surface at
temperatures between 120 and 300 K. Formation ofthis
double-bonded species resulting from j3-methyl transfer
to the surface is consistent with the mechanism suggested
for the neo-pentyl thiol decomposition discussed above
(scheme 2). In the case of neo-pentyl thiol
decomposition, this double bond is not observed in the
HREELS spectra due to the ready formation of
isobutylene and its desorption from the surface at this
temperature. For the methyl substituted dodecanethiol,
however, the chain-chain interactions appear to stabilize
the intermediate on the surface, allowing observation of
the carbon -carbon double bond in the spectrum at tem-
peratures up to 300 K.
Above this temperature, it is postulated that the double
bond reacts with adjacent adsorbate to form oligo-
merized species on the Fe(lOO) surface. This conclusion
is based on the thermal stability of the overlayer formed
after adsorption of the dodecanethiol and warming to
400 K. HREELS spectra continue to show evidence of
C-H and C-C bonding in the overlayer at tempera-
tures as high as 500 K. Hydrogen continues to desorb
from the decomposing overlayer even for temperatures
near 600 K. It would be interesting to probe the effect of
still longer hydrocarbon chains on the stability of the
j3-methyl substituted thiols. Evidently, methyl substi-
Organic Monolayer Corrosion Inhibitors 533

Mass 2 Mass 56 (x 100) Mass 57 (xIO)

Hydrogen Isobutylene Neopentane

1L

O.75L

A OAOL

~ L-----t-
O.25L

100 200 300 400 500 600 700 100 200 300 400 500 600 700100 200 300 400 500 600 700

Figure 4 TPD of neopentyl thiol on the Fe(lOO) surface as a function of neopentyl thiol exposure: mass 2, hydrogen; mass 56,
isobutylene; mass 57, neopentane.

tution at this position blocks the P-hydrogen transfer
pathway for decomposition, making the adsorbed over-
layer more kinetically stable on the surface. It also
appears that chain-chain interactions between adjacent
adsorbed thiolates help to stabilize the molecular
overlayer. This allows the transient carbon-carbon
double bond that is formed when the P-substituted methyl
migrates to the surface at higher temperature to remain
on the surface long enough to participate in the proposed
oligomerization reaction.
B. Oligomerization Processes on Iron
Oligomerization is also observed in the adsorption and
reaction of thiophene on the Fe(lOO) surface [27].
Thiophene is an interesting model corrosion inhibitor
as thiophene, and a number of related compounds are
already present in crude oil. It is also quite interesting
based on the results of the previous thiol decomposition
studies. In the case of thiol decomposition, the strong
Fe-S interaction of the thiolate weakens the C-S bond
in the overlayer, and P-hydrogen elimination provides a
kinetically favorable pathway for thiolate decomposition.
Electron delocalization in the aromatic ring structure of
thiophene decreases the electron density on the sulfur
atom. Ifthe sulfur acts as the ligation atom for the interac-
tion with the surface, the Fe-S bond will be weaker than
in the thiols, which in turn is expected to stabilize the
organic overlayer species. In addition, the C-C and
C-S bonds in the ring would be expected to be more
stable than in the alkanethiols due to the resonance
stabilization in the n system.
534 Bernasek

Me
Me_t)vle
Me Me I
Me-C
\ ." Me CH,\-
I
CH,
\-
S,
H
- 100 K
Me_t."Me
I
CH,
\-
S
S
"
H
H

~
~
Fe Fe

Me \ , .Me
Me-C·
150K J -- -----. CH,
I
\-

S"
Me,.. ",Me H
C" M\ "Me
M e~ • Me Me-\n
C~2 H~
St,
•
260 K

Me \
380 K -------. C=CH,
/ -
Me

-------.
Me"..C'" Me
Me~ "Me

~ Fe
H

'~
H

-
500 K

C
s
Fe
C
L-
Scheme 2

Again, a combination of thermal desorption
spectroscopy and vibrational spectroscopy are used to
follow the decomposition process on the Fe(lOO) surface
(Scheme 3). Figure 5 shows the thermal desorption
spectrum for hydrogen desorption from the
decomposition of thiophene as a function of thiophene
exposure. A broad desorption peak apparent at low
coverages splits into two distinct desorption features as
perature peak moves to lower temperatures as the
thiophene exposure increases, whereas the high tempera-
ture peak moves to higher temperature with increasing
exposure.
Vibrational spectra identifY the physically adsorbed
intact thiophene molecule on the surface at low
temperatures, based on the presence ofa strong v(C-H)
stretching band at 3080 cm -I, as well as intact thiophene
\ 1

thiophene coverage increases. Curiously, the low tem- ring modes at 1390 cm -1 and C-H out-of-plane bending

....l.....-
 Organic Monolayer Corrosion Inhibitors 535

H H
n~O.l.l (g)
H~\!..?-H

.......
S
+ s c

~ lOOK >530K I
r~'i
......
300K
l''s'/J:

Scheme 3

~
"
Mass 2
Hydrogen
..."'.
modes at 720 cm -I, as seen in Fig, 6, When the surface is
heated to the temperature of the onset of hydrogen 3.0L
~ desorption (200 K), the vibrational spectrum can be
assigned as an upright intact ring species, with significant
molecule-surface interactions evident. This species is
identified in the vibrational spectrum as the surface is I.5L
I heated through the first hydrogen desorption peak and
up to the rate ofmaximum desorption ofthe second peak,
suggesting that the thiophene ring structure stays intact
1.0L
on the surface up to 520 K. At surface temperatures
higher than the second hydrogen desorption peak, the
vibrational spectrum shows only strong bands due to O,75L
Fe~S and Fe~C stretching motions, suggesting com-
plete decomposition of the thiophene overlayer.
Figure 7 illustrates the result of the thermal 0.50L

decomposition of deuterium-labeled thiophene on the

Fe(lOO) surface. In this case, 2,5-dideuterothiophene is
O,30L
adsorbed on the Fe(lOO) surface, and mass 2 (H 2 ), mass
3 (HD), and mass 4(D 2 ) are monitored in the
decomposition. The clear separation of the two hydrogen O.l5L

desorption features into a purely D 2 peak at low tempera-

ture and a purely H 2 peak at high temperature, with no O,05L
mixing of isotopes evident, suggests a mechanism for
the thermal decomposition of thiophene on the Fe(lOO)
surface. Thiophene undergoes C~H bond scission at o 200 400 600 800 1000
both rt. positions on the Fe(100) surface at temperatures Temperature (K)
as low as 100 K. Once C~H bond cleavage occurs at
the rt. position, adjacent thiophene molecules can form Figure 5 Hydrogen TPD from thiophene on the Fe(100)
C~C bonds between molecules, forming an oligomeric surface as a function of thiophene exposure. Adsorption
thiophene species on the surface. This species appears temperature is 100 K.
536 Bernasek

o 1000 2000 3000 4000

Energy Loss (em-')

Figure 6 HREELS spectra of 3.0 L thiophene adsorbed on the clean Fe(lOO) surface at 100 K and then annealed at the indicated
temperatures. Peak assignments are discussed in the text and in Ref. 27.

to be quite stable to further decomposition, with the
vibrational spectra indicating that the thiophene ring
structure is intact to temperatures as high as 550 K. At
this temperature, the C~H bonds in the fJ-positions
cleave, resulting in the higher temperature hydrogen
desorption peak and the eventual destruction of the
thiophene ring structure. Atomic carbon and atomic
sulfur are left on the surface after this final decomposi-
tion step. Again, oligomerization within the organic
monolayer suggests the possibility of improved corrosion
resistance by the molecular inhibitor due to increased
thermal stability and improved mechanical stability of
the overlayer. Preliminary corrosion testing using
impedance spectroscopy indicates that the oligomerized
thiophene coating is effective in increasing the capaci-
tance and resistance ofthe treated iron sample, effectively
slowing corrosion (Fig. 8). More extensive corrosion
testing is needed.
Oligomerization is also observed in the electrochemi-
cal formation of polyaniline on iron and steel surfaces
[28]. Several workers have commented on the possible
use of polyaniline coatings for corrosion protection of
mild steel [29-31]. In this case, oligomerization to form
a stable mechanical film is not the only route to corrosion
protection of the underlying iron surface. Polyaniline
coatings are evidently active redox inhibitors as well [32].
Recent work has put this conjecture on a rather solid basis
[28]. Cyclic voltammetry studies have suggested that
f
,
Organic Monolayer Corrosion Inhibitors
1~ D 2
~\
M_a_s_s_4
HD
Mass 3
Mass 2
o 200 400 600 800 1000
Temperature (K)
Figure 7 Desorption ofH 2 • HD. and D 2 from the Fe(lOO) sur-
face after exposure to 3.0 L 2,5-dideuterothiophene at 100 K.
undoped polyaniline appears to be capable of oxidizing
iron [33]. Air reoxidation of the polymer coating makes
it difficult to monitor directly changes in the oxidation
state of the polyaniline overlayer, however. X-ray
photoelectron spectroscopic studies of the polymer coat-
ing can be used to monitor this possible redox chemistry
in an environment that avoids air reoxidation.
Beard and Spellane [28] examined the N(ls) region of
the x-ray photoelectron spectra of polyaniline prepared
by the oxidative polymerization of aniline with
ammonium persulfate [34] and subsequently coated onto
cleaned cold-rolled steel samples. The relative amounts
ofamine nitrogen and imine nitrogen in the spectra pro-
vide a direct measure of the oxidation state of the
537
450 ~----------------------,
325
E
:s..200 ++
++ +++ + +++
+ +
"r + -iP"+ + +
75 +
+ +
....jw... "'"
11 '\ +
-50 L~~---I~~~--'-~~~---L~~~...l-~~~
o 160 320 480 640 BCD
Z,. (ohm)
Figure 8 Nyquist plot for carbon steel electrode in 0.5 M
phosphoric acid: bare steel electrode (.) and steel electrode
covered with oligomerized thiophene (+). Electrode potential
was held at 0.5 V vs. SeE.
polyaniline coating. In the absence of oxygen, the steel
appears to reduce the polyaniline coating. In the
as-prepared polyaniline sample, the ratio of amine to
imine nitrogen is about 1.8, indicative of the air-stable
oxidized polyaniline. The N(ls) region of the polyaniline
deposited on the steel samples from solution showed a
ratio of amine to imine nitrogen closer to 4, indicative of
considerable reduction of the polyaniline coating. When
the coated steel samples were heated in air and sub-
sequently analyzed by XPS, the amine-to-imine ratio
returned to that characteristic of the air-stable oxidized
material.
This observation is particularly relevant to the possible
mode of operation of designed molecular organic
corrosion inhibitors. The ability of iron or steel in contact
with the polyaniline coating to reduce the polymer
material in the absence ofoxygen and the reoxidation of
the polymer coating in contact with the air provide a route
to the passivation ofthe active iron substrate. The organic
(polyaniline) coating may assist in the formation of a
stable adherent oxide on the reactive metal by way of
controlled redox chemistry in the polymer overlayer.
This approach, combined with the formation of a
mechanically and thermally stable oligomer inhibitor
layer, may provide improved corrosion inhibition
strategies.
c. Inhibitor Driven Surface Structural
Modification
As a final example ofsurface science studies ofmolecular
corrosion inhibitors, a recent investigation of passivation
by phosphorous deposition is described (eM Friend,
538
personal communication). In this case, the interaction of
trimethylphosphite with the Fe(llO) surface was
examined using thermal desorption, x-ray photoelec-
tron spectroscopy, and LEED. This species adsorbs
molecularly on the clean iron surface at low temperatures
and remains intact up to a surface temperature of250 K.
At this temperature, the P(OCH3h species decomposes
to form adsorbed methoxy and atomic phosphorous. As
the surface is heated to above 430 K, the adsorbed
methoxy decomposes, yielding Hz and CO products.
Preadsorbed phosphorous alters the decomposition
pathway for subsequently adsorbed trimethylphosphite.
In addition to Hz and CO, formaldehyde is observed as a
decomposition product. The relative amount of formal-
dehyde decomposition product increases with increasing
phosphorous precoverage. This behavior is similar to that
observed for the decomposition ofmethoxy formed from
the adsorption ofmethanol on sulfur or oxygen-modified
Fe(lOO) surfaces [35-37] In the case of methoxy
decomposition on the adsorbate modified Fe(lOO)
surface, the relative amount of formaldehyde produced
increased with sulfur or oxygen precoverage. This
behavior is in contrast to the effect of sulfur or oxygen
precoverage on the decomposition of methoxy on the
Fe(llO) surface [38]. For the Fe(llO) surface, no formal-
dehyde production is observed, regardless of sulfur or
oxygen precoverage. This observation suggests that
phosphorous adsorbed on the Fe(llO) surface may cause
a restructuring of the surface, resulting in an iron over-
layer with (100) orientation, which more closely
resembles the structure of the sulfur or oxygen modified
Fe(lOO) surface. This recent study begins to provide
atomic level insight into the operation of phosphorous
containing-inhibitor molecules. Further work is clearly
needed to develop the broad understanding of inhibition
mechanisms necessary for the a priori design of effective
inhibitor molecules. The studies presented in this chapter
provide examples of a molecular approach to corrosion
inhibition chemistry.
IV. CONCLUSIONS
The examples presented in this chapter describe the use of
model systems to understand the behavior of molecular
corrosion inhibitors. Methods of UHV surface science
have been applied to the study of the structure and
bonding of molecular corrosion inhibitors on well-
characterized single-crystal model substrates. Thermal
stability of these overlayers and their thermal decom-
position pathways have been identified. The results
of these studies have been used to suggest the syn-
Bernasek
thesis of molecular corrosion inhibitors with improved
thermal stability and increased corrosion inhibition
performance.
In the examples presented here, a facile kinetic
pathway for thermal decomposition of n-alkyl thiols has
been identified. Appropriate substitution to block this
decomposition pathway results in increased overlayer
thermal stability. Increased thermal stability is also
observed when a molecular oligomerization process can
occur in the inhibitor overlayer. Evidence for this process
is obtained from studies oflong-chain fJ-substituted thiol
decomposition and from thiophene decomposition
studies. Oligomerization is also observed for polyaniline
overlayers. In addition, the redox active nature of the
overlayer suggests an additional corrosion inhibition
strategy. Finally, a recent study of the mechanism of
decomposition of a model phosphorous-containing
inhibitor suggests that surface structural changes may
occur when inhibitor molecules interact with a protected
surface. This possibility also must be considered in the
molecular approach to corrosion inhibitor design.
ACKNOWLEDGMENTS
Supported by the U.S. Department of Energy and by
Exxon Research and Engineering. This work is a collab-
oration involving Dr. Trikur Ramanarayanan of Exxon
Corporate Research and Professor Andrew Bocarslyof
the Department of Chemistry, Princeton University. I
thank them and our students and postdoctoral associates
for many interesting and stimulating discussions.
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1. MG Fontana. Corrosion Engineering. 3rd ed. New York:
McGraw-Hill, 1986, pp.I-5.
2. L Gawerick. ed. Corrosion in the Petrochemical Industry.
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3. TA Ramanarayanan, DJ Srolovitz. J Electrochem Soc
132:2268, 1985: TA Ramanarayanan, J Mumford, J
Electrochem Soc 136:1581,1989.
4. PA Schweitzer. In: PA Schweitzer, ed. Corrosion and
Corrosion Protection Handbook. 2nd ed. New York:
Marcel Dekker. 1989, p.47.
5. HH Uhlig, RW Revie. Corrosion and Corrosion Control.
New York: J.Wiley, 1985.
6. LH Dubois, RG Nuzzo. Annu Rev Phys Chern 43:437,
1992.
7. Y Xia, M Mrksich, E Kim, GM Whitesides. J Am Chern
Soc 117:9576, 1995.
8. A Kumar, H Biebuyck, GM Whitesides. Langmuir
10: 1498, 1994.
9. SL Bernasek. Annu Rev Phys Chern 44:265, 1993.
Organic Monolayer Corrosion Inhibitors
10. AT Hubbard, ed. The Handbook of Surface Imaging and
Visualization. Boca Raton, FL: CRC Press, 1995.
II. G Ertl, J Kiippers. Low Energy Electrons and Surface
Chemistry. Weinheim: VCH Publishers, 1985.
12. GA Somorjai. An Introduction to Surface Chemistry and
Catalysis. New York: J.Wi1ey, 1994.
13. D Porter,TB Bright, DL AHara, CED Chidsey. J Am Chern
Soc 109:3559,1987.
14. L Strong, GM Whitesides. Langmuir 4:546,1988.
15. GM Whitesides, PE Laibinis. Langmuir 6:87,1990.
16. J Li, KS Liang, N Camillone, III, TYB Leung, G Scoles.
J Chern Phys 102:5012, 1995.
17. N Camillone, III, CED Chidsey, GY Liu, G Scoles.
J Chern Phys 98:3503,1993.
18. GE Poirier, MJ Tarlov. Langmuir 10:2853, 1994; GE
Poirier, ED Pylant. Science 272: 1145, 1196.
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20. TS Rufae1, RJ Koestner, EB Kollin, M Salmeron, JL
Gland. Surf Sci 297:272, 1993; J Benziger, RE Preston. J
Phys Chern 89:5002, 1985; DR Huntley. J Phys Chern
93:6156,1989.
21. LC Cheng, AB Bocars1y, SL Bernasek, TA Raman-
arayanan. Langmuir 10:4542, 1994.
22. LC Cheng, AB Bocarsly, SL Bernasek, TA Raman-
arayanan. Langmuir 12:392, 1996.
23. CD Bain, EB Troughton,YT Yao, J Evall, GM Whitesides,
RG Nuzzo. J Am Chern Soc 1ll:321, 1989.
24. MR Albert, J-P Lu, SL Bernasek, DJ Dwyer. Surf Sci
221:197,1989.
539
25. K Meagher, K Shafer, AB Bocarsly, SL Bernasek,
unpublished work, 1998.
26. K Shafer. Adsorption and Decomposition of Model
Corrosion Inhibitors on an Fe(lOO) Surface. Senior
Thesis, Princeton University, 1996.
27. LC Cheng, AB Bocars1y, SL Bernasek, TA Raman-
arayanan. Surf Sci 374:357, 1997.
28. BC Beard, P Spellane. Chern Mater 9:1949,1997.
29. G Mengo1i, MT Munari, P Bianco, MM Musiani, J App1
Po1ym Sci 26:4247,1981.
30. DW Berry. J E1ectrochem Soc 132:1022,1985.
31. G Troch-Nage1s, R Winard, A Weymeersch, L Renard.
J Appl Electrochem 22:756,1992.
32. B Wessling. Adv Mater 6:226, 1994.
33. T Kobayashi, H Yoneyama, H Tamura. J E1ectroana1
Chern 177:281, 1984.
34. AG MacDiarmid, JC Chians, AF Richeter, NLD
Somasiri, AJ Epstein. In: L Alcacier, ed. Conducting
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35. J-P Lu, MR Albert, SL Bernasek. Sur Sci 258:269, 1991.
36. J-P Lu, MR Albert, SL Bernasek, OJ Dwyer. Surf Sci
218:1,1989: J-P Lu, MR Albert, SL Bernasek, DJ Dwyer.
Surf Sci 239:49, 1990: J-P Lu, MR Albert, SL Bernasek.
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37. 18 Miller, J Schwartz, SL Bernasek. J Am Chern Soc
115:8239,1993.
38. TS Rufael, JD Batteas, CM Friend. Surf Sci 384:156, 1997:
PH McBreen,W Erley, H Ibach. Surf Sci 133:L469, 1983.
31
Structure of Thin Anodic Oxide Films Formed on
Single-Crystal Metal Surfaces
Philippe Marcus and Vincent Maurice
Ecole Nationale Superieure de Chimie de Paris, CNRS- Universite Paris VL Paris, France
ABSTRACT
Data on the structure ofthin anodic oxide films (passive
films) formed on well-defined single-crystal surfaces of
non noble metals (Fe, AI, Cu, Ni, Cr, FeCr, and FeCrNi)
are reviewed, with emphasis on atomic scale informa-
tion obtained by scanning tunneling microscopy. The
following aspects are considered: the growth mechanism
ofthe thin anodic oxide films and the role ofthe substrate
defects, the crystallinity of the passive layers and the
nature ofthe defects, and the effect ofpotential and aging
under polarization on the structure and composition of
passive films.
I. INTRODUCTION
Thin oxide layers formed on metallic surfaces modifY
considerably the reactivity of the substrate and represent
a major mean of protection of metals and alloys against
corrosion. Data on the chemistry and structure of these
passive films are necessary to understand and predict
their properties, in particular their resistance to break-
down and localized corrosion.
There are now many available data on the chemical
composition of oxide films formed on passivable metals
and alloys. Surface chemical analysis techniques such as
x-ray photoelectron spectroscopy (XPS), Auger electron
spectroscopy (AES), secondary ion mass spectrometry
(SIMS), and ion scattering spectroscopy (ISS) have been,
and still are, very useful to obtain such data. x-ray absorp-
541
tion near-edge spectroscopy presents interesting per-
spectives of in situ determination of the chemical
composition.
In sharp contrast, there has been for a long period a
lackofdata on the structure ofpassive films. This is in part
due to the difficulty ofanalyzing the structure ofultrathin
films on often rough substrates, using, e.g., reflection
high-energy electron diffraction (RHEED) or grazing
incidence x-ray diffraction. The advent of near-field
microscopies (scanning tunneling microscopy [STM]
and atomic force microscopy [AFM]) has opened up
new prospects in this field. With these techniques, direct
imaging of the structure with atomic resolution can now
be performed in both ex situ (ultrahigh vacuum [UHV]
or air) and in situ conditions.
This chapter reviews STM data obtained by ex situ and
in situ STM on the anodic oxidation of metals (Fe, AI,
Cu, Co, Ni, Cr) and alloys (FeCr, FeCrNi), with special
emphasis on atomically resolved structures. The reviewed
data include data obtained in our group on single-crystal
surfaces (Cu(lll), Ni(lll), Cr(llO), Fe-22Cr(l1O), and
Fe-I8Cr-13Ni(lOO)), and data obtained in other groups
on Fe, AI, and FeCr polycrystais and on Ni(lll), Ni(lOO),
and Co(OOOI) single-crystals.
Some aspects of the chemistry of the passive films are
first briefly summarized. The formation of passive films
and the role of the substrate defects are then illustrated
with data obtained on Fe, AI, Cu, and Co. The highly
crystalline character of the oxide films formed on Ni
and the nature of the defects are presented. The effect of
542
aging under polarization on the chemical composition
and structure of passive films containing chromium
oxide is demonstrated with data obtained on pure Cr
and on FeCr and FeCrNi alloys. The implications of the
aging effects in the stability and the breakdown of passive
films are discussed. Finally, the combination of ex situ
and in situ measurements and the relation between the
chemical information and tunneling mechanisms are
discussed together with the perspective of future
developments.
II. BRIEF SUMMARY OF THE CHEMICAL
NATURE OF PASSIVE FILMS
A brief summary on the chemical structure of passive
films is given here. More detailed information on the
growth and the nature of passive films, the composition
ofpassive films formed on stainless steels, and the break-
down of passive films can be found in recent reviews by
MacDougall and Graham [1], Clayton and Olefjord [2],
and Strehblow [3].
Anodic passive layers form on many reactive metals.
On Fe, Cr, Ni, and Cu, they have semiconducting
properties and grow only up to a few nanometers in
thickness. Metals like AI, Nb, Ta, Ti, Zr, and Hf form
insulating oxide films that may grow up to several tens
of nanometers in thickness. These oxide films show a
potential drop at the metal-oxide and oxide-electrolyte
interfaces and in the passive layer. The electric field in
a passive layer of a few nanometers thickness is of the
order of 10 6 Vlcm. This enables the migration of ions
through the film at room temperature with current
densities of some few pA/cm2 or less. On metals such
as Fe, Cr, Ni, and stainless steels in strongly acidic
electrolytes, the passivity results from the slow dissol-
ution kinetics of the oxides.
According to the data obtained by surface analytical
spectroscopic techniques such as XPS, AES, SIMS, and
ISS, the passive films have a complex chemical structure
that is generally described by a bilayer or duplex model
[1,2]. Oxides and hydroxides are present and separated
in different layers. The thickness and the structure of the
related sublayers may change with the electrode potentiaL
the polarization time, the composition of the bulk alloy,
and the composition of the electrolyte. When the passive
film can be described by the bilayer model, the inner
and outer sublayers correspond to oxides and hydroxides,
respectively. The oxide layer is thought to result from the
dehydration of the passive film mostly constituted of
hydroxide in the initial stages of passivation. Some
aspects of this chemical structure are presented below
for Cr and stainless steels.
Marcus and Maurice
III. GROWTH AND STRUCTURE OF THIN
ANODIC OXIDE FILMS
A. Polycrystalline Fe and AI
Bhardwaj et al. [4] were the first to report STM images of
passive films. They studied by in situ real-time STM
imaging the anodic oxidation of polycrystalline iron in a
borate buffer solution ofpH 8.4. They proceeded by alter-
nating oxidation steps at increasing anodic potentials
(from -0.455 to +0.5 V/NHE) and reduction steps at
cathodic potential (-0.75 V/NHE).
After reduction of the natural oxide at the cathodic
potential, relatively flat surfaces were produced, suppos-
edly corresponding to the metal substrate. The resolution
of the measurements did not allow them to measure
monoatomic steps nor the Fe lattice. Upon oxidation at
anodic potential, rougher surfaces were at first produced,
with patches or clusters of nanometer dimensions. These
patches were observed in the first image after the
oxidation step, indicating instantaneous formation on
the time scale of the data acquisition. Upon continuous
imaging at the same oxidation potential, the surface was
observed to smoothen. This was attributed by the authors
to the completion of the passive layer by a fusing effect of
the patches. This effect is indicative of a coalescence
process. When the potential was stepped back to the
cathodic value, surface roughening was first observed
followed by smoothening within minutes ofpolarization.
These topographic changes were attributed to the
reduction of the passive film.
The vertical dimensions of the patches produced at
first by oxidation were found to increase from about 1to
about 4 nm when the anodic oxidation potential was
increased. This suggested an increasing thickness of the
passive film for increasing values of the oxidation
potential. This was supported by the increasing time
periods necessary to reduce completely the passive film
at cathodic potential. These results suggest that the
growth process of the passive film with formation of
patches or islands fusing together is related to a
nucleation, growth, and coalescence mechanism.
More recently, Ryan et al. [5] reported on the atomic
structure of the passive film formed in borate buffer sol-
ution on pure Fe sputter-deposited thin films. The data
show that long-range crystalline order is obtained both
in ex situ and in situ conditions ofexamination, evidenc-
ing the crystalline nature ofthe passive film. This was con-
firmed by in situ x-ray scattering measurements of
Fe(llO) and Fe(OOl) passivated in borate buffer solution
that provided further structural information [6]. The
passive film is nanocrystalline with a crystallite size of
about 5 nm. The film structure is based on the cubic
Structure of Thin Anodic Oxide Films 543

structure of Fe304 with the same 0 2- lattice. The occu- i (lJA.cm")

pancy of the octahedral and tetrahedral cation sites is , -1.2
, , ISHE
, , ,
__I _ l
80% and 66%, respectively. There is a 12% random occu- 500 , , ,
I t I I \ I I I I

pancy of the interstitial tetrahedral sites by cations. --r-,--r-,--r-,--r-,--r-

• I I I I I , I I
__ __ __ __ L_
250
_~ ~ _ ~ L _ ~ L _ ~

Bhardwaj et al. [7] also studied the passivation of ,

I
t
I
I
I
I
I
I
)
I
I
I
I
I
I
I
I
--r-,--r-,--r-'--r-.--r-
polycrystalline Al in sodium hydroxide (0.01 M). They I I I I I I I I

o .J L ~ ".1_ L

also observed that reduction (at -1.135 V/NHE) of the

oxide formed at anodic potentials (from -1.05 to
-0.975 VlNHE) reproduced the original substrate sur-
face and that when the potential is increased in the posi-
tive direction, an oxide begins to grow nonuniformly as
small humps or patches ofnanometer dimensions, which
coalesce after longer elapsed times or at more positive
potentials. As in the case ofiron, these results suggest that
the formation of the passive film occurs via a nucleation,
growth, and coalescence mechanism.
B. Initial Stages of Oxidation of CU(111)
Single Crystals
Morphological changes of the well-defined structure of
single-crystalline Cu electrodes have been the subject of
anumberofSTM andAFM studies related to adsorption
[see 10-14, for example] and dissolution [see 11, 12, 14,
for example]. The anodic oxidation of Cu in a borate buf-
fer solution ofpH 9.3 has been recently investigated in situ
in our laboratory [8,9]. In this surface science approach
of corrosion, well-defined surfaces of single crystals are
used.
The (111) orientation ofCu was selected.Well-defined
single-crystal surfaces characterized by a terrace and
step topography were prepared for Cu by mechanical
polishing followed by electrochemical polishing in
orthophosphoric acid [see 8, 9 for details]. The electro-
polished surface was transferred through air to the elec-
trochemical STM cell where the oxidized surface was
reduced by a potentiodynamic (10 mV S-I) cathodic
treatment from about -0.2 VlSHE (i.e., about 0.2 V
below the open circuit potential) down to about
-1.12 V/SHE where hydrogen evolution occurred. Fig-
ure 1 shows the voltammogram obtained after this
pretreatment with the characteristic oxidation and
reduction peaks.
The metallic surface obtained is shown on Fig. 2a. It is
characterized by a terrace topography with steps having
no preferential orientation. The atomic flatness of the
terraces is indicative ofthe reduction ofthe natural oxide.
The steps are mostly monoatomic with a measured height
of 2.0 ± 0.3 A, to be compared with the bulk value of
2.08 A, and the terraces are from 1to 20 nm wide. The sur-
face profile is characterized by a succession of ascending
and descending steps. This succession indicates that the
-250
-500
E (V1Pt)
Figure 1 Voltammogram recorded on Cu(lll) in the 0.1 M
borate buffer solution (pH 9.3) in the ECSTM cell (10 mV S-I).
relatively high density of steps does not result from a
substrate disorientation. It is thought to result from the
electropolishing procedure.
The formation of the single CU20 layer film could be
observed at 0.03 VlSHE, which corresponds to the begin-
ning of the first oxidation wave. Figure 2 shows the
Cu( 111) surface before and during formation ofthe CU20
film at this potential. The potential was stepped from - 0.7
to 0.03 V/SHE at the end of the downward scan of the
image shown in Fig. 2a (see black arrow). The evolution
of the topography during passivation can be observed
from bottom to top in the image shown in Fig. 2b. At first
(i.e., in the lower part of Fig. 2b), the terrace topography
is mostly affected by a roughening of the steps. This is
indicative of a preferential dissolution of the metal and
formation of the oxide at the substrate steps. The lateral
dimensions ofthe first grains that could be detected at this
magnification are 1.5 to 3 nm laterally and 0.25 to 0.3 nm
vertically, i.e., slightly higher than the Cu(ll1)
monoatomic step of 0.2 nm. This may correspond to the
formation of monolayer island of Cu2o. Grains could
also be detected in terraces but they represent a minority.
This evolution was followed, in the upper part of Fig.
2b, by the development of a grainlike topography. The
terraces observed before passivation could only be
detected then in very local areas because they were almost
entirely covered by protrusions assigned to oxide grains.
Subsequent imaging at the same potential (Fig. 2c) con-
firmed this topography evolution and the complete disap-
pearance of the terrace topography of the surface.
Larger grains were observed suggesting a coalescence
process.
These measurements indicate that at the potential of
0.03 V/SHE, the formation of the Cu20 passive film is
nearly completed within the time necessary to record
one image in our experimental conditions. i.e., about
544 Marcus and Maurice

Figure 2 In situ STM topographic images recorded at -0.7 VI SHE before (a) and at +0.03 V/SHE during formation of the CU20
passive film in a borate buffer solution (b) and (c), It = 0.8 nA, Etip = -0.32 V/SHE. The potential was stepped at the end ofthe meas-
urement of (a) as pointed. (b) Is the first scan (upward) after the potential step, allowing the observation of the nucleation and growth
of the passive film from bottom to top. (cl Is the third scan (upward) after the potential step. (a) AZ = 2.4 nm. (b) AZ = 4.9 nm. (c)
AZ=14.2 nm.

100 s. Measurements with a step-by-step increase of the
potential allowed more detailed observations and
showed that the roughening of the steps is initiated
between -0.01 and 0 VlSHE and that there was no dissol-
ution within the terraces (i.e., pit formation) at this
potential. Anodic dissolution in the terraces (pit forma-
tion could be observed above 0.01 VlSHE, but this was
not the preferential dissolution process.
The following mechanism is proposed to account for
the evolution of the topography during formation of the
passive film. It is based on the competition between dis-
solution and passivation (i.e., blocking of the dissolution
by oxide formation). Both processes take place
preferentially at the steps as indicated by the roughening
of the steps. The slow dissolution of the terraces at the
steps generates a retraction ofthe terraces, i.e., a step flow.
This dissolution may not be even because of the varying
atomic structure of the steps. The first protrusions that
are detected at the steps are assigned to oxide nuclei.
The oxide nuclei are thought to pin down the retraction
of the terraces by blocking the dissolution locally. Hence,
the roughening of the steps results from two local effects:
a step flow due to dissolution and an anchoring of the
steps due to oxide nucleation. As the reaction goes on,
Structure of Thin Anodic Oxide Films
the metal dissolution may continue around the oxide
nuclei. In this way, the oxide nuclei can be partially
isolated from the initial terrace and form oxide islands.
The same process may continue on the flowing steps not
yet passivated (or anchored) and hence lead to the com-
plete consumption of the initial terrace and its replace-
ment by oxide islands.
At higher potential (0.Q1-0m VISHE), the rates of
these reactions increase. Dissolution takes place within
terraces and leads to pit formation, but this is not the pref-
erential site. New steps are then created that can act as
preferential sites of passivation. Further growth of the
oxide film is expected to proceed by three-dimensional
thickening with consumption of Cu from the substrate
below the oxide nuclei. Thickening of the oxide has been
deduced from the instability of the STM measurements
detected after prolonged polarization at 0.03 V/SHE or
very rapidly at higher potential (> 0.05 V/SHE). It is
thought that the density of states in the oxide film is then
decreased and leads to the formation of a band gap (of
about 3 eV [15] in the thicker oxide films), which does
not allow tunneling in the conduction band of the oxide
film [9].
These data obtained on Cu(111) confirm the previous
data on Fe and Al concerning the formation ofthe passive
film by a nucleation and growth mechanism. They show
in addition that substrate steps act as preferential reaction
sites in this process showing the major influence of the
substrate defects.
C. Oxidation of Co(0001) Single Crystals
Ando et al. [16] recently reported atomic-scale data on
the initial stages of oxidation of Co(OOOl) in 0.05 M
Na2S04 at pH 3. Their data confirmed the preferential
nucleation at the substrate monoatomic steps with
growth of oxide islands on the upper terrace. The
observed oxide islands have an hexagonal lattice with a
measured parameter ofca. 0.31 nm that is consistent with
the lattice parameters of CoO(111) (0.302 nm) and of
Co(OHh(OOOl) (0.317 nm). The close-packed directions
are parallel to those ofthe substrate, and the coincidence
cell is (5 x 5) leading to the observation of a Moire
pattern. The measured height of these islands is
0.25-0.3 nm, i.e., higher than the substrate monoatomic
height of0.2 nm and similar to that recorded in the initial
stages of passivation of Cu(111) [8,9]. This is attributed
to the formation of monolayer islands of CoO(111) or
Co(OHh(OOOl). Because Co does not passivate in this
acidic solution as confirmed by the potentiodynamic
curves [16], it is likely that the formation of the oxide
islands on the Co(OOOl) surface corresponds to the initial
545
stages of anodic dissolution, in which case the observed
islands would rather correspond to Co(OHh(OOOl).This
study indicates that future investigation at atomic resol-
ution should provide an atomistic view of the complete
passivation process, possibly allowing to determine more
precisely the role of the structure ofthe step.
IV. CRYSTALLINE PASSIVE FILMS ON NICKEL
Lev et al. [17] were the first authors to investigate, on poly-
crystalline Ni in 0.5 M H2S04, the possibility of in situ
STM imaging of transitions induced by anodic
polarization of passivable metal surfaces. At the rest
potential and in the active region (-0.1 VlSCE), the
images were reproducible. Current vs. tip-surface dis-
tance curves showed the exponential decrease character-
istic of the tunneling mechanism. When the potential
was stepped in the passive region (0.7 V/SCE), erratic
images were recorded under the same tunneling con-
ditions. The current vs. tip-surface distance response
was asymmetric and spread over large distances, which
is not typical of tunneling. This effect was attributed to
mechanical fractures ofthe tip with the passive layer. Sur-
face deposition of a nickel sulfate film resulting from the
extensive dissolution produced at this low pH (Ll) by
the potential step may also have been responsible for the
failure to record STM images of the passive film in this
experiment as indicated by successful in situ measure-
ments performed later on at higher pH, 13 [18] and 3
[20,21].
A. Ex Situ STM Study of a Ni(111) Single
Crystal
More recently, ex situ and in situ STM imaging has been
performed in our group to investigate the anodic oxide
films formed on (111)-oriented Ni single-crystal elec-
trode in aqueous sulfuric acid solutions [11,23]. The
ex-situ study [22,23] was the first investigation of passive
films on metals with achievement of both lateral and ver-
tical atomic resolution. The surface preparation was very
critical. The samples were electrochemically polished
and annealed at high temperature (1275 K) in a flow of
pure hydrogen for several hours. These pretreatments
were necessary to produce large atomic terraces of the
substrate (see, e.g., the images in Fig. 6). After transfer
under hydrogen to an electrochemical cell located in a
nitrogen-filled glove box, the passive films were produced
in 0.05 M H2S04 by potential steps from the corrosion
potential value to three different values in the passive
region (+550, +650, and +750 mY/SHE) and polari-
546 Marcus and Maurice

zation at this potential for 12 min. Data obtained pre-

viously by RHEED had shown that the passive film
s
formed in these conditions is crystalline [24]. .:
The ex situ STM analyses were performed in air. Modi- 8
fications of the passivated Ni surfaces with respect to the N

nonpassivated one were recorded on two different lateral

scales. On a mesoscopic scale of hundred nanometers,
islands were observed. Their size was found to decrease
and their density was found to increase with increasing
passivation potential. Their shape varied from trigonal
contours with ledges oriented along the main
crystallographic directions ofthe substrate, to hexagonal
contours still with ledges oriented along the main
crystallographic directions, and finally to non-
I\H
symmetrical contours with nonoriented ledges after
passivation at +550, +650, and +750 mY/SHE,
respectively. These variations have been assigned to the
competition, during the early stages of the passivation,
between metal dissolution and formation of the passive
film. Rougheningdue to dissolution increases with poten-
tial and is expected to produce a higher density of islands
with less oriented ledges.
On these submicroscopic islands (possibly) corre-
sponding to grains of the passive film, a stepped
crystalline lattice was observed on the atomic scale. A
typical image is shown in Fig. 3. The lattice parameters
measured on the terraces of the stepped lattice
(0.3 ± 0.02 nm) are consistent with those of the (111)
orientation of NiO (0.295 nm), the inner component of
the passive film, and with those of the (0001) orientation
of {3-Ni(OHh (0.317 nm), the outer component of the
passive film that is about one monolayer thick [25-28].
The possible role of the hydroxyl groups in the tunneling
mechanism is discussed below.
The measured lattice parameters and step density were
found to be independent of the passivation potential. Figure 3 Ex situ STM topographic images of the passive film
The density and height ofthe steps correspond to an aver- formed on Ni(lll) in 0.05 M H 2 S0 4 at +750 mY/SHE. The
age tilt of 8 ± 50 between the surface of the film and the upper image shows the stepped crystalline structure
plane of the terraces. The resulting epitaxy relation- (Vt = +0.135 V, It = 0.8 nA, 112 = 0.9 nm). The lower image
shows the lattice recorded on the terraces (Vt = +0.111 V,
ships between the oxide inner layer and the substrate
It = 0.5 nA, 112 = 0.6 nm). The unit cell and two point defects
are NiO(433)IINi(l1l) with NiO[O!l]! INi[O!l] and are marked.
NiO(765) I INi(lll) with NiO[l2l]! INi[12l]. The tilt may
partly result from a relaxation of the interfacial stress
due to a mismatch of16% between the lattice parameters
of the oxide film and those of the metal substrate. An The (111) orientation of the oxide terraces is normally
atomistic model of the interface between a l-nm-thick unstable because of its polar nature [29]. It is, however,
(according to the XPS measurements [25-28]) NiO(111) produced by passivation, which is attributed to the
layer tilted by 8 0and the Ni(lll) substrate is shown in Fig. stabilization ofthe surface (lower surface energy) caused
4. It illustrates different chemical terminations of the by the surface hydroxyl groups of the hydroxide layer. A
oxide film and possible atomic displacements (marked similar feature was observed in UHV experiments for
by arrows) at the interface toward the nearest threefold oxide films grown from the gas phase [29-32]. The tilt
hollow sites of the substrate. associated to the presence ofterraces and steps at the sur-
Structure of Thin Anodic Oxide Films 547

• • • • • • • • • • • • • • • Ni
• • • • • • • • • • • • • • Ni
• • • • • • • • • • • • • • Ni
• • • • • • • • • • • • • • • Ni

NIIII\IIINlor':L _ 3-fold hollow

sites
[OIl] • [211]

Figure 4 Atomistic model ofthe passive film on Ni(III). Section profile along [2-1-1] ofthe interface between the thin oxide film and
the metal substrate constructed from bulk parameters in the case ofthe NiO(433)1 INi( III) with NiO[O-II] 1INi[O-II] epitaxy (8.02° tilt
between the (Ill) planes of the oxide and those of the substrate). The atomic planes and nodes are indicated. Different terminations
of the oxide film are illustrated. The vector of the coincidence cell along [2-1-1] is 4.J3 times that of the substrate. Possible atomic
displacements at the interface toward the nearest three-fold sites ofthe substrate are indicated.

face of the passive film also reflects a preferential dissol-
ution at steps in the passive state. This is a direct obser-
vation of the fact that the dissolution of the oxide is
governed by a step flow process.
In addition to steps and kinks at the surface ofthe pass-
ive film, other crystalline defects such as point defects,
possibly related to vacancies, have been imaged. One
example is also shown in Fig. 3, where a divacancy is
imaged. The presence ofcrystalline defects at the surface
of the passive film may play a key role in passivity
breakdown. Steps and kinks correspond to sites of
reduced thickness of the passive film where the barrier
effect of the film is expected to be weaker. These defects
may also constitute preferential sites of adsorption of
aggressive ions such as chloride ions.
B. In Situ ECSTM Study of Ni(100) and Ni(111)
Single Crystals
The highly crystalline nature ofthe passive film formed on
Ni has been confirmed in three different in situ STM
studies. One study concerned a different crystallographic
orientation of the electrode in a different electrolyte:
Ni(lOO) in 1 M NaOH [18]. At low potential (-0.7 to
-0.5 V/NHE), oxidation resulted in the formation of
a well-ordered rhombic structure resistant to reduc-
tion and assigned to the irreversible formation of
the Ni - Ni(OH)2 interface. At increasing potential, a
distortion of this rhombic structure was first observed,
followed at higher potential (> 0.18 VlNHE) by a
quasi-hexagonal structure with a nearest neighbor
spacing consistent with either {J-Ni(OHh(OOOI) or
NiO(lll). These results indicate that independently ofthe
substrate orientation (Ni(1 00) or Ni(III», the passive film
is crystalline and is NiO(lll) oriented and terminated by
a [3-(0001) hydroxide layer in (1 x 1) epitaxy on the oxide
layer. Data on the morphological changes associated with
the transition between hydrous Ni(OHh (Ni(II» and
hydrous NiOOH (Ni(III» can be found in Chen etal. [19].
The second study concerned Ni(lll) in 0.05 M
Na2S04 at pH 3.0 [20]. It was also reported that the pass-
ive film formed between -0.15 and 0.25 V/SCE exhibits
a nearly hexagonal lattice whose parameters are consist-
ent with those of NiO(lll) and [3-Ni(OHh(OOOl). With
increasing potential, it was found that the number of steps
present at the passive film surface increased. The oxide
plane was tilted from 6 to 15° from the (111) substrate.
Hence, these results confirmed the tilt of the passive film
surface previously observed ex situ and suggest that this
tilt may depend on the potential for passivation between
-0.15 and 0.25 VlSCE [20].
The third in situ STM study of the passivation of
Ni(1ll) has been performed in 0.05 M H 2S04 + 0.095 M
NaOH (pH 3.0) [21]. The higher pH used with respect to
our previous ex situ study [12,23] was selected to limit
the dissolution occurring during passivation and thus to
548 Marcus and Maurice

r
'1
The metallic surface obtained by cathodic reduction,
1BOO.0

1100.0 I shown in Fig. 6a exhibits mostly monoatomic steps

oriented along the two main crystallographic directions
of the substrate. Fig. 6b shows the (Ill) atomic lattice of
11000.0 r parameter 0.25 ± om nm. Recent thermodynamic cal-

~ 600.0 l I'
culations show that Hand OH can be adsorbed on Ni in
aqueous solutions at a potential of -0.06 VlSHE [33].
The observation of the (1 x 1) lattice indicates that no
ZOO.O I, ,
superstructure or substrate restructuring occurs in these
conditions.
-ZOO.O r-r~"f~===~=-_L-_-----.JL-_-----.J
_ __----l_ _----l-=,j The passivated surface was investigated after stepping
-beO.O -ZOO.O ZOO.O 600.0 1000.0 1100.0 1BOO.0
E(mV/SHE) the potential from -0.06 V/SHE to 0.45, 0.55, 0.75,0.95,
and 1.15 V/SHE. The investigated range of potential
Figure 5 Polarization curve recorded on Ni(1ll) in H 2 S0 4 covers the entire width of the passive region. Two types
0.05 M NaOH 0.095 M (pH 3) at a scan rate of 5 mV s -1. The of topography were observed, depending on the tunnel-
box indicates the cathodic reduction pretreatment. ing conditions: a grain like structure observed in con-
ditions of higher biases and lower tunneling currents
and a crystalline structure observed in conditions of
prevent the possible precipitation of sulfates. Surfaces lower biases and higher currents (Fig. 7a and b,
were prepared as in the earlier ex situ work. After transfer respectively). The setpoint current could not be varied
through air to the electrochemical STM cell, the natural extensively because of tip-surface mechanical coupling
oxide film could be removed by a potentiodynamic at high current and possible tip damage. It was then the
(5 mV s-l) cathodic scan from -0.01 to -0.64 V/SHE variation of the bias that permitted to observe the two
and back to -0.06 VlSHE. The voltammogram shown structures more effectively.
in Fig. 5 shows this pretreatment and the active-passive The grain like structure is assigned to the hydroxide
transition and passive region recorded during the outer part of the passive film. whereas the crystalline
potentiodynamic anodic scan. structure is assigned to the oxide inner part. This assign-

Figure 6 In situ STM images ofthe Ni( Ill) metal surface recorded in 0.05 M H 2 S0 4 + 0.095 M NaOH at -0.06 VlSHE, showing the
terrace topography (It = 1.13 nA, Etip = -0.34 V/SHE, ~Z = 1.96 nm) and the atomic lattice (It = 9 nA, E tip = -0.055 V/SHE,
~Z = 4 nA). The orientation ofthe substrate directions and the unit cell are marked.
 Structure of Thin Anodic Oxide Films 549

I
I
tI

Figure 7 In situ STM images ofthe Ni(lll) surface passivated in 0.05 M H 2 S0 4 +0.095 M NaOH, showing the grainlike outer struc-
ture (a) and the crystalline inner structure (b). (a) E=+0.95 V/SHE, It =0.52 nA, E t ip=0.27 V/SHE, i1Z= 1.76 nm. (b)
E = +0.95 VlSHE, It = 0.58 nA, E tip = 0.32 VlSHE, i1Z = 1.45 nm. The orientation of the substrate directions is marked in (b). The
inset in (b) shows the atomic lattice of the crystalline structure (E = +0.75 V/SHE, It = 5 nA, Etip = 0.16 VlSHE, i1Z = 0.02 nm).

ment is supported by the fact that the crystalline inner
structure was observed in conditions of higher setpoint
currents for which the tunneling distance is decreased.
It is also based on the observation that the grainlike struc-
ture was measured above the crystalline structure in
intermediate conditions, suggesting two different
topographic layers of the passive film. Because, in situ,
the variation of the tip potential was restricted, it was
easier to observe the inner crystalline structure in the
conditions oflower biases, i.e., for passive films formed
in the lower part of the passive region than for passive
films formed in the upper part of the passive region for
which the bias was higher.
Ex situ imaging confirmed the effect of the bias on the
observation of these two types of structures and allowed
us to rule out the possibility that the differences were
due to the passivation potential. The assignment of these
structures suggests that at the higher biases, local states
ofthe hydroxide are involved in the tunneling mechanism
that are excluded at the lower biases. Due to this exclusion
at lower biases and to the decreased tip-surface distance,
the tip penetrates into the hydroxide layer and the
crystalline inner structure is imaged.
Figure 7a shows the grainlike structure for a passive
film formed at 950 mViSHE after 3 h of polarization.
The lateral size ofthe grains was observed to increase with
aging under polarization from 2 to 5 nm after 30 min to
2 to 8 nm after 3 h. No effect ofthe passivation potential
on the lateral grain size was observed. These observations
suggest that the grain structure corresponds to a true
topographical feature of the passivated surface rather
than to an imaging artifact for which an effect of the
imaging bias, and consequently of the passivation
potential, would be expected. The increase of the lateral
size of the grains with aging under polarization may cor-
respond to a coalescence process modifYing the grainlike
structure. This process is illustrated by the aggregation
of grains that can be observed in Fig. 7a and suggests an
intermediate stage in the formation oflarger grains.
Figure 7b shows the inner crystalline structure of the
passive film formed at 950 mViSHE. It is characterized
by the presence of terraces from 2 to 10 nm wide and of
triangular shape. Their edges are formed by steps
oriented along the main directions of the substrate. The
step height is 0.12 ± 0.Q3 nm, i.e., characteristic ofthe dis-
tance between cations and anions planes in NiO(lll)
and Ni(OHh(OOOl). These characteristics have been
found to be independent of the passivation potential
and of the conditions of aging under polarization.
High-resolution imaging on the terraces of this
crystalline structure revealed the atomic lattice shown in
the insert of Fig. 7b. It is nearly hexagonal with nearest
550
neighbor spacings of 3.0 ± 0.3 nm. This is consistent, as
in the previous studies described above, with the lattice
parameters of both NiO(ll1) and Ni(OHh(OOOI). It is
likely that these images correspond to the interface
between the oxide inner layer and the hydroxide outer
layer of the passive film.
These images indicate that the inner part ofthe passive
film, which is constituted ofnickel oxide (NiO) according
to the XPS data [25-28], is crystalline and is covered by
a monolayer of hydroxide in (l xl) epitaxy at the interface
between the two compounds. The symmetry of the
observed lattice indicates that the NiO inner layer is
(111 )-oriented and nearly parallel to the Ni(lll) substrate.
The measured step height is consistent with the reticular
distance between 0 and Ni planes in NiO( Ill) (0.121 nm)
and between OH and Ni planes in Ni(OHh(OOOI)
(0.115 nm). This suggests that the imaged terraces could
be alternatively terminated by 0 (or OH) and Ni planes.
The dimensions of the terraces indicate a local tilt
ranging from 0.7 to 3.4° from (Ill), different from those
reported previously [20,22,23].
These in situ measurements confirm the crystalline
structure ofthe passive film formed on Ni (111), previously
observed ex situ [12,23]. They show that a well-defined
structure tilted by a few degrees from NiO(lll) is pro-
duced in the inner part of the passive film. The nature of
the crystalline defects (kinks and steps), possibly
influencing the film resistance to breakdown, is also con-
firmed.When imaged at higher bias, a grainlike structure
of the passive film is observed, which is assigned to the
hydroxide outer layer of the passive film.
V. STRUCTURE OF ANODIC OXIDE FILMS
(PASSIVE FILMS) ON CHROMIUM AND ON
CHROMIUM-CONTAINING ALLOYS
(STAINLESS STEELS) AND THE EFFECT OF
AGING UNDER POLARIZATION
A. Composition and Structure of the Passive
Oxide Films Formed on Cr(110),
Fe-22Cr(110), and Fe-18Cr-13Ni(100)
Single Crystals
Ex situ STM has been applied in our group to the investi-
gation of the anodic oxide films formed on chromium
and on ferritic and austenitic stainless steels. Ferritic
stainless steels are FeCr alloys with a body-centered cubic
structure, whereas austenitic stainless steels have a
face-centered cubic structure stabilized by the addition
of nickel (FeCrNi alloys). In all the cases, XPS measure-
ments were also performed because a precise knowledge
of the surface composition is necessary for the interpret-
Marcus and Maurice
ation of the STM data. The single crystals used in these
studies were Cr(llO) [34], Fe-22Cr(llO) [35], and
Fe-18Cr-13Ni(lOO) [36].
Surface preparation treatments included successively
mechanical polishing, electrochemical polishing, and
annealing at 1175 K for several hours in a flow of pure
hydrogen at atmospheric pressure. Samples were then
transferred under hydrogen to a nitrogen-filled glove
box where passivation was performed. The electrolyte
was 0.5 M H 2S04. The electrodes were passivated by a
potential step to +0.5 V/SHE, which is in the middle of
the passive region. The potential was maintained at this
value for 20 min, 2 h, 22 h (20 h on Fe-18Cr-13Ni(lOO»,
or 60 h (for Fe-22Cr(llO) only). The passivated electrodes
were then transferred, without exposure to air, to the
UHV chamber of the XPS spectrometer and in air for
STM analysis.
Table I summarizes the results obtained on the
crystallinity, the thickness and the composition of pas-
sive films formed on Cr(lW), Fe-22Cr(l1O), and
Fe-18Cr-13Ni(lOO), as obtained from the combined
STM and XPS measurements [34-36]. These data are
presented for increasing periods of aging under
polarization at +0.5 V/SHE.
The XPS data [34-36] show that these passive films
can be described by a duplex layer model. The inner part
of the passive films on the stainless steels consists of a
mixture of Cr203 and Fe 203 oxides significantly
enriched in Cr203 in comparison with the bulk con-
centration. The outer part of these passive films is almost
exclusively formed of chromium hydroxide, Cr(OHh.
This structure is in agreement with previously reported
results for ferritic [37-49] and austenitic stainless steels
[50,51]. For the austenitic alloy, only traces of nickel
hydroxide are detected as previously reported [2,44,50].
The metallic layers underneath the passive film are sig-
nificantly enriched in chromium in the case ofthe ferritic
alloy, whereas they are significantly enriched in nickel in
the case of the austenitic alloy [35,36].
The chemical effect of aging under polarization is to
decrease the thickness ofthe hydroxide outer part and to
increase the thickness of the oxide inner part (the total
thickness remains nearly constant). Also, the chromium
enrichment is increased in the inner part during aging.
There is no significant effect of aging on the composition
ofthe metalliclayers underneath the film. This aging effect
on the composition of the passive films can be described
by an anodic reaction of dehydroxylation that consumes
chromium hydroxide from the outer part of the film and
metallic chromium from underneath the film and pro-
duces chromium oxide in the inner part ofthe film [35,36].
For aging between 20 min and 2 h, this reaction proceeds
 Structure of Thin Anodic Oxide Films 551

Table 1 Size of Crystalline Areas, Thickness, and Chemical Composition of the Anodic Oxide Films Formed on Cr(lIO),
Fe-22Cr(lIO), and Fe-18Cr-13Ni(100) at +O.S v/SHE in O.S M H2S04, Calculated from STM and XPS Data [34-36]
Passivation time Passive film composition Cr(llO) Fe-22Cr(llO) Fe-18Cr-13Ni(l00)

~l.S nm Onm ~1 nm
Outer layer 11 ±1 A IO±IA 18± I A
thickness and Cr(OHh 100% 100% 99%,
composition Ni(OHh 0% 0% 1%
20 min
2±IA 7±IA s±IA
Inner layer Fe203 0% 12% 19%
thickness and FeO 0% 0% 39%
composition Cr203 100% 88% 42';';0

Modified metallic
layer under the c::;sA c::;sA c::;sA
passive film Fe-Cr-Ni 0-100-0% 60-40-0% SO-IS-3S%

~3nm ~lnm ~3nm

Outer layer 6±IA s±IA 18 ±I A
thickness and Cr(OHh 100% 100% 96%
composition Ni(OHh 0% 0% 4%
2h
Inner layer 6±IA 11 ±I A 6±IA

I thickness and
composition

Modified metallic
Fe203
Cr203
o'Yo
100%
10'1;)
90%,
38%
62'1;)

I layer under the

passive film

Outer layer
Fe-Cr-Ni
c::;sA
0-100-0%

~3nm
7±IA
c::;sA
SS-4S-0%

~Snm
2±IA
c::; sA
20-30-S0%

::::10 nm
13±2 A

I
thickness and Cr(OHh 100% 100% 97%
composition Ni(OHh 0% 0% 3%
22 h
Inner layer 7±IA 12±1 A 9±IA
thickness and Fe203 0% S% 17%
composition Cr203 100% 9S% 83%

Modified metallic
layer under the c::;sA c::;sA c::;sA
passive film Fe-Cr-Ni 0-100-0% SO-SO-O% 3S-1S-S0%

less rapidly on the austenitic alloy than on the ferritic alloy:
An equivalent thickness of 1.62 and 3.74 A of Cr203 is
formed on the austenitic and ferritic alloys, respectively.
For aging between 2 and 22 h, no significant evolution of
the extent ofhydroxylation is detected on Cr. The reaction
proceeds more rapidly on the austenitic alloy than on the
ferritic alloy because the equivalents of 3.75 and 1.5 A of
Cr203 are formed, respectively. However, the reaction is
less rapid for both alloys than during aging from 20 min
to 2 h.ln conclusion, the quantitative XPS measurements
of the thickness and the composition of the passive films
show that the effect of aging under polarization is a
dehydroxylation reaction producing Cr203 and that its
kinetic depends on the alloy substrate.
On Cr, the STM measurements revealed a surface
corrugated on the nanoscopic scale. A typical image is
shown in Fig. 8. The topography is characterized by dis-
ordered protrusions of! to 4 nm lateral dimensions that
induce vertical variations of 0.4 to 0.8 nm amplitude.
This topography is independent of the passivation con-
ditions. On the atomic scale, ordered domains are
detected, as shown in Fig. 8. Their structure is presented
552 Marcus and Maurice

c hydroxide layer I::::':'i:l!ill oxide layer

r,!~;,....;,

Figure 8 Ex situ STM images ofthe passive film formed on Cr(lW) in 0.5 M H 2S0 4 at +0.5 VlSHE after 22 h ofpolarization. (a) The
disordered protrusions of nanoscopic dimensions (Vt = +0.8 V, It =0.3 nA, ~Z = 0.5 nm). (b) Ordered domains assigned to
IX-Cr203(0001) nanocrystals (VI = +0.8 V, It = 0.7 nA, ~Z = 0.5 nm). (c) Model section of the passive film with oxide nanocrystals
in the inner part cemented by the hydroxide outer layer.

below. These ordered domains are surrounded by areas
where no structural periodicity is evidenced, which are
assigned to the hydroxide outer part of the film. No
crystalline defects are detected at the boundaries of the
ordered domains.
In terms of resistance to breakdown, the topographic
variations of the hydroxide outer part also suggest sites
of reduced thickness of the passive film as shown by the
model section presented in Fig. 8. The barrier property
of the film is expected to be diminished in these sites.
However, crystalline defects are not evidenced in these
sites likely because they are cemented by the amorphous
structure of the hydroxide. Therefore, they are expected
to offer higher resistance to film breakdown. In addition,
the amorphous structure of the hydroxide is expected to
minimize the variations of coordination of the surface
atoms at crystalline defects and therefore to provide a
good chemical passivity at these sites. Hence, the
nanocrystalline structure of the oxide and the role of
cement played by the hydroxide would be responsible for
the superior passivity of the film formed on Cr.
The structure of the passive films formed on the Cr,
FeCr, and FeCrNi substrates at +0.5 VlSHE (and from
+0.3 to +0.7 VlSHE on Cr(llO) and Fe-22Cr(1l0)) is
characterized by the presence of crystalline areas. The
atomic structure observed in these crystalline areas is
identical on pure chromium and on the two alloys.
High-resolution STM measurements ofthe atomic lattice
are illustrated by the topographic image shown in Fig. 9,
observed on Fe-22Cr(llO). The lattice superimposed to
the STM image in Fig. 9 shows the arrangement of the
measured corrugations according to the lattice nods.This
lattice is nearly hexagonal with nearest-neighbor
spacings of the order of 0.29 ± 0.04 nm. It is consistent
with the distribution ofthe atomic sites in the basal plane,
(0001) oriented, of a-Cr203 which is the major constitu-
ent present in the inner part of these passive films as
deduced from the XPS measurements. The (0001)
orientation ofa-Cr203 is also shown in Fig. 9. The assign-
ment of the measured lattice to Cr203 is directly
supported by the measurements made on Cr(lW) [34]
for which the number of crystalline areas that could be
Structure of Thin Anodic Oxide Films
(a)
Figure 9 (a) Ex situ STM image of the passive film formed on Fe-22Cr(1l0) in 0.5 M H 2S04 at +0.5 VlSHE and aged 63 h under
polarization (VI = +0.8 V; It = I nA, LiZ = 0.12 nm). The nearly hexagonal lattice is superimposed. (b) Top view and side view of a 2
oxygen layer and 2 chromium layer slab arranged according the stacking sequence of IX-Cr203(0001). The average period ofthe atomic
sites in this basal plane is 0.28 nm.
detected by STM was observed to increase when the
amount of Cr203 in the inner layer of the passive film,
measured by XPS, was increasing, showing the relation
between the presence of the crystalline areas and the
amount of chromium oxide present in the inner part of
the passive film. Moffat et al. [52] also reported an ex situ
STM investigation of Cr(llO) passivated in 1 M H 2S04.
Their images confirmed the presence ofordered domains
consistent with the structure of ct-Cr203, oriented (0001)
and parallel to Cr(llO). Thus, the passive films formed
on Cr(lIO), Fe-22Cr(lIO), and Fe-18Cr-13Ni(100) all con-
tain crystalline areas consisting of ct-Cr203(0001), which
is the favored orientation developed epitaxially in the
inner part of the film.
B. Structural Modifications During Aging of
the Passive Oxide Films on Cr(110),
Fe-22Cr(110), and Fe-18Cr-13Ni(100)
Single Crystals
The most striking effect on the crystallinity of these pass-
ive films is that of the aging under polarization. Indeed,
it has been observed that aging of the passive film in the
aqueous solution enhances the crystallinity ofthe passive
film (Table 1). On Cr(1IO), this was mostly characterized
553
(b)
by an increase of the density of the crystalline areas, lim-
ited to about 3 nm in lateral extension. On Fe-22Cr(11O),
this was characterized by a transition between the
absence of crystalline areas after 20 min of polarization
to the presence of crystalline areas limited to about
5 nm (in lateral size) after 22 h of polarization. Areas
extending over at least 10 nm could be detected after
60 h of polarization. On Fe-18Cr-13Ni(100), this was
characterized by the increase of the lateral dimensions
of the crystalline areas from about 1 nm after 20 min of
polarization to at least 10 nm after 20 h of polarization.
This effect is illustrated by the images shown in Fig. 10
that compare the crystallinity observed on Fe-22Cr and
Fe-18Cr-13Ni for identical passivation periods.
Hence, these results on the atomic structure of the
passive films on chromium-containing Fe-base alloys
clearly show that a crystallization process is favored by
aging under polarization. The crystallization is not com-
plete in the conditions investigated and the topography
of the passive film is intermediate between that recorded
on passivated Ni(lll) (complete crystallization with large
crystals) and that recorded on passivated Cr(llO)
(nanocrystals cemented by noncrystalline areas). It
shows the presence of both crystalline defects and
noncrystalline areas. The major difference between the
554 Marcus and Maurice

Figure 10 STM images ofthe Fe-22Cr(1l0) (left) and Fe-18Cr-13Ni(100) (right) surfaces recorded after passivation in 0.5 M H 2 S0 4
at +0.5 V/SHE for 2 h(a) and (b) and for 22 h (c) and (d). (a) V t = +0.476 V,It = 1.9 nA, ~Z = 0.28 nm. (b) V, = +0.969 v.. It = 1.2 nA,
~Z = 0.4 nm. (c) V, = +0.77 V, It = 1 nA, ~z = 0.2 nm. (d) V t = +0.6 V, It = 0.9 nA, ~z = 0.3 nm. The nearly hexagonal lattice is
marked when observed.

ferritic and austenitIc stainless steels is that the
crystallization proceeds more rapidly on the austenitic
alloy as revealed by the larger extension of the crystalline
areas measured on this alloy as compared with the ferritic
alloy for similar conditions of aging under polarization.
For prolonged aging beyond 22 h, this difference is
attenuated as larger crystalline areas are also observed
on the ferritic alloy. Thus, it appears that the presence of
nickel as an alloying element has a beneficial effect on
the rate of the crystallization process of the passive film.
Ryan et al. [53,54] studied ex situ and in situ poly-
crystalline FeCr surfaces prepared by sputter deposition
and passivated also in sulfuric acid at a low potential.
The noncrystalline character of the passive film formed
on FeCr alloys has been confirmed in situ after I h of
passivation [54]. In this study, it was observed that after
I h of passivation, the amount of disorder increased
sharply for a Cr content of the alloy between 14.7 and
16.5°/<,. The effect of aging was tested only in ex situ
conditions, and it was observed that it favors the
(re)crystallization of the passive film for 18 and 21 % Cr
content [53]. The structural order observed in the passive
film was consistent with the (0001) orientation of
iX-C r 2 0 3.
It appears from these studies that both the Cr content
of the alloy (and the related chromium enrichment of
the passive film) and the conditions of aging of the film
are critical factors governing the crystallization of the
passive film. Our interpretation is that the formation of
Cr203 in the inner part of the film and its crystallization
r
Structure of Thin Anodic Oxide Films
are two distinct processes. This is deduced from the fact
that the passive films with the higher concentration of
Cr203, formed on the ferritic alloy in the early stages of
passivation, exhibit the smaller extension of the
crystalline areas. The results indicate that a fast pro-
duction ofchromium oxide does not favor the formation
of large crystalline areas. One reason could be that this
fast production rate would lead to a high density ofoxide
nuclei on the ferritic alloy, detrimental to the growth of
large crystalline areas.
Besides the Cr content of the alloy, the dissolution of
the alloy, which is a competitive process in the initial
stages of passivation, plays a role in the Cr enrichment
in the oxide inner layer of the passive film in its initial
stages of formation. It is known that the presence of Ni
as alloying element in stainless steels tends to decrease
the dissolution rate, which was confirmed in our study
[35,36]. Because the passivation of Cr is much faster
than the one on Fe and Ni, a higher dissolution rate is
expected to create a higher enrichment in Cr of the
initial passive film. This is confirmed after 20 min in
our experiments, time period after which the passive
film contains more Cr203 on the ferritic alloy than on
the austenitic alloy.
The Cr content ofthe alloy and the dissolution rate can
be invoked to explain the difference of crystallization
and composition of the passive films measured after
20 min of polarization. A factor that possibly affects the
modifications of the passive film upon further aging
under polarization (after 20 min) is the enrichment in
the metallic phase underneath the passive film. This
phase is enriched in Cr in the case of the ferritic alloy,
whereas it is enriched in Ni in the case of the austenitic
alloy [35,36]. A possible effect of the Ni enrichment in
the austenitic alloy would be to limit the rate at which
the metallic Cr becomes available for the dehydroxylation
reaction and hence to limit the rate of chromium oxide
formation. This limitation would be more effective in the
early stages of aging of the passive film. It would leave
more time for the advancement ofthe crystallization pro-
cess of the chromium oxide already formed and hence
would lead to the formation of larger crystalline areas
on the austenitic alloy surface. For more prolonged aging
(after 2 h), the effect of the Ni enrichment in limiting the
rate of Cr supply would decrease because the rate of for-
mation of the chromium oxide has decreased (the film
being already enriched in chromium oxide). At this point,
the rate of the crystallization process would match more
effectively the rate offormation of chromium oxide. This
would lead, after prolonged aging, to crystalline areas of
similar extension on the ferritic and austenitic alloy, as
observed experimentally.
555
It is interesting to relate these STM and XPS data on
the role ofaging under polarization on the structure and
composition ofpassive films with the previously reported
beneficial effect of aging on the resistance to passivity
breakdown and pitting [47,48]. For Fe-17Cr alloys
passivated in 0.5 M H2S04 and in neutral solutions, aging
of the passive film under polarization in the absence of
chloride or in the presence of chloride but below the
pitting potential increases significantly the pit initiation
potential. It suggests that the crystallization of the chro-
mium oxide inner part of the passive films is beneficial
to the resistance to breakdown and pitting. The beneficial
effect of aging under polarization is explained by both
an enrichment in chromium oxide by dehydroxylation of
the outer part of the passive film and a more advanced
crystallization ofthe chromium oxide inner part. A better
control of the crystallization process is provided by the
presence ofNi in the alloy.
VI. DISCUSSION
A. Comparison of Ex Situ and In Situ STM
Measurements on Passivated
Single-Crystal Metal Surfaces
A major requirement for the interpretation of
high-resolution images acquired by STM is a precise
knowledge of the chemistry of the investigated surfaces.
For example, the interpretation ofthe STM data recorded
in the study of the passive films formed on Cr, FeCr, and
FeCrNi [34-36] would have been almost impossible
without the knowledge of the distribution ofthe different
phases within the passive films. Such chemical infor-
mation can only be obtained in ex situ conditions using
surface analytical techniques (e.g., XPS). The correlation
of this chemical information with the structural infor-
mation deduced from STM has been a major objective
of the ex situ STM investigations ofpassive films on vari-
ous substrates. This approach must then be completed
by in situ structural investigation.
One advantage of ex situ investigations is to stop
dynamic processes taking place in situ, and this favors
high-resolution imaging. However, the drawback is that
the electrode must be removed from solution, which
may cause modifications of the surface species. The
extent ofthe modifications due to removal ofthe electrode
depends on the stability ofthe anodic layer upon rinsing,
exposure to air or inert gas at atmospheric pressure or to
reduced pressure (from vacuum to UHV) and therefore
this stability should be tested in the conditions of the ex
situ investigation. A critical evaluation of the differences
related to the conditions of the STM measurements is
556
necessary. The similarities between ex situ and in situ
studies reported on Ni [18-23], Cr [34,52], and FeCr
alloys [35,53,54] show the relevance of this combined
approach.
In addition to the precise knowledge of the chemistry
of the passive film, there is another requirement for the
investigation of the crystallinity and atomic structure of
the passive films: it is to work with well-defined substrate
surfaces. The criterion of a well-defined surface is the
observation of atomic terraces. This is obtained with
single-crystal surfaces. The use of such surfaces allows
one to study passive oxide films formed on metal
substrate planes of the desired crystallographic
orientation and to minimize and control the possible
influence of the substrate defects on the defects of the
passive film.
B. Chemical Composition of Surface Oxide
Films and 1\Inneling Mechanisms
A general feature ofpassive films is that they consist ofan
inner oxide layer at the metal interface and an hydroxide
layer in the outer part of the film. On Ni for example
[25-28], the thickness of the oxide inner part is about
0.4 to 1.2 nm and that of the hydroxide outer part is at
most about 0.6 nm (one monolayer ofNi(OHh(OOOI) is
0.459-nm thick). The STM measurements of the atomic
lattice do not allow discrimination clearly from the
measured lattice parameters between NiO(lll) and
j'J-Ni(OHh(OOOI) planes. By STM, the only possible evi-
dence ofthe hydroxide layer has been found in our in situ
images performed at higher biases for which a grainlike
structure is observed, superimposed on the crystalline
topography observed at low biases and assigned to the
oxide layer.
Two possible tunneling mechanisms can be consid-
ered. One mechanism, that would occur at low bias,
involves tunneling from the tip to the empty states of
the oxide layer (in agreement with the p-type character
of the oxide and the polarization conditions) through
the hydroxide layer. In this case, it is expected that the
oxide layer is imaged (and not the hydroxide layer).
The integrity of the hydroxide layer during measure-
ments depends then on the width of the tunneling gap.
If it is smaller than 0.6 nm, the hydroxide layer may be
penetrated and damaged by the scanning tip. If the
oxide-hydroxide interface is measured, the recorded
images suggest that the monolayer-thick hydroxide layer
is in epitaxy on the crystalline NiO host lattice with a
(1 x I) relationship. The relatively low bias conditions
that have been used to image the crystalline oxide struc-
ture (from 0.05 to about 0.6 V) indicate either a relatively
Marcus and Maurice
narrow band gap (but unlikely according to band gap
values of the literature for NiO: 3.5-4 eV [55]) with
tunneling in the conduction band or a significant den-
sity of states located near the Fermi level and possibly
forming a subband in the band gap of the oxide. The
OH groups at the oxide- hydroxide interface may corre-
spond to these surface states and then have a role of
centers in the tunneling mechanism.
The other possible mechanism that would occur at
high bias involves tunneling from the tip to empty
states of the hydroxide layer. The density of these empty
states would be higher than that of the states involved
in the first mechanism, thus giving a different imaging.
In this case, the hydroxide layer can be imaged. The
grainlike structure that is imaged in these conditions
reflect then the spatial distribution of the empty states
of the hydroxide layer that are involved in this
mechanism.
On Cr, FeCr, and FeCrNi [34-36], the non ordered
areas measured by STM have been assigned to areas
where the hydroxide layer would be thicker on the basis
of data recorded on passive films containing only dis-
persed islands of oxide in the inner part, whereas the
ordered areas were assigned to oxide crystals. It is likely
that a layer of OH groups is also present on the ordered
domains assigned to IX-Cr203, hence suggesting that a
mechanism involving tunneling to empty states related
to OH groups could also exist on the oxide areas. The
presence of these OH groups could possibly explain the
observed deviations, at the surface of these areas (Figs. 8
and 10), from the perfectly ordered hexagonal arrange-
ment of the basal plane of IX-Cr203.
C. Outlook
In addition to the structural measurements reviewed
here, STM offers the possibility of performing local
spectroscopic measurements (current vs. bias curves).
These measurements can be performed in situ and ex situ.
Ex situ UHV conditions are, however, more appropriate
to ensure the non conductivity of the tunneling barrier
between surface and tip. Such measurements on passive
films formed on Ni and Cr should provide valuable infor-
mation on the local conductivity of the films. This is a
promising perspective for the local characterization with
high resolution of the electronic properties of passive
films.
Breakdown and pitting initiation in chloride media
also represent an area of promising perspectives for the
local characterization with high resolution of passive
films. This is a problem of major technical importance
in materials science. The direct observation of preferen-
Structure of Thin Anodic Oxide Films
tial sites ofattack ofthe oxide films by chloride would pro-
vide a better understanding ofthe key factors in localized
corrosion.
VII. CONCLUSIONS
This review of STM studies of thin anodic oxide films
formed on well-defined surfaces of passivable metals
and alloys show that novel data can be obtained by direct
imaging of the surface structure. The reviewed data pro-
vide direct evidence of, e.g., the formation of passive
oxide films by nucleation and growth, their crystallinity,
their epitaxy, and the nature ofthe defects present in pass-
ive oxide films.
The fully crystalline character of the film on Ni has
been demonstrated by STM. The nature ofdefects (steps,
kinks, vacancies, points of reduced thickness) has been
elucidated. This is important for a better understanding
of the breakdown of passive films. The unique corrosion
resistance ofthe film on Cr may be related to the observed
structure with oxide nanocrystals cemented by a
noncrystalline hydroxide. The effect of aging under
polarization ofpassivated ferritic and austenitic stainless
steels was found to be an increase of the crystallization
ofthe oxide films that, in combination with the enhanced
enrichment of Cr3+ in the passive film, is beneficial to
their resistance to pitting.
Many more results are expected to be produced in the
future on the atomic structure ofpassive films, including
the local interactions ofimpurities and anions with pass-
ive films and especially with surface defects, the local
conductivity of passive films derived from spectroscopic
measurements at specific sites, and chemical features
derived from spectroscopic imaging. All these data
should further improve our understanding ofthe relation
between structure and properties ofpassive oxide films.
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,
I
,
32
Surface Oxidation of Noble Metal Electrodes
",
Gregory Jerkiewicz
University ofSizerbrooke, Sizerbrooke, Quebec, Canada
ABSTRACT
This chapter compares the oxide growth mechanism
under gas- phase and electrochemical conditions. The dif-
ferences between the surface oxide and the bulk-type
one and their distinct physical and chemical properties
are presented. Various oxidation reaction pathways
involving OHchem or 0chem, as an intermediate ofthe pro-
cess, are reviewed. Three experimental procedures
applied to formation of surface oxides, namely
potentiostatic polarization, galvanostatic polarization,
and potential cycling, are discussed. A review of numer-
ous in situ and ex situ techniques used to characterize
the chemical nature ofthe surface oxides, their thickness,
and the degree of hydration is presented. The sur-
face-oxide growth can be limited by various processes
such as the electron transfer, the interfacial escape of the
metal cation from the metal, the surface place exchange,
and the transport of the metal cation across the film.
Because each ofthese rate-determining steps can give rise
to a distinct kinetic formulation (kinetic law), mathemat-
ical equations are provided for each ofthem. Diagnostics
criteria, which can assist one in examination ofthe mech-
anism and kinetics applicable to the system under study,
are presented and discussed. Selected results for the sur-
face oxidation of Rh, Pt, and Au under potentiostatic
conditions are presented and discussed to illustrate the
theoretical consideration.
I. INTRODUCTION
Surface oxidation of the noble metal as a physico-
chemical process refers to an electron (or electrons)
loss by its outer-most layer. During the process, the
559
neutral metal atom (M) undergoes transition to a met-
allic cation (MH). The electron loss is accompanied by
an electron gain by the species that is the oxidizing agent,
molecular oxygen in the case ofgas-phase oxidation [1-4]
or the H 20 molecule or the OH- anion in the case of
oxide formation in aqueous solutions [5-8]. The ability
of the noble metal to form an oxide (or oxides), a sulfide,
etc. has been a subject of an intense scientific discussion
due to their inherent noble nature (their intrinsic
inertness), thus unsusceptible to form an oxygen- or
sulfur-containing species. The issue resides in the ability
of the noble metal to sustain its valence electrons upon
exposure to molecular oxygen or O-containing species,
such as H20 or OH-. However, an analysis of the
electronegativities of the respective elements involved in
the oxidation indicates that the tendency of 0 or S to
accept electrons outruns that of the noble metal.
Moreover, the values of the enthalpy of formation of
numerous noble metal oxides (or sulfides) are negative
pointing out to the stability of the oxidized, not neutral,
species. Thus, thermodynamics clearly and indisputably
reveal that the oxidation of the noble metal is a real pro-
cess that can set in under specific conditions. Because this
review deals with oxidation ofthe noble metal in the aque-
ous solution, we focus our attention on the surface oxide
formation.
In the discussion on the oxidation ofthe noble metal, it
is essential to distinguish between formation ofbulk-type
oxides and surface oxides. During the former, the entire
sample of the noble metal, thus all the metal atoms,
undergoes oxidation with formation of a new
three-dimensional (3D) chemical entity. The newly
560 Jerkiewicz

formed bulk-type species has its characteristic physical development ofa quasi-3D crystal lattice [16].
and chemical properties and catalytic activity [1-4]. The
chemisorption
surface oxide possesses its unique characteristics and 2M + O 2 ) 2M - Ochern (1)
some of them are as follows: the surface oxide on the
noble metal is thin and seldom exceeds the thickness of e transfer 2+ 02-
several or tens of monolayers (ML); it is bound to the M - 0 chern ) M - (2)
metal substrate by means of cohesive forces that are
In the case ofelectro-oxidation ofthe noble metal, the
characteristics of the system; its electronic and magnetic
process requires presence of an oxidizing electrolyte
properties often differ from those characteristic of the
(O-containing species, such as H 20 in the case ofacidic
bulk-type oxide, and the variation of the electronic
solution or OH- in the case ofoxidation in basic solution)
properties gives rise to modification ofthe work function;
and an electric field. In acidic solution, for instance, two
its lattice structure differs from that of the underlying
distinct pathways are recognized [5,11,15,17-20]. The first
metal; and a significant mismatch ofthe metal and oxide
pathway involves the following steps. The H 20 discharge
lattice parameters might lead to formation of an
results in formation of electroadsorbed hydroxyl group,
incommensurate structure or a disordered layer, and it
OH chern [reaction (3)]. The process is followed by a
results in strain in the metal-oxide interface that can
place-exchange between the metal surface atoms and
affect the adhesion of the oxide to the metal.
OH chern species [reaction (4)]. Subsequently, an electron
An oxide film present on the noble metal markedly
transfer and departure of H (in the form of H+) from
influences the mechanism and kinetics ofvarious anodic
OH chern leads to formation of electroadsorbed 0 2-
processes or anodic redox reactions at the surface by
and M2+ [Fig. 1b and reaction [5]). Restructuring or
[9-15]
reconstruction of the array of OHchern groups and
1. Affecting the energetics of the reaction at the double top-most metal atoms leads to a quasi-3D surface phase.
layer;
electro-adsorption +
2. Changing the electronic properties of the metal M + H 20 ) M - OHchern +H +e
surface; (3)
3. Imposing a barrier to charge transfer across the sur-
face oxide film;
place exchange, lattice formation
4. Influencing the adsorption behavior of reaction M - OH chern ) OHchern - M
intermediates and/or products at the catalytic (4)
surface, principally through effect (2) and a related
site-blocking effect.
electron transfer 0 2- M 2+
OH chern - M ) - + H+ + e
(5)
II. GENERAL REPRESENTATION OF THE The second pathway involves the following steps. The
STEPS INVOLVED IN "HE SURFACE-OXIDE H 20 discharge occurs with departure of two Hs (in the
DEVELOPMENT form of H+) and it leads to electroadsorbed 0, Ochern
[reaction (6)]. The process is followed by a place exchange
Surface oxides on noble and other metals can be formed with simultaneous transfer of two electrons between M
by application of gas-phase and electrochemical tech- and 0chern, and it leads to a quasi-3D lattice comprising
niques [1-8]. Oxidation of a divalent metal, for instance, 0 2- and M 2+.
under gas-phase conditions may be represented as
follows. During the oxidation, the O 2 molecule electro-adsorption 2 +
approaching the metal surface undergoes dissociation,
M + H 20 ) M - Ochern + H + 2e
which is followed by formation ofa chemisorbed oxygen, (6)
Ochern [reaction (1)]. Consequently, a transfer of two elec-
trons from M to Ochern takes place resulting in creation - 0 etransfer.latticeforrnation 0 2- _ M 2+
M chern ) (7)
of 0 2- and M 2+ [reaction (2) and Fig. 1a for a divalent
metal). It ought to be stressed that the formation of It should be added that the electronic nature ofOH chern or
Ochern and the subsequent development of 0 2- are two Ochern on the metal surface is not well understood. It
separate surface processes and the electron transfer and may be said that due to the strong electron-withdrawing
creation of the ionic species can occur concurrently with characterofOHchern or Ochern, they possess a partial nega-
 Surface Oxidation of Noble Metal Electrodes
METAL OXIDE GAS
0'-
\
METAL OXIDE ELECTROLYTE
1 molecule results in OH chern , which then undergoes a surface
1
I
tive charge; thus, there exists already a partial charge
transfer between M and OH or 0, M b+ - OH b- or
M b+ - 0 6-, respectively, due to local electron density
redistribution. The charge transfer is completed upon
development of the quasi-3D lattice through the place
exchange mechanism or the surface reconstruction (or
restructuring). Finally, it ought to be stressed that the
above-presented pathways represent one of the simplest
cases, namely growth of a simple M 2+ - 0 2- type oxide.
In the occurence of mixed oxides that comprise both
0 2 - and OH-, the oxide formation may contain more
56]
METAL OXIDE ELECTROLYTE
Figure 1 Visual representation of surface oxide development
under gas-phase and electrochemical conditions, in acidic
solution, on a divalent metal. (a) Under gas-phase condition,
the O 2 undergoes dissociation and the process leads to develop-
ment of Ochern' Subsequent transfer of two electrons across the
interface results in formation of ionic species, 0 2- and M 2+;
simultaneously, the creation of a quasi-3D metal-oxide struc-
ture occurs. Under electrochemical conditions, two different
pathways may be distinguished. (b) The discharge of the H 20
place exchange with a surface metal atom. This interfacial turn-
over is followed by further discharge of OH chern , and creation
of 0 2- and M 2+ in a quasi-3D crystal lattice. In this pathway,
two electron transfer processes occurs independently. (c) The
discharge of the H 20 molecule results in Ochern, which then
undergoes a place exchange with a surface metal atom. The
water discharge is a two-electron process. This interfacial turn-
over is followed by creation of 0 2- and M 2+ in a quasi-3D
crystal lattice.
steps and, consequently, the mechanism becomes more
complex. At present, it is not apparent if the development
of0 2- proceeds through Ochem as a two-electron process
or whether it takes place in two distinct steps, through
OHchem. Clearly, the development ofa surface-type oxide
at the metal -electrolyte interface involves distinct steps,
and each ofthese fundamental processes can play the role
ofarate-determining one. However, what is certain is that
the electric field, which is established across the
metal-electrolyte interface, assists the development of
the ionic species and the electron transfer through a var-
iety of ways that is discussed in a subsequent section.
562
III. EXTENT OF SURFACE OXIDATION
The extent of surface oxidation accomplished by
utilization ofelectrochemical means is related to various
properties of the substrate at which the process occurs
and to the experimental procedure applied to form the
oxide. They are as follows:
1. The metal nature and its ability to form one or more
oxide species that can be elucidated on the basis of
the Pourbaix diagrams [21];
2. The polarization procedure applied to form the sur-
face oxide (see below);
3. Electrolyte composition and its pH.
Above, it is discussed that a stable surface oxide affects
kinetics and mechanism of various faradaic and redox
anodic processes [8-15]. In particular, the surface valence
band structure of an oxidized metal differs from that of
the native metal giving rise to distinguishable adsorption
properties of the reaction intermediates and products,
and creation of a barrier to charge transfer [22]. In the
case of anodic oxidation of adsorbed inorganic/organic
species, the potential region in which the process takes
place can overlap that of the oxide formation; thus, the
overall current density measured experimentally corre-
sponds to both electrode processes occurring con-
currently. Presence of the surface oxide can also alter
the kinetics, the mechanism, and the pathways ofthe pro-
cess, resulting in a reduced or enhance electrochemical
activity and in new reaction products [14,15].
The amount of the surface oxide formed on the noble
metal may be expressed in a variety of ways: the oxide
mass, mox, that can be determined ex situ and in situ by
gravimetry; the oxide charge density, qox, most com-
monly determined by the oxide reduction through a var-
iety of electrochemical techniques such as charging
curves, linear-sweep voltammetry (LSV), cyclic vol-
tammetry (CV), and coulometry; and oxide thickness,
dox , that can be determined by application of scanning
or transmission electron microscopy combined with
microtoming. X-ray photoelectron spectroscopy (XPS)
and Auger electron spectroscopy (AES) combined with
Ar+ spattering provide a good appraisal of the number
of MLs of the oxide.
IV. ORIENTED OXIDE OVERGROWTH
The issue ofthe adhesion ofthe oxide film to the substrate
and the tendency of the oxide to protect the metal is
directly related to the structure of the oxide and the rela-
tive volumes ofthe oxide and the metal. Thus, it is necess-
ary to present the principles of the oriented overgrowth
Jerkiewicz
and to deliberate on the misfit factor, M [23,24]. The
oriented overgrowth, which is applicable to thin oxide
films (ofless than 10 ML; adetail evaluation ofthe critical
thickness is based on the value of M; see further dis-
cussion), is based on the following assumptions: It is
accepted that the thin surface oxide maintains the
geometry of the metal from which the oxide originates
and due to differences in the radii of Mz+ and 0 2-, there
is strain within the film but it is insufficient to alter the
structure of the oxide that, thus, assumes the geometry
of the underlying metal. The extent to which the oriented
overgrowth of the metal oxide takes place may be
effectively evaluated on the basis of the misfit factor [24]:
M= (::)-1 (8)
where aM is the lattice parameter of the metal substrate
and aox is the natural spacing of the oxide monolayers.
Frank and van der Merwe [23,24] defined the critical
misfit, M o as follows:
M _ 2 (11 a2 )~l/2
0-- ----.M (9)
n 2H
where 11 is the force constant and H = Hi + U, Hi stands
for the enthalpy ofsolution ofthe metal cation in the oxide
and U is the potential energy ofdiffusion ofthe metal cat-
ion across the oxide. For a typical metal oxide monolayer,
M is greater than M 0 by 0.09-0.14 (9-14%). Under such
conditions, the surface oxide is in an energetically meta-
stable equilibrium, and it accepts the crystallographic
structure of the metal substrate. To create dislocations in
the oxide, the misfit factor has to exceed M o by at least
0.40 (40%). Thus, the treatment [23,24] demonstrates that
indeed the surface oxide assumes the structure of the
metal from which it originates.
V. PROCEDURES OF FORMATION OF
SURFACE OXIDES
The extent ofsurface oxidation, thus the amount ofoxide
formed on the noble metal, is determined by the
physicochemical properties inherent to the metal and by
the chemical composition of the electrolyte and its pH.
Moreover, the amount ofthe oxide formed on the metallic
substrate is directly related to the electrochemical
experimental conditions applied to form the surface
oxide. Three approaches are commonly used to grow a
surface oxide film on the noble metal: potentiostatic
polarization; galvanostatic polarization; and potential
cycling. Before their presentation, it is important to
 Surface Oxidation of Noble Metal Electrodes
emphasize that the paramount aspect of research on
surface oxidation of the noble metal is the cleanliness
of the experimental setup, which comprises the work-
ing, counter, and reference electrodes; the cell; the
electrolyte; and the inert gas passed through the
working-electrode compartment [25,26]. At present, it
is well known that single- crystal and polycrystalline elec-
trodes ofnoble metals (such as Pt, Rh, Pd, Au, Ag, Ir) give
reproducible and well-defined CV transients in aqueous
solutions of H 2S04, HCI0 4, NaOH, etc. These transients
are a fingerprint of a clean and well- characterized
surface, and even trace amounts ofimpurities or mechan-
ical (thermal) stress in the electrode surface give rise to
new features in the CV profiles. Even in the case of poly-
crystalline electrodes, the CV profiles differ if the elec-
trode is contaminated or if it has a significant amount of
mechanical strain originating from the preparation pro-
cedure [25,26]. The surface-oxide growth, whether
accomplished by potentiostatic or galvanostatic
polarization, is often accompanied by generation of mol-
ecularoxygen. Ifthe surface oxide is subsequently charac-
terized by a reduction transient, then it is essential to
pass a neutral gas through the working-electrode com-
partment during the oxide development to ensure that
I
f
no O2 reduction current overlaps that of the oxide
reduction. To ensure absence of molecular oxygen in the
electrolyte, the reduction transient can be arrested at the
I potential of zero current density, E;=o [12].
A. Potentiostatic Polarization
The oxide formation through application of
potentiostatic polarization involves polarization of the
noble-metal electrode at a well-defined, anodic potential,
Ep, for a given polarization time, tp (Fig. 2a). To ensure
reproducibility of the results, other experimental par-
ameters that can affect the extent of surface oxidation,
such as temperature, are maintained constant. Before
the potentiostatic polarization at Ep, the electrode is
scanned in its characteristic potential range to verifY its
cleanliness and absence of surface blocking species (Fig.
2a). During the potentiostic polarization, the current
density can be easily monitored and recorded. The latter
data can be used in a subsequent scrutiny ofthe catalytic
properties of the oxide layer. Because the surface-oxide
growth is often accomplished by the electrode polar-
ization at potentials well above the thermodynamic
(equilibrium) reversible potential ofthe oxygen evolution
reaction (OER), EClER = 1.23 V; the total polarization
current density corresponds to two processes that occur
concurrently, namely the oxide formation and the elec-
trolytic 02 generation, iT = io x + iOER. Thus, the overall
563
charge density, which passes through the system and
which can be determined by integration of the iT vs. tp
transient, corresponds to the two distinct processes and
qT = qox + qOER· It is impossible to differentiate
between the charge density associated with the oxide
growth and that with the OER only on the basis of the iT
vs. tp transients for every E p. The amount ofcharge passed
across the system and associated with the oxide growth
can be readily determined from the oxide-reduction
LSV transient after the oxide development. During this
LSV scan, typically from Ep to the thermodynamic
(equilibrium) potential of the hydrogen evolution
reaction (HER), E HER = O.OOV; the oxide film becomes
reduced; integration of i vs. E transient leads to determi-
nation of the oxide charge density, qox. Once qox has
been determined, one can easily assess qOER.
B. Galvanostatic Polarization
The oxide formation through application ofgalvanostatic
polarization involves application of a constant anodic
current density, ip, to the noble-metal electrode for a given
polarization time, tp (Fig. 2b). As in the case of
potentiostatic polarization, other experimental par-
ameters are maintained constant to ensure repro-
ducibility of the results. Before the polarization at ip, the
electrode is scanned in its characteristic potential range
to verifY its cleanliness and absence of impurities that
can affect the oxidation. During the galvanostatic
polarization, the potential can be monitored and
recorded as a function of tp (Fig. 2b). Assessment of the
Ep vs. tp transient leads to meaningful deduction of the
catalytic properties of the oxide layer during its
development. In the case of the galvanostatic
polarization, the oxide growth and the OER can occur
concurrently. The onset of the OER can be readily
detected from the E p vs. tp transients; as soon as Ep
exceeds E OER ' the OER sets in. Thus, the total current
density represents both electrode processes,
qT = qox + qOER. As in the case of the potentiostatic
polarization, the charge associated with the oxide
growth, qox, is determined from the LSV transient after
the oxide growth. For a meaningful appraisal of the
amount of the oxide formed, the LSV scan should com-
mence at the potential established at the end of the
galvanostatic polarization and it should end at E HER . It
ought to be stressed that the lower limit of the electro-
chemical characterization of the oxide layer depends on
the feasibility of its reduction at potentials positive with
respect to E HER. It is the case for most of the oxide films
on noble metals. However, if the complete oxide
reduction requires potentials negative with respect to
564 Jerkiewicz

E p =' const. ---- !j

tp 1

I 1

1 I
E2 -------/\ /\ ~ I 1
\ OUTGASSING 1\
/\------ E2
I 1

1
E;=O---I----
I v

/1
E] ----I V V 1
\---- E ]
I 1 1

I I I
1 1 1

I 1 OXIDE 1 OXIDE I

CYCLING ;01 Il'ORMATIOl'fICHARACTERIZATIONI E

CYCLING
(a)

auto-adjusted
E transient

i
1

E 2 ------- ------- E 2
: OUTGASSING
E.-o---
r--- WITH INERT

1 : /1
,- GAS
E] ---- ---- E]

1 I 1

1 I I
I OXIDE I OXIDE IE
CYCLING---lOI E FORMATION ;oICHARACTERIZATIONI-- - CYCLING

(b)

Figure 2 (a) Potentiostatic polarization. Diagram showing the E vs. t program used to condition the electrode before the oxide
growth, to form the surface oxide, and to characterize it. E p and tp are the polarization potential and time, E I and E 2 are the
potential limits of the scanning, and E;=o refers to the potential of zero current. (b) Galvanostatic polarization. Diagram showing
the E vs. t program used to condition the electrode before the oxide growth, to form the surface oxide, and to characterize it.
ip and tp are the polarization current density and time, E I and E2 are the potential limits of the scanning, and E;=o refers to
the potential of zero current. (c) Potential cycling. Diagram showing the E vs. t program used to condition the electrode before
the oxide growth, to form the surface oxide, and to characterize it. Epl , Ep2 , and tp are the upper and lower limits of the potential
cycling and the polarization time, respectively, E 1 and E2 are the potential limits of the scanning, and E;=o refers to the potential
of zero current.

L
 Surface Oxidation of Noble Metal Electrodes
E1 -------
Ei=o---r--- WITH INERT
1I
I
1 OXIDE
CYCLING---+~'l·oE---;;F""ov;RM~"A'--;;T~I""O"N:;---;oICHARACTERIZATIONj-EE---
(e)
EllER' the electrochemical characterization through LSV
becomes troublesome and other experimental tech-
niques should be used (see below).
C. Polarization Through Potential Cycling
The oxide growth through potential cycling differs from
the potentiostatic and galvanostatic polarization in the
sense that in this methodology, neither the potential nor
the current density is maintained at a given value. The pro-
cedure involves application of multiple potential
transients, over a restricted potential range, to the
noble-metal electrode (Fig. 2c). In this approach, the
lower limit of the potential cycling is fixed at a value that
is substantially above the potential range within which
the surface oxide undergoes complete reduction.
However, it is well known that certain oxide layers have
numerous oxide states, as it can be deduced from an
LSV oxide-reduction scan. The various oxide states
1 possess their distinct reduction potentials that can be
related to distinguishable Gibbs energies of reduction.
I
i Thus, in the case ofoxide films possessing various states,
their respective reduction potentials can be distributed
over a wide range, say some OA-O.7Y. This experimental
methodology involving potential cycling allows one to
scan the potential over a limited region within which
one oxide state is reduced whereas another remains
unaffected. This unique polarization procedure can be
used in preparation of thick hydrous oxide films [6,7].
However, this approach has its drawbacks. For instance,
it is troublesome to interpret the current-density
transients because the polarization potential undergoes
continuous variation. Nevertheless, integration of the
565
I
I
------- E
1
: OUTGASSING
: /1
I
I
GAS
I
I
I OXIDE 1
CYCLING
positive-going iT vs. tp transients allows one to determine
the charge density corresponding to the oxide formation
and the OER in each cycle, whereas integration of the
negative-going transients leads to elucidation of the
charge density ofthe reduced oxide and molecular oxygen
in each transient. Subsequent characterization of the
oxide by application of an LSV scan results in determi-
nation of the charge density of the film still present on
the surface after multiple potential cycling. Finally, as in
the case of the other methods, before application of the
potential cycling procedure, the electrode is scanned in
its characteristic potential range to verifY its cleanliness
and absence of site blocking species.
VI. EXPERIMENTAL TECHNIQUES OF
EXAMINING THE SURFACE OXIDE
The selection of the experimental technique applied to
examine the surface oxide on the noble metal depends
on the information sought and on the feasibility of cer-
tain experiments [27]. However, it ought to be stressed
that to elucidate the amount of the oxide, its structure,
the degree of its hydration, the oxidation state of the
metal cation, and the electronic properties, seldom does
one experimental technique suffice. In a systematic
research, a combination of suitable and complementary
experimental techniques should be used. The following
experimental techniques can be conveniently applied
to the research on the surface oxidation of the noble
metal.
566
A. X-Ray Photoelectron Spectroscopy
XPS [28,29] provides the information about the oxidation
state of the metal cation (MZ+) and can distinguish
between 0 2 - and OH- on the basis of the chemical shift
of the binding energy of the species. When coupled with
Ar+ spattering, it leads to elucidation of the com-
positional depth profile and to a good assessment of the
oxide thickness. It is an ex situ technique and requires
transfer of the oxide from an electrochemical cell to an
ultrahigh vacuum (UHV) surface analysis chamber; the
transfer might lead to dehydration of a hydrous oxide.
B. Auger Electron Spectroscopy
AES [28-32] allows precise determination of the atomic
concentration of metal and oxygen within the top-most
surface layer of the oxide. A subsequent quantitative
analysis based on the shift of the AES spectra and vari-
ation of their features leads to deduction of the chemical
composition of the oxide layer. Hydrogen determination
is not possible; thus, it is impossible to distinguish
between 0 2- and OH-. When combined with low-energy
electron diffraction, it leads to elucidation ofthe structure
of the oxide layer, whose composition is already known
on the basis of AES characterization. As in the case of
XPS, it is an ex situ UHV-based technique and might
result in a loss ofwater molecule constituting the surface
oxide layer.
C. LSVand CV
LSVand CV [33-36] are very precise techniques in deter-
mination of the oxide charge density based on the inte-
gration of the oxide-reduction LSVor CV transient. The
applicability of these techniques depends on the
reducibility of the surface oxide within one scan and on
the potential region within which the oxide reduction
occurs. Once the surface-chemical composition of the
surface oxide has been established, LSVand CVallow
one to determine the amount of the surface oxide with
the precision ofsome 2-3% ofa ML. They are in situ tech-
niques that allow identification of different oxidation
states of the metal cation or distinct oxide phases formed
on various metallic grains (in the case of polycrystalline
substrates). They lead to discrimination of various ener-
getic states of the oxide that can arise from different sur-
face structures or different degrees of hydration. Upon
combining with systematic examination of the impact of
the scan rate on the reduction profiles, LSVand CV serve
as an important source of information on the oxide
reduction kinetics.
Jerkiewicz
D. Electrochemical Quartz Crystal
Nanobalance
Electrochemical quartz crystal nanobalance (EC QCN)
[27] allow one of measure the mass change at the
metal-oxide interface associated with the oxide forma-
tion and reduction. Because EC QCN determines the
overall mass response, one needs to take into account
the displacement of the water molecules and/or
adsorbed anions in the interpretation of the mass
response. Thus, examination of the oxide growth in the
submonolayer region is troublesome. However, determi-
nation of the mass change associated with the growth
of multilayer films is powerful. It is an in situ technique,
and when combined with in situ oxide charge determi-
nation (by CV and LSV), it constitutes a powerful
experimental tool.
E. Ellipsometry
Ellipsometry [37] allows one to examine changes in the
parameters 'II (relative amplitude attenuation) and ~
(relative phase retardation) of an elliptically polarized
light beam brought about by the surface oxide. Sub-
sequent theoretical data treatment leads to determination
of the oxide thickness ifJ and the real (n) and imaginary
(k) component of its refractive index, 0'); it is an in situ
technique that can be conveniently applied to the study
of formation of multilayer and monolayer oxide. When
coupled with other experimental techniques that provide,
for instance, the oxide charge density, it is a powerful tool
in elucidation of the oxide thickness and presence of
hydriding water molecules.
F. Mossbauer Spectroscopy
Mossbauer spectroscopy [27] is based on the recoil-free
emission and the resonance absorption of nuclear
gamma rays. It can be applied as an in situ experimental
technique. It allows one to examine the influence of the
chemical bonding, different oxidation states, the metal's
own electrons, and the charge of the ligands on the
Mossbauer spectra. These interactions can be interpreted
in terms of the crystal or amorphous lattice structure
and presence of the oxide hydration. The technique can
be applied to study certain nuclei that give nuclear
resonance effects.
G. Surface X-Ray Scattering
Surface x-ray scattering [27] is based on an analysis of the
x-ray diffraction pattern formed upon interaction of the
incident beam with the electrode surface. It is recognized
thatit allows probing long-range order in the surface layer
 Surface Oxidation of Noble Metal Electrodes
ofthe metal. The technique can be used to study the struc-
ture of surface oxides, the adsorbed water, and the struc-
ture formed by adsorbed species. The main advantages
ofx-rays are weak interactions with the matter (no sample
damage during the analysis) and the wavelength of the
radiation, which is comparable with the interatomic
distance. Thus, the x-ray diffraction pattern is a direct
measure of the crystal lattice geometry and interatomic
spacing. The weak interaction of the x-rays also permits
an analysis of the crystal structure beneath (buried) the
adsorbate; thus, they lead to determination of the vari-
ation of the substrate structure brought about by the
adsorbate.
VII. SURFACE-OXIDE GROWTH
MECHANISMS AND RESPECTIVE
KINETICS
In the representation ofthe fundamental steps involved in
the electrochemical development of a surface oxide on
the noble metal, it was mentioned that the process con-
sists ofvarious steps (Fig. Ib and c):
1. Adsorption of H 20 (acidic solution) or OH- (basic
solution);
2. Formation of OHchem or Ochem;
3. Place exchange (flip-over) between OHchem or Ochem
and the surface metal atoms;
4. Escape of the metal cation from the metal surface
into the oxide (this involves formation of the
quasi-3D oxide lattice) at the inner metal-oxide
interface, under the condition that the place
exchange does not set in;
5. Electron transfer across the interface.
An analysis of these basic steps involved in the very
initial oxide development clearly indicates that each of
them can be the rate-determining one in the formation
of the surface oxide on the noble metal. It should be
realized that the development of the oxide layer differs
from the growth of the 3D bulk-type oxide. In the case
of thick oxide films comprising hundreds or thousands
of MLs, the process is often limited by the transport of
the metal cation (Mz+), the oxygen anion (0 2 -), or the
electron transfer through the oxide film, which often is a
semiconductor or an insulator [3,4]. Moreover, thick
oxides on certain transition metals can possess a signifi-
cant number of lattice defects, delocalized electrons,
and/or excitons whose transport across the film can affect
the oxide growth kinetics through their contribution to
i the charge transfer. This is not the case in the event offor-
mation of a very thin (monolayer and submonolayer)
oxide on the noble metal. At present, it is well known
j
)
567
that four fundamental processes can become the
rate-determining step giving rise to distinct growth
kinetics.
It is well established that the formation ofthin surface
oxides on the noble metal often follows either the
logarithmic or inverse-logarithmic growth kinetics,
each originating from a distinct process being
the rate-determining one [1-4,11,13,33,36]. Examina-
tion of the applicability of the logarithmic or
inverse-logarithmic kinetics to the system under scrutiny
is often verified by plotting the oxide charge density,
qox, or its reciprocal, l/qox, vs. logarithm of the
polarization time, log tp. However, this approach may
be misleading, especially if the experimental results do
not cover several orders of magnitude of tp, say from
seconds to hours. The theoretical treatment of the oxide
growth kinetics should begin by determination of the Xo
and Xl parameters, which are defined as follows [1-4,13].
Xo= J-KkT
-2
8nnq
(10)
X _qaV
1- kT (11)
where K is the relative primitivity of the film, n is the
number of metal ions per unit oxide volume (cm 3), q is
the charge of the metal cation (MZ+), V is the potential
across the oxide, a is the distance between metal cations
in the film (or between the metal atom and the metal cat-
ion at the inner metal/oxide interface, designated a'), k
is the Boltzmann's constant, and T is the temperature.
The experimentally determined thickness of the surface
oxide film, X, can assume values either smaller or greater
with regard to Xo and Xl; the mutual relation between
X, Xo, and Xl determines the applicability of particular
kinetics and growth mechanism. Before examination of
the relations between X, Xo, and Xl, it ought to be stressed
that Xl < Xo. This is of importance in establishing the
relation between X, Xo, and Xl because the value of X o
is not always known due to the difficulty in elucidating
the value of K for monolayer oxide films.
(A) X » Xo, thus X » Xl (thick oxide films). The oxide
growth kinetics are governed by the transportofthe metal
cations (MZ+) from one interstice to another in the film.
Mathematical treatment leads to two parabolic time laws.
(B) X « Xo (thin oxide films). In this case, the electrons
penetrate the oxide by the tunneling and leave metal cat-
ions behind; a strong electric field becomes established
across the interface; its intensity equals E = VIX (E has
values in the 10 7 _10 8 V cm- l range). This strong field
568
can enforce directional escape of M Z+ from the metal sur-
face or cause a directional movement of MZ+ in the film.
The following two cases are distinguished.
(Bl) Xl < X < Xo (thin oxide films). The diffusion rate of
Mz+ is proportional to the field and determines the oxide
growth kinetics. Mathematical treatment leads to two
parabolic time laws.
(B2) X< Xo and X < Xl (very thin oxide films). The
electric field strength is so great that the migration of
M Z+ is no more proportional to it. Their motion is over-
whelmingly in one direction and the rate of oxidation is
determined by the rate of escape of Mz+ from the metal
surface into the oxide. This mechanism gives rise to
inverse-logarithmic growth kinetics.
A. Interfacial Electron Transfer
The growth ofthe surface oxide on the noble metal can be
limited by the electron transfer across the thin oxide layer,
if the other steps proceed significantly faster [4,38].
Because a thin surface oxide on the noble metal is in many
cases electronically conducting, it is not evident how it
could become the rate-limiting step in the oxide growth,
and the origin of this behavior requires further
explanation. It is important to recall that there exists the
space-charge effect at the metallic oxide-electrolyte
interface and that due to the electron overspill effect, the
surface electron density protrudes toward the electrolyte,
giving rise to a local charge redistribution. An analysis
of the charge distribution across the interface indicates
that the transfer of electrons across the oxide is impeded
because they must move against their potential energy
barrier. Under such conditions, not many electrons suc-
ceed in passing through the oxide layer as ionic species,
which normally migrate under the influence of the elec-
tric field. The transfer of the electrons from the conduc-
tion band of the metal to the adsorbed intermediate can
occur only through the electron tunneling effect. The elec-
tronic current due to the electron tunneling may be con-
verted to the oxide thickness, X, that is represented by
the following equation:
h
X=A+ ~=lntp (12)
4n y 2m e Va
where h is the Planck constant, tp is the oxidation time, me
is the electron mass, Va is the height of the potential
energy barrier, and A is a constant that originates from
the solution of the Schrodinger equation for the electron
transfer across a one-dimensional time-dependent
potential-energy barrier. An analysis ofEq. (12) indicates
that the slope of the X vs. In tp relation allows unambigu-
0us determination of the potential-energy barrier. It
Jerkiewicz
ought to be stressed that the unit of the oxide thickness,
X, is the meter; thus, in the case of electro-oxidation of
the noble metal, it is essential to convert the oxide charge
density (g, C cm -2) to the thickness (X, m). It is important
to add that the current that originates from the electron
transfer across the oxide (via electron tunneling) does
not depend on T. Thus, if the oxide growth is limited by
the electron transfer, then the amount ofthe oxide formed
should not depend on T.
B. Escape of the Metal Cation from the Metal
into the Oxide
It is mentioned above that under specific conditions the
strength of the electric field established across the oxide
can be very large. Under this strong field, the rate of
oxidation can be determined by the rate of escape of
Mz+ from the metal surface into the oxide at the inner
metal-oxide interface. The origin of this behavior is as
follows. In absence of the external electric field, the ions
have to move across a potential barrier U. On the other
hand, in presence of the external field, the barrier V is
lowered by the factor 0.5 qa'
E, where E = VIX (Fig. 3).
The overall formula of the growth rate is as follows:
ax =
- H)
NOvexp ( - - exp - - (qaIV) (13)
at kT XkT
Oxide
H-I
a' I I a
Distance
Figure 3 Schematic representation of the potential energy
profile for a metal cation escaping from the metal surface into
the growing surface oxide film assisted by the strong electric
field established across the interface; a' is half of the distance
between the surface metal atom and the metal cation in the
oxide; a is half of the distance between two metal cations in the
oxide film 0' > a); H = Hi + U, where Hi is the heat of solution
of the metal cation in the oxide; U is the activation energy of
diffusion of the metal cation in the oxide; E is the electric field
across the oxide and E = VI X.
 Surface Oxidation of Noble Metal Electrodes 569

where N is the surface density of atoms, 0 is the volume

of oxide per metal atom, v represents the surface metal
atom vibrational frequency (usually of the order of Metal- --Oxide
10 12 S-I), H = Hi + V, Hi is the enthalpy of solution
of the metal cations in the oxide, V is the activation
energy barrier of diffusion of the metal cation in the /
oxide, a' is half the distance between the metal atom
and the metal cation at the inner metal-oxide interface. /'
Solution and rearrangement of Eq. (13) leads to the
following relation: /
~=~ln(XIU) +~Intp (14) /
X Xl Xl XI Developing dipole
where XI = qa' V /kT, U = NOv exp( -H/kT), and XL is
/' ~potential difference X
the limiting thickness the oxide can reach following /
these kinetics. An analysis of Eg. (14) indicates that the
slope of the I1Xvs. In tp relation leads to determination
of the electric field across the oxide, E, as long as one /
is able to assess the M -- Mz+ distance at the metal~oxide
interface. Determination of E (which should be of the
/ I

/
o
I
order ofl0 7 V cm- I ) by this theoretical approach allows I d I
one to double check the applicability of these kinetics. J--- --t M
An analysis of Eq. (14) reveals that the IIX vs. In tp I .1 Dipole
or 1
relation leads to an inverse-logarithmic kinetic law [1,2]. .. Moment, J..l.

c. Place Exchange Between OH chem and
Surface Metal Atoms
In the case ofcertain submonolayer or multilayer oxides
(but still very thin), the oxide growth can be direct logar-
ithmic in polarization time, yet a different surface
physicochemical process is the rate-determining step.
The model [18,39] suggests that there exists variation of
the surface potential, X, at the oxide-solution interface
that is associated with the place exchange between the
OHchem (or Ochem) surface species and the top-most sur-
face metal atoms, M. This modification of Xinfluences
the rate of deposition of OH groups and subsequently
the rate of the surface oxide growth. A schematic rep-
resentation of the situation is shown in Fig. 4. According
to this model, the place exchange between OHchem and
M (the turn-over or flip-over) brings about a modifi-
1 cation of the effective electric potential across the
I interface. The following equation describes the rate of
interchange ofOHchem species with M atoms:
(15)
where /1</J is the electrostatic potential difference
associated with the surface array of OHchem species,
/1Xt = Xo - Xt is the difference between the initial surface
Figure 4 Model for the partially oxidized surface of a noble
metal. The graph illustrates the profile of the interfacial poten-
tial difference, including the coverage-dependent potential
component, X, which arises from the M-OH surface dipole
and the place-exchanged OH - M dipole species.
potential before the turn-over and right after it, f3 is the
symmetry barrier, J1 is the dipole moment of the M -OH
surface dipole, dis the oxide thickness, and Q/Fmeasures
the extent ofdeposition ofthe OHchem species. Integration
of Eq. (15), taking into account all applicable conditions
[39], results in the fOllowing kinetic equation:
4nNA2f3J12 Q = (Xo - /1</J )2f3J1
I ( d RT )
n 4nkNA2f3J12 + d RTF dR T
+ In(t + r')
(16)
where t is the oxidation time and r' is an integration con-
stant. The above equation demonstrates that the relation
between Q and In t is a linear one, thus pointing out to a
logarithmic kinetic law.
570
D. Field-Assisted 'n'ansport of the Metallic
Cation
In the case of oxides thicker than just a few MLs, the
potential difference established across the oxide results
in a low electric field. For these conditions, the oxide
growth rate becomes controlled by the rate of diffusion
of the metal cation, MZ+, in other words by its transport
(hopping) from one interstice to another within the oxide
layer (not at the metal-oxide interface). The rate of the
oxide growth is expressed by
ax = 4a nvq VQ x (_~)
2 instance), which subsequently becomes available on
(17)
at kTX e p kT
Integration of this formula leads to the following kinetic
relation:
2
2 8a nvqVQ ( U)
x = kT exp - k T t + C (18)
The above formula shows that the relation between the
oxide thickness, X, and the oxidation time, t, is a
parabolic one, thus pointing to a parabolic kinetic law
[1-4,33].
E. Diagnostics of Kinetic Laws
It is shown above that the development of a surface oxide
on the noble metal involves numerous steps and that each
of them can become the slowest one, thus the one that
limits the growth kinetics. In most of the cases, each par-
ticular rate-determining step gives rise to a distinct
kinetic law. A detailed scrutiny of a genuine metal-oxide
system is often troublesome, and the applicability of a
specific kinetic law to the system under study requires
kinetic and mechanistic diagnostics. The following
approach should be assumed to meaningfully examine
the oxide-growth kinetic law that describes the system
under investigation.
1. It is useful and important to assess the values of the
parameters X o and Xl [Eqs. (10) and (ll)], and sub-
sequently to related them the thickness of the oxide
film, X. Appraisal of X with regard to X o and Xl
immediately allows one to exclude some growth
mechanisms and thus certain kinetic laws.
2. It is practical to examine the applicability of a par-
ticular kinetic law by plotting the oxide thickness,
X, or its charge density, qox, or their respective
reciprocals, 11X or 11 qox, vs. logarithm of the
polarization time, In t, or finally the squared oxide
thickness, X 2, vs. In t. These tests, if carefully
executed, can serve as a good indicator of the suit-
Jerkiewicz
ability ofa given kinetic law to the system under study.
However, it should be added that to perform these
tests, experiments should be conducted over a wide
extent of polarization times, so that several decades
of In t can be examined.
3. Once a particular kinetic law has been deduced to
well describe the system under investigation, it is
advisable to conduct a careful and detailed numerical
analysis by a direct application ofthe kinetic formula
to the experimental data. The values of numerous
parameters (such as the field across the oxide, for
the basis of numerical calculations, should fall in
the range that is imposed by the growth mechanism
[13].
VIII. EXAMPLES OF FORMATION OF
SURFACE OXIDES
Developmentofsurface oxides on noble metals has been a
subject of extensive research and numerous review
papers; thus, it is impossible to review all the findings.
However, to illustrate applicability ofthe above presented
growth mechanisms and the respective kinetic laws, some
selective results need to be presented and discussed. Here,
attention is given to three noble metals: rhodium,
platinum, and gold. In all three cases, the surface oxide
growth is accomplished by application of the same
experimental methodology, namely the potentiostatic
polarization. It ought to be stressed that Rh, Pt, and Au
undergo surface oxidation upon anodic polarization
even in the potential region corresponding to water
stability, thus below EgER [5-7,9-15,39-48]. The extent
of oxidation depends on E p , tp, and T. In general, the
higher the polarization potential and the longer the
polarization time, the greater the magnitude of the metal
oxidation.
A. Rhodium
In 0.5 M aqueous H 2S0 4 solution, the growth of the first
oxide layer on Rh proceeds in the 0.55-1040 V, RHE,
potential range,and it involves two steps [Eqs. (19) and
(20)]. Upon extension of the potential beyond lAO V,
the development of RhO(OH) takes place [Eq. (21)]
[13,14,40].
Formation
Rh + H20 ~ RhOH + H+ + e
(19)
0.55-0.75V
 Surface Oxidation of Noble Metal Electrodes 571

(a) (b)
RhOH + 2H 20 ~ Rh(OHh + 2H+ + 2e
(20)
0.75-1.40V
RhO(OH)
2Rh(OHh + Rh ~ 3RhO(OH) + 3H+ + 3e
(21)
> 1.40V

It is worthwhile emphasizing that although the oxide

development proceeds in three steps, its reduction
involves just two processes [Eqs. (22) and (23)]; this can
be deduced from XPS data and the presence of two fea-
tures in a LSVoxide-reduction profile.
Reduction
---Rh
3RhO(OH) + 3H+ + 3e ~ 2Rh(OH)3 + Rh
(22)
l.30-0.90V

Rh(OHh+3H+ +3e ~ Rh+3H20

(23)
0.30-0.05V
Extensive research on the growth ofsurface oxides on Rh
under potentiostatic conditions (Ep from 0.80 to 2.40 V
i- and tp up to 104 s) demonstrates that the Rh(OHh layer
grows to a limiting thickness of 3 ML and that it is
sandwiched between Rh and the outer film consisting of
RhO(OH) (Fig. 5). An analysis of the charge density of
the Rh surface oxides formed by anodic polarization at
t 0.8:sEp :s2.4 V and for 100:s tp :s 104 s leads to the
observation that they are of two-layer nature and that
they do not surpass 3 equivalent ML of Rh(OHh and
1 ML of RhO(OH) on top of the latter. Examination of
the relation between X, Xo, and Xl reveals that under
these experimental conditions, X < XI and X < X o (for
a typical potential drop of 0.5 V across the oxide, XI
assumes a length that corresponds to some 58 ML of
Rh(OHh) [13]. The plots of l/qox vs. log tp, thus the
inverse- logarithmic relations (Fig. 6), reveal linearity as
soon as the oxide charge density exceeds a value corre-
sponding to 1 ML of Rh(OHh. These tests indicate that
the growth of Rh oxides thicker than 1 ML of Rh(OHh
follows the Mott-Cabrera kinetics, which imply that the
process is limited by the rate of escape of Rh3+ from the
metal into the oxide [13,14]. On the other hand, growth
ofthin oxide layers on Rh under 0.7 :s E p :s 1.4 Vand
10° :s tp :s 104 s conditions, thus a monolayer oxide
film, is logarithmic in time (for 278:s T:s348 K; see
Fig. 6 for T = 298 K). This observation indicates that
the growth kinetics can be limited either by the
place-exchange mechanism or by the electron tunneling
across the oxide. However, the second mechanism
Figure 5 Visual presentation of the scheme of the sur-
face-oxide growth on Rh. Initially, Rh(OHh is formed and it
develops to a limiting thickness of 3 ML (a). Subsequently, the
formation of RhO(OH) commences, with Rh(OHh being
sandwiChed between Rh and RhO(OH) (b). During reduction,
RhO(OH) is converted to Rh(OHh and subsequently, at a lower
potential, to Rh.
implies that the amount of the oxide film developed
should be Tindependent, because the electron tunneling
does not depend on T [Eq. (12)]. Because the growth of
monolayer oxides on Rh is T dependent and because the
amount of the oxide developed increases upon T
augmentation, it may be concluded that the initial forma-
tion of Rh(OHh proceeds through the place-exchange
mechanism.
The slope of the l/qox vs. log tp (Fig. 7) leads to a
meaningful examination of the potential drop across the
film, whereas the oxide charge density results in eluci-
dation of the oxide thickness [13,14,38]. Combination of
these parameters leads to determination of the electric
field across the oxide, which is found to be of the order
of 10 7 V cm- I ; its intensity matches the requirement
imposed by the Mott-Cabrera mechanism.
B. Platinum
The surface oxidation ofPt is one ofthe most investigated
noble metal-oxide systems, and a detailed examination
of the existing results is beyond the scope of the present
paper [11,12,17-20,43-52]. At present, it accepted that in
572 Jerkiewicz

r--.
I 0.8 V

-
r"l
0
K
3
'-"
N
S C,)
......I I 1.0 V

U 2
::t

---
......
I
><
r:l 1 J ;.~~----~ - • 2 ML Rh(OH)3
~3 ML Rh(OH)3-
oJ j j

0 1 2 3 4 5
log tp
Figure 6 Oxide film growth plots expressed in reciprocal of the oxide reduction charge densities, I/qox, vs. logarithm of the
polarization times, log tp, for various polarization potentials, E p , between 0.80 and 2.40 V, RHE, T = 298 K.

0.5 M aqueous H 2S04 solution, the initial development The place exchange occurs before the further oxidation
of Pt oxide proceeds in the 0.85-1.40 V, RHE, range, ofPtOH to PtO and departure ofH+. Another alternative
and it involves the following steps [Eqs. (24) and (25)]. mechanism that involves simultaneous transfer of two
electrons is also proposed [Fig. Ie and reaction (6)] I: 19,20],
1200 T--------------- but these findings are not supported by surface x-ray
scattering data, which indicate that OHchem on the Pt sur-
1000

~~~~===it==:B=-==~I
~~~"::::::::::i::::::::::~:::=::§
r"'l
face and just beneath it (buried through the turnover
'E: 800 ~~ ~~ ~~-'V 8
:8~~~ process) are distinguishable species [51]. Upon extension
II
(,;)
of the potential well beyond 1.40 Yand prolongation of
==
_ == .::::
_ ::::: --0- ==
_" ::=cr- ~ :8::::::
_ == - :-- ~O
: :. ::::::0
~
'--.
600
~_
._
"--.-n-- -::8----8 E tp ,the growth ofPt02 on top ofPtO takes place [Eq. (26)]
[12,43-52].
\
g:::::: ~ •• ~ 3t ~~.:§~•••• c
400 p
~ Formation
~
200 C ) " " - - - _ _0 - - - - 0 - - - 0

Pt + H20 -+ PtOH + H+ + e 0.85-1.10Y

0 ~,
(24)
o 2 3 4 5

log t p
place exchange +
PtOH ) PtO +H +e 1.10-1.40Y
Figure 7 Rh oxide growth plots expressed as the charge
(25)
density, qox vs. logarithm of the polarization time, log tp, at
T=298 KforO.7::: Ep :::2.4 V and 10° ::: tp ::: 104 s.Thearrow
indicates the increase of E p from 0.70 to 1.40 V, RHE. The data
demonstrate linear relations between qox and log tp for the
PtO + H20 -+ Pt02 + 2H+ + 2e > 1.40Y
whole range of qox. (26)
 Surface Oxidation of Noble Metal Electrodes 573

Ellipsometry [50], XPS [49], and electrochemical C. Gold

[12,47,48] studies on Pt oxidation reveal that the growth
The development ofsurface oxides on Au is also an exten-
ofPtO proceeds to a limiting thickness of2 ML and that
sively studied system [54-57]. At present, it is understood
Pt02 grows on top ofthe latter without reaching any limit.
that the very initial development of the Au oxide involves
The initial growth of the 2 ML of PtO and the first ML
the OH chem species and that it participates in the sub-
of Pt02 is a slow process. However, once the first Pt02
sequent development of AuO or AU203. The growth
layer (on top of 2 ML of PtO) has been formed, the
of multilayer oxides proceeds according to the
growth kinetics increase some 100-400 times, depending
inverse-logarithmic kinetics, which are limited by the rate
on the polarization potential (the augmentation is pro-
ofthe place exchange. It is accepted that in 0.5 M aqueous
nounced the most for 2.1 ::s Ep ::s 2.3 V). It should be
H2S04 and KOH solutions, the development ofAu oxides
added that under strong polarization conditions, the Pt
proceeds in the following steps (is basic solution the first
oxide film experiences anodic dissolution. The process
process involves discharge ofOH-):
can be detected from the presence of leveling off of the
Formation
qox vs. log tp plot, thus when qox begins to approach a
"limiting" charge density, even if the polarization poten- (29)
tial is extended [12]. The reduction behavior of thick Pt
oxides, those comprising PtO and Pt02, is rather
unexpected. Upon the potential decrease, PtO becomes place exchange A
AuOH ) uO + H + e (30)
the first species to undergo reduction, and it leads to Pt
covered with Pt02 [Eq. (27)]. Subsequent conversion of Upon extension of the potential well beyond 1.50 Vand
Pt02 to Pt takes place at a lower potential that reduction prolongation of tp, the growth of an oxide species with
ofPtO [Eq. (28)]. Au in the 3+ oxidation state commences:
Reduction
(31)
Pt/2PtO/nPt02 + 4H+ + 4e ~ Pt/nPt02 + 2H20
0.60-0.30V Ellipsometry and electrochemical results [57] indicate
that the Au oxides comprise two layers: the inner a. film
(27) and the outer f3 film (Fig. 9). The ellipsometry data dem-
onstrate that the a. film grows to a limiting thickness of
Pt/ nPt0 2 + 4nH+ + 4ne ~ Pt + 2nH20 (28)
0.30 - O.lOV (a) (b) (e)

An analysis of the existing spectroscopic and electro-

chemical data leads to conception of a general scheme
offormation and reduction of surface oxides on Pt elec-
trodes (Fig. 8).
A recent study [53] on the potentiostatic oxidation of
Pt(lOO) and Pt(111) electrodes reveals that the initial sur-
face oxide formation proceeds significantly faster on
Pt(100) than that on Pt(111). This behavior can be easily
explained, once the surface coordination number of the
fcc(l1l) and fcc(100) surfaces are taken into account
(nfcc(lOOl = 8 and nfcc(lll) = 9, respectively). It is apparent
that the very initial oxide formation proceeds either
through the discharge of H20 to OHchem or 0chem, with
subsequent creation of a quasi-3D lattice comprising
Pt2+ and 0 2-. This development ofPtO proceeds via the
Figure 8 Visual presentation of the scheme of the sur-
+ place exchange (turnover) mechanism. Because the pro- face-oxide formation and reduction of Pt. Initially, PtO is
cess requires breaking of the Pt-Pt surface bonds to formed and develops to a limiting thickness of 2 ML (a).
accommodate the arriving Ochem (or OHchem), it becomes Subsequently, the formation of Pt02 commences, with PtO
apparent that it should occur faster on Pt(lOO) than on being sandwiched between Pt and Pt02 (b). During reduction,
Pt(l1l), as it is observed experimentally. PtO is converted to Pt, with Pt02 residing on the Pt substrate (c).

-{
574 Jerkiewicz

(a) (b) data on Au oxidation reveals that the growth of the inner
1 200
oxide, AuO or Au(OHh, proceeds to a limiting thickness
I
400
0
/ of 3 ML in acidic solution and I ML in basic solution.
~
/
300 / 150 ~ /
/ / The ellipsometry results do not allow One to easily dis-
/ /
E tinguished between the hydrous and nonhydrous oxide
~ 200
A /
P / ~ 100 P //
species; thus, the species that can exist are either AuO
" / /
" /
/0
or Au(OHh. The higher oxide species, AU203 or
"" 100 ~.//d/ I "" 50
/
c/ Au(OHh, resides on top ofthe lower oxide. Examination

o~~~
./
9/ a of the growth kinetics [57] show that the process follows
o---{]- - -G---a
I the inverse-logarithmic kinetics with two distinct linear
100 200 300 400 0 300 600 900 1200 1500
regions. The transition from One mechanism to another
tp tp
/ S / S
falls close to I/qox = 0.10 mC- 1cm 2; at present, the ori-
gin of this behavior is not well understood. An analysis
Figure 9 Experimentally determined relation between the of the existing spectroscopic and electrochemical data
thickness, d, ofthe IX (inner) and fi (outer) oxide films on Au elec-
for the Au-oxide system leads to conception of a general
trodes vs. the polarization time, tp, as determined by in situ
ellipsometry measurements. (a) Oxide development in 0.5 M scheme offormation and reduction of the surface oxides
aqueous H ZS0 4 solution at Ep = 2.15 V, RHE, and T= 298 K. On Au, which is visualized in Fig. 10 and which shows that
(b) Oxide development in 0.5 M aqueous KOH solution at the "lower"Au oxide is sandwiched between the metallic
Ep = 2.23 V, RHE, and T= 298 K. substrate at the "higher" oxide that constitutes the outer
layer.

0.55 nm in acidic solution and 0.28 nm in basic one,

whereas the f3 film grows without reaching any limit. The
spectra shown in Fig. 9 are characteristic of a highly
absorbing thin film adjacent to the metallic substrate
and with a second film, on top of the thin one, which is
most probably a hydrous form ofAUZ03 or Au(OHh [57].
Interpretation of the electrochemical and ellipsometry
ACIDIC SOLUTION
(a) (b)
(a)
IX. CONCLUSIONS
The above presented discussion of the mechanisms and
kinetic laws describing the surface oxidation of noble
metal electrodes indicate that the atomic-level under-
standing of the process is lacking despite the existence
of abundance of data. The existing results are mostly of a
qualitative nature, thus indicating that theoretical treat-
BASIC SOLUTION
ment of the data can be done and that it can contribute
to the understanding of the fundamental steps involved
(e) (d)
in the process. Advancement and application of modern
Au,O,or
surface science techniques to electrochemical research
Au(OH), opens a new avenue for exploration, because utilization
of these techniques will lead to elucidation of structural
parameters of the surface oxide. For instance, X-ray
scattering can assist one in determination of surface
structural parameters of the oxide layer, whereas STM
,
can allow one to observe new surface structures or surface

l
disordering that follows the oxide development. Another
research pathway that can be easily explored is the oxide
growth on single-crystal electrode surfaces. This explo-
ration can result in examination of the specificity of the
Figure 10 Model I. Diagram ofthin and thick Au oxide films oxide growth with regard to the structure of the metallic 1
I
formed in acidic solutions. (a) Quasi-2D film having a limiting substrate. Temperature-dependent research is of particu- i
thickness of 3 ML of AuO or Au(OH)z ; (b) thick Au oxide film
lar importance because it leads to detection of numerous
consisting of the quasi-2D oxide and the quasi-3D oxide film,
AuzO) or Auz(OHh, residing on top of it. Model II. Diagram oxide states that can develop on the metal substrate under t
of thin and thick Au oxide films formed in basic solutions. (c) particular conditions. Electrochemical quartz crystal
Quasi-2D film having a limiting thickness of I ML of AuO or nanobalance is an inexpensive technique, which provides
Au(OH)z; (d) thick Au oxide film consisting of the quasi-2D an abundance ofuseful data on the hitherto unclear issue
oxide and the quasi-3D oxide film, AuzO) or Auz(OHh, resid- of hydration of the surface oxide. In summary, the oxide
ing on top of it. growth on the noble metal under electrochemical con- ~
 Surface Oxidation of Noble Metal Electrodes
ditions is an underinvestigated area ofresearch that can be
explored by application of modern electrochemical and
surface-science techniques. The latter can shed light on
the fundamental events involved in the surface - oxide for-
mation and on the atomic level structure of the sur-
face-oxide layer. This research is of vital importance to
modern surface electrocatalysis, design and develop-
ment of novel semiconducting materials, thin deposits
on oxide-layer substrates and formation ofpatterned sur-
face structures.
ACKNOWLEDGMENTS
An acknowledgment is made to the NSERC of Canada
and Ie FCAR du Quebec for support of this research. We
than Dr. G. Vatankhah for his help in preparation of the
figures. The results presented in the review are the result
of many years of research done in collaboration with
Prof. B. E. Conway, Prof. G. Tremiliosi-Filho, Dr. 1. 1.
Borodzinski, Mr. F. Villiard, M.Sc., and Mr. L.-H.
DallJ\ntonia, M.Sc.
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Stoicoviciu. Electrochim Acta 31:1051, 1986.
55. H Angerstein-Kozlowska, BE Conway, A Hamelin, L
Stoicoviciu. J Electroanal Chern 228:429, 1987.
56. H Angerstein-Kozlowska, BE Conway, K Tellefsen, B
Barnett. Electrochim Acta 31:1051, 1986.
57. G Tremiliosi-Filho, L-H Dallf\ntonia, G Jerkiewicz. J
Electroanal Chern 422:149, 1997.

J<

t
l
~
 33
Differential Electrochemical Mass Spectrometry as a Tool for
Interfacial Studies
Helmut Baltruschat
University ofBonn, Bonn, Germany
t
ABSTRACT
Using an appropriate experimental setup, differential
electrochemical mass spectrometry can be used to
characterize submonolayer amounts of adsorbates on
polycrystalline and single-crystal electrode surfaces by
means oftheir desorption. One possibility to achieve this
is to oxidize a carbonaceous species to CO 2, which is
quantitatively detected in the mass spectrometer. Many
i adsorbates can also be desorbed at certain potentials as
such or as the hydrogenated product, allowing a more
direct characterization of the adsorbates. In some cases
a nonreactive desorption can be induced by displacement
with a second adsorbate, yielding additional information.
I. INTRODUCTION
In heterogeneous catalysis, one of the most often used
techniques for the identification of adsorbates is
thermodesorption mass spectrometry [1,2], which is
sensitive enough to allow the detection of desorption
products in the submonolayer range. It is used for the
quantitative determination of adsorbate states, desorp-
tion products, surface reaction mechanisms (esp. by
using isotope exchange reactions), and kinetic studies of
the desorption reaction, including the determination of
activation energies and the reaction order. Besides Kelvin
probe measurements, it is probably the least expensive
ultrahigh vacuum (UHV) technique.
577
Of course, this technique is not directly applicable to
the solid phase-electrolyte interface. Notonly is the mass
spectrometric determination of species from an electro-
lyte more difficult (how to achieve this is one of the main
topics of this chapter) but also desorption cannot be
triggered by increasing the temperature due to the limited
temperature range at least in aqueous systems. Luckily,
desorption of many species can be achieved by applying
an appropriate potential, which therefore replaces tem-
perature as the variable.
Historically, the technique evolved out of the mass
spectrometric determination ofgaseous electrochemical
reaction products as developed by Bruckenstein [3]. It
was later improved by Wolter and Heitbaum [4,5] so that
the time constant became short enough to allow the
on-line detection of electrochemical reaction products,
e.g., during cyclic voltammetry. Due to a proper design
of the vacuum system, including two pumping stages,
product formation rates were detected; to distinguish
the technique from product sampling, i.e., integrating
approaches, the method was called "differential." Even at
the beginning it was sensitive enough to detect desorption
products corresponding to about one monolayer of
adsorbed species at porous electrodes.
In some respect, differential electrochemical mass
spectrometry (DEMS) resembles the membrane intro-
duction mass spectrometry [6]. This technique is used in
analytical chemistry to detect trace amounts of nonpolar
molecules in water; thin nonporous membranes (silicon
orTeflon) are used to separate these molecules from water.
578
The nonporosity ofthe membranes has the advantage that
much less water is reaching the vacuum; therefore, special
pumping is not necessary. The drawback, however, is the
relatively large response time ofusually more than 10 s.
A review article on DEMS appeared in 1991 [7].
Therefore, after having described the technique, most
examples deal with later developments.
II. INSTRUMENTATION
A. Teflon Membrane: Interface to the Vacuum
It is essential for DEMS to be able to separate the volatile
products from the electrolyte. Fortunately, for aqueous
systems and also for some organic electrolytes, e.g., pro-
pylene carbonate [8] and other solvents containing
dimethylamine as constituent [9], this can be achieved
by using porous Teflon membranes. Because of their
hydrophobicity, the liquid does not penetrate through
them, whereas dissolved gaseous and other volatile
species readily evaporate in the pores.
The critical pore size for aqueous electrolytes depends
on the surface tension of water and the contact angle
between water and Teflon. It is calculated to be r < 0.8 J-lm
[4]. The Teflon membrane is usually supported by a glass
or steel frit.
A typical Teflon membrane (e.g., from Gore-Tex) is
75 J-lm thick and has a nominal pore width of20 nm with
a porosity of 50%. To achieve low time constants, the elec-
trode has to be positioned very close to the membrane.
One way to achieve this is to sputter the electrocatalyst
layer, e.g., Pt, onto the Teflon membrane. The resulting
catalyst layer typically has a thickness of 50-80 nm and
a roughness factor between 5 and 10 (a simple model of
such an electrode is shown in Fig. I). Alternatively, as
was done in the first DEMS experiments, a metallic
lacquer (e.g., Doduco from Diirrwachter KG, Germany)
containing small metallic particles can be painted onto
the Teflon membrane. It has the advantage of a large
roughness factor (50-100), permitting larger overall
product formation. The disadvantage is the lower mech-
anical stability, and a much higher thickness (50 to
100 J-lm) leads to less well-defined diffusion behavior.
Other electrode types and electrochemical cells are
discussed below; the common feature, however, is the
Teflon membrane.
B. Vacuum System
Despite the hydrophobicity of the Teflon membrane, an
appreciable amount of electrolyte evaporates. Because
the flow is molecular within the pores, a value of
J'=0.09 mbar L S-1 cm- 2 is calculated [4] fora porosity
Baltruschat
(a)
(b)
(c)
(d)
(e)-
Figure 1 Schematic representation of a typical "sputtered"
electrode. (a) Electrolyte, (b) catalyst sputter deposited, (c)
Teflon, (d) pores in the membrane; and (e) vacuum.
of 0.5 and a vapor pressure for water of 23 mbar at
20°C, which corresponds to 0.25 mL of water per hour.
The highest expected vapor pressure lies at around
100 mbar (water at 40°C), corresponding to a flow of
J'= 0.4 mbar L S-1 cm- 2 .
Under stationary conditions, this amount has to be
pumped by the pumping system:
J'=pxS (I)
With an upper limit of 10- 3 mbar in the ion source and a
pumping speed S of 200 L S-I, a flow of 0.2 mbar L S
is allowed and therefore an electrode area of 0.5 cm 2 is
acceptable.
The time constant r for the detection of a species is
directly given by the ratio of the ionization chamber vol-
ume Vo (total volume of the chamber in which the ion
source is situated; first pumping stage) to the pumping
speed, as seen in the following: under nonstationary con-
ditions, the change ofpressure (e.g., after a sudden change
of J') is given by
= J' - P x
Vodpldt
with the solution:
S (2)
,
P = (1' I S) x (I - e- tjr ) (3)
where r = Vol S. With a pumping speed of 200 Lis and a
volume Vo of 1 L, a time constant of 5 ms is thus
obtained, which is much less than the time constant
'.
attainable with the electrochemical cells (see below).
The analyzer section, ofcourse, has to be pumped sep-
arately to achieve la pressure below 10- 5 mbar. A 50-Lis
turbomolecular pump is sufficient. Figure 2 shows a typi-
cal experimental setup. The electrochemical cell is con-
nected to the first vacuum chamber via a valve at
position 5. Another valve at position 6 leads to the cali-
bration volume (see below). A shutter between the .
 DEMS as a Tool for Interfacial Studies
5
T 6
Figure 2 The vacuum system. I and 2, Rotary pumps; 3 and 4,
turbomolecular pumps; 5, connection to the electrochemical
cell; 6. connection to the calibration leak; 7, ion source; 8,
quadrupol rods; 9, secondary electron multiplier. (From Ref.
44.)
ionization chamber and the analyzer section allows the
difference in pressure. The secondary electron multiplier
(10) is oriented 90° offaxis, which has the advantage that
light from the filament does not reach the multiplier.
Higher stabilities are obtained using gas-tight ion
sources, because the filament operates at a lower pressure
than that existing in the ionization chamber.
The effort of pumping can be largely reduced by
allowing a much higher pressure in the chamber of the
first pumping stage of, e.g., 10- 2 mbar and by simply
pumping with a rotational pump at an accordingly lower
pumping speed [10]. A sufficiently low time constant
can easily be achieved by reducing its volume. In this case,
the ion source has to be placed in a separate chamber that
is pumped together with the analyzer of the mass
spectrometer by a simple turbo molecular pump of
50 Lis. A commercial gas inlet system can be used. The
disadvantage of such a system is that condensation or
multilayer adsorption of the species might occur in that
pressure range (cf. the vapor pressure of naphthalene,
which is only 0.1 mbar at room temperature); heating of
the gas inlet system may thus be necessary.
Product formation rates can be easily monitored by
recording the corresponding ion current. The mass
spectrometrically determined ion intensity Ii is directly
proportional to the partial pressure Pi of that species i
and therefore
..., (4)
579
whereaisa proportionalityconstant,J i = dn/dt = J;'/RT
is the incoming flow in mol S-I. KO thus contains all
settings of the mass spectrometer and the ionization
probability of the corresponding species.
When the species is produced electrochemically, J i is
given by the faradaic current h corresponding to that
process:
J i = N IF/(zF) (5)
where z is the number of electrons, F is the faraday
constant, and N is the transfer efficiency, i.e., the ratio of
the amount of the mass spectrometrically detected
species to the total amount of species produced
electrochemically. N may be less than I because a part of
the produced species diffuses away from the electrode
into the electrolyte. When the current efficiency is not
equal to 100%, h has to be replaced by its product with
the current efficiency. Therefore,
Ii = (K* /z)IF (6)
with K* = KO N/F. Experimentally, both the low time
constant of the vacuum setup of several ms and the
proportionality of Ii with the faradaic current were
verified [4,5].
Calibration of the mass spectrometer is achieved by
connecting a separate calibration volume Vc to the first
vacuum chamber via a calibration leak (e.g., a leak valve).
J;
The inflow rate is then given by the pressure decrease
in the calibration volume dpc/dt:
KO can thus be calculated from the pressure decrease in
the calibration volume, i,e., from a plot of the ion current
Ii vs the differentiated pressure Pc.
This calibration procedure cannot only be used for
gases (most commonly CO 2) but also for volatile
liquids. Special care, however, has to be taken that no
adsorption or absorption occurs in a part of the cali-
bration setup. Because of the limited linear range and
a possible interference of the partial pressure of H 2 0
on the sensitivity, the same conditions as during the
measurement should exist during calibration of the
instrument. In particular, this means that during
calibration, the electrochemical cell is connected to
the vacuum system.
In some cases calibration is possible when using a
known electrochemical reaction, such as hydrogen
evolution. From Eq. (6), K* and N· KO are obtained
580 BaItruschat

straight away. Often the oxidation of adsorbed CO on Pt

electrodes is used to calibrate the mass spectrometer from
C02. The integrated faradaic oxidation current and the
integrated ion current for CO2 have to be used. In this
case, however, double-layer charging effects, which
amount to 20% of the oxidation charge even after back-
ground substraction, have to be taken into account. The
reason is the different double-layer charge at a given
potential in the double-layer region with and without
adsorbed CO and additionally the shift of the point of
zero charge due to the adsorption of CO [5,11,12].
cr=:::::::::::::: I Slainiess sleel

PTFE ring
C. Cell Types

1. Conventional Cell for OEMS I. Glass

The cell shown in Fig. 3 is optimized to have a low volume.
This allows the use ofexpensive isotopically labeled com-
pounds for mechanistic studies. In its first version, the
cell body was made of Teflon; we now use glass because
Kalrez tighlener

~PTFEring
the porosity of the former sometimes leads to the
absorbance oforganic species. ---4 .

The electrode has already been described in Chapter 1. . - - - - - P l a l i n u m wIre

It is mechanically supported by a steel frit. The response
time for an electrochemical experiment was determined
to be about 0.1 s [13], which is much larger than that of
the vacuum system but still low enough for most electro-
chemical experiments.
A continuous forced convection may be achieved
by simply introducing the electrolyte via a Teflon tube
close to the electrode surface. When using volatile
educts, it has to be kept in mind that due to
evaporation, its concentration close to the surface of
a sputtered electrode may be largely reduced, even
when the electrochemical reaction is not diffusion
limited. The electrochemical reaction (and also the
adsorption process) and evaporation are competing
processes. In the case of the thicker lacquer
electrodes, the thickness of the porous electrode may
be comparable with the thickness of the Nernstian
diffusion layer (if the evaporation is diffusion limited)
and the educt concentration may be different at the
electrolyte side and at the Teflon membrane side of
the porous electrode.
2. Cells with Defined Convection
Transport ofspecies to the electrode can be largely accel-
erated and also better defined by using rotating
electrodes. In some cases it might therefore be interesting
to use a rotating porous electrode as an inlet system to
the mass spectrometer as it was described [14].
~
I---=:J ~"" Porous
PTFE membrane
(spullered WI'Ih plalinum)
Sleel fril
v........ Stainless steel
Figure 3 The conventional cell for DEMS.
Using such a rotating inlet system, the transfer
efficiency N can be determined under defined diffusion
conditions from a plot of the diffusion limited faradaic
currents from hydrogen evolution vs. the corresponding
values of Ii for different rotation speeds.
Using sputtered platinum electrodes, a transfer
efficiency above 0.9 was obtained even at high rotation
speeds. Obviously, in the whole range of rotation speeds
the concentration gradient across the catalyst layer is
much larger than the concentration gradient away from
the electrode into the bulk electrolyte, with a cor-
respondingly large Nernstain diffusion layer (cf. Fig. 4).
Using lacquer electrodes 50 to 100 pm thick, the transfer
efficiency only approached 0.7 at low rotation speeds
and was 0.3 at high rotation speeds. Here, the diffusion
layer from the surface of the electrode to the Teflon
membrane is comparable with the diffusion layer in the
bulk electrolyte.
 DEMS as a Tool for Interfacial Studies
c
membrane catalyst electrolyte
layer
x
Figure 4 Product concentration profile. bE, Thickness of the
electrode; bN , diffusion layer thickness. (From Ref. 14.)
The situation is somewhat different when the transfer
efficiency for the desorption products of an adsorbate
layer is considered. For the case of a fully covered
electrode, the product is formed evenly distributed within
the catalyst layer, including the pores (and not only
., formed at the macroscopic surface). Therefore, for
;
carbon dioxide formation from adsorbed CO on Pt,
transfer efficiencies slightly above 0.5 were found for the
lacquer electrode even at high rotation speeds, whereas
the transfer efficiency for the sputtered electrode still
was around 0.9.
To avoid the technically demanding rotational
feed-through into the vacuum, a much simpler approach
was described [15]. Here, a cylinder made up of an inert
material rotates approximately 5 mm above the station-
ary porous electrode. Defined mass transfer to the elec-
trode is achieved by the rotational flow.
3. Cell Types Allowing the Use of Massive
Electrodes
To be able to use massive electrodes, e.g., single-crystal
electrodes for DEMS, the thin layer cell of Fig. 5 was con-
structed [16,17]. The massive electrode with a diameter
of 1 cm is separated from the porous hydrophobic Teflon
membrane by a 50- to 100-{tm-thickelectrolyte layer. Vol-
atile species produced at the electrode surface diffuse to
the Teflon membrane within 2 s. The Teflon membrane
(75 {tm thick, pore width 0.02 /tm, porosity 50%) is
mechanically supported by a steel frit. The distance
between electrode and Teflon membrane is ascertained
by a spacer (or two to achieve a doubled distance; ID,
581
------=:t11~~).\=----(g)
(1)
Figure 5 Thin-layer cell. (a) Electrode holder; (b)
single-crystal electrode; (c) connection to reference electrode,
second counter electrode, and electrolyte outlet; (d) cell body
made from titanium; (e) steel frit; (f) stainless steel support;
(g) microporous Teflon foil, interface between electrochemical
cell and vacuum; (h) connection to counter electrode; (i) elec-
trolyte inlet via needle valve; (j) Teflon spacer, 50-lOa Jim
thickness; inner diameter 6 mm. (From Ref. 16.)
6 mm; OD, 12 mm) made from the same Teflon
membrane. Because of compression of this soft spacer,
the distance is less than the nominal thickness.
The cell body is made out of passivated titanium
because of its mechanical stability and inertness (the
passivating procedure has to be repeated from time to
time). Attempts to use Kel-F were not successful due to
its hydrophobicity, which leads to the formation of gas
bubbles in the capillaries (or at the junction between
capillaries and the Teflon membrane or spacers).
Two capillaries positioned at opposite sides serve as
electrolyte inlet and outlet and as a connection to the ref-
erence and counter electrode. Because ofthe large ohmic
potential drop (product of current and electrolyte res-
istance) in the thin layer ofelectrolyte, it is advantageous
to use two counterelectrodes both in the outlet and inlet.
By connecting both counterelectrodes to the potentiostat
via different resistors, the total current is divided into
two parts such that the current through the capillary to
the reference electrode is much less than 50% ofthe total
current. Connecting some current flow through the
capillary to the reference electrode also leads to a much
higher electronic stability. Potential oscillations may
occur otherwise.
582 Baltruschat

To test the applicability of OEMS for various

--1 9
substances, an aqueous solution of test analytes was
delivered to the cell and the mass spectrometric ion cur-
• • •ilLiiii-"'}"'?e : / / / / / - / ./-- "'"
rent was recorded as a function of the flow rate u = dVldt
./
and, after calibration of the mass spectrometer, con-
(b)
verted to flux 1 through the membrane (Fig. 7a; the work-
(aj
ing electrode was replaced by a glass dummy). The
straight line corresponds to the assumption of complete
-',- '10 turnover ofthe incoming species. As expected, sensitivity
as given by the ratio lie is highest for gases and lowest
for hydrophilic substances. Obviously, the transfer of

10
Figure 6 Dual thin-layer cell from experiments under con-
stant flow through (Kel-F). I, Kel-F support; 2, Kalrez
• carbon dioxide (a)
tightener; 3, single crystal; 4 and 5, Teflon tighteners; 6, porous
v benzene
8-1
Teflon membrane; 7, stainless steel frit; 8, stainless steel connec- 0 methyl formiat
tion to the vacuum system and the mass spectrometer; 9, + methanol
capillaries for flushing with Ar; 10, inlet-outlet capillaries; II,

1:1
connecting capillaries. (a) Side view of Kel-F body of the cell; r3\O
,,'5
(b) top view ofthe cell. ~

.. •
\'1-_

---..., ,-

This cell can be used for both desorption experiments 2-1

"
,/
•• • v
v
'IV"" o
under stopped flow conditions and for the measurements o 0 0 0 0
of product formation rates during faradaic reactions +
+ + + ,+ I r
under continuous flow. In the first case, nearly all of the 2
'
4
I
6 8 10 12
desorption product can diffuse within 2 s to the Teflon U I ~l S·l
membrane, where it evaporates. (Experimentally, we
obtained transfer efficiencies N in the range of 0.9-0.95
[18].) During a continuous flow of electrolyte, however, a
considerable part of the product is transported out of
the thin-layer volume and lost, because a part ofthe prod-
uct is formed close to the outlet of the cell and has no
chance to reach the Teflon membrane. Experimentally,
transfer efficiencies of 0.2 and below for practical flow
rates of 1 J-iLls and above were found [19].
Better suited for faradaic reactions, which have to be
performed under a continuous flow of electrolyte on
account of the rapid depletion of the reactant in the
thin-layer cell, is the "dual thin-layer cell," shown in Fig.
6. Here, the complete cell consists of two separate com-
partments for the electrochemistry and the mass
spectrometric detection. The electrolyte first enters the
thin-layer compartment in front of the electrode
("wall-jet" geometry) and then flows through four
capillaries into the lower compartment, where volatile Figure 7 Performance of the dual thin-layer cell. (a) Ion
currents converted to flux and normalized by the concentration
products can reach the Teflon membrane. This cell offers
(C02; 38 mM; benzene, 23 mM; formic acid methylester,
the additional advantage that it can be combined with a 2 mM; methanol; 2 mM). (b) Plot of the faradaic current of
quartz crystal microbalance; then, one of the electrodes CO oxidation at Pt (0) and the corresponding mass signal for
ofthe quartz is also used as a working electrode for OEMS C02 (*), both converted to the flux J; 0.5 M H2S04 saturated
[20]. by co. E=I V.
 DEMS as a Tool for Interfacial Studies
soluble species is not diffusion limited. Under identical
conditions, benzene was even detected at concentrations
of 1 flM, demonstrating the high sensitivity of the
technique.
In electrochemical thin-layer flow cells, the faradaic
current is proportional to U X withx = 113 for diffusion lim-
ited processes, as long as the flow rate u = d Vldt is not so
small that most ofthe incoming species reacts at the elec-
trode surface. In the latter case, h is proportional to the
amount of species entering the cell and therefore to u l .
The same proportionality should hold for the ion current.
However, a logarithmic plot of the data gives a value of
0.6 for x in the case of C02 and also Ar, which might
reflect a certain similarity of the cell to wall-jet cells, for
which x = 3/4.
The collection efficiency II is the ratio of reacting
species [given by h /(z x F)] to the amount of species
entering the cell compartment:
II = IF/(zF x C xu) (9)
Similarly, the collection efficiency for the mass
spectrometric part of the cell is given by
h = I;/(Ko x cp x u) (10)
This value can be obtained from Fig. 7a by forming the
ratio between the experimental value and the value given
by the straight line. In an electrochemical experiment,
the concentration of the product in the fluid leaving the
electrochemical part of the cell is given by
Cp = h/(zF xu) (11)
Therefore,
Ii =hKoh/(zF) = N Koh/(zF) (12)
and the collection efficiency of the "detection" cell h is
identical to the transfer efficiency N as defined in Eq. (5).
This is not the case for the cell depicted in Fig. 5! A plot
of the faradaic current of CO oxidation at Pt and the
corresponding mass signal for CO 2, both converted to
the flux 1, is shown in Fig. 7b. Collection efficiencies,
as given by the ratio of mass spectrometric to the
faradaic current signal, are close to those expected from
Fig. 7a. This and their high values approaching 1 at low
flow rates confirm the suitability of this cell for quanti-
tative measurements.
A simpler approach, also allowing the use of massive
electrodes, was previously described [21]. Here, the gas
inlet is a pinhole, several micrometers in diameter,
located at the hemispherical end of a glass tube, 4 mm
in diameter, which is covered by a Teflon film of 50 flm.
r
II
II
583
Electrodes can be used in the hanging meniscus
arrangement. A further advantage is the small overall
amount of substance entering the vacuum system via the
pinhole. However, a disadvantage seems to be that the vol-
atile products are sampled not only from a small cylindri-
cal volume between the pinhole and the electrode
surface in front of the pinhole but from a larger volume.
The superposition ofthe products' planar diffusion away
from the surface and the spherical diffusion to the pinhole
leads to a complicated time dependence and larger
response times.
A rotating rod in front of the porous Teflon membrane
was also used as a massive electrode [22]. The use of single
crystals, however, makes no sense, and mass transfer
and transfer efficiency are less defined than in the
thin-layer cells and the rotational flow cell described
above.
The study of single crystals under illumination is also
possible using the cell of Fig. 8 [23]. Here, volatile prod-
ucts diffuse sideways through the ring made out ofaTeflon
membrane. Because of the large response time, low scan
rates of2 mVis have to be used.
III. CHARACTERIZATION OF ORGANIC
ADSORBATES
Organic adsorbates play an important role not only as
intermediates in electrocatalytic reactions but also as
inhibitors of corrosion and brighteners in metal plating.
When studying these adsorbates, the fundamental ques-
tions are as follows:
Is the adsorption associative or dissociative, i.e., does
bond breaking occur upon adsorption?
What is the exact orientation and composition of the
adsorbate?
How stable is the adsorbate and how does the coverage
depend on concentration and potential?
Which are the desorption reactions?
What is the influence of the atomic structure?
In the following, it is shown that DEMS is a versatile
method in finding answers to these questions.
With DEMS, adsorbates can be characterized by
determining the amount and nature ofdesorbing species.
Desorption can be induced either by displacement by
other adsorbates, such as adsorbed hydrogen or
underpotential deposition (UPD) ofCu, or by a reactive
desorption, such as oxidation or hydrogenation.
Examples presented here focus on work done with
single-crystal electrodes and the effect bf single-crystal
orientation.
584 Baltruschat

flushed through the cell (typically 1 mL at a flow rate of

20 !iLls) at a fixed potential in the double-layer region.
After an electrolyte exchange with the supporting electro-
lyte (still at the same potential), a potential sweep is
gas inlet, started to induce reactive or nonreactive desorption.
etc. The cyclic voltammogram and the corresponding
reference mass spectrometric cyclic voltammogram (MSCV) for
and CO 2 during the oxidation of the benzene preadsorbed at
counter a Pt(lll) electrode are shown in Fig. 9 [24].
(a) electrode Oxidation proceeds in two well-separated steps. The
MSCV shows that no CO 2 is formed during the first peak
but only during the second one. Complementary exper-
iments in an H cell have shown that the adsorbate is not
desorbed after the first peak. The CO 2 detected in the
110 mm working second peak is the only detectable oxidation product.
electrode As shown by the ion current for CO 2 in the second and
high vacuum third sweep, complete oxidation of the adsorbate is not
(lO-6 mbar) achieved in the first cycle. From an integration of the ion
current over the three sweeps, the total amount of CO 2,
and therefore the total benzene coverage, can be
(b) calculated. A coverage of 0.26 nmollcm 2 is obtained.
The charge in the first oxidation peak amounts to one
1- electrolyte fourth of the total oxidation charge. Because oxidation
'I'- m
60 11 membrane
- electrode
- silver epoxy
ofbenzene to benzoquinone requires the release of6 elec-
trons or one fifth of the 30 electrons corresponding to
- back contact the complete oxidation to CO 2 , it is probable that
adsorbed quinone is formed as an intermediate, accord-
ing to
to mass spectrometer
Figure 8 A DEMS cell for using massive electrodes under
illumination. (a) Schematic drawing of the cell. (b) Detail of
the inlet system. (From Ref. 23.)
2
/////
+ 2 H20 -
°V O + 6 H+ + 6 e-

A. Benzene
Benzene is an ideal model compound to study adsorption
on Pt electrodes and the versatility of DEMS for two
reasons: it adsorbs quickly and irreversibly and the mol-
ecule is stable enough to stay intact upon adsorption
and not to break apart and lead to a variety of adsorbed
species, as is the case for, e.g., ethene (see below).
The typical experimental procedure for studying
adsorbates is as follows. After annealing, the cleanliness
of the single crystal is checked by cyclic voltammetry in
the supporting electrolyte, e.g., sulfuric acid. The crystal
is then transferred to the DEMS cell (Fig. 5), its surface
being protected by a droplet of electrolyte. After having
again been checked for cleanliness by cyclic voltammetry
and, sometimes, holding the potential at -50 mV to
achieve desorption of possible contaminants, the new
electrolyte containing the adsorbates (e.g., benzene) is
/////
(13)
The oxidation of adsorbed benzene on Pt(llO) and
Pt(100) and also on a roughened Pt(111) electrode is very
similar to that on a polycrystalline electrode and only
occurs in the oxygen adsorption region, leading to CO2
[24,25]. The faradaic current and the ion current can be
used to determine the coverage of the electrode with
benzene. A comparison of the faradaic oxidation charge
with the integrated ion current indicates five electrons
per formed CO 2 molecule consistent with complete
oxidation to CO 2 . When oxidation charges are evaluated
separately for the first and subsequent sweeps, it is found
not only for benzene but also for toluene [26] and acetone
[27] that the number of electrons per CO 2 molecule is
higher than the overall number in the first sweep and
lower in the subsequent ones. This means that in all these
cases adsorbed intermediates are formed that are in a
higher oxidation state than the educt.
 DEMS as a Tool for Interfacial Studies
2.0
«
E
N
1.0
- 1.4-
I
0
......
0.0
-1.0
0.0 0.5 1.0 1.5 E/Vrhe
Figure 9 Oxidation of benzene preadsorbed on Pt(lll). Ead, 0.3 V; C(benzene), 2 X 10-4 M; v, 0.025 Vis, 0.05 M H2S04. (a) Cyclic
voltammetry, (b) mass spectrometric cyclic voltammogram (MSCV). (From Ref. 24.)
In many cases, desorption can also be induced by
sweeping the potential in a negative direction after
adsorption and electrolyte exchange. This is demon-
strated again for benzene adsorbed on Pt(lll) in Fig. 10.
The negative potential limit of -50 mV is far in the
hydrogen evolution region to make desorption as com-
plete as possible. The cyclic voltammogram in the sub-
sequent sweep has a form typical for Pt(lll) in sulfuric
acid and shows that desorption ofbenzene is nearly com-
plete. The mass spectrometric cyclic voltammograms,
which were recorded in parallel for m/z = 78 (benzene,
Fig. lOb) and m/z = 84 (cyclohexane, Fig. lOc), show that
benzene is desorbed at potentials below 150 mVand that
cyclohexane is formed below 50 mV Integrating the cor-
responding ion current and taking into account the differ-
ent fragmentation probabilities for benzene and
cyclohexane, it shows that on Pt(111) only one sixth of
the adsorbate is hydrogenated, whereas the remaining
part is desorbed as benzene.
This ratio is reversed when the experiment is
performed with a roughened Pt(lll) electrode, which is
known to behave similar to a polycrystalline Pt electrode.
Here, 15% of the adsorbate cannot be cathodically
desorbed but are desorbed as C02 in a subsequent poten-
tial sweep into the oxygen adsorption region.Yery similar
is the behavior at the Pt(llO) electrode, at which all
adsorbed benzene is hydrogenated to cyclohexane. In
none ofthe cases could another cathodic desorption pro-
~
585
1.6 m/z=4-4-
(b)
0-«
-
"'0
......
~
1.2
1.0
0.0 0.5 1.0 1.5 ElVrhe
duct, such as cyclohexene or cyclohexadiene, be detected.
Adsorbate coverages calculated (after calibration of the
mass spectrometer for benzene, cyclohexane, and C02)
from the sum of the integrated ion currents for desorbed
benzene, cyclohexane, and the C02 formed during
oxidation of the residual adsorbate in the subsequent
positive sweep agree well (to within 15%) with that calcul-
ated when the adsorbate is directly oxidized to C02. In
all cases, it is around 0.3 nmollcm 2 .
Again, this coverage agrees well with that found for
benzene adsorbed on Pt(lll) in UHVand suggests that
the benzene molecule is adsorbed in a flat ("'16") orient-
ation. It also agrees with the Pt(1ll)-(J21 *J21)RlO.9°
benzene adlattice recently observed by scanning
tunneling microscopy [28], for which the theoretical
coverage is 0.34 nmollcm 2 .
It is obvious that hydrogenation only occurs at
roughened surfaces or at the Pt(llO) surface, which has a
fairly open atomic structure. Only little or no hydro-
genation occurs on Pt(lll) or on Pt(100). Most probably
the reason is the stabilization of a polar intermediate
state during hydrogenation on the open surfaces, where
the electron density is varying locally due to the
Smoluchowski effect, which is missing on more densely
packed surfaces. Another reason may be a weaker
adsorption of benzene on Pt(lll) and Pt(lOO), leading to
desorption at a less low potential, where hydrogenation
does not yet occur.
586 Baltruschat

This is different at Pt(lOO). Here, only one third of the

(a) adsorbed benzene is desorbed as such; the remainder
~ 0.5 stays on the surface even after extensive cycling to

- 0.01 'J =_,C

-100 mVand can only be oxidatively desorbed as CO2.
When using C 6D 6, most desorbed benzene is C6D6, but
also other isotopic isomeres were observed, predomi-
nantly C6D4H2 [25]. This points to the existence of an
112-oriented adsorbate, which involves the cleavage of
-0.5
two C-H bonds. Such an 112 orientation was postulated
for hydroquinone and its derivates adsorbed on poly-
crystalline Pt on the basis of coverage data determined
-1.0 by the thin-layer electrode technique [29].

,.H I I
(b)
rn/z=78
I When doing similar experiments using Pt(llO) or
polycrystalline Pt, all or most of the adsorbate is
hydrogenated. Using C6D6, desorption leads to C6H2D6

~<...
as the predominant species (ca. 30%), but all isotopic
111 isomers with a lower D content (down to C 6H 12 ) are also
3.0 present. This can be understood if one assumes that

--
s;z
during hydrogenation an intermediate is formed, which
is in equilibrium with the educt: HID exchange is possible
2.0 in the reverse reaction of the preceeding equilibrium.

-- 0:
y: <0
/////
+H+
~ , +
'-• .'

/////
D
H --
OHH
+

,.,< 6.0
...~ (14)

- 4.0
So far, however, the possibility cannot be excluded that
the HID exchange occurs during adsorption or in the
adsorbed state. Here, displacement of the adsorbate in
the double-layer region by another adsorbing species
can give additional information. In the experiment
depicted in Fig. 11, benzene adsorbed at 0.4 V was dis-
placed still at the same constant potential from a porous
0.01 " )' ';> o. . I polycrystalline electrode by introducing Cu2+ ions into
0.0 0.5 1.0 1.5 ElVrhe the solution [30].The cathodic current is due to the forma-
tion of the Cu- UPD layer; an ion current for m/z = 78
Figure 10 Cathodic desorption ofpreadsorbed benzene from but not for m/z = 84 is detected. Integration shows that
Pt(ll!). (a) Cyclic voltammetry. (b) MSCV; m/z = 78 (benzene). 70% of the adsorbate are displaced as benzene. Further
(c) MSCV; m/z = 84 (cyclohexane). (From Ref. 24.) desorption of benzene can be achieved when sweeping
the potential in Cu-free solution in cathodic direction,
as shown in Fig. 9. The amount of cyclohexane formed is
More information can be obtained by using deuterated still negligible, and only a small amount of carbonaceous
benzene. When adsorbing benzene-d 6 in light water on species remains on the surface, as shown by the sub-
Pt(lll) and desorbing it in the same electrolyte, the sequent MSCV for CO2 (the peak at 0.7 V in the CV cor-
absence ofan exchange ofD-atoms by H (D/H exchange) responds to dissolution of Cu- UPD). The same
in the desorbing benzene indicates that no C-D bond experiment, using C 6 D 6 , shows that a D/H exchange
cleavage occurs. takes place neither during adsorption nor in the adsorbed
DEMS as a Tool for Interfacial Studies 587

To verify this, cyclohexene was adsorbed on Pt(llO) in

the thin layer cell and, after electrolyte exchange and still
-0.Q1 under potential control, 10- 4 M Cu2+ containing sulfuric
acid was slowly introduced into the cell (cf. Fig. 5) at a flow
-0.Q2 rate of 0.2-0.05 ,ilL/s. The flow rate has to be low enough
« for the desorbing species to reach the vacuum with a high
E probability, i.e., the residence time of the electrolyte in
" -0.Q3
the thin-layer volume has to be high compared with the
time constant ofdiffusion from the electrode to theTeflon
-0.04
membrane, which is approximately 2 s.
The only detectable species is benzene. As in the case
-0.05
ofpreadsorbed benzene, about one third ofthe adsorbate
stays on the surface and is detected as CO 2 in a sub-
(a) sequent anodic sweep. However, despite the low flow rate,
around 20% of the adsorbate is neither detected as ben-
zene nor as CO 2 in the anodic sweep. This may not only
12
be the case because benzene desorbing from the surface
« close to the outlet of the cell has no chance to reach the
... 9 electrolyte vacuum interface but also because of edge
...,
effects. In a similar experiment, using the porous elec-
....o trode in the conventional DEMS cell, at least 95% of the
" 6 adsorbate is detected as benzene. Therefore, cyclohexene
is dehydrogenated on polycrystalline Pt and Pt(llO),
indeed (cf. Fig. 12).
3
On Pt(lll) the situation is different: Because the
adsorbate formed on this surface is only desorbed as a
OL..- --'-_-'-_..J...._.......---I. ...J...._-'------J
minor volatile species, it is probably cyclohexanol, which
50.0 130.0 210.0 290.0 370.0 450.0
(b) is formed by addition ofwater to the double bound similar
I 5 to the case of ethene (see below) [31].

Figure 11 Displacement of benzene. (a) Current transient

during Cu deposition onto polycrystalline Pt covered by
preadsorbedbenzene. E,OA V;c(Cu2+), I mMinO.S MH 2 S0 4 •
(b) Ion current for benzene (m/z = 78). (From Ref. 28.)
state, confirming that the first step of the hydrogenation
reaction is also responsible for the D/H exchange and
therefore has to be reversible.
B. Cyclohexene
Another illustrative example for the use of this displace-
ment technique is the adsorption of cyclohexene. In
experiments involving potential sweeps into the hydrogen
region, the adsorbate formed out of cyclohexene on
Pt(llO) is completelydesorbed as cyclohexane. In the case
of polycrystalline Pt, some benzene (~20%) is found in
addition to cyclohexane. The adsorbate formed from
cyclohexene therefore behaves similar to adsorbed
benzene. This already suggests (but does not prove) that
cyclohexene is dehydrogenated to benzene upon adsorp-
tion on these surfaces.
C. Ethene
In UHY, ethene is probably one ofthe most often studied
molecules. It has now been established that at low
temperatures, ethene adsorbs as a di-a-bound species
on Pt(lll) and Pt(llO), which transforms to ethylidyne at
about room temperature [32-35]. Attempts to study the
adsorbate formed from ethene on Pt electrodes by Fourier
transform infrared (FTIR) spectroscopy have, so far,
not been successful (E. Pastor, personal communication,
1994).
On both Pt(lll) [36] and Pt(llO) [31], oxidation of the
adsorbate formed from ethene starts at potentials only
slightly positive of an adsorption potential of 0.3 V For-
mation of CO 2, though, is retarded by at least 200 mV
This is similar to benzene adsorbed on Pt(lll), although
no such well-separated peaks can be distinguished; this
means that oxidized intermediates are formed before
being completely oxidized to CO 2. The number of elec-
trons necessary for the formation of a CO 2 molecule out
ofthe adsorbate decreases from 6 at an adsorption poten-
588
<
(~
:> <:::5.
~
////////////////////////Pt .///////////////////////////////////
Figure 12 Illustration ofthe displacement process. (a) Adsorption ofcyclohexene as benzene (b). (c) Displacement.
tialofO.3 V to nearly 3 at an adsorption potential of 0.9 V,
suggesting that at higher potentials adsorption proceeds
oxidatively.
Again, more information on the adsorbed species is
obtained from experiments in which the adsorbate is
desorbed at low potentials, as demonstrated in Fig. 13
for a Pt(ll 0) electrode. Ethane, butane, and methane (not
shown) are formed. Experiments with C 2D 4 show that
HID exchange is nearly complete: Approximately 80%
ofthe ethane and butane are do species, and 20% are cor-
responding d l species.
Oxidation of the remaining adsorbate (Fig. 14) shows
that parts of the adsorbate stay on the surface, half of
which is oxidized in a peak at 0.7 V [37]. This is indicative
of adsorbed CO, which is substantiated by comparing
the amount ofCO 2 formed in this peak to the correspond-
ing oxidation charge, yielding an nox of two electrons
per CO 2 molecule formed. Because such a well-defined
oxidation peak, which is typical for adsorbed CO, is not
present when the adsorbate is oxidized without
preceeding cathodic desorption, we conclude that this
CO is formed during the cathodic sweep. The formation
of C 18 0 16 0 after adsorption in H 218 0 proves that the
adsorbate contains oxygen (Fig. 14).
Similarly, when the adsorbate is oxidized in H 218 0
after adsorption in H2 16 0 without cathodic desorption,
a significant amount of C I8 0160 is formed below
0.8 V, largely exceeding the amount of C 18 0 2. The
oxygen-containing adsorbate might be formed by
oxidative addition ofwater to the double bound:
+H,o -e- OH -e- OH
H,C=CH,
/
H,C_CH,
/
H,C-CH
-H+ I - H' I I
IIIIIII III/III
Baltruschat
5>
(~ (hi •
The results for different adsorption potentials are
summarized in Fig. 15. The more positive the adsorp-
tion potential, the lower the overall amount of
adsorbed species and the higher the amount of
adsorbate, which can be desorbed as methane, and also
the amount of adsorbed CO, except for 0.9 V, a poten-
tial at which this CO is directly oxidized to C02. The
amount of methane is correlated to the amount of CO
formed during the cathodic sweep, where CO is formed
only although oxygen is present in the original
adsorbate. Therefore, it is probable that an
oxygen-containing C2 adsorbate is formed, the amount
of which increases with increasing potential and which
decomposes at low potential to methane and adsorbed
co.
The reaction scheme in Fig. 16 summarizes the likely
reactions and the structures of the adsorbate states. It
seems clear from the results shown in Fig. 13 that besides
the abovementioned oxygen-containing species, another
adsorbate state is formed, leading to ethane, possibly
di-(J-bound ethene (C 2)13 and butane. Whether the
dimerization occurs upon adsorption or upon cathodic
desorption still has to be clarified.
All the adsorbates that cannot be cathodically
desorbed belong to a third adsorbate state
[(C 2)Lstate], possibly ethydidyne, as known in UHV,
but it is also possible that its molecular identity is
not different from the previous one. The existence
of a further fourth adsorbate state is revealed when
trying to displace adsorbed ethene by other
adsorbates. The using of 1-, CO, or Cu 2+ leads to
H,C-C=O
desorption of about 10% of the adsorbate as ethene
I I [38]. It is tempting to assume that this state corre-
IIIIIII sponds to a weakly n-bound species, recently
(15) observed in UHV [39].
DEMS as a Tool for Interfacial Studies 589

PU110l Ethene E = O.7V

ad (a)
15 r-....,....-r-....,....---,,....---.----,--r---,.--.---,.---.----,
(a)
10
<{

.(-or-----jr---=~~~~~~_+_-__=---~O:::::':"-__l
5
« -4
Jl

o
ri
0l----ff-~;;:z=-;;;;;;:i:::;:::~;------~
-a
" -5
······m/z = 44 (C ' ·0 2' , (b)
'.
,'. .
··,·· ....
- - m/z = 46 IC'BO'·O)
-10
0.15

<(
(b) ~ 0.1

.
..
,"",-,:",,\,/"
' ~~-:
:
; , 0.05
'.~ r',. ,.,'..~:. •...

:: m/z = 43(C H ) ,\,..:~.:;. "./"':' r : :..:.::: :, : .

1.2 , ',/ 4 10
, (-
N
« v
... o o.a
I 0.2 0.4 0.6 1.2 1.4 ElY
o
ri

" 0.6 Figure 14 Oxidation of the cathodically nondesorbable

O'---------'------JL----L-----J_--L----.l._---'------'-_...L---'-_...L---i
-0.3 o 0.3 0.6 0.9 1.2 1.5
E/V RHE
Figure 13 Cathodic desorption of preadsorbed ethene on
Pt(llO). Ead , 0.7 V; Cethene, 5.5 X 10- 3 M; v, 12.5 mVls, 0.1 M
H2S04. (a) Cyclic voltammetry: - - , first reduction sweep;
- - - -, second reduction sweep; - - , sweep in the supporting
electrolyte before adsorption. (b) MSCV: - - , m/z = 27
(ethane and butane); - - -, m/z = 43 (butane). (From Ref. 31.)
Similar adsorbate states exist on a Pt(lll) electrode.
However, cathodic desorption is less complete, and the
(C2)Y state is more abundant than on Pt(lW).
D. Ethanol and Propanol
Studies of the adsorption and oxidation of ethanol are
usually motivated by its possible use as a fuel in fuel cells.
Here, as in the case ofmethanol, the adsorbate is believed
to act as a catalyst poison; therefore, the conditions of
adsorbate of preadsorbed ethene on Pt(llO); adsorption in
H2180/H2S04. Cathodic sweep and oxidation in
H2160/H2S04. Ead, 0.5 V; Cethene, 5.5 X 10-4 M; v, 12.5 mVls,
0.1 M H 2S0 4. (a) Cyclic voltammetry: - - , first sweep; - --,
sweep in the supporting electrolyte before adsorption; - . - '-,
shape of the voltammogram after a few sweeps to 1.45 V. (b)
MSCV for C1602 and C I6 0 18 o. (From Ref. 37.)
the adsorbate formation and its possible reactions are of
primary importance.
After adsorption at Pt(lW) and after a subsequent
electrolyte exchange at a constant potential of 0.3 V,
methane desorbs during a potential sweep in a negative
direction. This is seen in the MSCV for mlz = 15 (Fig.
17) [37]. On porous Pt and after adsorption from 0.1 M
ethanol solution, also the desorption of ethane was
observed [40]. Complete D/H exchange occurs in the
formed methane; in the case of ethane, D/H exchange is
only complete for the C(-C atom, as shown by using CH3
CD 2 OH in H 20 [41].
The residual adsorbate is oxidized mainly in a peak at
0.7 V, indicative of adsorbed CO, and in the oxygen
adsorption region. The most straightforward interpret-
ation would be that CO is formed from the COH group
(i.e., the C(-C atom), whereas methane originates from
the methyl group.
590 Baltruschat

1.2 I
o co, leO likel (a. )

[9 co, J 10

r
• Methane

o Ethane « 5
1~ ,,//\c:.:'~j
]
lO

1
09
o Butane I
0 0

~
ri
""-
06 -5
c
"
L
~ II II II ~ -10

0.3
- - - m/z = 15 (methane) (0)

_._._ .. m/z = 44 (CO I ri

2 !.
,!
; I
0' m oog WI m I
0.04 i i
i i
0.3 0.5 0.7 0.9 i i
« i i
Ead c i i
i ,
""- ; ~

Figure 15 Desorption products of ethene on Pt(llO). (From 0.02

, \
; \

A.-"4/"-·-'-~'>:::;~_::-]
Ref. 31.)

24j
C H

Pd
pt, < 0.3 V
lTl
(C2 )u (Cl' (C2)y
pt, 0.7 V

(C-C-O)ad
I

0.0
I

0.3
I

0.6

Figure 17 Cathodic desorption of preadsorbed ethanol from

0.9 1.2 E/V

FH3 Pt(lW) and subsequent oxidation of the remaining adsorbate.

>CT C< >p-q< ~ H2q-9=O Ead , 0.3 V; Cethanol, 0.1 M; v, 0.0125 Vls,O.1 M H 2 S0 4 . (a) Cyclic
IIIIIIIII voltammetry: , first sweep in cathodic direction;

~U-UPD I
-. -. -, subsequent oxidation; "', Pt(lW) in supporting
C2 H4
"'' [' ' "'l"" ''''''[;v electrolyte; - - - cyclic voltammetry after a few cycles between
0.06 and 1.45 V. (b) MSCV. (From Ref. 37.)

<0.2 V
I I
- = = - - - > C02 C02
C2H6
C4 H10
cathodic sweep. Obviously, a CO-like species is formed
<0.2 V
from both C atoms. Moreover, this experiment shows that
V only a part of the f3-C atoms are cathodically desorbed.
CH4 + COad > CO The amount of l3C02 decreases in both oxidation
I >0.7 V
2 regions, whereas the amount of l2C02 is hardly affected.
It is also informative to evaluate the number ofelectrons
corresponding to the formation of one CO2 molecule in
Figure 16 Surface reactions ofethene as suggested by DEMS
(adsorbates in italics are hypothetical structures). the two oxidation regions. Whereas for the oxidation
of adsorbed CO a value of nox = 2 is expected, the
experimental value for the oxidation peak at 0.7 Vis more
A closer inspection using l2CH3l3CH20H, however, than 4 without preceeding cathodic sweeps and still 3.4
shows that the reactions are more complicated. Figure after the desorption of methane. Therefore, other species
18 shows the MSCV for l3C02 and 12C02 for the than CO are oxidized at this potential. This is substan-
oxidation of the adsorbate with and without preceeding tiated in an experiment, where the adsorption ofethanol
DEMS as a Tool for Interfacial Studies 591

0.4 0.7 V, both C 16 0 18 0 and C 16 0 Z are formed, whereas in

<E the oxygen adsorption region, only C 16 0 z was detected.

-...
c:
IV
I..
0.2
Therefore, because no oxygen exchange occurs in
adsorbed CO, also C atoms not yet bound to oxygen
atoms are oxidized to COz in the peak at 0.7 V. In the oxy-
I..
::s gen adsorption region, an nox of five to six electrons is
U obtained, as expected for CH x species (x = 1~3). The
results were very similar for Pt(lIO) and a polycrystalline
0 Pt electrode [37].
The questions remain of what the actual nature of the
adsorbate species is and whether the C~C bond cleavage
already occurs during adsorption or during the cathodic
-0.2 sweeps. Other techniques have to be used to gain
additional information. With FTIR spectroscopy, it
was possible to exclude the presence of adsorbed CH3
or CHz species [40]. Instead, it was suggested that
-0.4
=COH~CH3, ~OCHz CH3, --CO~CH3, and CO
were present on the surface; CO would be formed simul-
taneously to methane even at an adsorption potential of
0.3 V, which is close to that where CH 4 formation starts
in the cathodic sweep.
,:',
,I The possibility of splitting the C~C bond
electrocatalytically is of primary importance for the
...>-
I/)
use of ethanol in fuel cells, where a complete com-
bustion is necessary. Figure 19 shows the cyclic vol-
...c:c:
IV
tammetry and the MSCV in an ethanol-containing
electrolyte: to distinguish between the oxidation prod-
ucts COz and CH 3CHO (ethanal), ethanol-d s was
used here [44]. In the anodic sweep, the ion intensity
mlz = 45 for COz is larger than that for ethanal; however, the
true ratio of the two species has not been evaluated.
Because of the higher solubility of ethanal in water,
a larger part of this product remains in the aqueous
mlz = 44 phase. In the cathodic sweep, the amount of ethanal
is much larger than that of COz. Thus, ethanal is
the main oxidation product during ethanol oxidation
o 0.4 0.8 1.2 and the C~C bond cleavage, leading to COz only
occurs to a minor extent. Formation of COz in the
Potential I V anodic sweep is probably mainly due to oxidation of
the adsorbed species. Because some COz is formed
Figure 18 (a) Cyclic voltammogram of lzCH313CHzOH during the cathodic sweep, there is the possibility of
adsorbates on sputtered Pt (real area, 10 cm z) in 0.05 M HZS04• a C~C bond cleavage during a continuous oxidation.
Ead , 0.30 V; sweep rate, 0.01 Vis. (b) Simultaneously recorded Using a direct methanol fuel cell at 175°C and direct
e
mass signal for m/z =44 2 CO z) and 45 ( l3 CO z). - - , direct mass spectrometric detection of products. Wang et
electrooxidation; - - -, oxidation after the application of four
al. [45] found up to 40% COz, besides 60% ethanal.
cycles between 0.35 and 0.05 V; ... ,Ptclean surface. (From Ref
40.)
This ratio was hardly influenced by using a Pt- Ru
alloy [45]. Similar experiments have been performed
with I-propanol [43,46]. I-Propanal is the main
[42] and propanol [43] was performed in H z18 0 and, oxidation product formed above 0.4 V. Above 0.7 V
afterwards the adsorbate was oxidized in H z160. As propionic acid is also formed as detected by FTIR.
shown in separate experiments, a complete exchange of Cathodic desorption of preadsorbed I-propanol leads
OH takes place during the adsorption. In the peak at to formation of ethane and propane.
592 Baltruschat

Ij/pA
44 44: C~ (b)
4
48: D:3C-C:~
IIIJA
o I

3 49: D:3C-C-OH
[j\
150

2
100
4Q----

50 49
~48
44.. /~ 44
48---
oH ~ 'r
Y......! I ~/I
1;;:;':1:0. '"
I 01 I I I I I I I
o 0.5 1.0 Erhe/V
-50

-100
IjlpA' (e)
48
-150

-200
2
- ._49
48

44

48
00 I -,_ I .'_ I I ul!l

Figure 19 Oxidation ofethanol on a porous Pt-lacquerelectrode (10- 2 M ethanol in 0.5 M H 2 S0 4 , v,3.1 mVls) [42,44]. (a) Cyclic vol-
tammetry (thin line without arrows: supporting electrolyte). (b) MSCV for the ions as indicated, anodic sweep with ethanol-ds in
solution. (c) Same as (b), cathodic sweep. (From Ref. 44.)

E. Other Organic Adsorbates on Pt which is present in the Hz formed in methanol reformers;

Ofprimary importance in fuel cell research is the adsorb-
ate formed from C 1 compounds, which acts as a catalyst
poison. It is now generally accepted that this species is
Co. Except for confirming the identity of this species by
evaluating the number of electrons necessary for
oxidation to CO z, DEMS is superior to simply using
cyclic voItammetry in elucidating the onset potential of
oxidation and coverages, especially when using less noble
catalysts or bimetallic catalysts, because of the appreci-
able pseudocapacitive currents on those surfaces. The
same is true for the adsorbate directly formed out of CO,
for Pt- Ru catalysts pseudocapacitive currents have been
shown to amount to 50% ofthe overall oxidation charge
[20].
In addition, halogenated methanes and 1,1,1,
trichloroethane and tetrachloroethene have been
studied by DEMS [47,48]. Astonishingly, all of the
adsorbates formed behave in a very similar way: cathodic
desorption leads to methane and ethane and, in the case
of tetrachloroethene compounds, also to propane.
Therefore, in all ofthese cases CH n (with n ~ 2) fragments
seem to be formed, involving a C-C bond cleavage
in the case of tetrachloroethene. Adsorption of
 DEMS as a Tool for Interfacial Studies 593

trichloroethane accordingly leads to species desorbing as

ethane and propane. HID exchange is appreciable. In
addition, an adsorbate behaving like adsorbed CO is
08
formed.
Results achieved by DEMS clearly show that many lal

organic species form a variety of adsorbate states.

0.4
This has also been shown for acetonitrile [49],
dimethylsulfoxide, and sulfolane [50]. In the case of
<{
acetonitrile it is particularly interesting that a part of the E 0
{>'

adsorbate formed at Pt in the double-layer region is "-

desorbed at more anodic potentials without being
oxidized, similar to benzene adsorbed on Rh or Pd (see -0.4
below). Oxidation of nitrogen-containing organic
adsorbates not only leads to CO 2 but also nitrogen oxide
and, in the case ofadsorbed aniline, to HCN [51].
The high sensitivity of DEMS is demonstrated by the - - m/z=44 (C0 , l.cycle) lb)
2
fact that even desorption products of biphenyl, desorbing 0.1 -------- m/z=44 (C0 , 2.cyclel
2
as biphenyl from a Pt(lll) electrode, and naphtalene,
desorbing as naphtalene and as the partially 0.08
hydrogenated tetralin, were detected [52].
<{

F. Adsorbates on Less Noble Electrodes ~ 0.06

Organic adsorbates are often used as inhibitors of ," ~ ... ...... - ,:

0.04
corrosion or as brighteners in metal plating. Fundamen- .... --»-- .. --_.-
tal studies of the adsorption on these less noble metals,
0.02
..., _ .. ..
_.~~~==-----'""' .
like Cu, Ni, or Fe, are much more difficult. Metals like
Pd and Rh can serve as model electrodes, because the nor-
mal potential of the corresponding metal electrodes is in
(c)
'-'-'-'- m/z=78 (benzene)
between that ofPt or Au and the above mentioned metals.
In Fig. 20, the cyclic voltammetry and MSCVofa poly- - - m/z=84 (cyclohexanel
crystalline Rh electrode with preadsorbed benzene in 0.06
sulfuric acid is shown [51]. A part of the adsorbate is
desorbed cathodically as benzene or cyclohexane, but a
<{
significant part is also desorbed as benzene during the ~ 0.04
subsequent anodic sweep at potentials where oxygen
adsorbs. Only a part ofthe adsorbate is oxidized to CO 2•
Note that an appreciable amount of CO 2 is formed out
002
of the adsorbate during the cathodic sweep at potentials
where adsorbed oxygen is reduced, indicating the necess-
ity of a partially uncovered surface for the oxidation
reaction. -0.2 0 0.2 0.4 0.6 0.8 1.2 1.4 EIV
Similarly, when CO is adsorbed on an Ni electrode and
the potential is changed to more positive values, only a Figure 20 Cathodic desorption ofpreadsorbed benzene and
part is oxidized to CO 2 and the other part is desorbed as subsequent oxidation of the remaining adsorbate at poly-
CO, the relative amounts depending on the pH [53]. crystalline rhodium. Ead' 0.15 V; v, 25 mYls, 0.5 M H2S04;
Cbenzene, 2xlO- M. (a) Cyclic voltammetry: -~, first cycle
2

(initial cathodic direction); - - -, second cycle; -. -. -, in

IV. FARADAIC ORGANIC REACTIONS
The hydrogenation reactions described in the previous
sections are reactions of species previously adsorbed,
usually at a different potential. From these, the continu-
supporting electrolyte. (b and c) MSCV. Below 0.1 V, the ion
currents of cyclohexane and benzene are enlarged by a factor
oflO. (From Ref. 51.)

I
i
594 Baltruschat

7 I
0
I i. ''''.\
6 ~
-0.02 (a) (c),\ . '\\... \. m/2 ~ 30 (ethane-dO)

-0.04
1 «
-rl
5 \.
\.
\{
\
<{
(l)
-rl

0
I 4 " ,'-
\ ~
o-0.06 ..-l
\ '
\

~ "
........
..-l 3 ~
~ \ \
-0.08 \ \
2 I- A\ \ \
\ \
-0.1

~
1 ~ (ethane-d 4 )

-1\;'.2 ",0

., ~ (b) m/2 = 32 (ethene-d 4\

I
(d)
14.5
<{ 4.4
0
«
N
M
o 4.2.
-rl

0
I

..-l ..-l 9
"- 4
..;.._ ........

3.8
3.5
3.6
.. ~
3.4 I I I I I I I I I I I
-2 I I I ! ! I )
-0.2 o 0.2 0.4 0.6 0.8
-0.2 o 0.2 0.4
E/V RHE E/V RHE

Figure 21 Bulk hydrogenation of ethene-d 4 at Pt(IlO). (a) Cyclic voltammetry in 0.1 M H 2 S0 4 ; flow rate u = 0.45 ,uLls; scan rate
v=12.5 mY/so (b) Decrease of educt signal ethene-d 4 (5.5xlO- 4 M) (m/z=32). (c) Increase of product signals: - - , m/z=34
(ethane-d4 ); - . - . -, m/z = 30 (ethane-do). (d) Increase of product signals: - - , m/z = 33 (ethane-d3); and m/z = 31 (ethane-d)).
(From Ref. 16.)

ous reaction of species from the bulk has to be dis-
tinguished. Here, adsorbed intermediates may be
formed, but this occurs at the same potential as the con-
tinuous reaction; moreover, their surface concentration
may be very low. Such intermediates therefore may but
do not have to be different from those preadsorbed
species. To distinguish reactions of an adsorbate
accumulated on the surface and the "bulk" reaction, it is
advantageous to work under conditions ofconstant mass
transport, e.g., by using a constant flow of electrolyte in
the thin-layer cells (cf. Fig. 5 or 6) or by using forced con-
vection.
A. Continuous (Bulk) Hydrogenation
The hydrogenation of most of the unsaturated species
mentioned above has also been studied by DEMS. It
usually leads to the formation of the alkane correspond-
DEMS as a Tool for Interfacial Studies
ing to the carbon skeleton. The influence of the surface
structure of Pt electrodes on the hydrogenation has been
studied for ethene [16], ethine [21], and cyclohexene [31].
As for desorption reactions, the Pt(1W) surface or
roughened surfaces are much more active than the pteIll)
surface. Hydrogenation of ethene and acetone [27] in
deuterated electrolyte( on using the deuterated com-
pound in light water) results in a broad distribution
of the isotopic isomeres formed (cf. Fig. 21). Because
hydrogenation of the preadsorbed species results in a
nearly complete HID exchange (e.g., adsorbed CzD 4 is
hydrogenated to C zH 6 ), the residence time in the
adsorbed state, where the HID exchange is occuring, is
comparable with the overall hydrogenation rate. Accord-
ing to the reaction sequence ofEq. (16), obviously the first
step of hydrogenation (after adsorption) is reversible and
occurs at a rate comparable with the final hydrogenation
and desorption step. (If the addition of the first proton is
fast, i.e., if this reaction is in equilibrium, complete HID
exchange should occur. If the final step is fast compared
with the first one, no HID exchange can occur.)
+H+. e- + H+. e-
- H+, e-
~ +H+ e- + H+ e-
(CZD3H)ad --:..- (CZD3HZ)ad -----'-- CZD3H3
- H+, e-
(16)
B. Reactions on Ib Metals
In the case ofAu, Ag, and Cu, adsorption ofmost organic
species is muchweaker than on Pt; therefore, most DEMS
studies deal with faradaic reactions.
1. Unsaturated Hydrocarbons on Au
Ethene is oxidized on Au in sulfuric acid to COz,
acetaldehyde, and acetic acid, which was identified by
FTIR [54,55]. Propene has been shown to yield acetone,
acetaldehyde, and COz upon oxidation [56]. Allyl alcohol
and propargyl alcohol are oxidized to COz and acrolein
or propargylaldehyde; respectively, propargyl alcohol
can be reduced to propene, propine, and allyl alcohol [57].
Only ethine and propargyl alcohol form strongly bound
adsorbates.
595
2. Reduction of COz
Copper is known to be a good catalyst for reduction of
COz. In carbonate solutions, however, a variety of prod-
ucts are formed. DEMS is ideally suited to study the rela-
tive amounts of the volatile products, mainly methane
and ethene, as a function ofelectrolyte composition, etc.
[22,58]
3. Hydrogen Evolution During Formaldehyde
Oxidation
Probably one of the most puzzling electrochemical
reactions, which is also ofgreat technological importance
in currentless metal deposition, is the hydrogen evolution
during formaldehyde oxidation at Ib metal electrodes
and at potentials very positive to the reverse hydrogen
evolution potential. It has been known for a long time that
this reaction proceeds via the overall equation
Using DEMS, this has been verified by Jusys and Vaskelis
[59-62], who have also studied the kinetic isotope effect
and who, by using isotopic isomers, verified that the
evalved hydrogen solely originates from the formaldehyde
molecule and not from water. When using a mixture of
HCHO and DCDO, not only Hz and Dz but also HD
are formed; therefore, both atoms in the hydrogen mol-
ecule originate from separate formaldehyde molecules,
which is only possible if hydrogen atoms are adsorbed
on these electrodes [63]. It is clear that Hz molecules are
not oxidized at positive potentials at Ib metals because
their dissociation is not possible at these surfaces. It is,
however, astonishing that adsorbed H atoms are not
oxidized either but desorbed as Hz.
v. INORGANIC REACTIONS
Besides carbon, the element with the largest number of
abundant volatile compounds is nitrogen. Reaction of
nitrogen compounds are therefore well suited for being
studied by DEMS. Among these are N0 2 [64,65], lead-
ing to NOz upon oxidation and NzO upon reduction,
and NHzOH [64], leading to a variety of oxidation pro-
ducts. The reduction of NO was also studied on Au
single-crystal electrodes [66]. N 3 is oxidized to Nz, NO,
NO z, and NzO on Au and Pt electrodes. Only on Pt
electrodes it is also reduced, leading to Nz, N zH 4, and
possibly NH3 [67].
Using 180-tracers, it has been shown that no oxygen
exchange occurs during Oz evolution at Pt oxide [68]
but at RuOz [69]. Interestingly, even the formation of
RU04 could be observed mass spectrometrically. Further
596
studies of other elements involve the reduction of As,
deposited on Au, to AsH 3 (A. Diilberg and H.
Baltruschat, unpublished data 1991), the photocatalytic
oxygen and chlorine evolution at TiO z electrodes [70],
and the photocatalytic corrosion of InP single-crystal
electrodes to PH3 [23].
VI. CONCLUDING REMARKS
We showed here that DEMS can be used for both on-line
detection of electrochemical reaction products and the
study of adsorbates. Reaction and desorption products
can be determined semiquantitatively. Because in many
cases several products are formed, it is important to know
their amounts to distinguish between the main and side
reactions.
As to the detection of electrochemical reaction pro-
ducts, it has the advantage over other methods, e.g.,
chromatography, of being fast and highly sensitive.
Amounts below 1 nmol can be easily detected. Thus, it is
ideally suited for studying reactions at single-crystal elec-
trodes with their limited overall surface area; besides,
the maximum time ofreaction at single crystals is limited
due to their possible deterioration by contaminants. In
comparison with FTIR spectroscopy, DEMS has the
advantage ofan easier potential control, because the thin
layer is 50-100 /lm thick instead of only (ill-defined)
1 flill. The disadvantage of course is that only volatile
products can be detected.
For the study of organic adsorbates, FTIR
spectroscopy again is the technique most often used
besides DEMS. Both techniques yield complementary
information. Different adsorbate states and their
reactions can be identified semiquantitatively by DEMS
(including their oxidation states). Additional information
about the binding geometry and elementary composition
can often be obtained using isotopically labeled com-
pounds. For elucidation of the exact nature of the
adsorbate, a spectroscopic method like FTIR has to be
used (see Chapter 21). The sole use of such a method,
however, is not able to yield complete information
because only adsorbates with a vibrational dipole to the
surface can be detected and because it is not quantitative.
For such (semi-) quantitative measurements, DEMS is a
powerful technique.
ACKNOWLEDGMENT
Thanks are due to the Deutsche Forschungsgemeinschaft
for generous financial support.
Baltruschat
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34
Electrode-Solution Interface Studied with Electrochemical
Quartz Crystal Nanobalance
Maria Hepel
State University ofNew York at Potsdam, Potsdam, New York
ABSTRACT
In this chapter, theory and basic principles of the
electrochemical quartz crystal nanobalance (EQCN)
operation are presented. Converse piezoelectric effect,
frequency-mass correlations, viscoelastic effects, effect
of solution viscosity and density on resonant frequency,
and other effects contributing to the frequency shift are
discussed. Various applications of the EQCN are
reviewed. These include reaction mechanisms on metal
electrodes, adsorption of ions and organic molecules,
underpotential deposition ofmetals, monitoring of elec-
trical double-layer structure changes at electrodes,
and selected examples of conductive polymers. The
ap;>lications presented are not limited to monitoring
mass changes at the electrode-solution interface. The
EQCN also determines the point of zero charge, elastic
properties of films, viscosity of solutions, etc. Wealth of
information about the structure and properties of films
on electrodes can be retrieved from measurements of
resonant resistance, dissipation factor, and admittance
of piezoeloectrodes. The combination of EQCN with
other surface science techniques may enhance the scope
of measurements. The resonators, EQCN cells, and
measurement instrumentation are also described.
I. INTRODUCTION
The electrochemical quartz crystal nanobalance
(EQCN) technique has been primarily used for studies
of thin films at an electrode evaporated onto a quartz
599
single-crystal resonator. Recently, the unique capabili-
ties of this technique combined with other methods have
been innovatively exploited to expand the scope of use
and to develop a variety of new exciting applications.
In this chapter, the use of the EQCN to measure in
situ minute mass changes at an electrode surface during
electrochemical processes and to study interfacial
phenomena is described. This chapter focuses on a few
selected applications of EQCN in interfacial electro-
chemistry rather than providing an exhaustive review
of the area.
The EQCN technique itself was created as an out-
come of the discovery [1] that quartz crystals can
oscillate when immersed in a liquid phase and exhibit
similar resonance frequency behavior to that in a gas
phase, though strongly damped. The quartz crystal
resonators have been used previously as the quartz
crystal microbalance (QCM), introduced by Sauerbray
in 1959 [2], for deposition rate monitoring of thin films
in ultra-high vacuum systems.
Nomura et al. [1] was the first to demonstrate the use
of the QCM for mass measurements in a liquid during
the electrochemical experiments. When QCM is used
in situ in electrochemical experiments, allowing simul-
taneous monitoring of the electrochemical parameters
of the system and the effective mass of the electrode,
then the terms electrochemical quartz crystal
microbalance (EQCM) or electrochemical quartz
crystal nanobalance (EQCN) are used. EQCN has
become an important tool in electrochemistry.
600 Hepel

FRONT VIEW Quartz Crystal V\Bfer

14 mrndia.
Thickness Extensional
0.15 mm thick

.J' .f
Fundamental
Au Electrode
5mmdia.

J- o"ertone1: rl·-- ! ··.. +-·:.

3rd Steel Contact Spring
:J~ =If.
5th Overtone

..Face Shear

..,,
········7'
.
Length-Width
Flexure
Isolating Holder

D
'
'
-.
.f
,,
· ,.
: ' :~
L~! ...... I
Contact Pins

t.. ... -'

Air Solution
(a)
(\M:)
(b)

Figure 1 (a) Vibration modes ofvarious piezoids. (b) Quartz crystal resonator in a standard holder.

II. THEORY AND BASIC PRINCIPLES OF frequency vs. temperature stability, and is widely avail-
OPERATION able at reasonable cost. The frequency vs. temperature
characteristics of the AT cut crystal unit are illustrated
A. Piezoelectric Effect in Fig. 2.
An AT-cut crystal oscillates in a shear mode. For the
The piezoelectric effect was discovered by Jacques and AT cut, the fundamental frequency of vibrations is
Pierre Curie in 1880. They found that when mechanical inversely proportional to the wafer thickness that is
stress was applied to the quartz surface, a corresponding
electrical potential across the crystal developed that was
proportional to the applied stress. Shortly after their 100."r-----------------------------, ·4'
initial discovery, they found the converse piezoelectric 90
RELATIVE ANGLE CHART
AT Cut Crystal Unit ·z
effect in which application of a voltage across the crystal

~~ ~~
0'
induced a corresponding mechanical stress. The con- .2'
verse piezoelectric effect is the basis of the EQCN C~

i~~~~
•

operation. A crystal oscillating in a shear mode is pre-

sented in Fig. la and a typical quartz crystal in a crystal So 0
f
holder is presented in Fig. Ib. u..·20
S
When a quartz single crystal is sliced at different ~.~
angles to the crystallographic axes, different piezoids -60
~ained. The most common quartz cut used is the
~Lcut, which is prepared by slicing through a quartz
·90 ! IIIIIIIII IIIIIIIIIIIIIIIIIIIIII I
·~5 -15 ·3~ ·2~ ·1 ~ .~ ~ I.' 2l .1.' 4.' ~~ 65 7l K5 95 IO~

crystal at an angle of 35°15' with respect to the x-axis. Temperature in ·C

Other cuts made from quartz are X cut, Y cut, BT cut,
CT cut, DT cut, NT cut, and GT cut. Of the various cuts, Figure 2 Dependence ofthe resonant frequency on tempera-
the AT cut has become the most popular because it is ture for AT-cut quartz crystals (0') and crystals cut with small
available at relatively high frequencies, exhibits excellent deviations from 35°15' (-4' to +10'). (From Ref. 5.)
Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance
0.130 mm at 10 MHz. For higher frequencies, crystals
begin to be too thin and fragile to handle safely.Therefore,
a frequency increase is achieved by increasing the order
of harmonics because an AT-cut crystal can resonate at
odd integer multiples of the fundamental frequency. This
mode of operation is called overtone mode. e.g., third
overtone, fifth overtone, etc., and is illustrated in Fig. la.
Application ofan electric field across the crystal produces
a shear strain proportional to the applied potential. This
deformation is elastic for quartz and quartz covered with
a very thin rigid film. For such films, assumptions can
be made that the acoustic properties of the film are ident-
ical to those of quartz.
B. Frequency - Mass Correlations
The relationship between mass changes and frequency
changes was given by Sauerbrey [2]:
(I)
where !J.f is the measured frequency shift, fo is the fre-
quency of the quartz crystal before a mass change, !J.m is
the mass change, A is the piezoelectrically active area Pq
is the density of the quartz (Pq = 2.648 gicm 3 ), and J,lq
the shear modulus (J,lq = 2.947 X 1011 g cm- I S-2). The
Sauerbrey equation assumes that acoustic impedance is
identical for the film and quartz and that the frequency
shift resulting from a mass deposited at some radial dis-
tance from the center of the crystal will be the same
regardless of the radial distance.
The negative sign in Eq. (I) indicates that addition of
mass to the resonator results in a decrease in its resonant
fre uency and vice versa. EquatTon-Cl) IS frequently pre-
sented in the 0 oWIngform:
(
--- ,._~--~-----~.,
..
l !J.f = -Cf!J.m
'_--'. .~
(
-v-/
(2)
where C f is a constant and can be determined by
calibration.
When mass is deposited or removed, this linear
relationship very accurately describes the frequency
change for very small mass loadings (less than 2% change
in the resonant frequency due to the mass change). When
the overlayer is thick, Eq. (2) is no longer linear and cor-
rections for this case have been developed [3-5]. In Eq.
(2) it is assumed that the added mass is evenly distributed
over the electrode and that the mass is rigidly attached
to the electrode, with no slip or deformation to the
oscillatory motion.
601
C. Effect of Solution Viscosity and Density on
Resonant Frequency
When the QCM crystal is transferred from air into the
solution, the shear wave damping occurs, causing large
changes in resonant frequency. Kanazawa and Gordon
[6,7] provided an equation that sho'Ystli~~!hefrequency
cpang~jIlQ!!f~4~'yimm~rsionin asolut~oi~~-_r~!~}~fio
the density PL
.. and
.. -...... ... viscosity -...
YfL of that solution:
.. - .
--~-~,-_ --~._ - _ _-,~,~,' -" ,." " "---~,-,..~
,3/2( (3)
, A.I'
\ ilj = -jO YfLPL/nJ,lqPq)1/2 :
A similar study has been reported by Hager [8].
Bruckenstein and Shay [9] investigated the effect of sol-
ution temperature and viscosity and height of liquid
above the crystal and correlated the results with theory.
D. Viscoelastic Effects
For viscoelastic films, Reed et al. [10] derived Eq. (4) for
the case when both the shear modulus and the viscosity
of the film are taken into account:
!J.f = -2fi /(p qJ,lq)I/2)[(!J.m/ A) + {!J.(YfLPd/2/(4nfo)I/2}]
(4)
The resonant frequency change ofthe shear vibration ofa
quartz crystal with the piezoelectrically active area A
characterized by a shear modulus J,lq, a density Pq, and
the resonant frequency fo in contact with a liquid of den-
sity PI and viscosity Yfl not only is affected by rigid mass
changes !J.m [2] but also by viscosity changes !J.(YfI PI) in
the interface [7].
When a transversal velocity of the quartz surface is
equal to the adjacent liquid layer, nonslip boundary con-
ditions can be assumed. In such a case, a viscous
penetration depth is proportional to the viscosity,
because liquid films show no elasticity. The mass of this
liquid layer with a thickness equal to the thickness of the
decay layer of the acoustic wave (j [7]
(5)
where OJ is the angular frequency of the thickness shear
mode vibrations of the piezoid and causes the vibrating
mass to increase and the resonant frequency to decrease.
The resonant resistance change of the crystal, on the
other hand, is solely determined by the viscosity change
!J.(YfLPL)I/2 [8,11-14] and allows one to discriminate
between viscosity and mass changes. Reed et al. [10]
presented a general model of viscoelastic overlayer
from which limiting cases should be retrievable. Their
expression for the electrical admittance agrees exactly
with that obtained by Benes [IS].
602 Hepel

Several authors reported on the viscoelastic properties teristics of a thin polymer film. Their method is unique
of thin films probed with a quartz crystal resonator compared with others in that it probes the film properties
[16-26]. In the case ofviscoelastic films, the measured fre- at a frequency where the vibrational amplitude is the
quency shift will not be due only to mass changes, and smallest, minimizing nonlinear contributions. They
Eq. (2) is not valid. One solution to this difficulty is to demonstrated [28] that the shear mode quartz resonators
use an impedance analyzer to record the admittance can be used to investigate solvent dynamics in polymer
characteristics near the resonance rather than just a fre- films at high concentrations that are inaccessible by other
quency shift. The change in film rigidity can be detected experimental methods.
by measuring the resonant resistance, dissipation factor,
or the peak near the resonant frequency. This technique E. Equivalent Circuit of a Quartz Crystal Unit
would be useful even for heavily loaded resonators that
For a theoretical model analysis as well as for a better
could not support oscillations in an oscillator circuit.
understanding of measured variables, it is important to
The intrinsic resonant frequency is then identifiable as
introduce an equivalent electrical circuit for a quartz
the frequency at which the real part ofthe admittance (i.e,
crystal and a quartz crystal unit (which includes also
the conductance) is a maximum. The resonance shape
crystal electrodes and holder). The equivalent electrical
would be characterized by a set ofparameters that makes
circuit ofa quartz crystal unit operating at a frequency of
possible the measurement ofadditional observables. This
the natural resonance is presented in Fig. 3a.The capacitor
approach, although perhaps too expensive for routine
Co represents the shunt capacitance that includes the
use in thickness monitoring, is ideal for studying the
metal electrodes evaporated onto the crystal surface, hol-
effects ofloading a quartz resonator with visoelastic layer,
der, and leads. The remaining "RLC" elements compose
where the existence of more than one material property
the motional arm of the crystal, that is, L\-the motional
requires that more than one observable is determined.
inductance representing the vibrating mass of the crystal
The electrical admittance (the reciprocal of impedance)
C\-the motional capacitance reflecting the quartz
con~insJnformation about the energy stored and- the
elasticity, and the resistance R 1, taking into account bulk
power dissipated inhQth.th~.9s.cillatorand t4~.p~fiUr'5mg
losses occurring within the quartz crystal. The equivalent
medium.
circuit for a quartz crystal alone (without electrodes and
Martin etal. [16] providedamodel in which the electri-
holder) is represented by the motional arm's RLC
cal admittance has been derived for an AT-cut quartz
elements. The introduction of electrodes and holder has
crystal simultaneously loaded by a surface mass layer
a pronounced influence on electrical characteristics of a
and a contacting Newtonian liquid. Their model is a
quartz crystal unit. Typical values of passive elements in
modified Butterworth-Van Dyke equivalent circuit,
the equivalent circuit for a lO-MHz AT-cut quartz crystal
having circuit elements that are explicitly related to physi-
unit are as follows: L\ = 0.0098 H, C 1 = 0.026 pF,
cal properties of the quartz, perturbing mass layer, and
R\ = 5 ohm, and Co = 8.5 pFWhen a quartz crystal res-
contacting liquid. Surface mass accumulation causes a
onates in a solution, the motional arm in the equivalent
simple translation in frequency of the resonance peak,
circuit has to be extended to include also the elements
whereas increasing the density - viscosity product of the
reflecting the mass loading (Lso1n ) and energy dissipation
contacting solution causes both a translation and the
(R so1n ) due to the viscoelastic damping. The equivalent
damping of the resonance peak. With their model,
circuit for a quartz resonator in solution is presented in
changes in surface mass can be differentiated from
Fig. 3b. The circuit includes also the inductance L m that
changes in solution properties.
is due to the mass loading resulting from adsorption or
Noel and Topart [27] reported that surface structure
deposition of species from the solution. The L m term is of
can be studied by impedance analysis, that inductance
primary importance for the EQCN measurements.Values
is a linear function of mass for elastic and viscoelastic
for the remaining elements are usually kept constant
films, and that the calibration range of EQCNs is
during the measurements.
extended by impedance analysis. These advantages result
from the separation of mass and energy loss measure-
F. Measurables and Admittance
ments by decomposition of the composite resonator
Characteristics
admittance into inductive and resistive components,
respectively. The admittance spectrum of a quartz crystal unit
Katz and Ward [28] developed a method based on a depicted in Fig. 3c shows two frequencies at which there
high-frequency thickness shear mode AT-cut quartz is a zero phase shift, fo.s and fo,a. The lower of the two
resonator to probe dynamically the mechanical charac- frequencies,fo,s, is close to the series resonant frequency
I
• Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 603

resistance because the frequency ofthe admittance maxi-

mumfmax is very close to the resonant frequency, as given
by

fmax = Is(l - L1) (6c)

and often, though inappropriately, identified with Is.

When the frequency applied to the crystal from an exter-
nal generator is increased above fa,s, the crystal unit
appears inductive in the circuit. A second zero phase shift
I I
frequency, fo,a, is achieved when reactances of the
~--11--"'" motional inductance Ll and the combined shunt
Gil capacitances C t cancel out. The fo,a is close to fa and often
identified withfa (which does not take into account the
(b) damping effect). These parallel resonance frequencies
are given by the equations
IVI/mS

90 r-========--:-;-===----:::::::::===='
fa = (1/2n)J(Ct + C\)/CtC\L\ =1,(1 + C 1/2Ct )
(7a)

o I-----_----:-~:'.------:--/;,lo~ti.:---------j
\
r-z....- (7b)
\
\
\,
.... _-- .... ---- Because the admittance is at the minimum close to fa, the
-90 L-----l_----L_-"-_---'--_--'---_J.....-._l.--.l-----l.---J 0 equivalent resistance is very high and the fa frequency is
frequency: cenler 5933 kHz. total span 20 kHZ
often called the antiresonantfrequency. The frequency of
(c)
the admittance minimumfmin is given by
Figure 3 Equivalent circuit ofa quartz crystal unit oscillating
(7c)
in air (a) and in solution (b). (c) Admittance spectrum of the
complete quartz crystal unit in the vicinity of its resonance. 1m
is the resonant frequency of the motional arm; Is is the serial At frequencies higher thanfo.a, the crystal unit appears
resonance-frequency of the complete equivalent circuit; J;, is capacitive in the circuit.
the parallel resonance-frequency of the complete equivalent The relative quality, or efficiency of oscillations, of
circuit. (From Ref. 29.) crystal units is characterized by the quality factor Q. The
sharper the admittance peak, the narrower the crystal
bandwith (equal to fo,a - fa",) and the higher the value of
Q. The quality factor Q can also be expressed by the
Is,which is solely determined by the quartz crystal equation
motional arm elements L\ and C\ and neglects losses
due to the energy dissipation:

Is = 1/(2nJC\L\)
It can be readily shown [29] thatfo.s is given by
fo.s = Is(1 + L1)
where L1 = CtI(8n 2CJi,,2 LT/ RT), C t = Co + Cx, and Cx is
the parallel load capacitance. At this frequency, the
crystal unit appears to the driver circuitry as a resistive
element causing no phase shift. This resistance is called
the series resonant resistance, Rs . This is a very small
(6a)
For quartz crystal units in air, Q approaches 10 6 . When
immersed in solution, quartz crystals lose much of the
sharpness of the admittance peak and the value of Q
(6b) drops typically by three orders of magnitude. It happens
often that the driver circuits that work well for crystals in
a gas phase do not oscillate with crystals immersed in a
solution, which is a direct consequence of the lower Q
factor. Therefore, for work with liquids, recommended
are only oscillators specially designed and tested for
use in EQCN systems.
604
G. Dissipation Factor
In addition to the resonance frequency, there is one more
EQCN property that can be measured with relative
simplicity, namely the dissipation factor, D, ofthe crystal.
The dissipation factor is the inverse of the Q factor. If
the film slips on the electrode, frictional energy is dis-
sipated and D can then, in principle, be used to infer the
coefficient offriction of the adsorbed film. Furthermore,
if the film is viscous, energy is also dissipated due to the
oscillatory motion induced in the film (i.e., by internal
friction in the film). Generally, if D is measured simul-
taneously withf, one has in principle access to a quantity
that can indicate whether Sauerbrey Eq. (2) is applicable
or not.
Rodahl et al. [30] discussed the validity of Sauerbrey
Eq. (2) when the EQCN is loaded with viscous overlayers
that mayor may not slip. They demonstrated that by
measuring the dissipation factor together with the
resonance frequency, it is in some cases possible to use
the EQCN as an accurate nanobalance even when
assumptions about film rigidity and no slip conditions
are not met. They stressed the importance of measuring
both the resonance frequency and the dissipation factor
of the EQCN when dealing with deposits that may slip
on the electrodes or are viscous, because changes in D
indicate when ~fcannot be directly translated into a mass
using the Sauerbrey equation.
H. Other Effects Contributing to Frequency
Shift
In addition to viscoelastic effects, the measured fre-
quency shift (~f) ofthe EQCN might be a result of several
other effects [31-38]. The interactions of a piezoelectric
electrode with a viscous medium will contribute to an
additional loading of the electrode and a frequency
decrease [6-9,31]. When the viscosity of solution is con-
stant during the electrochemical experiment, its contri-
bution can usually be neglected.
Surface roughness can drastically affect the measured
frequency [32,33]. Using impedance spectroscopy, Beck
et al. [33] analyzed the influence of the surface
microstructure on frequency changes. A liquid that was
rigidly coupled to the surface by inclusion into voids or
narrow channels was distinguished from the liquid that
was viscously coupled to the surface [33]. As long as the
roughness is not larger than the acoustic wavelength, con-
formance to the Sauerbrey equation can be expected.
When surface roughness is constant during electro-
chemical experiment, its contribution can be eliminated
or at least minimized by calibrating the system.
"epel
It was also observed that the resonance frequency ofa
quartz crystal depends on the elastic energy stored in
the quartz. This effect provides the possibility of
measuring simultaneously changes of mass and surface
stress at the electrode [34,35].
The compression effect was described by Susse [36].
When pressure of the fluid increases up to 104 atm, the
frequency of the quartz crystal changes linearly [36]. The
effect of temperature on frequency can be minimized by
using AT-cut crystals (see Fig. 2) and by thermostating
the electrochemical cell or by using a dual quartz crystal
configuration [see Ref. 173]. Accurate mass determi-
nation from Sauerbrey Eq. (2) is possible ifthe active area
ofvibration is known precisely and the mass is distributed
uniformly.
Gabrielli et al. [37] performed calibration of the
EQCN in the case when ~m is uniformly spread on the
active electrode surface, but they also took into account
the localized mass changes. The latter effect is ofgreat sig-
nificance in localized corrosion studies.
Ward and Delawski [38] demonstrated a radial mass
sensitivity by simultaneous in situ measurements of
frequency and charge during copper electrodeposi-
tion in holes etched in a photoresist polymer on the
EQCN electrode. Their data indicated a Gaussian
mass sensitivity distribution with the greatest differen-
tial sensitivity in the center of resonator, decreasing
monotonically with increasing radius.
Depletion layer effects on the response of the EQCN
were reported by Lee et al. [39]. Frequency shifts
during voltammetric oxidation of 100 mM Fe(CN)~­
in 1.0 M Na2S04 solutions were observed. These fre-
quency changes were caused by variations in density
and viscosity in the depletion layer that accompany
oxidation or reduction of the electroactive species.
Bacskai et al. [40] provided an analytical description
of the differential sensitivity function and tested their
model for an electrode coated with polymer film with
uneven thickness.
Taking into account the effects described above, the
overall frequency shift of the EQCN can be expressed
as
~f = ~fmass + ~fviscosity + ~fporosity + ~fstress (9)
+ ~fpressure + ~ftemperature
For the EQCN applications as a mass sensor for thin
films on electrodes, the most important factor is the
mass effect, ~fmass, which must be separated from other
effects mentioned above. When an electrochemically
induced change in the oscillating mass, ~m, causes a p
change in the resonant frequency, ~f, then this mass
Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance
change is related to an amount of charge, AQ, described
by the modified Faraday's law:
(10)
where F is the Faraday constant, n the number of electro-
ns, Am the mass change for this reaction, and M w the
molar mass of species deposited onto or dissolved from
an electrode [g/mol]. M w is the molar mass of species
involved in electrochemical processes where all the
charge transfer involves only mass accumulation (or
removal) on the electrode and there are no further sec-
ondary processes such as chemical reactions. In the case
of more complex systems, M w = M*, where M* is the
effective net molar mass change determined on the basis
of the stochiometry of the reaction equation and it may
include also the total or partial solvation shells of ions
involved and the solvent and electrolyte uptake or release
as in the case of some ion-exchange polymers deposited
on piezoelectrodes. For every electrochemical process
that changes the mass of the working electrode, there is
a specific proportionality between changes in frequency
and charge:
(11 )
The slope of the plot offrequency shift vs. charge should
give the apparent molar mass of deposited species.
This allows the identification of the various species
formed at different stages during cyclic voltammetry,
chronoamperometry, or chronopotentiometry experi-
ments. Also, in situ measurements of frequency and
current allow one to distinguish between competing
reaction mechanisms by evaluating the slope of a
frequency-charge plot.
III. EXPERIMENTAL
A. Piezoelectrodes
The EQCN quartz crystals with Ag, AI, Au, Co, Cr, Cu,
Fe, Ni, Pt, and Zn electrodes are commercially available.
The most frequently used electrode material is Au. Most
metal electrodes require a thin (20-50 nm) adhesion
underlayer, usually made of Cr, Si, or Ti. The standard
electrode pattern is a "keyhole" pattern (Fig. lb), but
ring/disk electrodes designed mainly for studies of
adsorption on modified quartz surface are also available.
The quartz crystals used should be of high laboratory
grade (commercial telecommunication or computer
clock crystals have too low frequency stability to be
utilized in EQCN measurements); lO-MHz crystals are
recommended because they offer very high mass
sensitivity and are sufficiently thick (0.13 mm) for safe
605
handling. Also frequently used are 5-MHz crystals, how-
ever their mass sensitivity is a few times less than for
10-MHz crystals. For lO-MHz crystals, the mass resol-
ution is typically below 0.1 ng and the maximum mass
loading for rigid films is ca. 100 f.1g. Therefore, one can
study both the submonolayer films and quite thick films
using these crystals. For adsorption measurements,
polished crystals should be used. If large mass changes
are to be monitored, low frequency crystals should be
used, e.g., 2- or 2.5-MHz AT-cut crystals.
B. Electrochemical Cell
TheEQCN crystals canbemountedin an electrochemical
cell in a variety ofways. They can be sandwiched between
two O-rings and attached in this way to a glass cell.Very
stable and reproducible oscillations are obtained when
the crystal is sealed with silicone adhesive to the hole in
the cell wall. Both the stationary and flowthrough cells
can be used. It is important that the stress on the crystal
introduced by the crystal mounting procedure is
minimized as much as possible. The hydrostatic pressure
in the cell has no influence on the resonant frequency so
the height ofthe solution in the cell can be changed at will
and no corrections are required. There are, however, cor-
rections necessary for the piezoelectrically active surface
area ofthe electrode. The entire surface ofthe metal elec-
trode (working electrode) deposited on the quartz surface
and exposed to the solution is electrochemically available.
Only that part of the working electrode that is "covered"
by the metal electrode on the other (air) side ofthe crystal
is piezoelectrically active. This means that for a keyhole
pattern of Fig. Ib, the piezoelectrically active area is
reduced to the disk area (i.e., flags extend in opposite
directions and do not cover each other). In electrochemi-
cal applications, quartz crystals with one side ofthe wafer
exposed to the electrolyte solution are used. The metal
electrode evaporated onto the quartz crystal serves as the
working electrode. The second metal electrode evapor-
ated on the opposite side of the crystal is exposed to the
air and serves only to complete the oscillator driver
circuit. It has no connections to the potentiostat circuit
other than through the quartz crystal (a dc insulator).
Thus, an oscillator can work together with a potentiostat
or galvanostat and the potential of the working electrode
deposited on the surface of the quartz crystal can be
well controlled. Basically, any electrochemical tech-
nique can be used, for instance, cyclic voltammetry,
chronoamperometry, chronopotentiometry, etc. Any
mass change at the working electrode due to
adsorption/desorption, film growth, new phase
formation, etching, corrosion, and others occurring
606
during a potential scan or transient experiment will result
in changes in the quartz crystal until resonant frequency
that can be readily calibrated in mass units.
c. Apparatus
Various oscillator driver circuits have been described in
the literature and reviewed. In our laboratory we used sev-
eral types of drivers, including the series TTL-IC type,
Miller, Colpitts, Pierce comparator, emitter coupled,
and Meacham circuits. Except for the Miller type, all
drivers showed fairly good frequency stability. It is
important that the oscillator circuit is well shielded
because energy is readily dissipated through air at the
high frequency ofoscillation (short radio waves).
In the EQCN measurement systems, the working elec-
trode is a common part of the oscillator and potentiostat
and it should be grounded to reduce energy dissipation
on the working electrode connections to potentiostat.
This condition is well addressed in ELCHEMA
potentiostats (PS-205 and PS-605) where the working
electrode is directly connected to the analog ground
FARADAY CAGE
POWER SUPPLY
EQCN-703 ,1
REMOTE PROBE
2
RECORDER OUTPUT
POWER SUPPLY
(on back panel)
CELL
QUARTZ CRYSTAL
RECORDER OUTPUT
Figure 4 Connections ofthe EQCN-700 electrochemical quartz crystal nanobalance system with potentiostat and microcomputer.
Hepel
(electrical common) that can be either shorted to the ac
ground (hard ground) or left floating. The Wenking
potentiostat or Pine Instruments RDE-4 potentiostat
may also be used. Potentiostats with the current
measuring resistor connected between the working elec-
trode and ground are not suitable for EQCN applications.
A measurement setup for EQCN measurements used in
our laboratory is presented in Fig. 4. It consists ofa Model
EQCN-700 electrochemical quartz crystal nanobalance
(ELCHEMA, Potsdam, NY) equipped with a faraday
cage and sensitive frequency-to-voltage converter
with a resolution of 0.01 ng using IO-MHz AT-cut
quartz crystals, an ELCHEMA Model PS-605
PotentiostatiGalvanostat with 1013 ohm input impe-
dance; and VOLTSCAN Real-Time Data Acquisition
and Control system based on high speed 16-bit D/A
and AID converters. The VOLTSCAN system pro-
vides a quick setup of the program waveform (up to 10
scans or steps in standard version), that controls the
potentiostat. This system allows us to simultaneously
monitor the electrogravimetric and voltammetric
characteristics, for instance, i vs. E and m vs. E or i vs. t
MASS
DAQ
BREAK-UP BOX
CURRENT
l
Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 607

and m vs. t, etc. Also, the system provides a quick means of

determining the effective molmass from the m vs. Qplots.
In the quartz nanobalance systems, shielding is of the
utmost importance. This is because the oscillator is open 1.2 2000 i
and susceptible to the surrounding electromagnetic noise
--
,,
Al
~
and parasitic capacitances due to the nature of the
measurements (quartz crystal in the electrochemical 0.8 "
,I 1600 ~
cell).The special shielding applied in the ELCHEMA sys-
tem reduces noise to a minimum. In addition, there is an
output filter on the nanobalance unit, two filters and
-<e
~
Z 0.4
, ~
1200 ~
~
speed control in the potentiostat, and averaging and digi- I
>
tal smoothing in software. When a true linear potential
~ \ U
scan is required (in 16-bit DAC, the staircase ramp has
0.3 -mV steps on a 10 -v range), we use a program waveform
;;l
U 0 "- 800 Z
~
~
0'
generator, ELCHEMA's Model FG-206F (scan rates,
1 mV/s to 999 kV/s). A disadvantage of the oscillator
-0.4
400
~
~
method is its inability to unambiguously discriminate
Start
between the mass and viscoelastically induced changes
in frequency. This problem can be overcomed by the use
o
of impedance or network analyzers that, however, -600 -400 -200 0 200
are very expensive. For quartz crystal immittance POTENTIAL, m V vs. SeE
measurements, we use a Model EQCN-900 system
(ELCHEMA) with frequency scanning. The system Figure 5 Linear potential scan characteristics of current vs.
measures the ac current flowing through the crystal potential (curve I) and apparent mass vs. potential (curve 2) for
(2-11 MHz), ac voltage across the crystal, and phase copper deposition and stripping on a Au-EQCN electrode in
shift. Thus, an entire spectrum ofthe piezoelectrodewhile 0.1 M H 2 S0 4 + 10 mM Cu(II) + 0.1 M NaCI recorded at scan
it is under potentiostatic control can be recorded. This rate V = 50 mYls. (From Ref. 41.)
system can also be switched to a standard EQCN
operation. For a routine film thickness monitoring, a
QCM from Maxtek Company is recommended. mediate encountered in the oxidation of Cuo to Cu(II)
in chloride solutions [41]. In this case, the frequency
decrease (mass increase) vs. potential characteristics
IV. SELECTED EXAMPLES OF THE recorded under the linear potential scan conditions show
APPLICATION OF THE EQCN a mass increase exactly at the potential where the inter-
mediate is being formed and a mass decrease exactly
A. Reaction Mechanisms on Metal
where the deposit is oxidized to Cu(II). This mechanism
Electrodes
is illustrated in the I vs. E and !1f vs. E characteristics in
The EQCN technique is undoubtedly a technique that Fig. 5 in the anodic-going potential scan.
should be used in conjunction with other methods in Presented in Fig. 5 are linear potential scan
mechanistic studies of electrode processes, so many of voltammetric and microelectrogravimetric character-
which are strongly dependent on the adsorption of istics for copper deposition and stripping from 0.1 M
reactants and/or intermediates. Here, the EQCN can H 2S04 +10 mM Cu(II) solution, containing 0.1 M NaC!.
help to confirm the adsorption/desorption processes The effect of C!- ions is clearly seen in Fig. 5 where two
manifested in microelectrogravimetric characteristics pairs of anodic and cathodic peaks are observed. The
recorded simultaneously with steady-state or relaxation peaks C!- Al can be ascribed to reactions of the
voltammetric characteristics. Because the EQCN fre- Cu(II)-Cu(l) couple and the peaks C2-A2 to reactions
quency shift is proportional to the molar mass of species ofthe Cu(l)-Cuo couple. The role ofCl- ions would then
deposited on the electrode. usually it is possible to dis- be to stabilize the Cu(I) intermediate by complexation.
tinguish between various adsorbates or logical alternative The frequency decrease-potential curve indicates,
reaction paths and to elucidate the mechanism. The however, that in the copper stripping stage, the mass
EQCN also helps to distinguish between a submonolayer decrease associated with the copper dissolution is
film and a multilayer film such as the film of CuCI inter- interrupted by a sudden mass increase in the region of
608
the anodic peak A2. This is clearly due to a buildup of the
Cu(I) concentration in the vicinity of the electrode
surface, as the Cuo dissolution takes place, and the
following precipitation of the sparingly soluble CuCI
compound. The resulting mass increase is due to the
added mass of the Cl- ions so that at the mass peak the
total mass is even larger than that of the original Cuo
deposit. Note that there is no indication of the CuCI for-
mation in the initial cathodic-going potential scan. Hepel
[41] concluded that the reaction intermediate (CuCl) is
deposited on the electrode surface in the potential range
from E= +50 mY to +120 mY vs. SCE. Because the
amount of the deposit can be quantified, the EQCN
together with voltammetric or transient techniques
describes the system in detail.
Another example of mechanistic studies are investi-
gations performed by Daujotis et al. [42]. The authors
used the EQCN to elucidate a complex reaction mechan-
ism of the electroreduction of silver(I) in the presence of
a cyanide ion as the sequestering agent. A parallel
reaction of the oxidation of an adsorbed cyanide ion on
an Ag-EQCN electrode was proposed and confirmed by
microelectrogravimetric data.
Ogle et al. [43] reported the use of the quartz crystal
microbalance for an in situ monitoring of initial stages
of the phosphatation process. Phosphatation is a chemi-
cal treatment of Zn-coated steel products during which
a surface layer of zinc phosphate crystals is formed. This
layer enhances the corrosion resistance of the final
product. The EQCN was used to monitor the changes in
mass that occurred when an electrodeposited Zn surface
was immersed in a phosphatation solution. The
mass- time profiles obtained were used to evaluate the
activity of the phosphatation solution qualitatively. The
shapes of the profiles were interpreted in terms of two
interrelated processes, the acid attack on the Zn (leading
to a loss of mass) and the precipitation and growth of
the phosphate film. The results were consistent with a
mechanism involving the nucleation and growth of
Zn3(P04h islands [43].
The effect of current, nickel nitrate concentration,
temperature, and ethanol on the deposition of nickel
hydroxide films was reported by Streinz et al. [44,45].
Nickel hydroxide is one ofthe most commonly used active
materials for the positive electrode in rechargeable bat-
teries. It is also an electrochromic material. To measure
the mass of Ni(OHh films, deposited electrochemically
from Ni(N0 3h solutions, the EQCN was utilized. The
objective ofthese authors was to quantifY electrochemical
deposition as a function of deposition conditions. The
changing mass recorded on the EQCN was demonstrated
to be the result of Ni(OH)2 deposition. Deposited mass
Repel
was observed to increase proportionally with applied
charge as suggested by previous investigators. Most
significantly, the rate ofdeposition was found to decrease
more than an order of magnitude as the Ni(N0 3h con-
centration increased from 0.2 to 2.0 M. The effect of
concentration was shown to be related to Ni(II)
concentration as opposed to solution pH or NO:] con-
centration. The decreased deposition rates in concen-
trated Ni(N03h solutions were attributed to the
formation of intermediates species [e.g., NiOH+ or
Ni4(OH)~+] that diffuse away from the reaction interface
before deposition can occur. Assuming the complex is
the polymeric species Ni4(OH)~+, a two-step precipi-
tation reaction was proposed [44]:
4Ni+ 2 + 40H- {:} Ni 4(OH):+ (12)
Ni4(OH)~+ + 40H- {:} 4Ni(OHh . \.- (13)
The effect of solution concentration on the deposition
rate is illustrated in Fig. 6, which plots mass vs. deposition
time in several solution concentrations ofNi+ 2 at 0.5 rnA
(2.5 rnA Icm 2). As discussed previously by these authors,
the mass was observed to increase linearly with time at
each solution concentration. However, they observed that
the rate of deposition (slope of the mass-time curve)
increased with decreasing Ni(N0 3h concentration. The
deposition rates at each concentration are indicated in
Fig. 6. Similar behavior (increasing rate with decreasing
concentration) was observed at other current values (0.1,
0.25, and 1.0 rnA) [44]. Coupling the deposition data with
the discharge data enabled the deposition efficiency and
the molecular weight of the deposited film to be calcul-
ated [45].
Use of the quartz crystal microbalance as a detector to
follow mass changes during the electrochromic process
taking place at a nickel oxide electrode was reported by
Cordoba-Torresi et al. [46]. The same method was used
by Mo et al. [47] to study in situ the microgravimetric
characteristics of electrodeposited nickel and composite
Nil Co hydrous oxide films on Au electrodes during redox
cycling in KOH electrolyte.
Bernard et al. [48] studied the kinetics of a nickel
hydroxide electrode in alkaline solutions by ac elec-
trogravimetric measurements in the frequency range
from 1 kHz to 0.01 Hz. They concluded that the quartz
crystal microbalance measurements under a sinusoidal
modulation elucidate the electrochemical kinetics of
ionic exchange processes. They found that the electro-
chemical reaction of nickel hydroxide involves both the
incorporation of hydrated alkaline cations and the
deprotonation reaction.
l
Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 609

110 4500
100 _ 0.2 lit Ni
14..:5 "g/mi"
90 ...... 0.5 lit Ni
80
..
.. 8.25 ",g/min
. -..
......
1.0 lit Ni
2.0 I,l Ni
4400
70
co
E,
60 4300
N
50 :r::
....
'"~
••-'3.1.:5 "g/min 0.97 "g/m;n.. ...:-
..
~ 40
...... ..•...... <l 4200
30
20
10
•
. .... •....
..........
.
.. . ?

••
. .
.
.. ,...•'-
4100
0
-10 4000
0 10 20 .:50 40
Time (min)
-1000 -500 o 500 1000 1500 2000 2500
Charge, IlC

Figure 6 A plot ofapparent mass vs. time at 0.5 rnA in various

Ni(N0 312 concentrations. Note that the rate of deposition
increases dramatically with decreasing solution concentration.
The deposition rates for each concentration are indicated on
the figure. (From Ref. 44.)
The effect of thiourea on copper electrode reactions
was investigated by Alodan and Smyrl [49] in sulfuric acid
solutions. They found that at concentrations of thiourea
higher than I mM, thiourea forms complexes with
cuprous ions in solution, causing negative shifts in the
open circuit potential for a copper electrode. The
complexation with thiourea also causes copper to dis-
solve to cuprous species even in sulfate media. At more
positive potentials, thiourea may react with cupric ions
and form a complex. At sufficiently high concentrations
of the cupric- thiourea complex, the formation of a
sulfate complex film was observed. It has been found that
the film forms reversibly upon cycling the copper elec-
trode potential. Also, there was no evidence of thiourea
incorporation into the deposit. This fact indicated that
the cathodic consumption rate of thiourea during the
copper deposition from acidic sulfate solutions is
negligible.
To confirm the involvement of cuprous species, cyclic
voltammetry experiments were performed with a
copper-coated EQCN electrode and its mass monitored
[49]. Figure 7 shows the dependence ofthe frequency shift
on the electrode charge recorded during a cyclic vol-
tammetry experiment for 5 mM thiourea in I M sulfuric
acid. From the slope of the EQCN resonant frequency
vs. charge passed, the equivalent weight for the material
that had been deposited and dissolved was estimated.
The slope ofthe line gave an equivalent weight of63 g/val,
which is very close to the equivalent weight of cuprous
species. The difference between the slope in the anodic
and cathodic direction in Fig. 7 was attributed by the
Figure 7 Frequency change vs. charge obtained from cyclic
voltammetry experiment of the copper electrode in I M
H 2 S0 4 + 5 mM thiourea. (From Ref. 49.)
authors to a residual oxygen reduction reaction that
lowers the slope of the mass-charge relation and lowers
the apparent equivalent weight in the cathodic region.
The EQCN results reported by Alodan and Smyrl [49]
suggest that the copper electrode dissolves to the cuprous
state in the presence of thiourea even in sulfate media,
according to the following reaction:
Electrochemical behavior and surface morphological
changes of copper substrates in nonaqueous solutions
in the presence of 2,5-dimercapto-I,3,4-thiadiazole
(DMcT) were described by Chi et al. [50]. Understanding
the performance ofthe DMcT-based polymer composite
cathode with a copper current collector is of importance
for rechargeable lithium batteries. Their voltammetric
results showed that DMcT inhibited electrodissolution
ofcopper at potentials negative of 1.0 V vs. SCE and their
EQCN results suggested the Cu dissolved mainly as Cu+,
which was stabilized by DMcT by forming a complex at
more positive potentials than 1.0 V. They also found that
in the presence of DMcT, surface of the substrate was
smooth, whereas in its absence, the copper dissolution
was a nonuniform process and the surface roughness
was increased causing the apparent efficiency of Cu dis-
solution to decrease well below 100%.
The frequency change during the dissolution and
deposition of copper is presented in Fig. 8a [50]. Figure
8b shows that the cathodic charge passed was always
much smaller than the anodic charge passed.
Furthermore, the plot of frequency change against the
charge passed presented in Fig. 8c allowed an estimation
610 Hepel

1200 increase in surface roughness caused by the Cu

N
1000 l OC : +1.0V:
:
OC
'---'
~ -0.8 V :
:
oc (a) electrodissolution. This conclusion about increased sur-
face roughness was confirmed by phase measurement
~ 800
Q)
interferometric microscopy.
Ol
c 600 It was also reported by Schumacher et al. [51] that the
Cll
..c. oxidation of smooth copper and silver electrode leads to
(,J
400 the surface roughening that persists when the oxide layer
>-
(,J
c 200 is reduced. The roughened surface was observed to relax
Q)
::::l on a time scale ofhours when held at reductive potentials,
CT
Q)
..... 0 and this was observed in situ by a quartz microbalance
u..
-200 and by differential capacitance methods. Studies of elec-
"500 0 500 1000 1500 2000 trochemical phase formation and dissolution by ac
35 quartz electrogravimetry was reported by Bourkane et
al. [52] for copper dissolution and copper deposition in
28 30.1 mC ~.'r---: \
(b) sulfuric acid medium.
: \
() 21 I
/ I"
~
The mechanism of deposition and dissolution of thin
E / \ 10.7mC films of diheptylviologen bromide using the quartz
--
Q)
Ol
14
I
f \.." L crystal microbalance technique in conjunction with
..... OCr
m I " -- cyclic voltammetric and potential step measurements
Cll
..c. 7 was studied by Ostrom and Buttry [53]. They demon-
()
_ _ _\ / Qa = 60.2 mC.cm"2
strated the uniformityofthe current density in their exper-
0 Oe = 38.8 mC.cm- 2 iments and verified the use of the EQCN measurements
L under such conditions.
-500 o 500 1000 1500 2000 To determine the apparent molar mass M"" the
Time /s following method was presented by Ostrom and Buttry
[53]. For potential steps well over the wave, the integrated
1200 Cottre! equation gives the total amount of material that
(c) has reached the surface at agiven time. In the authors' case
N 1000
of deposition of the reduced HV+ in the form of HVBr
--
I
Q)
Ol
800 with 100% efficiency, the integrated Cottrell equation
C gives the total mass deposited during a potential step.
Cll 600
..c.
(,J Equation (I5) [53] gives the dependence of the fre-
>- 400 quency change (4(, in Hz) on the time (t in s), after the
(,J
c potential step:
~ 200
CT
~ 0
u..
f..J = (2 x 10 6 )K MwDl/2Ctl/2n-I/2 (I 5)
-200
o 7 14 21 28 35
Charge change fmC where D is the diffusion coefficient (in cm 2 /s), C is the
concentration of the diffusing species (in mol/cm3), K is
Figure 8 EQCM results obtained at a Cu-coated (8 mm the proportionality constant (in Hz j1.g-1 cm 2 ), and M w
diameter) quartz crystal oscillator in 0.1 M LiBF4/(PC + EC)
is the apparent molar mass of the deposited species that
solution during the constant potential electrolysis. (a) Fre-
quency change, (b) charge change, and (c) a plot of frequency forms the film (in g/mol). One should expect that M"
change against charge passed. OC represents open circuit. value may be larger than the molar mass of HVBr if sol-
(From Ref. 50.) vent and/or ionic species were to be incorporated into
the film during its formation. The authors [53] proposed
a more direct measure of M w by using the slopes of the
ofthe apparent molecular weights ofthe dissolved Cu and 4fvs. t 1/ 2 and the Q vs. t 1/ 2 plots, where Sf (in Hz/s 1/ 2) is
deposited Cu as 56.4 and 83.6 g/mol, respectively. Differ- the slope obtained from the first graph and Sq (in
ences between the theoretical and experimental values C cm- 2 S-I/2) is the slope obtained from the second
of apparent molecular weights were explained by the graph, respectively.
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 611

The value of apparent molecular mass M w can be cal-

culated from the ratio of these slopes and is given by 810

(16) N 630
:I:

According to Ostrom and Buttry [53], this method does "u

)-
450
not require knowledge of either the diffusion coefficient ..,z
or the concentration, because both slopes depend on ..,a
:::J

270
these quantities in the same way. In Fig. 9a [53] the results It:
....
ofa typical potential step experiment are presented. <l
The frequency ofthe electrode decreases continuously 90.0
after the potential step, indicating on a mass gain at the
surface due to the HVBr deposition. For this experiment, I. 00 3.00 5.00 7.00 9.00
tis
the plot of Afvs. t l / 2 (the microgravimetric equivalent of
the Anson plot) is presented in Fig. 9b. The linearity of
I the plot indicates the general applicability of Eq. (15).
The excellent agreement between the Af vs. t l / 2 slope
810

and the formula mass of HVBr allowed the authors to

conclude that the compact film deposits with a relatively ~ 630

1 low surface roughness and with a current efficiency for

deposition of essentially 100%.
.....
)-

..,uz 450
A study oflithium deposition-dissolution processes in 5
a few selected electrolyte solutions by EQCN was ::1.... 270
reported by Aurbach and Moshkovich [54]. The authors <l
listed several benefits from the use of the EQCN to help 90.0
improve further understanding of the behavior of the Li
electrodes in the various electrolytes. These benefits I. 20 2.00 2.80 3.60
1l2
include the knowledge of the actual mass per electron t ts" 2
values calculated for Li deposition and dissolution steps,
the coulombic efficiency, and the mass balance per cycle Figure 9 (a) Relative frequency change vs. time for 10 s step
during repeated Li deposition-dissolution cycling. from E = +0.2 to E = -0.57 V for a solution containing 5 mM
HVBr2,0.3 M KBr, and 5 mM NaOH. (b) Plotofthe relative fre-
quency change vs. t l / 2 for the same step as in (a). (From Ref. 53.)
B. Adsorption of Ions and Organic Molecules

The in situ measurement of the adsorption of ions on an

electrode is an important aspect of electrochemistry.
The EQCN has been shown to be extremely useful for
an in situ observation of the solid electrode-solution
interface [55-60].
In general, all solution species, including solvent
molecules, may contribute to the frequency change of an
EQCN in the given potential range. In the double-layer
region, in the absence ofbulk phase formation processes,
we can list the important contributions as follows:
Af = - Kq(Arx-M~- + ArMXM~x
+Ar~_M~ + Ar~_Mc+ + ACMs + Amdifr)
(17)
where Afis the frequency change associated with changes
in surface coverage in (1) the inner Helmholtz layer, i.e.,
specifically adsorbed anions X-, ion pairs MX, and sol-
vent molecules S; (2) the outer Helmholtz layer, i.e.,
nonspecifically adsorbed anions A- and cations C+,
and solvent molecules; and (3) the diffuse part of the
double layer, contribution of all species through their
effect on the solution viscosity and density (Amdiff). In
Eq. (17), Ar; is the change in surface coverage by species
i and M,* is the effective molar mass of species i that
includes the mass of their solvation shells. The change in
surface coverage may be due to the change in solution
composition or to a change of the electrode potential. In
the latter case, it is often possible to scan the potential
through the point of zero charge (pzq, thus causing sig-
nificant change in the double-layer structure. Any
changes in the solvent dipole orientation and
adsorption/desorption processes are reflected in the fre-
quency shift. A species removed from the surface
(desorbed) is replaced by solvent dipoles and ions of the
electrolyte. Because the solvation shell crowding and
612 Hepel

electrostriction may be changed in the process as well,

caution should be exercised when modeling a simple
place exchange mechanism. 80

One of the main advantages of the EQCN tech-

nique in the study of adsorption phenomena is the 60
~
possibility of obtaining simultaneously voltammetric u
E
and electrogravimetric characteristics. From these U 40
data, the ratio between the electric charge passed ~
0-

and the corresponding mass change can be defined 20

for every experimental point as a function of the
potential applied. An equivalent molar mass can be 0
determined according to Faraday's law, which gives L.J.
direct information about the electrode reaction 0 0.4 0.8 1.2

species. The measurements are made on the same
surface. The conventional treatment of electrodes by
a repetitive oxidation-reduction cycling to obtain
reproducible voltammetry curves should be avoided
or used with caution, because the contribution of the
quartz electrode roughness (water entrapment) to the
overall mass must be controlled. Use of the
gold-covered quartz, overtone polished and properly
cleaned, allows the roughness contribution to be
minimized [56].
The formation of the adsorbed layers on solid
substrates will cause a change in surface concentration
r ad, and, in the case of involvement of charged species,
a corresponding change in surface charge qrn will be
observed. Both quantities are directly measurable, i.e.,
in situ and simultaneously, with the oscillating quartz
resonator technique and can be used for the calculation
of the thermodynamic parameters of the monolayers
[61,62]. The electrosorption valency 'Y of adlayers formed
at a constant potential E ad is described by
(Jqrn/Jrad)E,d = -yF (18)
Mass measurements made with the EQCN can be used to
determine both the adlayers' coverage and the electro-
sorption valency. In the presence ofthe excess electrolyte,
the value for the adlayers can be calculated from the ratio
of the charge passed qrn to the electrode coverage r ad at
constant potential.
The electrosorption valency, y for [- and Br- adsorbed
on gold electrode in the concentration range
(0.1-10 mM) was found by Deakin et al. [63] to be
1.01 ±0.05 and 0.39 ± 0.03, respectively. Figure 10 shows
the integrated current passed during the electrosorption
process vs. the electrode coverage calculated from the
EQCN frequency. Electrosorption valency obtained by
Deakin et al. [63] is in excellent agreement with that of
Kolb [64], who reported y = OAfor Br- on polycrystalline
gold in KC10 4 using different method.
rJ10 9 mol cm- 2
Figure 10 Integrated current vs. electrode coverage during
adsorption of Br- and 1- . Slope equals yF. (From Ref. 63.)
The value of the electrosorption valency 'Y is deter-
mined by the position of the ion in the interface, the
displaced charge, and the partial charge transfer to the
metal [65,66]. The heterogeneity constant C can also be
used to characterize adsorbate adlayers on metal elec-
trodes [66]. The heterogeneity constant C describes the
dependence of the adsorption enthalpy on the degree of
the surface coverage for the Temkin isotherm and can be
expressed by
(1/~qm(e=I))(Mqm/Jlogch'd = 2.303RT/C (19)
Stockel and Schumacher [57] outlined a procedure for
evaluating C with the help of EQCN. According to them,
Sauerbrey's equation can be combined with a faraday
type of law. The basic for this linkage is the fact that
the mass change ~m, which occurs due to an
adsorption/desorption process of ionic species, causes
the charge change ~qm at the surface, so that the latter
property can be expressed in terms of the frequency shift
~fby
~f = -K~qrn (20)
Besides known properties, the constant K =
2ftM / AyFf.ll/2C;1/2 contains the quantityy, which is deter-
mined by the amount of charge being involved in the
adsorption/desorption of ionic species and the mass M
of one mol of the adsorbate. Equation (19) can now be
rewritten in terms of the frequency shift ~fby expressing
~qm through ~f/K:
(1/~j(e=I))(MflJlogc)E"d = 2.303RT/C (21)
Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 613

±! 8 (a) •
..........
0.10 [Brl (mM)
OJ
~ 6 -
N
E
2.50
1.00
OJ
L
.....C>
to)
0.05
0.25
U ::l 0.05
OJ 0.00
E
'TI 4 <l

>. 0.00
u
c
Q;

6-2
Q; o (b)
L
u..

-4.5 -3 o~
-
0:::

Figure 11 Plot of (j,(vs.log C Br - recorded during Br- adsorp-

~ I
2
tion at different potentials. Ead: (0) -ISO mY; (D) -200 mY;
(x) -250 mY; (D) -300 mY. (From Ref. 57.)
3

-0.4 -0.2 0.0 0.2 0.4 0.6

Stockel and Schumacher [57] reported the electro-
sorption valency y determined by EQCN for Cl-, Br-,
and SO~- equal y = -0.06, }' = -0.34, and y = -0.5,
respectively. They also demonstrated that the hetero-
geneity constant C can be evaluated reliably from the
slope (bAf/<5logc)E,d' In Fig. 11, Af changes vs. log C Br-
for different potentials are presented. From slopes of
these curves, the heterogeneity constant C was found to
be 35.5 Kllmol, which is in good agreement with the
value reported by Sedlmaier and Plieth [65], who
reported the C value to be 35.6 Kllmo!.
Simultaneous normalized optical reflectivity and
EQCN measurements of the adsorption of bromide on
gold in aqueous solutions was applied by Mo et al. [58].
This dual technique approach allows the authors to estab-
lish correlations between the changes in weight and rela-
tive reflectivities associated with the adsorption of ions
on the electrode surface as a function of the applied
potential. In Fig. 12, a and b, mass change and AR/R vs.
potential were acquired simultaneously in 0.1 M NaF sol-
utions containing different bromide concentrations. All
curves are remarkably similar in shape with the exception
of the most dilute bromide solutions examined. Simul-
taneous in situ EQCN -A R IR measurements for the
adsorption ofbromide on the gold yielded results in excel-
lent agreement with those reported by other authors for
Potential (V vs. SeE)
Figure 12 Plots of (j,m (panel a) and (j,R/R (panel b) vs. poten-
tial data for a Au(poly) crystal acquired simultaneously in 0.1 M
NaF solutions containing different amounts of bromide. Scan
rate: 10 mYls. All curves shown in this figure were recorded
while the potential was being scanned in the negative direction.
(From Ref. 58.)
each independent technique. Mo et a!. [58] also reported
that plots of the change in the resonant frequency of the
EQCN vs AR IR were found to be linear with essentially
identical slopes in the potential region in which bromide
adsorption occurred, over an order of magnitude in bro-
mide concentration.
Arai et a!. [59] studied adsorption of iodide ion on
Au-EQCN and compared the results with those obtained
by specular reflection measurements. The data obtained
by both methods showed a close agreement. The potential
dependence of reflectivity change was essentially the
same as that of the frequency change determined by
EQCN. Maximum frequency change due to adsorption
at 1.0 x 10-4 M NaI at E = -0.1 V corresponded to
monolayer coverage, and thus it was possible to calculate
surface coverage, e, from a given frequency or reflectivity
614
change. They found 'Y for 1- to be 1.0 by both the specular
reflection method and EQCN, and this value is in agree-
ment with value of'Y = 1.01 ± 0.05 reported by Deakin et
al. [63].
Adsorption of acetate anions from acetic acid sol-
utions using EQCN method was studied by Malyszko et
al. [60]. From 11m changes, surface concentration of acet-
ate anions equal 1.12 x 10-9 mol cm- 2, assuming a
roughness factor of 1.49, was calculated. The effect of a
layer ofadsorbed acetate ions on the anodic oxidation of
Mn(II) and Co(II) was also analyzed [60]. Adsorption
of acetate ions from aqueous solutions was reported by
Wieckowski and coworkers [67,68], Horanyi and
Rizmayer [69],Yakovleva [70], and Rodes et al. [71].
The adsorption/desorption process of sulfate anions
was monitored in situ by Stokel and Schumacher [57]
using EQCN. They studied this process at a gold
piezoelectrode in the potential range from E = -0.2 V
to E = 0.5 V. A significant irreversibility for the forma-
tion and decay of sulfate adlayers on polycrystalline gold
surfaces was observed by these authors.
Potential dependence of bisulfate adsorption on poly-
crystalline gold, copper, and ordered and disordered
Rh(III)andPt(III)electrodesfromO.l MHCl0 4 + 0.1 M
H 2S0 4 solutions was reported by Zelenay and
Wieckowski [72] using radiochemical assay.
The adsorption ofanions on well-defined surfaces was
examined by Watanabe et al. [73] using the EQCN
method. The adsorption of bisulfate or sulfate anions
both on Cu-ad atoms and on the electrode substrates
was discussed quantitatively. It was demonstrated that
higher coverage with Cu-ad atoms and lower
adsorbability with bisulfate or sulfate anions were
obtained on the Pt electrode than on the Au, and these
effects could be ascribed to the difference in
electronegativity between Pt and Au substrates [73].
Kouznetsov et al. [74] studied electrosorption of sur-
factants and quaternary ammonium salts on gold EQCN
electrodes. These authors demonstrated by the use of
EQCN that benzyldimethyldodecyl ammonium bromide
(BDDB) influences both the cathodic and anodic process
on a gold electrode in 0.1 M Na2S04. Concentrations
of BDDB as low as 10- 5 M already increased the
overvoltage of the hydrogen evolution reaction. At
concentrations higher than 10- 4 M, BDDB was
electrosorbed at potentials higher than 0.4 Vand formed
a condensed film on the gold electrode. Upon the reversal
of the potential sweep BDDB desorbed, but about 10%
of the organic layer remained upon the reduction. The
equivalent molar mass of reaction species obtained from
EQCN measurements during the voltammetric scans
was calculated [74].
Repel
Adsorption of pyridine on gold surface has been
studied by several authors [75-81]. Systematic studies of
the adsorption of pyridine at polycrystalline Au and
oriented single-crystal surfaces ofgold from aqueous sol-
utions were performed by Lipkowski and coworkers
[75-78] using chronocoulometry. Wieckowski and
coworkers [79,80] investigated the pyridine adsorption
at a polycrystalline gold electrode using radiochemical
method. The dependencies of the surface concentration
ofpyridine on the electrode potential obtained agree very
well with those based on chronocoulometric measure-
ments except for the positive potential range (i.e., beyond
the "double-layer region").
Scendo and Malyszko [81] studied adsorption of
pyridine at polycrystalline gold using the EQCN method.
Figure 13 shows frequency change vs. potential curves
obtained in 0.4 M NaCl0 4 solution in the absence (curve
a) and in the presence of I x 10- 3 and 5 x 10-2 M
pyridine (curves band c, respectively). In the presence of
I xlO- 3 M pyridine (curve b), a rapid decrease (i.e., mass
~
(a) /----;:.
5 Hz
~
(b)~
~-
.....
<:1
(c)
----;:. ~
~
-1200 -600 o 600
E (mV V5. SCE(NaCI))
Figure 13 Frequency change vs. potential curves of
Au-EQCN electrode in an aqueous solution containing 0.4 M
NaC104 during a single cycling scan originating from
E = -0.8 V; sweep rate: 5 mV S-I; (a) residual, (b) 1 x 10- 3 M
Pyridine, (c) 5 xlO- 2 M Pyridine. (From Ref. 81.)
L
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 615

increase) is observed during the initial portion ofthe posi-
tive scan and reaches a minimum in the potential range
between E = -0.6 and E = -0.1 V as a result of the
adsorption of pyridine. Of great significance is the fact
that the frequency observed at the termination of the
cyclic scan does not equal the frequency at the start of
the scan. The above fact points to a slow desorption of
pyridine from gold surface. After each terminated run,
about 3 min were required to achieve the initial frequency
at a potential E = -0.8 V. In the case of a 5 x 10- 2 M
pyridine solution (curve c), the frequency shift is roughly
10 times greater than that observed on curve b. This
phenomenon was explained by drastic changes in the
coupling between electrode and solution as a conse-
quence of increased thickness ofthe liquid layer attached
(
to the electrode surface.
.~
Scendo and Malyszko [81] compared their results
obtained for 1x 10- 3 M pyridine solutions using the
EQCN technique with the radiochemical data reported
by Wieckowski and coworkers and found a good qualitat-
ive agreement. The maximum value ofthe !1m/Awas used
by Scendo and Malyszko to calculate the surface con-
centration of pyridine r Py equal to 7.4 x 10- 10 mol
cm -2, assuming a surface roughness of 1.7. This value
is close to that reported by Wieckowski (about
6.5xI0- 1O mol cm- 2).
Repel and Tewksbury [82,83] studied adsorption of
several drugs on bare gold electrode and binding of drugs
to ssDNA immobilized on thioctic acid/gold electrodes.
In Fig. 14a, the adsorption of neuroleptic drug,
thioridazine, on a bare gold electrode is shown. The
adsorption is followed by recording the apparent mass

I 50 ,.....
4.Ox10·'O
40
1:
<.J

3.Ox10· 'O "S

~ 30 5
5 ~
2.Ox10·'O
'"'" ~
::;=
20 OJ)

.=
~
..
10 1.0x10·'O Ii>
=>
U
~
0.0 <.J
0
't
-10 rJ'=
..l
0 100 200 300 400 500
(a) Time (sec)

800

600
,.....
OJ)
5
400
~
::;=
200

0 2000

(b) Time (sec)

Figure 14 (a) Apparent mass vs. time transient recorded for a smooth gold-EQCN electrode upon addition of an aliquot of 10 mM
thioridazine to acetate buffer solution. (b) Apparent mass vs. time transient recorded for an ssDNA Ithioctic acid modified gold EQCN
electrode upon addition of an aliquot oflO mM thioridazine to acetate buffer solution. (From Ref. 82.)
616
vs. time transient after addition of 10 mM thioridazine
aliquot to the acetate buffer. From this graph the
monolayer surface coverage r mono =4.37 X 10- 10 mol
cm- z of adsorbed drug was calculated. This cor-
responds to 38 AZ area per thioridazine molecule.
In Fig. 14b, binding of thioridazine to an ssDNA/
thioctic acid/gold modified electrode is presented.
Nomura and Kanazawa [84] studied adsorption of
metal ions using the EQCN method. Many metal ions
such as cadmium, cobalt(II), manganese(II), nickel,
and zinc are adsorbed onto a gold piezoelectric crystal,
resulting in frequency changes [84]. These metal ion
adsorptions occurred at pH values just below the pH
range of precipitation but not in the latter range.
The adsorption offerrocene [85] and heteropoly and
isopoly oxometalate anions (SiW 120:0, PzW 180~2' and
Hz W lZO~O) was also investigated using the EQCN
method [86].
C. Underpotential Deposition of Metals
Heterogeneous surface reactions are often strongly influ-
enced by the underpotential deposition (UPD) ofa sub-
monolayer of foreign ad-atoms on their surfaces under
precisely controlled conditions. In general, the work
function of an electrode at which UPD occurs must be
more positive than the work function ofthe metallic form
of the metal ion depositing at underpotential. As the
UPD coverage increases, the work function of the
substrate electrode shifts more negatively until the work
function of the active metal is reached. Then, the UPD
ceases and a deposition of the bulk form of the active
metal can occur. Usually, the metal with a higher work
function has the more positive standard electrode
potential, except when the free energy for the solvation
of ions of the higher work function metal is so negative
as to be predominant. Thus, to a first approximation, in
the absence of the unusual solvation effects we may
expect, as is seen, that ions of active metals undergo
UPD at more noble metal substrates. To design a
high-performance electrocatalyst, an in situ analysis of
the surface ofthe UPD layer at an atomic level of accuracy
is required. The EQCN is one ofthe most useful analytical
techniques, because it can detect in situ dynamic
momentary changes in mass of 10-9 g at the electrode
surface. For example, in the electrochemical oxidation
of formaldehyde and methanol, these reactions are
catalyzed by underpotentially deposited layers of lead
and tin on a platinum electrode [87,88].
The oxidation of formic acid proceeds through the
"dual-pathway" mechanism [89] that involves "reactive
intermediate" suggested to be a -COH or -CHO
Hepel
species [90,91] and a "poison intermediate," mainly CO
[92,93]. The oxidation offormic acid is inhibited because
of the formation of a poison intermediate that strongly
adsorbs on the electrode surface, leading to the blockage
of active sites for further oxidation. Underpotentially
deposited foreign metals, present on the electrode surface
in submonolayer amounts, will often alleviate the effects
ofpoisons. A pronounced electrocatalytic effect resulting
from UPD ad-atoms such as Pb, Bi, TI, and Cd has been
observed for the oxidation of formic acid [94-96]. The
oxidation offormic acid at Pt electrodes in the presence
of UPD Pb has been studied by Zhang and Wilde [97]
using EQCN technique. They reported that a careful
examination of the mass responses accompanying cyclic
voltammetry at constant potential experiments reveals
both the variations in UPD coverage ofPb and the effect
of adsorbed intermediates from oxidation offormic acid
on UPDofPb.
The same authors [97] found that at low concen-
trations of formic acid there is some suppression of
UPD Pb, and at high concentration offormic acid (0.1 M)
during the positive scan a significant positive shift in the
potential for removal of the UPD Pb was observed. On
the subsequent negative scan, the rapid reaction between
the oxidized Pt surface and formic acid removes the oxide
at a higher potential than normal and consequently
allows the UPD process to begin at a more positive
potential. According to these authors [97], the adsorption
ofthe intermediates formed during formic acid oxidation
is revealed through its effect on suppressing the UPD
coverage and the adsorption ofPb+ z cations. Mass data
recorded in this article [97] clearly show the presence of
the poisoning (strongly adsorbed) species formed during
the oxidation ofthe formic acid in the UPD region, which
results in measurable suppression of UPD coverage. The
amount of these poisoning species accumulated at the
surface was a function of both concentration of formic
acid and the potential. Mass data also assisted in the attri-
bution of the voltammetric peaks to removal of strongly
adsorbed species. Although strongly adsorbed species
inhibit UPD Pb, the reverse is also true. UPD Pb is effec-
tive in decreasing poisoning of the electrode, and thus it
gives rise to enhanced currents. The authors concluded
that EQCN is a convenient method to study competitive
adsorption phenomena. The effect ofincreasing coverage
of UPD Pb is to make the first peak at E = 0.1 V of
oxidation of formic acid more pronounced and to
decrease the size of the second peak corresponding to
the oxidative removal of poisoning species in the double
layer region. This effect is presented in Fig. 15. The increas-
ing coverage of Pb with time tads is clearly visible in the
mass responses.
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 617

N
I/IJA E, :r:

~
240
"'- X:R:R
ClJ 20 - f-00 X~XR
160
t.da
VI
0 0
° o
X9:.x~ ~ c
° XXX~XC c c
ClJ 40 -I- 0 o X X
80 r... 0
o 0
0
U 0 0
0 0
ClJ 60 -I- 0
0 "'l:i DO
>. DO
U
80 i- DOD
C DO
ClJ
~
100 i- DOD
00000
rr
ClJ I I I I I
r... I I I I I
L.... 200 400 600 800 1000
TiME? /s

Figure 16 Frequency decrease vs. time at various potentials:

0.074 V (D); 0.057 V (x); 0.016 V (0); -0.042 V (D).
Pd(II)-concentration: 10- 2 M; electrolyte: 0.5 M sulfuric acid.
(From Ref. 101.)

quency change of the EQCN as a function of potential.

0.0 0.4 0.8 1.2
EN (SeE)
Figure 15 Cyclic voltammograms and mass responses for
the oxidation of formic acid at UPD Pb-modified Pt in 0.1 M
HCI04 + 50 11M Pb 2+ + 9 mM formic acid, - . - tads = 240 s;
s; --- tads = 480 s. UPD coverages were estimated as f) = 0.19
(- - -), (J = 0.30 (- . -) and f) = 0.48 (- - -). The scan rate was
5 mV S-1 and the electrode area was 3.60 cm 2 . (From Ref. 97.)
+ the resonant frequency with time at various potentials
At higher UPD coverages, more free Pt sites are avail-
able for the bulk oxidation offormic acid (which gives rise
to the first oxidation peak) because poisoning is
decreased by the UPD atoms. Zhang and Wilde [97-99]
concluded that EQCN experiments offer an interesting
insight into the surface processes that occur during the
electrocatalytic oxidation of formic acid, glucose, and
methanol.
The UPD ofPb, Bi, Cu, and Cd was examined on gold
5-MHz piezoelectrodes in 0.1 M HC104 solution by
Deakin and Melroy [100]. The surface coverage of the
UPD layer on the Au surface was calculated from the fre-
Obtained surface coverage were in good agreement with
previous estimates obtained using other techniques. The
electrosorption valencies y were calculated from the
change ofcoverage ratios obtained from the EQCN data.
Value of)' for Pb (y = 2.0), Bi (y = 2.7) Cu (y = 1.4), and
Cd (y = 1.6 to 2.0) were reported. Deakin and Melroy
[100] concluded that the EQCN is a quantitative tool for
examining monolayer and submonolayer metal deposits.
The EQCN technique was applied by Stockel and
Schumacher [101] to the palladium/gold system to inves-
tigate adsorption and diffusion properties of palladium
onto/into the gold substrate. The electrosorption valency
y for palladium adsorbates was determined to be y = 1.8.
Other interesting aspects of the gold/palladium sys-
tem is presented in Fig. 16. In this figure, the change of
ranging from 0.074 to -0.042 Vis presented [101]. In Fig.
17, these curves are presented as a frequency decrease vs.
time. The slopes oflines in Fig. 17 vary with the potentials
applied, thus reflecting the influence ofthe surface cover-
age on the diffusion rate. The surface coverage depends
on both potential and concentrations of ions. From the
obtained slopes, an apparent diffusion coefficient of
D ~ 10- 17 cm 2 S-1 of palladium into the gold electrode
is estimated [101].
New interesting phenomena for UPD of Pb in 0.1 M
KOH and 0.1 M borate buffer were discovered by Hepel
et al. [102,103]. Customarily, UPD is ascribed to dis-
charge of dissolved metal ions, and the mass increase
618 Hepel

N
I
"-
OJ
VI
d
20
30
I~~ / _ _
';:~-=-::--­
"
Moss

..-=----
-------
OJ ~/
L 40 20
U C""'_ _ ~
OJ
-0 60 ~o
<[
::t.
>. 80
u
c
OJ 100
t-="
z
w
a:
0
- t
5:
:::s a: 1>
(J
OJ
a -10 CJ)
CJ)

L
w... 10 20 30
-20
~TiMe';~
-30
Figure 17 Evaluation of the data given in Fig. 16 in terms ofa
t 1/ 2
law. (From Ref. 101.) -40

would accompany such a UPD process. Surprisingly, a
decrease in the weight of the electrode occurred during
the entire cathodic process for Pb UPD rather than an
increase in weight that would be expected for a UPD
process involving deposition of a dissolved Pb species.
They found that during the Pb UPD formation process,
the entire cathodic charge is transferred to a
(Pb(II)l1igand)ads species that is already present on the
surface as an adsorbed monolayer. They attributed the
observed decrease in mass to ligand expulsion from the
electrode surface. This process of ligand expulsion is
spontaneous, occurs during UPD discharge, and is not
the same as ligand desorption. This effect is presented in
Fig. 18.
The current vs. potential curve in Fig. 18 for a
2.7 x 10- 5 M Pb(II) solution is pH 9.15 borate buffer was
obtained at a silver electrode while using the EQCN
technique. It exhibits one anodic current peak and one
cathodic current peak of nearly equal areas. The corre-
sponding mass vs. potential curve in Fig. 18 displays a
mass decrease at potentials in the cathodic peak current
region and shows a mass increase in the anodic peak cur-
rent region. Both of the latter results are properties of a
surface immobilized lead- borate complex. Thus, EQCN
data were used to evaluate the composition of an
adsorbed surface complex.
Hepel et al. [104] proposed that the anionic
Pb(II)-borate complex is adsorbed at E= -100 mVand
the decrease in mass during the negative-going potential
scan is caused by expulsion of anionic ligands produced
during the reduction process that results in Pb(O), i.e., dis-
-400
Figure 18 Linear potential scan characteristics ofcurrent and
apparent mass vs, potential obtained for an EQCN silver elec-
trode in 2.7 x 10- 5 M Pb(II) + 0.1 M borate buffer, pH 9.15. Tri-
angular waveform. Scan rate: 50 mV/s, Starting potential
E= -100 mY. (From Ref. 104.)
charged underpotentially deposited lead. The mass
increase during the positive-going potential scan from
E= -480 to E= -200 mV is interpreted as the
readsorption of borate anions concomitant with the
reoxidation of UPD lead to the surface adsorbed
Pb(II)- borate complex.Thus, the charge transfer process
for the formation of an underpotentiallead deposit and
the increase in electrode mass do not coincide at a silver
substrate. A different mechanism is observed for Pb
UPD at gold electrode [104].
Figure 19 shows the current and mass vs. potential
curves obtained at a EQCN gold electrode in a solution
containing 2.7 x 10- 5 M Pb(II) + 0.1 M borate buffer,
pH 9.15. A voltage scan rate of 50 mV/s was used between
an initial potential of E = +100 mVand a reversal poten-
tial of E = - 580 mY. The reversal potential is positive of
the one at which bulk lead deposits. The anodic peak cor-
responds to the stripping ofUPD lead to form a dissolved
Pb(II) species. It follows from the mass vs. potential curve
that the mass always increases concomitantly with the
passage ofcathodic faradaic charge and always decreases
as anodic charge flows. This result on a gold electrode is
in contrast to the result found at a silver EQCN electrode.

L
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance
20
-
10
«
:to 0 ___
=---~o
.....
z St~t
U.J
0:: -10
0::
a \.
--- .................................
I""~ ',.,;;,-~-----1
-20
-30
Start
-600 -400 -ZOO o tis
POTENTIAL. mV VS. SeE
Figure 19 Linear potential scan characteristics ofcurrent and
apparent mass vs. potential obtained for an EQCN gold elec-
trodein2.7 x 10- 5 M Pb(II) + 0.1 Mboratebuffer, pH 9.1. A tri-
angular waveform was used with a scan rate of 50 mY/so The
initial potential was E = +100 mY, and the reversal potential
was -600 mV (From Ref. 104.)
In Fig. 19, irreversibility of adsorption/desorption pro-
cesses is visible. The electrode is heavier at the end of the
first potential cycle than at the start.
Oifferent mechanisms for UPO processes for lead on
silver and on gold were explained by Hepel et al. [1 02~ 104]
by differences in PZC of both substrates. The PZC ofgold
is more positive than that for silver. The rational potential
ofgold is estimated to be 0.3-0.4 Vmore negative than at
a silver electrode at the start of UPO process. Thus, the
adsorption of the negatively charged anion Pb(B0 2 )3
would be electrostatically inhibited. For the gold elec-
trode as was expected, no evidence for adsorption of any
Pb(II)~ borate complex was found nor was there any evi-
I dence for anion expulsion during the discharge process
that formed UPO lead on gold. Mass changes for this
UPO process coincide with the charge-transfer process
1 under potential scanning conditions.
The effect ofpH over the range 1-13 on the UPO of Pb
at silver was also studied [103]. In perchloric acid sol-
utions and acetate buffers, where only cationic and
uncharged lead(II) species exist in solution, the UPO
process is accompanied by an increase in the mass of the
electrode. However, in borate buffers and sodium
hydroxide solutions, where anionic lead(II) species pre-
dominate, the UPO process occurs through the mechan-
ism of a preadsorbed lead-ligand complex and is
accompanied by a decrease in the electrode mass and
ligand expulsion during discharge.
619
t 50ng
1
45 Hz
;s::
»
CJ)
CJ)
A
50 100 150 200 250 300 350 400 450
Figure 20 Apparent mass changes vs. time transient upon
injection of Bi(III) into 0.1 M borate buffer of pH 10 free of
Bi(III). Final Bi(III) concentration is I xlO- 5 M. Silver elec-
trode potential E = 100 mV A: point of injection of Bi(III)
solution. (From Ref. 105.)
A similar mechanism as for UPO of Pb(II) was
observed by Hepel et al. [105] for UPO of Bi(III) at silver
electrode in borate buffers in the pH range 8-10. The sur-
face reduction process corresponds to the expulsion of
four B0 2 anions from the interface according to the
reaction Bi(B0 2 ); + 3e = Bi upd + 4 B0 2. Oirect evi-
dence for the adsorption of Bi(III) on silver EQCN
electrode is shown in Fig. 20.
The apparent mass vs. time transient was recorded
upon injection of Bi(III) into 0.1 M borate buffer (pH
10) when the silver electrode was potentiostatted at
E = -100 mY. No change in current at the electrode
accompanies this mass increase of 147 ng. The authors
[105] ascribe this mass increase to adsorption of an
anionic bismuth- borate complex induced by the positive
rational potential ofthe silver electrode during the injec-
tion of the Bi(III) solution into the buffer. These results
clearly show the effectiveness of injection experiments
such as these at the EQCN in providing a simple con-
venient method for the demonstration of adsorption
process. The authors concluded that the combination of
the EQCN and voltammetric measurements is a powerful
means of elucidating UPO mechanisms, determining
the composition of adsorbed UPO metal-ligand com-
plexes and in some cases tracking expulsion of ligands
from the electrode surface.
The phenomenon ofligand release from an adsorbed
metal UPO-ligand complex was also discovered for
other ligands. Hepel [106] reported potentially controlled
release of the organic ligand melanin from adsorbed
620 Hepel

100 IIII Ii Ii Ii iiili •• I"j IIII Ii i" I' Ijlll, IIIII11I I, j IIII Ii i lilll' illl II i ,'1, r i Iii! 'I 200 experiments to provide a quantitative relationship
!,~s__ ~ _ ~ between the amount of Ag ad-atoms and adsorbed
I' 150 hydrated-anions during the formation and removal of
/'
II-.'
, ,,
, 1'-
, ---- ~---
Ag-adlayer.
The deposition and dissolution processes of copper
i 50 100
ad-atoms on gold and a platinum electrode in sulfuric
....~ ,
," I'.,t'f gf
acid solutions were investigated by Watanabe et al. [108].
50 Using EQCN, it was found that the weight loss in the
/ I
Cll
a.. en removal ofthe Cu-adlayer from the Au substrate was con-
a.. <'" /'
CI)
;j ~Curre~ ~
siderably larger than that expected from Faraday's law,
U o
~
o :E whereas the deviation for the Pt substrate was very small.
~
These authors concluded that their EQCM study gave a
-50 quantitative relationship between the amount of copper
ad-atoms and that ofadsorbed anions and that their data
are in agreement with results obtained by an EXAFS
-5_° 600 ''~400"~200'" "~""" '2'~a'" "4~a'" "t.'Ja"" '6'~a'" 'i'O~0100
study [109].
Potential vs. SeE ,mV

Figure 21 Linear potential scan current vs. potential (solid D. In Situ Monitoring of Electrochemical
line) and apparent mass vs. potential (dashed line) character- Double-Layer Structure Changes at
istics obtained at Au-EQCN electrode in solution: 2x10- 4 M Electrodes
Cu2+ + 0.064 giL melanin +0.01 M acetate buffer. Scan rate:
v = 50 mY/so (From Ref. 106.)
The application of EQCN method to monitor in situ the
electrochemical double-layer structure changes at gold
electrode has been reported [110-113]. Kautek et al. [110]
UPD metal- melanin complex. This biopolymer, developed a few double-layer models and compared them
melanin, has the ability to form complexes with many with experimental data using EQCN technique. Accord-
metal cations, including lead and copper. It was found ing to Kauteket al. [110], a mass change dm on the active
that the melanin ligand can be reversibly attached to and surface area A affecting the measured frequency (d/)
released from the surface of the copper UPD modified according to Eq. (1) consists of the contributions of cat-
Au electrode by the potential scanning in the region of ions (C) and anions Vt) with hydration shells of various
the fast UPD charge/discharge processes, as presented extents, depending on their surface density r (in
in Fig. 21. The strong mass increase observed upon the mollcm 2), bonding state, and position in the outer (0)
copper UPD oxidation corresponds to the melanin or inner (I) Helmholtz plane:
uptake from the solution. The melanin molecules bind
to the copper ions adsorbed on the electrode surface.
A
Dom = (raenlea + raAmAa + rIxmxI
(22)
During the UPD discharge, the electrode mass decreases + r~xm~x + dm6 + dmr)A
sharply, indicating the release of the melanin ligands. A
mass increase would be expected in this case if the metal Any roughness changes are considered by the term ofthe
ions were deposited on the electrode surface during the sum dm r . Acoustic decay layer changes are symbolized
UPD discharge process. by dm6.
The multicomponent surface interactions have also The cation ion mass Me and the number ofwater mol-
been observed between melanin, the amino acid tyrosine, ecules a of mass MH 2 0 in the solvation shell of the cation
and Pb+ 2 ions [106]. It should be emphasized that constitute the solvated cation mass mg:
piezoelectric resonator can serve not only as detectors
nl~ = Me + aMH 0
2
(23)
for adsorbable molecules but can also be used as very
sensitive probes in studies ofsurface interactions between The surface coverage rg
depends on the potential.
various adsorbates and to obtain new information on Kautek et al. [110] concluded that species in the rigid
the formation of surface complexes. The surface modifi- outer and inner Helmholtz layer can be treated as rigidly
cation of the sensor electrodes makes them especially coupled masses, whereas ions spread out into the diffuse
attractive thanks to the increased selectivity by a better double layer or solvent structures contribute according
control of adsorption by a proper selection of the elec- to a change of viscosity and density in part of the decay
trode potential. Uchida et al. [107] performed EQCN layer of the acoustic wave. The latter contributions are
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 621

characterized by

~I
cu
q=O
auq=O

(24) lAI! AlI

-0.5 +0.5
Kautek et al. [110] also reported that cations and anions
with hydration shells of various extents contribute to the
surface mass loading depending on their surface density,
bonding state, and position in the outer or inner
Helmholtz plane.
Specifically adsorbed anions, like sulfate and
hydroxide, reside in the inner Helmholtz plane and have
direct bonding contact to the substrate. They are
stripped of almost half of their original solvation shell
and function as counter charge carriers analogously to
completely solvated anions in the outer Helmholtz
plane. Their saturation coverage is limited by lateral
electrostatic repulsion and steric crowding by their
solvation shells. When anions adsorb specifically and
form neutral ion pairs with alkali metal cations, electro-
static repulsion and solvation shell crowding is
:<t
minimized. They contribute much more strongly to the
double-layer loading than specifically adsorbed
partially hydrated ions and nonspecifically attracted Figure 22 Current and frequency vs. potential curves for
species. According to Kautek et al. [IlO] the reason is Au-EQCN film in 0.5 M KOH. Scan rate: 0.02 V S-I. (From
that ion pairs can attain higher surface excess because Ref. 1l0.)
they exhibit no net lateral electrostatic repulsion and
practically no hydration shell crowding. The
double-layer region of gold in 0.5 M KOH is presented Tsionsky et al. [Il2, II 3] studied the double-layer region
\ I
in Fig. 22. They reported frequency difference ofgold electrode in 0.1 M HCl0 4, KN03, and KOH using
MOl = -15 Hz and mass difference t1mOl = +84 ng, EQCN method. The authors observed frequency shifts
respectively, in a 0.5 M KOH solution. This difference even though the ions of these electrolytes are not specifi-
was measured between the potential range from cally adsorbed and there is no faradaic reaction that
E = -0.77 V to E = +0.39 V The frequency started could lead to the formation of adsorbed species through
decreasing when scanning in the negative direction. t1f charge transfer. Tsionsky et al. [Il2] developed a model
1 steeply fell around -0.20 V, which has been described in which they assumed that the liquid in a thin layer near

t
as the PZC on a cathodic scan. The important con-
clusion can be drawn from this experiment, that EQCN
can be used for PZC determination.
The studies of Kautek et al. [14,IlO] shows that
~I
sensitive, electrochemical, phase-stabilized quartz
·1:.··.··
the surface has a higher viscosity, because of the high
concentration of ions and the high electrical field in this
region.
Seo and Ueno [Il4] investigated the changes in surface
energy ofa gold electrode in deaerated 1 M NaCI0 4 sol-

"' nanobalance measurements can give insight into ion
adsorption, solvation, hydrogen bonding, and water
clustering at charged surfaces.
Hepel and Tewksbury [Ill] studied the electrical
double-layer region of optically polished gold in 0.1 M
NaF, KF, RbF, and CsF solutions in the absence and
with addition of specifically adsorbing anions SO~-,
OH-, Cl-, and Be. They concluded that EQCN can
be used to investigate the electrical double-layer pheno-
mena on metal electrodes.
utions with and without iodide ions using the potentially
modulated piezoelectric gold electrode. These exper-
iments allowed them to evaluate the potential of elec-
trocapillary maximum or PZC of a gold electrode. They
also found that the addition of iodide ions shifted the
PZC significantly in a negative direction, indicating the
strong adsorption of iodide ions. The surface excess of
iodide ions, t1r, was evaluated and used to calculate the
electrosorption valency, y = -0.84 for 1- near the PZC
[Il4].
622 Hepel

E. In Situ Compositional Analysis of Thin ~ ,

Semiconductor Films
(a) a
a
Electrodeposition is a widely used method for preparing c
c
thin films of CdS, CdSe, CdTe, and other sem- c
20 c
iconductors. Contamination of the semiconductor film c c
with side products has deleterious effects by creating Cl
c
c
surface states with energy in the band gap of the :::l
c
D

semiconductor. Therefore, there is a need for the in situ E D

D
10 D
compositional analysis of semiconductor films. c
D
Rajeshwar and coworkers [115-117] developed a new a
D
electroanalytical protocol for the in situ compositional a
analysis of semiconductor thin films based on anodic
stripping voltammetry in conjunction with EQCN. The o I · • • I • •. • , • • , • •I • '• I
i
• • t • I• Ai • t I
o 100 200 300 400 500 600
mass loss associated with the stepwise anodic stripping
of the thin film constituents was used by these authors tIs
for their selective quantitation. Selective monitoring of 100 1'----------------------
various thin film constituents was possible via control D D D D D D D D D D

of the stripping potential, which gives a clear advantage (b)

D D
80 D D
relative to other ex situ techniques that have been tra- D
D
ditionally used for semiconductor material analysis. D D

However, the contribution from the surface roughness t:- 60

1 D D

to the total frequency change caused by deposition .!!

Oi
stripping has not been taken into account in their a:
method. Next, the same authors proposed a modified .
o
40
••
procedure for real-time monitoring of the film compo- :0 • •••
sition during its growth. This new procedure combines 20 ••
coulometry with EQCN experiments. The authors ••
pointed out two advantages of the new protocol: the • • • • • • • • • • I

compositional profile of the thin film and its evaluation o I , i i i ' i i i ' , i i

o 100 200 300 400 500 600

with time was monitored in real time and the combined
EQCN -coulometry approach did not require a
calibration.
For CdSe films formed at E = -0.60 V, SeQ and CdSe
are the only two possible components in the film. Myung
et al. [117] derived the following two equations:
WT(t) = WSe(t) + WCdse(t) (25)
QT(t) = 6F WCdse(t)/ M Cdse + 4F Wse(t)/ M Se (26)
tis
Figure 23 (a) The film component mass, WCdSe(t) and W,,(t),
as a function of time for the film electrodeposited at
E= -0.55 V from the solution 0.5 M CdS0 4+5 mM
Se02 + 0.1 M Na2S04. Deposition time: 10 min. (b) The molar
ratio of the film as a function of time computed from the data
in (a). D, CdSe; +, Se. (From Ref.ll7.)
\,

The left hand sides ofEqs. (25) and (26) contain the exper-
imentally measured parameters WT(t) and QT(t) from
EQCN and coulometry, respectively. On the right hand
sides, the W, are the masses of a given component in the
film at time t, M CdSe and M Se are the molar masses, F is
the Faraday constant, and the numbers 6 and 4 in Eq. (26)
correspond to the electron stoichiometry of CdSe (6e-)
and SeQ formation (4e-), respectively. Equations (25)
and (26) contain two unknowns, WCdSe(t) and Wse(t),
which may be solved as functions of time.
Figure 23 contains the compositional profiles of the
film deposited through 10 min at E = -0.55 V from the
solution containing 0.5 CdS0 4+5 mM Se02+0.l M
Na2S04. From Fig. 23 it is evident that CdSe content of
the film increases monotonically but the free selenium,
SeQ, shows a "peaking" behavior.
l
Myung et al. [118] also developed an in situ
photoelectrochemical EQCN to use as a diagnostic probe
of photoelectrode corrosion and stabilization. As a
model system they studied n-CdSe/SO~-. In their
method, the working electrode illumination is coupled
with mass, photocurrent. and charge measurements.
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance
F. Conductive Polymers
Much has been published worldwide dealing with differ-
ent aspects of conductive polymers. Among conductive
polymers, polypyrrole (PPy) and polyaniline have been
of great interest because of their good stability and easy
preparation by electropolymerization. In this chapter,
only selected articles in which EQCN was used to study
kinetics of polypyrrole electropolymerization, ion
dynamics, doping level, and effects of different dopants
in polypyrrole are discussed [119-145].
The electropolymerization reaction of pyrrole is
complex and is affected by many variables, including
electrode material, potential, solvent, temperature,
additives, and even the type of anions used during
the electropolymerization. It was noticed by many
researchers that the conductivity and mechanical proper-
ties of PPy films are very dependent on the nature of the
anions in the polymerization solution [119-127]. A gen-
eral feature ofelectronically conducting polymers is that
their redox transformation between the insulating and
conducting forms is accompanied by ion movements
between the solution and the polymeric film necessary
for preserving the electroneutrality of the layer. A very
elegant method for measuring such phenomena is
EQCN. This very sensitive method gives information on
the deposition mechanism during electropolymerization
and on the amount of ion insertion during the doping
process.
Baker and Reynolds [128] studied the anodic
e1ectropolymerization of pyrrole and concurrent depo-
sition of PPy onto gold in acetonitrile and propyl-
ene carbonate using tetraethylammonium tosylate,
tetrabutylammonium tetrafluoroborate, and lithium
t perchlorate. Measured charge and mass were used to
monitor the efficiency of the polymerization/deposition
as a function of a film thickness and electrodeposition
rate. The authors concluded that for their thin PPy films
t there was very strong evidence for adherence to the rigid
film behavior. Baker and Reynolds [128] also studied the
effect of pyrrole concentration on the polymerization
efficiency. Their work demonstrated that the early stages
of film formation are affected by the solubility of the
oligomers formed and that the efficiency of the
electropolymerization is electrolyte dependent. The
electropolymerization process exhibits second-order
reaction kinetics and its rate is limited by the radical
coupling step.
Otero et al. [129] studied the kinetics of the PPy
e1ectrogeneration in acetonitrile solutions. They found
that water content had a great influence on the kinetics
ofthe electropolymerization. The authors concluded that
623
under polymerization conditions in the presence ofwater
impurities in acetonitrile, an oxide layer is formed on
the metal. The oxide layer seems to behave like a catalyst:
the greater the water content, the more PPy is produced.
The EQCN technique is a very unique and convenient
method to study ion dynamics in conductive polymer
films. In the simplest case the redox switching of neutral
PPy to its cationic form involves the uptake of anions.
These polymers may exhibit anion exchange character.
In contrast to films containing small mobile anions, some
polymer films have been reported to act as cation
exchange membranes [122,126,130-135]. In composite
PPy films prepared in the presence of large anions, the
charge compensation involves incorporation of cations
because the large anions are not easily released from the
polymer matrix after being entrapped in it during the
electropolymerization process.
Topart and Noel [136] determined the doping level, d,
of PPy film doped with several counter anions
tetrafluoroborate BF4 (TFB), tosylate (TOS), dodecyl
sulfate (DDS), and cyclodextrin (CYC 14 -). The doping
level, d, was calculated from the slopes of Ama vs. Qa
curves presented in Fig. 24. The curves in Fig. 24 are
linear, which indicates that the Sauerbrey equation is
valid in this charge range. Using this procedure, the dop-
ing level can be calculated under the conditions that the
contribution of solvent to mass changes is negligible.
The same authors reported that the doping level obtained
300
250
f';l
e
\) 200
-e..
OIl
::1.
150
<I
100
• PPy-DDS
o PPy-TOS
50
o PPy-CYC
• PPy-TFB ~
0
0 100 200 300 400 500 600
Figure 24 EQCN mass Ama vs. charge Qa consumed during
the electropolymerization at 0.8 V of PPy films doped with
TFB, TOS, DDS, and CYC counteranions. A line corresponds
to several hundred data points taken dynamically. Only a
few data points are highlighted with icons. (From Ref. 136.)
624
Table 1 Influence ofAnion on EQCN Determination ofDop-
ing Level ofPPy Films Grown at 0.8 V
equiv molar mass ofanion (~maF)Qa
M~nion (g/mol) (g mol-I) Doping level, d
TFB 87 43.56 0.51
TOS 171 52.77 0.34
DDS 265 59.22 0.26
CYC 14 - 2200/14 = 157.1 44.58 0.21
for PPy-TOS (medium size anion) agrees well with that
found by elemental analysis [137]. The various doping
levels, d, calculated from data in Fig. 24 are presented in
Table 1. The size of anions increases in the following
sequence: TFB < TOS < DDS < Cye. For large counter
anions like DDS and CYC, a lower value of d was
obtained than generally found for large incorporated ani-
ons [136]. For PPy-TFB, however, the doping level
obtained was much greater than expected. This was
attributed to solvent incorporation in the pores of the
polymer that contributes to the measured mass and
consequently results in an erroneous determination of
the doping level [128]. Topart and Noel [136] also investi-
gated possible stress-related effects on insertion of coun-
ter anions and found that no stress effects were detected
for their PPy-TOS and PPy-TFB films.
Topart and Noel [136] measured the impedance of
quartz resonators to monitor in situ viscoelastic phenom-
ena in PPy films during electropolymerization. For that
purpose, they measured simultaneously the damping
resistance, charge, and frequency. From these data they
[136] found that films doped with medium size (TOS)
and large (DDS, CYC) counter anions exhibited a small
increase of resistance up to a charge ofca. 0.4 C cm -2 or
up to a frequency shift of 10 kHz. The PPy-TOS film
appeared to have the most elastic behavior. For these
films, the doping level can be calculated based on the pro-
cedure presented in Fig. 24 because in this charge range
the contribution of solvent to mass changes is negligible.
The relative changes in resistance for PPy-TOS film have
not exceeded 2 %. It was found that in the case of a small
counter anion, BF4 -, resonance resistance changes
significantly, because these small anions drag solvent as
they enter the polymer matrix causing swelling ofthe film.
This liquid, "rigidly" coupled in the film, causes an
erroneous determination of the doping level in the case
of small anions. Topart and Noel [136] concluded that
the porosity of deposited polypyrrole films decreased
with increasing dopant anion size and decreasing doping
level and that their thin PPy-TOS and PPy-TFB films
behaved as rigid films.
Hepel
Muramatsu et al. [138] used a similar imped-
ance-EQCN method to study an in situ micro-
rheology of PPy films deposited on 9-MHz AT-cut
quartz crystals by cyclic voltammetry and by a
galvanostatic method from KN03 solutions. For thin
films, small changes in the resonant resistance were
observed. For thicker films (N) 10,000 Hz), the res-
onant resistance was changed in the range of 100-
600 Q. They observed swelling of the film obtained
under constant current conditions with i = 6 mA cm- 2 .
The EQCN technique has also been used to diagnose
the type of ion dynamics in PPy films doped with other
large anions such as poly(vinylsulfonate) [126],
hydroquinone, anthraquinone 2-sulfonate [130], melanin
[122,132,133], flavin adenine dinucleotide (FAD) [133],
and heparin [135].
The concentration of the fixed positive sites (PPy+) in
the PPy film is electrochemically controllable by
adjusting the potential. Thus, it is possible to prepare a
PPy film of such a concentration of incorporated anions
that by varying the electrode potential, films with
dominating anion dynamics, dominating cation
dynamics, or mixed ion dynamics are obtained [130].
A PPy/melanin film with "mixed ion dynamics" is
presented in Fig. 25 [130].
The EQCN is an excellent method ofchoice to test the
type of ion dynamics in polymer films. By mixed ion
dynamics, it is meant that it depends on the potential
range whether the electrolyte cations or the electrolyte
anions are exchanged [130]. For the PPy/melanin film
presented in Fig. 25, at potentials more negative than
-200 mY, cations are exchanged and in the same film at
potentials more positive than 0 mVanions are exchanged
[130]. These composite films can be "switched" between
a cation-exchanger state and an anion-exchanger state
by varying the potential. It was also reported that
PPy/melanin and other composite PPy films can be
switched between a cation-exchanger state and an
anion-exchanger state by varying the pH of the solution
[130]. Use of the EQCN technique allowed the author to
control the composition ofprepared films and to evaluate
their relative doping level [130]. Since the effective-
ness of doping is based on the relative number of
negative charges introduced by the dopant, the relative
doping level can be best determined by analyzing
frequency-charge or mass-charge characteristics. The
position of the minimum of the fE characteristics in
Fig. 25a (or fQ, Fig. 25b) determines the value of the
I
relative doping level XD, according to the formula [130]
XD = qcatlQ = (QRed - QN)/(QRed - Qo,) (27)
I
l
I
I,
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance 625

100

80 150

60 100
."
:u
<:J. 40 ... ::-:_---------- ~
......... 50 cm
z:
~ 20 o
z
W
o -<
cm
0::
0:: 0 o
::J :u
u -50
-20 ~
III
-100 !"
-40 ~

-150
-60

':--::-::::--~=_=_-____=:'=_--_:'=_::__-~.,,---------L---L---..L::::I - 200
-1000 -800 -600 -400 -200 0 200 400
POTENTIAL, mV vs. SeE
(a)

Ul
D
z
-<
:r:
u
'"
'"
«
::E

QRed
tQN 1 Qo.

CHARGE -
(b)
t
Figure 25 (a) Linear potential scan characteristics of the current (solid line) and frequency (dashed line) vs. potential at
PPy/melanin-modified gold EQCN electrode in an aqueous deoxygenated 0.1 M NaCl solution. Atriangular waveform was used with
a scan rate of 50 mV S-I. (From Ref. 130.) (b) Schematic diagram of the mass change vs. charge for doped PPy films with mixed
ion-dynamics. (From Ref. 130.)

where qcat is the charge of counter cations in a fully
reduced PPy film, QRed, QN, and Qox are the charges used
to obtain a fully reduced, neutral, and fully oxidized PPy
1
film, respectively, starting from either a fully oxidized or
fully reduced PPy state. The neutral state corresponds to
the minimum on thefE characteristic and can be readily
determined. For accurate determination, the potential
scan rate should be minimized to reduce the hysteresis
on thefvs. E characteristics. The mean value of Xo from
the positive- and negative-going potential scans can also
be calculated. The composite PPy films reported in that
paper had Xo close to 0.5. referred to the PPy oxidized
state at E = +400 mV vs. SCE, i.e., to the upper limit of
the potential window of all characteristics recorded. The
relative doping level Xo can be controlled by changing
the electropolymerization conditions. It was controlled
by varying the dopant concentration in the solution used
for PPy deposition [130].
Use of the EQCN to study controlled release of
neuroleptic drugs upon potential step application was
also reported [132-134]. The authors concluded that
the EQCN technique is a convenient in situ method for
controlled electroincorporation/electrorelease studies
[132-134,139].

1
626
The idea of studying the incorporation of metal
nanoparticles into a matrix of conductive polymer film
using the EQCN was explored by Bose and Rajeshwar
[140] and Hepel [141]. In these articles, two different pro-
cedures for the preparation of PPy films containing
nanodispersed platinum particles are described. Bose
and Rajeshwar [140] reported that their PPy/PtO films
exhibited high catalytic activity toward the hydrogen evol-
ution reaction and O 2 reduction. Hepel [141] tested
PPy/PtO nanoparticles films for the electrocatalytic
oxidation of methanol. In these articles, procedures for
calculating doping levels of composite films are
described.
Incorporation of semiconductor particles into con-
ductive polymer was also reported. The n-CdS particles
were synthesized in situ in PPy film [131], and formation
of these particles was monitored by measuring the fre-
quency shift using EQCN technique.
The electrodeposition ofseveral metals such as Ag, Ni,
Cd, and Cu on polypyrrole [144,145] or inside a
composite PPy matrix was investigated [142-145], and
the amount of deposited metal was monitored in situ by
measuring the EQCN frequency changes. The effect of
the composition of PPy substrate on the
e1ectrodeposition ofcopper and nickel was also reported
[145].
G. Other Applications
Many interesting examples of EQCN applications and
other details about EQCN can be found in a number of
review articles written by Schumacher [56], Buttry [146],
Ward [147], Deakin and Buttry [148], and Buttry and
Ward [149].
Hillman and coworkers [150,151] made a significant
contribution in presenting a novel analysis of EQCN
data for electroactive polymer films. Their model
encompasses a variety ofobserved phenomena, including
"break-in," charge- and -mass-trapping, structural evol-
ution with redox cycling, and kinetic decoupling of ion
and solvent transfer. They analyzed transport processes
that occurred during redox cycling of thin films of
po1y(thionine) [152-156], poly(vinylferrocene) [157], and
poly(thiopene) [158].
Polyaniline [159-167] and other polymers were also
extensively investigated by many researchers using the
EQCN technique. Electrooxidation ofmethanol on plati-
num doped polyaniline electrodes [168] and the pho-
toreduction of polyaniline films containing Ti0 2
particles in methanol solution [169] have also been
studied using EQCN technique.
Hepel
Other applications of EQCN not covered in this
chapter include metal plating [142-145], corrosion
studies [170-172], molecular recognition [173], elastic
softening of thin films [174], liquid crystals [175,176],
hydration numbers and hydrogels [177-179], clays [180],
determination of contact angles, surface tension,
wetting velocities [181,182], phase transitions of
Langmuir - Blodgett films [183,184], self-assembling
monolayers [185-187], dissolution of the anisotropic
conductors [188], and DNA hybridization [189]. Use of
dual quartz crystal microbalance compensation using a
submerged reference crystal was reported by
Bruckenstein et al. [190] Applications of piezoelectric
sensors for immunoassay were reviewed by Guilbault
and coworkers [191,192] and SkliLdal et al. [193].
Evident from this chapter, EQCN applications are
not only limited to monitoring mass changes at
the electrode- solution interface. Characterization of
solid -liquid interfacial properties such as roughness,
rheology, stress, solvophilicity, viscoelastic effects of
films, viscosity of solution, and dissipation factor D can
also be obtained. Information about competitive
adsorption, adsorption isotherms, surface interactions,
PZC, double-layer structure, ligand release, mechanism
of UPD, and mechanism of interfacial reactions can be
provided.
Wealth ofinformation about conductive polymers and
other thin films including ion dynamics, solvent
transport, solvent swelling, kinetics of polymerization,
etc. can be obtained. In addition, evaluation oflatera1 dis-
tribution of mass can also be investigated. The scanning
electrode quartz crystal analysis as a technique for map-
ping distribution of mass and measuring interfacial
rheology was described by Oyama et al. [194]. It was
l
found that the qualitative mapping of the mass distri-
bution is possible with a lateral resolution of 1-2 mm.
Viscoelastic properties of the load on the quartz surface
were also measured qualitatively by the same authors.
The present trend is to implement other
surface-sensitive in situ techniques that can be used along
with EQCN. Combination of EQCN with impedance,
capacitance, or resistance was already discussed. A
powerful combination is EQCN and scanning tunneling ~
microscopy (STM). Wang et al. [195] demonstrated the
feasibility of combined STM - EQCN experiments for
studies ofadsorption and desorption of FAD.
The design of a combined scanning electrochemi-
cal microscope and quartz crystal microbalance
(SECM - EQCN) with separate potential control of the
tip and substrate was described by Cliffel and Bard [196].
The SECM - EQCN was used to study etching of a thin
Ag layer. c.
 Electrode-Solution Interface Studied with Electrochemical Quartz Crystal Nanobalance
A new technique of absorption spectroelectro-
chemistry at grazing incidence in combination with
EQCM was reported by Xie et a1. [197]. It has been
used to investigate the electrochemical process of
Cu(II) deposition and stripping in an ammonia buffer.
Simultaneous UV-VIS spectroelectrochemical and
EQCN measurements were performed by Shimazu et
a1. [198] and Mo et a1. [47]. The combination of infrared
spectroscopy, Raman spectroscopy, EXAFS, and AFM
with EQCN is also advantageous. EQCN experiments
with controlled hydrodynamics are also feasible. A
rotating electrochemical quartz crystal microbalance
was designed by Marlot and Vedel [199] and was used to
study the electrode-position of copper-selenium com-
pounds onto gold electrode. EQCN was adapted by
Arkam et a1. [200] to a submerged impinging jet cell to
carry out in situ mass measurements in well-defined
flowing electrolyte conditions. They tested performance
of this new device for cathodic efficiency evaluation of
the nickel electrodeposition.
EQCN is now used in many laboratories as a routine
tool that is complementary to other methods. When it is
properly used it can provide many details on interfacial
phenomena occurring at the electrode-solution inter-
face that was previously unattainable. Many new exciting
applications of EQCN will certainly emerge in near
future.
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 35
Electrochemical Properties of Carbon Surfaces
Richard L. McCreery
Ohio State University. Columbus. Ohio
ABSTRACT
The electrochemical behavior of diamond and graphitic
carbon materials are summarized, with particular atten-
tion toward electron transfer reactivity. Carbon elec-
trodes are considered with respect to three major
variables that affect their electrochemical performance:
electronic properties, surface cleanliness, and catalytic
sites. The electronic properties vary significantly for
ordered graphite, glassy carbon, and boron-doped
diamond, and the density of electronic states can have a
significant effect on electron transfer rates. In particular,
ordered graphite exhibits outer sphere electron transfer
rates that are two to four orders of magnitude lower that
those on glassy carbon. Surface cleanliness is a strong
function of surface preparation, particularly polishing,
heat treatment, and anodization. For some outer sphere
systems such as Ru(NH 3 )t 2/+ 3, surface films have small
effects on electron transfer rate because the electron can
tunnel through thin films. For other systems, however, a
surface catalytic site is necessary and adventitious sur-
face films can dramatically decrease electron transfer
rates. Surface oxides are an additional factor that affects
reactivity, and methods to reduce or control surface oxide
coverage are discussed. Oxide-free glassy carbon and
closely related hydrogen terminated GC show quite differ-
ent behavior toward those redox systems that are affected
by surface functional groups. Finally, boron-doped
diamond is discussed as a recent addition to the collec-
tion of carbon electrode materials with possible funda-
mental importance. Diamond represents an electrically
conducting material with a very unreactive surface, and
this property may be useful for analytical and electro-
synthetic applications.
631
j
~ ...
I. INTRODUCTION
Carbon materials* differ from metals in several signifi-
cant properties of fundamental interest to electrochemi-
cal applications [1-4]. These differences can be used to
particular advantage with carbon electrodes, but they
can also result in special problems with reproducibility
and surface preparation. The often unique properties of
carbon as an electrode material provide a framework for
this chapter, and a brief overview is useful as an
introduction. First, carbon has varied and often aniso-
tropic electronic properties, ranging from essentially
metallic character in disordered graphite or glassy
carbon to semimetallic behavior in highly ordered
graphite. Not only can carbon have substantially different
electronic properties from metals, but different types of
carbon can differ from each other, leading to variations
in interfacial capacitance, adsorption, and electron
transfer kinetics. Second, carbon surfaces adsorb a wide
range of materials, hence the use of activated carbon as
commercial adsorbent. This adsorption can be
nonspecific physisorption or specific chemisorption to
particular surface functional groups. Third, carbon
exhibits richer and more complex surface chemistry than
metals, with a variety of functional groups and surface
oxides. Although carbon surfaces oxidize spontaneously
in air or with an applied potential, oxide formation is gen-
erally irreversible. Fourth, carbon electrodes are capable
* "Carbon" refers to the Sp2 graphitic allotrope unless stated
otherwise. Doped diamond and related Sp3 hybridized
materials are discussed briefly in a separate section.
632 McCreery

of forming strong covalent bonds with a wide variety of
surface modifiers, thus providing an attractive sub-
strate for fabricating chemically modified electrodes.
Fifth, although carbon surfaces may be oxidized
electrochemically, these reactions are slow compared
with metals, and carbon surfaces are relatively inert in
electrochemical processes, yielding a wide useful poten-
tial window. Taken as a whole, these properties make
carbon unique as an electrode material, with electronic
properties similar to a metal or semimetal but surface
chemistry derived from the wide diversity of organic
chemistry.
The attractive electrochemical properties of carbon
materials have been exploited in a variety of important
applications, but they often come with a fairly steep price.
The propensity of carbon for adsorption yields surfaces
with a variety of unintentional adsorbates, usually of
unknown identity. Many electrochemical applications
depend on the presence of particular surface oxides, but
oxide coverage is often difficult to control or stabilize.
Surface oxides are difficult to remove from carbon once
present, and a carbon surface cannot be annealed like a
metal. The consequence of these properties is a very
strong dependence of carbon surface structure and
behavior on surface history [5-13]. Not only is a wide
range ofcarbon materials available and in common use,
but there is also a huge array of pretreatment procedures
practiced by different labs and users. So carbon electrode
surfaces vary greatly from lab to lab and day to day, com-
plicating attempts to relate surface structure and behav-
IOr.
Because of the complicating effects of surface
history, the objective of exploiting carbon's unusual
properties for electrochemical applications becomes
inseparable from the requirement for control of surface
II. CARBON ELECTRODE MATERIALS
The graphitic allotrope ofcarbon continues to dominate
electrochemical applications, despite the recent intro-
duction of fullerenes and conducting diamond.
Fullerenes are electroactive and have been studied exten-
sively by electrochemists [14-17], but they are not in gen-
eral use as electrode materials and are not discussed
further. With the advent of vapor deposition techniques
for producing synthetic diamond films, it is possible to
prepare boron-doped diamond that is sufficiently con-
ductive for electrochemistry [18]. The term "graphite" is
used somewhat generically and often incorrectly, but it
generally refers to a Sp2 hybridized microstructure with
parallel sheets of hexagonal rings, as in Fig. 1. Strictly
speaking, graphite is more precisely defined, as a
material with interplanar spacing of 3.354 A and
microcrystallites with an in-plane dimension (La) of at
least a few tens ofangstroms. The term "graphitic" is used
more broadly than graphite and includes a variety
---+- +- L c
HOPG: Edge Plane
c-axis
t
La
~ Basal Plane

structure. As shown later, different redox systems show

varying sensitivity to the variable properties of carbon Glassy carbon:
and the irreproducibility of surface pretreatment. Based
on this preamble, the chapter is divided into three main
sections. Initially, the structure and properties of
carbon materials are discussed, with emphasis on elec-
trochemical consequences. Then, methods for pre-
paring and modifYing reproducible carbon surfaces
are addressed. Finally, a classification of redox systems
is outlined, based on the effects of carbon surface
structure on electrochemical behavior. Throughout the
discussion, it is useful to keep in mind the properties
of the carbon that affect electrochemical behavior:
substrate structure, surface oxides, and physisorbed
impurities. The overall objective is to understand how Figure 1 Schematic structures of HOPG and glassy carbon.
these structural factors affect electron transfer, elec- La and L c denote coherence lengths along in plane (a-axis) and
trocatalysis, stability, etc. out ofplane (c-axis) axes.
Electrochemical Properties of Carbon Surfaces 633

Table 1 Physical Properties of Some Carbon Materials

Resistivity
La (A) (ohm-em) Density (glee)

Polycrystalline graphite ~300 10- 3 1.8

HOPG >10 4 4 x 10- 5 (il-axis) 2.26
0.17 (c-axis)
Pyrolytic graphite ~1000 2.18
Glassy carbon ~50 4xlO- 3 1.5
Carbon fiber >100 ~1O-3 1.8
Carbon black ~20 ~0.5 1.3-2.0
B-doped diamond [18] N.A. 0.1"
Diamond N.A. >10 8 3.51

a For I 0;;, boron doping.

N.A., Not applicable.
Source: Ref. 3.

Table 2 Electrochemical Properties of HOPG and Glassy Carbon

Capacitance" r AQDS b kO for Fe(CN)63/~4 kG for Ru(NH 3 )t 3/+2

(IlF/cm 2 ) (pmol/cm 2 ) (cm/s)C (cm/s)C

Basal plane
Cleaved d 0.6-7 <1-64 10- 5 _ 10- 3 10- 3 _ 10- 2
Low defect <I <I <10- 5 9xlO- 4
Edge plane ~70 >200 ~O.l

Glassy carbon
Polished ~33 186 0.002-0.05 0.24
Laser activated ~34 336 >0.5 >0.4

a Observed capacitance per unit ofgeometric area (CO).

b Saturation coverage of anthraquinone 2,6 disulfonate in I M HCI0 4•
c In 1 M KCI. kO will be used to designate the heterogeneous electron transfer rate constant at the formal potential, £,'. Many discussions
use the symbol k s.h .
d Observations depend greatly on defect density.

of materials with layers of hexagonal sheets of carbon
atoms but not necessarily 3.354 A spacing or large
microcrystallites. Glassy carbons and carbon fibers are
graphitic, but certainly not "graphite." Some graphitic
materials used as electrodes are listed in Table 1, along
with some of their physical properties.
A. Highly Ordered Pyrolytic Graphite
Highly ordered pyrolytic graphite (HOPG) is a special
case of graphite materials, analogous to a single crystal
of a metal. The graphite sheets are oriented on a macro-
scopic (i.e., centimeter) scale, with La> 1 ,urn. The physi-
cal properties and many electrochemical properties are
highly anisotropic as a result [3,19]. Table 2 lists several
"edge" surfaces. Because the electrochemical properties
of graphitic edges differ so much from the basal plane,
the observed basal plane behavior depends strongly on
the presence of defects. Defects such as pits, step edges,
and crevices have been observed on HOPG basal plane
by scanning tunneling microscopy (STM) and scanning
electron microscopy (SEM), and their density can be
reduced but not eliminated [7,19]. To appreciate the quan-
titative consequences of defects, consider an electron
transfer reaction that requires an edge plane site, so that
k~dge = 10- 1 cm/s and kbasal = 10-6 cm/s. * If the
observed rate for a slightly defective basel plane is a
*k is used to designate the heterogeneous electron transfer rate
O

electrochemical observations for HOPG, showing the constant at the formal potential, EO'. Many discussions use the
large difference between the "basal" (hexagonal) and symbol ks.h.
634
weighted average of these rates, with IJ edge being the
fractional coverage ofedge plane, the observed k is given
O
by [20]
k~bs = IJedge k;dge + (1 - IJedge)kbasal
For these hypothetical parameters, a 1% defect density
(IJedge=O.OI) yields a 10 3 increase in observed rate over
the true basal plane value. For this reason, macroscopic
electrochemical observations of kG, capacitance, and
adsorption are strongly dependent on HOPG
preparation. Furthermore, HOPG is quite fragile and it
is easy to unwittingly introduce defects during handling.
In one STM study of cleaved HOPG, a typical HOPG
basal plane surface had an average IJedge of 0.01 [19].
1. Surface Electrochemical Properties of HOPG
It has been recognized for some time that the basal plane
of HOPG exhibits anomalously low capacitance com-
pared with the edge plane [21]. Without special effort to
reduce defects, the observed capacitance (CO) for HOPG
basal plane is 2-7 ,uF/cm2 in 1.0 M KCI, compared with
30-70,uF/cm 2 for glassy carbon and ~70 ,uF/cm2 for
HOPG edge plane. Co for selected low defect HOPG
basal plane surfaces is <1 ,uF/cm2 whereas intentionally
defective basal plane can yield a CO of > 7 ,uF/cm2 [7].
The unusually low capacitance of basal plane HOPG is
a clue to its electronic properties and has been attributed
to its semimetal character [21,22]. A low density of elec-
tronic states near the Fermi level results in a space charge
capacitance that is in series with and smaller than the
double-layer capacitance associated with the electrolyte.
It is generally accepted that defects fill in this low density
of states, thus increasing the observed capacitance on
edge plane or on defective basal plane [23].
Adsorption to basal plane HOPG is also strongly
affected by defects and has been investigated in detail for
anthraquinone 2,6 disulfonate (AQDS) [l9]. On a low
defect surface (as judged by STM), AQDS adsorption is
undetectable by voltammetry, whereas near-monolayer
adsorption is observed on defective basal plane, GC, or
HOPG edge plane (Table 2). A mechanism involving
nonspecific physisorption to local dipoles at defects has
been proposed, because the amount of AQDS adsorbed
is significantly larger than the defect area measured by
STM [19].
Electron transfer rate constants (k for 18 inorganic
O
)
redox systems were significantly lower on basal plane
HOPG than on GC [23]. GC has similar electrochemical
properties to edge plane HOPG and is a more reproduc-
ible model for edge plane behavior. Observed rate con-
stants were one to three orders of magnitude lower on
McCreery
low defect HOPG basal plane than on GC, much too large
an effect to be attributed to surface roughness. This rate
difference did not correlate with the £0 or charge of the
redox system, but there was a weak correlation between
(1) kG for either surface and the homogenous self-exchange
electron transfer rate. The slow rates of electron transfer
on basal plane HOPG have been attributed to its
semimetal character, particularly the low density of elec-
tronic states [1,23]. By analogy to semiconductor
electrodes, rates for electron transfer are depressed if the
density ofelectronic states near the £0 ofthe redox system
is low. This low density region covers a fairly wide poten-
tial range for HOPG, wide enough to include most aque-
ous redox systems.
Although the semimetal characteristics of HOPG are
offundamental interest, they are not ofextensive practical
value for electrochemical applications. Significant care
must be taken to keep the defect density low, and it is easy
for a given observation to depend more on defects than
true basal plane. The basal plane is easily damaged, and
the defect density is usually quite variable. As we will see
later, most carbon electrode materials are so "defective"
in this context that the semimetal character of HOPG is
completely washed out.
B. Pyrolytic Graphite
Pyrolytic graphite (PG) is much less expensive and more
common than HOPG and has a longer history in electro-
chemical applications. Although it has smaller
crystallites than HOPG andis much more defective, it still
retains the orientation of graphitic planes, and bulk PG
has obvious basal and edge surfaces. Because the defect
density is so much higher than HOPG, PG lacks the low
capacitance and semimetal character, and electron
transfer to PG basal plane is faster than that to HOPG.
Edge plane pyrolytic graphite (EPG) is a popular elec-
trode material, in which a small block of PG is mounted
such that the edge plane is exposed to the solution and
may be polished, derivatized, etc. The EPG electrode is
reactive toward adsorption, has many oxide functional
groups, and is fairly reproducible in its electrochemical
properties. The EPG surface is generally rough on a
microscopic sale, leading to high capacitance and micro-
scopic surface area.
c. Polycrystalline Graphite
Polycrystalline graphite (PCG) in the form of powders,
rods, and a variety of preformed shapes is the material
most often referred to as graphite. The crystallites retain
the layered anisotropic graphite structure, but crystallites
are randomly oriented. On a scale larger than the
Electrochemical Properties of Carbon Surfaces
microcrystallite size (typically >100 A), PCG's proper-
ties are isotropic. Depending on manufacturer and grade,
the density, porosity, and conductivity of PCG vary. Of
particular importance is the heat treatment temperature
(typically >2000°C), which has a significant effect on
conductivity. Most PCG materials are sufficiently porous
to permit incursion of the solvent into the solid, and
methods to control such permeation include the addition
of wax or organic liquid to block pores in solid PCG.
Alternatively, powdered PCG may be mixed with organic
liquids to form the widely used carbon paste [3,4].
D. Glassy Carbon
Glassy carbon (GC) is one of the most popular carbon
electrode materials because it is polishable, mechanically
strong, and nonporous to solvent. GC is made by heat
treating an organic polymer, often polyacrylonitrile or
phenolic resin. Heat treatment is slow (several days) and
under high pressure, resulting in expulsion of noncarbon
atoms and formation of the ribbon like structure in
Fig. 1. The properties are somewhat dependent on final
heat treatment temperature, with designations such
as "GC-20"and "GC-30" indicating final heat treatment
at 2000 and 3000°C, respectively [3,4].
E. Diamond Electrodes
Vapor deposition techniques developed for fabricating
thin films of Sp3 carbon can be adapted to making
diamond electrode surfaces. Diamond itself has a
resistivity much too high for electrochemistry, but its con-
ductivity may be increased by heavily doping it with boron
[18,24,25]. A boron source such as B203 or BN is present
during diamond film deposition, and the final boron con-
centration is 10- 4 to 1%. The high boron level results in
sufficiently low resistivity (0.1-100 Q-cm) that ohmic
potential error becomes negligible. Boron-doped
diamond often includes small domains of Sp2 graphitic
carbon, and care must be taken to distinguish between
electrochemical processes occurring at the diamond sur-
face and those on graphitic inclusions.
III. SURFACE PREPARATION
As noted in the Introduction, the propensity ofsp2 carbon
for adsorption and oxidation leads to significant varia-
bility in surface structure, with accompanying variability
in electrochemical behavior. Awide variety ofsurface pre-
treatments have evolved for carbon electrodes, based on
polishing, heat treatments, anodization, chemical
oxidation, surface derivatization, etc. The effects of sur-
face history can be classified into three general areas,
635
which vary in relative importance depending on the
application. First, the ratio ofexposed edge plane to basal
plane can vary from a nearly zero edge plane on basal
plane HOPG to 100% edge plane on EPG. Second, cover-
age by surface impurities may range from near-zero to
a mono- or multilayer. Such "impurities" may be
intentional, as on modified electrodes, or adventitious
and of unknown identity. Third, almost all carbon
surfaces have a nonzero coverage of oxygen containing
functional groups, referred to here as "surface oxides."
Each aspect ofcarbon surfaces can affect electrochemical
behavior, and each type of pretreatment can affect all
three. It is often difficult to measure or control these
variables in electrochemical processes, and many of the
existing pretreatment procedures have been developed
empirically. We consider the three general aspects of
surface preparation separately and then consider how
they affect electrochemical behavior.
A. Edge/Basal Plane Ratio on Carbon
Surfaces
Section II. A. discussed the unusual electronic properties
ofHOPG basal plane. Although these properties are eas-
ily disturbed by defects, they can be important for HOPG
itself and for the side of ordered carbon fibers parallel to
the fiber axis. An additional and more practically import-
ant aspect of basal plane is its low chemical reactivity.
Edges provide the "sites" for attack by oxygen to form sur-
face oxides. In fact, basal plane itself is inert toward
dioxygen, unless the temperature is high enough to form
oxygen atoms [26]. As we see later, certain electron
transfer reactions are catalyzed by certain functional
groups that can exist only on edge plane. Such reactions
will obviously depend strongly on the edge/basal ratio at
the surface.
The distinction between "electronic" and "chemical"
effects of the edge/basal ratio should be emphasized, in
part because it bears on the common use ofthe word "site"
to describe a reactive region on carbon electrodes.
The properties discussed in Sec. II. A. 1. (e.g., low
capacitance) were attributed mainly to electronic effects,
particularly the semimetal character of perfect HOPG
basal plane. A consequence of this electronic phenom-
enon is slow electron transfer to many redox systems, such
as Ru(NH3)t3/+2, Ir CI 62/- 3, etc. If the semimetal char-
acter is disturbed by a defect, the density of states fills in
and the electron transfer rate increases. For these elec-
tronic reasons, the defect may be considered a site for
electron transfer but one that is not identified with a par-
ticular functional group or chemical structure. On the
other hand, a defect necessarily produces exposed edge
636
plane and may form functional groups or provide reactive
unsatisfied valences. These chemical features of a defect
may catalyze a reaction, provide a locus for adsorption,
etc., in addition to causing the electronic disturbance pre-
sent at any defect. In this case, the term "site" implies a
more specific chemical effect and is meaningful in the
context of a particular electrochemical reaction. In Sec.
V, several examples of redox systems that are affected by
such "electronic" and "chemical" factors are noted.
Ifwe use (}edge to designate the fractional coverage of a
given carbon surface by edge plane, we can consider the
effects of surface treatments on the edge/basal ratio. A
rough estimate of (}edge can be inferred from Raman
spectroscopy, for which the ratio of two band areas
(D I E zg ratio) tracks the degree of structural disorder [3].
"D" refers to the "disorder" band at ca. 1360 cm- 1 ,
whereas "Ez g " refers to the graphite band at ~1580 cm- 1
(also labeled "G" in some treatments). Higher edge
density causes higher DI Ez g ratio and smaller
microcrystallite size (La). A simple model for (}edge
assumes cylindrical graphite crystallites of diameter La
and height L e , randomly oriented as in PCG. Ifthe sur-
face edge density reflects that of the bulk, then (}edge = 2
Le/(L a + 2 L e) for this simple approximation. Most com-
monly used carbon electrode materials have a fairly high
(}edge and a D I Ez g ratio above a few percent. For example,
GC and EPG have D I E zg ratios of 0.1-1.8 and edge plane
densities up to 100%. Exceptions include HOPG basal
plane (D I E zg < 0.005, (}edge < 0.005) and the side of highly
ordered carbon fibers. A Raman peak ratio greater than
zero indicates disorder and the presence of edge plane.
However, a surface with a negligible D I E zg ratio may still
have edge plane defects present.
GC has the highest D I E zg ratio ofthe carbon materials
commonly used in electrochemistry and has the smallest
values of La and L e. Based on the structure of GC, an
exposed surface has a high (}edge, but not as high as EPG
or HOPG edge plane. Polishing increases (}edge for all
carbon materials, because the crystallite size can be
reduced but not increased by mechanical abrasion. With
the exception of near-perfect HOPG basal plane, all
carbon electrode materials are electronically disordered
but vary in the density of "chemical" sites.
(}edge may also be increased by chemical means, most
commonly by electrochemical pretreatment (ECP)
[9,10,12]. Anodic ECP has been shown to increase the
DI E zg ratio for HOPG as well as GC, implying that the
graphitic lattice is being disturbed. STM and Raman
spectroscopy of HOPG anodization support a mechan-
ism in which anions intercalate between the graphite
planes, causing delamination [27-32]. Delamination
reduces the value of L e but does not necessarily reduce
McCreery
La, because the graphite layers may separate without
damage to the planes. In the case ofaqueous electrolytes,
the electrode potential upon intercalation is sufficiently
positive to cause carbon oxidation and/or gas evolution
[31,32]. The resulting mechanical strain and functional
group formation cause breakup of the graphite planes,
leading to smaller La.
B. Impurities on Carbon Electrodes
Discussion ofsurface cleanliness on carbon electrodes is
fraught with hazards, because many of the common
terms used to describe "cleanliness" are poorly defined.
With the exception of near-perfect HOPG basal, carbon
surfaces are prone to adsorption, leading to a wide range
of surface compositions. Strictly speaking, the only truly
"clean" carbon surface exists only in ultrahigh vacuum
after extensive heat treatment or ion etching. At the other
extreme, a carbon surface may be covered by a thick film
(> 1000 A) ofoxide or other modification, intentional or
adventitious. Section IV is devoted to intentional chemi-
cal modification, and attempts to control adventitious
impurities are discussed here.
1. Benchmarks for Surface Cleanliness
Many procedures for "cleaning" carbon electrodes were
developed empirically, with the objective of maximizing
performance for a particular electrochemical appli-
cation. Because different observables (such as electron
transfer rate, adsorption, etc.) may depend on different
surface properties, the optimum cleaning procedures
may differ for different applications. For example, we will
see in Sec.V that Ru(NH)t 3/+ z electron transfer kinetics
are only slightly affected by the level of surface oxides,
whereas Fe+ 3/+ z kinetics are much faster when oxides
are present, due to an electrocatalytic electron transfer
route. So a cleaning procedure may affect these two redox
systems differently, depending on any accompanying
oxidation.
To provide a benchmark for the presence of adven-
titious impurities, one needs an electrochemical
phenomenon sensitive to the presence of such impurities
but not to other factors such as resistivity or oxide
coverage. Of course, oxides may be considered
impurities, but we discuss them in a separate section (III.
C.). The heterogeneous electron transfer rate (kO) for the
Fe( CN)~3/-4 couple has been used extensively as a bench-
mark [3-5], mainly because it was believed initially to be
a "simple, uncomplicated" redox system. It is now clear
that it is far from uncomplicated, with a rate constant
and an ET mechanism that depend on cation identity
and concentration, pH, and cyanide adsorption [3,33].
Electrochemical Properties of Carbon Surfaces 637

Table 3 Fe(CN)6 3/- 4 Kinetics on Carbon and Platinum Surfaces

kO (cm s-l)a Reference

Glassy carbon
Polished (conventional) 0.005 3
Polished (high speed) 0.098 3
Polished (ultraclean) 0.14 5
Polished 0.06 36
(Al z0 3 /Nanopure)
PG 0.007 (0.5 M KCI) 3
PCG/Hexane paste 0.003 3
PCG/Nujol paste I xlO- 4 3
Vacuum heat treatment 0.14 35
Laser activated >0.5 34
Fractured >0.4 34
HOPG
Low defect <10- 5 23
Cleaved 10- 5 _10- 3 23
Edge plane ~0.1 23
B-doped diamond 0.001 (0.1 M KCl) 24
Platinum (flame) 0.24 3
Platinum (laser activated) 0.55 33

a I M KCI unless noted otherwise.

However, its rate is dependent on surface impurities and
does not appear to depend on surface oxides. Given the
extensive data available on Fe(CN)~3/-4 and its well
established sensitivity to adventitious impurities, it is used
here as a benchmark, imperfect though it is. Detailed
discussions of the ET characteristics of Fe(CN)~3/-4 are
available [3,5,33], but we use it here as a pragmatic
indicator of surface cleanliness. Table 3 summarizes
observed rate constants for Fe(CN)~3/-4 for a variety of
surface preparations. A larger array of redox systems is
considered in Sec.v.
2. Polishing
Although polishing methods vary widely from high
speed mechanized techniques to much gentler hand
polishing, the cleanliness of the polishing materials is
critical. Notice in Table 3 that the rate constant observed
for hand polishing in dry alumina with ultrapure water
is as high as those for more aggressive approaches. A
common pitfall is the use ofcommercial alumina slurries,
which contain deagglomerating agents. The use of dry
alumina (Buehler) slurried with "Nanopure" water
(Barnstead) onTexmet polishing cloth (Buehler) followed
by sonication in NanoBure water yields observed rate
constants for Fe(CN)~ 1- 4 (l M KCI) of 0.03-0.09 cmls
[36]. The highest ko for polished GC reported in the litera-
ture is 0.14 cmls in similar conditions after a significantly
more arduous polishing procedure [5]. As a point of
reference, the highest kO observed on any carbon surface
for Fe(CN)~3/-4 is ~0.50 Is [34]. Therefore, polishing
with clean reagents can result in rate constants within an
order of magnitude of the highest observed.
3. Cleaning by Heat Treatment
Heat treatment is often used to modifY the oxide coverage
on carbon surfaces, but it also can remove impurities.
Fagan et al. [35] showed that vacuum heat treatment
results in a low oxide GC surface with fast Fe(CN)~3/-4
kinetics (Table 3). Such treatments are cumbersome for
routine use but can provide better defined surfaces than
polishing.
4. Fracturing
In an attempt to produce a pristine GC surface in an
electrochemical cell, a procedure for in situ fracturing
has been developed [34-37]. A small rod or post of
GC embedded in epoxy is broken in solution, thereby
immediately exposing the new surface to the solution,
with no polishing or air exposure. The surface roughness
of such surfaces depends on the fracture mechanics,
but the "mirror" region is macroscopically smooth.
The fractured surface supports high kO values for
Fe(CN)~3/-4 (kO > 0.4 cm/s) and appears to have a low
01 C ratio. The microscopic surface area is approximately
twice that of polished GC, as judged by capacitance and
STM images. Although the fractured surface is not con-
638 McCreery

Table 4 Oxygen/Carbon Atomic Ratio for Carbon Surfaces

O/C Ratio (%) Reference

Polished (conventional) 8-15 3

Polished in Ah03/Nanopure 14 38
Polished in Al 2 0 3/cydohexane 4 38
Fractured in air 5 39
Fractured in dry box 1.4 39
Vacuum heat treatment 6 35
Vacuum heat treatment 1.6 38
Ar+ sputtered in ultrahigh vacuum <I 38
Electrochemically pretreated 23 10
Electrochemically pretreated 22 9

venient to prepare, it can be useful for considering history
effects on redox reactivity. Furthermore, the common
method of cutting a carbon fiber before use, to expose a
disk electrode, is likely to be similar to fracturing in its
effects on the carbon surface.
c. Surface Oxides
Because oxygen chemisorbs to most sp2 carbon surfaces,
it is very difficult to avoid oxide formation for electrodes
used in air. The initial OIC ratio for carbon surface varies
greatly with surface history and may also increase with
time ofexposure to air. The OIC ratio measured by XPS
for a variety of carbon electrodes is listed in Table 4. The
distribution of particular oxygen containing functional
groups is fairly difficult to determine and may itself vary
with time and sample history. Carbonyl and phenolic
groups are quite common, with carboxylates generally
less populous. However, such generalizations are of lim-
ited value given the wide variety of both OIC ratio and
oxide distribution.
1. "Oxide Free" Carbon
It is clear that abrasion or heating in an anaerobic
environment removes chemisorbed oxygen. This
oxide-free surface has numerous unsatisfied valences that
can chemisorb O 2 from air to reform surface oxides.This
process is not instantaneous at room temperature but
does repopulate the surface with oxides over a minutes
to hours time scale.
HGC and basal plane HOPG are special because they
lack the unsatisfied valences that are apparently necess-
ary for oxide formation at room temperature. As shown
in Fig. 2, the OIC ratio on HGC stays low for more than
1month in air. As discussed in Sec.Y. G., HGC has many
of the electrochemical properties of GC, without its
propensity to oxidize. Because HGC does not have the
unusual electronic properties of basal plane HOPG and
is not expected to depend so heavily on defects, it may be
an attractive alternative to GC for applications where
control of surface oxygen is important.
::r-- --- --e."" GC "O->'%)-- - -- - - - - '1::
10
10

---
Vacuum heat treated
#-
Strictly speaking, it is possible to keep most carbon .Q B Cyclohexane/alumina polished ~ B
surfaces free ofchemisorbed oxygen only in an ultrahigh ~
U
vacuum environment. Basal plane HOPG is unreactive a 6
to 02 at room temperature but does react with atomic oxy-

J~-~_.- . ,
4
gen that forms at elevated temperatures [26]. However,
most carbon surfaces ofelectrochemical interest have sig-
nificant edge plane present, which reacts spontaneously
with 02. Figure 2 shows the 0 I C ratio as a function of time o 1 2 3 4 5 6 7 10 100 1000
air exposure for several GC surfaces. With the exception time of air exposure/h
ofthe H-terminated surface (HGC), all surfaces that start
with a low OIC ratio pick up oxygen, although it takes Figure 2 Surface O/C ratio for various GC surfaces exposed
several hours in air to increase to 7-10% 0/ C. to air between XPS analyses.
Electrochemical Properties of Carbon Surfaces 639

IV. MODIFICATIONS TO CARBON

ELECTRODES
In part because of the propensity of Sp2 carbon toward
adsorption and its ability to form covalent bonds with a
variety of materials, a wide range of surface modifica-
DNPH
tions have been devised for carbon electrodes. A compre-

§
hensive review would be prohibitively long for this ~
chapter, but some generalizations and common pro-
cedures are appropriate. Ofparticular interest are surface
modifications based on physisorption, chemisorption,
oxidation, and polymer film formation.
f

~
-
~

II
OH +
0_
4=.>-NO,
d. )--J
O,N
f}
~ ~
~

~
~
0-

ON
,
~O+
I ~
~

NO,
HCI

A. "Native" Modification
The title to this section may seem to be an oxymoron, but
it does have a point. Almost all carbon electrode surfaces
are "modified" compared with the innate Sp2 carbon
structure. A polished surface has 8-15 % oxygen/carbon
ratio, most carbon surfaces have physisorbed impuri-
ties, etc. The term "adventitious" is used to indicate
unintentional modifications involving oxides and
adsorbates. Table 4 shows that the level of adventitious
oxides can be varied to some degree by the choice of
polishing medium and the level of adsorbed impurities
varies significantly with polishing reagents. As noted in
Sec.v, these adventitious modifications can significantly
affect electrochemical behavior.
DNBC
Figure 3 Two derivatization reactions for surface carbonyl
and phenol groups. DNPH, dinitrophenylhydrazine; DNBC,
dinitrobenzoylchloride. (See Ref. 38.)
Fig. 4. The reduction of diazonium salts has been shown
to yield a compact monolayer on GC and also appears
to attack basal plane HOPG, albeit at a slower rate. The
resulting C-C bond is quite stable and does not appear
to be subject to hydrolysis like the ester linkage. The
carboxylate oxidation has been studied less extensively
but does use a more readily available reactant.
D. Polymer Modifications

B. Physisorption Polymer films have been applied to carbon electrodes to

engender selectivity for size or charge, to protect from
Spontaneous physisorption to carbon is fairly common, adsorption by large molecules, or to provide particular
particularly for large aromatic adsorbates. For example, chemical functionality. For example, a thin film ofNafion
many reports exist on porphyrin adsorption on EPG applied from a solution of soluble Nafion in alcohol
and GC to catalyze oxygen reduction [40,41]. AQDS, results in selectivity for cations [49,50]. The coated elec-
rhodamine 6G, phthalocyanines, and methylene blue
form monolayers on GC that can be observed with
Raman spectroscopy [42]. Physisorption is often suf-
ficiently strong that adsorbed layers are retained even in
the absence of the adsorbing species in solution.

C. Chemisorption
¢ N
+ e' GC
R

W
In addition to oxides, adventitious or otherwise, a variety
of materials have been chemisorbed to carbon to modifY
its surface and electrochemical behavior. In many cases,
binding is through an existing oxide site, using ether or
ester linkages. The oxide density is often enriched before
- [R.] + e" + cO 2 - GC

chemisorption, using an oxygen plasma or other means

[3,43,44]. Some examples of chemisorption to oxide
groups are shown in Fig. 3.
Two relatively recent procedures involve covalent
bonding to carbon sites by aggressive reagents generated
electrochemically [45-48]. The reactions are shown in
Figure 4 Electrochemical derivatization of initially unfunc-
tionalized carbon surfaces by diazonium reduction or
carboxylate oxidation. (From Refs. 45-47.)
640
trode is much more sensitive to dopamine (a cation at pH
7) than to ascorbate (an anion), even though the two sys-
tems have similar redox potentials. Cellulose acetate has
been applied to carbon surfaces and then treated with
base to generate holes of approximately similar size [51].
The film permits small molecules to reach the carbon sur-
face but excludes large molecules that might permanently
inhibit electron transfer.
Carbon is a common substrate for modification by
redox polymers, which may be applied as relative thick
films (~1000 A) [52]. In addition, a large literature exists
on binding enzymes to carbon to make electrochemical
probes that are sensitive to biological components [53].
v. ELECTRODE KINETICS AND
ELECTROCATALYSIS
Due to the aforementioned difficulties in preparing
well-defined carbon surfaces, the relationship between
surface structureand electrochemical reactivity is less well
understood on carbon compared with metal electrodes.
However, an integrated description ofthe surface proper-
ties that control ET kinetics, adsorption, and background
current is beginning to emerge, and several useful con-
clusions are available. This section describes a classifi-
cation of redox systems according to the dependence of
their ET rate constants on particular surface properties.
Before addressing specific redox reactions on carbon
surfaces, a brief review of some of the factors affecting
electron transfer rates is provided in Sec.V A., including
tunneling, Frumkin effects, and electrocatalysis.
A. General Factors Underlying ET Kinetics
In the simplest case, the heterogeneous ETrate constant,
kO, is exponentially dependent on the distance between
the electron donor and receptor. In the case ofa redox sys-
tem such as Fc+ /Fc (Fc=ferrocene), it has been estab-
lished that the observed rate constant follows
k~bs = kOe-/l d (2)
where f3 and kO are constants and d is the distance between
the electrode surface and the redox center at the time the
electron transfer occurs [54,55]. This behavior is consist-
ent with that observed for two redox centers in a rigid
molecule, where ET does not involve an electrode and
has been thoroughly characterized for homogeneous
systems. In the context of carbon electrodes, it is import-
ant to note that ET does not require "direct" contact
between a redox center and the carbon surface but may
occur over a distance greater than the molecular size [38].
McCreery
The electron may tunnel through an adsorbed "spacer"
(intentional or otherwise) with the observed rate
decreasing with spacer thickness. The tunneling constant
f3 varies from 0.14 to >1.0 A-I, depending on the nature
of the spacer layer. For example, a 3-A thick spacer on a
carbon electrode and a [3 of 0.5 A-I yields a decrease of
a factor ofe-1.5 (a 78 % decrease) compared with the rate
with no spacer. The rate with no spacer (kO) in turn
depends on the inherent ET kinetics ofthe redox system,
which depends on reorganization energy and other
factors not related to the carbon surface. Predictions
based on Eq. (2) assume that tunneling is the only factor
affecting ET kinetics for a given redox system on a par-
ticular surface, in which case rates at carbon should be
the same as metals in the absence ofother complications.
In this case, the electrode is acting as a source or sink of
electrons, and the rate is determined by the inherent ET
kinetics ofthe redox system and the tunneling distance.
A second factor determining observed ETrates is the
possibility ofdouble-layer effects, particularly a Frumkin
correction [56]. A charged interface can alter the local
concentration of a redox system and change the effective
driving force. Such effects are difficult to predict on
carbon because the potential of zero charge is usually
not known. However, electrostatic effects on ETrate have
been observed for conditions that lead to charged func-
tional groups on carbon, such as surface carboxylates.
In conditions where the surface is negatively charged,
rates to cationic redox centers are often enhanced and
rates to anionic redox systems are depressed. For
example, deprotonation of surface carboxylates on
GC increased the observed ET rate constant for
)t 3 2
Ru(NH 3 /+ by a factor of about 2, whereas it
decreased the rate for Ir Cl 62/- 3 by about 50% [11].
Larger effects ofsurface charge have been reported for
carbon electrodes that have been intentionally oxidized
to form multilayer films. These oxide films are believed
to be anionic, and preferentially adsorb cations over ani-
ons [3,4]. A related example is the effect of a Nafion film
mentioned earlier that can preferentially permit cations
to reach the carbon surface. Although such effects have
an electrostatic origin similar to classical Frumkin
effects, they involve an often "thick" (i.e., multilayer)
modification and adsorption and are both larger in
magnitude and more complex than classic double-layer
effects.
A third surface effect on electrode kinetics comes
under the general heading ofelectrocatalysis. For the cur-
rent purposes, we consider an electrocatalytic system to
involve a surface interaction that increases the observed
rate above that expected from tunneling. As noted earlier,
tunneling requires the electrode to serve only as a source
Electrochemical Properties of Carbon Surfaces
Table 5 Electron Transfer Rate Constants for Ru(NH 3
kO (cm/s)
Basal plane HOPG 9xlO- 4
PolishedGC 0.24± 0.Q7
Fractured GC 0.27
Reduce O/C (VHT) 0.24
Nonspecific adsorbers 0.13
B1ock-OH (DNBC) 0.15
Block C=O (DNPH) 0.13
Nitrophenyl monolayer 0.12
Metal electrodes 0.5-1.0 (57)
Laser-activated GC 1.1 (58)
" Observed kO divided by that for polished Gc.
Source: Ref. 38 except as noted.
or sink for electrons, and no direct interaction of the
redox center with the electrode surface is assumed. This
mode ofETis sometimes called "outer sphere" by analogy
to homogeneous ET reactions. Electrocatalytic or inner
sphere reactions include some type of chemical interac-
tion between the surface and the redox system. This inter-
action may take the form of complexation, ligand
substitution, chemisorption, etc., but in any case has the
effect of accelerating electron transfer. In addition, such
mechanisms often depend on specific surface groups
and are quite sensitive to surface history. We identitY
several electrocatalytic mechanisms on carbon and
note their distinctive features compared with simpler
systems.
This brief general discussion about tunneling,
electrostatic, and electrocatalytic effects on electrode
kinetics is certainly not comprehensive but does provide
a framework to discuss a variety of observations for
carbon electrodes. We now consider several examples
and begin to devise a systematic classification of
redox systems according to their behavior on carbon
electrodes.
B. Tunneling Mechanisms
The simplest case of an ET rate determined mainly by
the distance between the electrode and the redox center
has been observed for several redox systems on carbon
electrodes. Most sp2 carbon materials used in electro-
chemistry, including GC, polycrystalline graphite, and
carbon fibers, are sufficiently disordered to have elec-
tronic properties similar to metals. For the carbon
materials with metallic electronic properties and
reasonable conductivity (the exception being HOPG
basal plane), the electron transfer kinetics should be
641
)t3/+2 (I M KCI)
kO, relative"
0.004
1.0
1.1
1.0
0.54
0.62
0.54
0.50
2-4
4.6
similar to those observed on a metal electrode. A further
requirement for the observation of the "simple"
tunneling mechanism is the behavior of the redox sys-
tem as an outer sphere system, with no catalysis by
chemical interactions with the surface. When both con-
ditions are met, we expect the ET rate on carbon to be
similar to that on metals, and also that there is no pro-
nounced dependence on the presence of particular sur-
face functional groups. We refer to such redox systems
informally as "tunnelers."
)t
An example of this simple case is Ru(NH 3 3/ + 2 on
GC in 1 M KCl. Ru+ 3/+ 2 complexes are substitution inert
and quite stable, and exhibit well-defined
voltammograms at relatively fast scan rates (~20 Vis).
)t
Observed kO values for Ru(NH 3 3/+ 2 are shown inTable
5, and several key observations are available from these
results. First, the unusual electronic properties of basal
plane HOPG result in an anomalously low kO value. As
noted earlier, this effect is conceptually important but of
limited practical value, because low-defect HOPG basal
plane is fragile and difficult to prepare. Second, polished,
fractured, and laser-activated GC exhibit kG values in
the range of 0.24-1.1 cm/s. So nominally "unmodified"
disordered carbon exhibits kO values in a fairly narrow
range. Third, intentional modification ofparticular func-
tional groups or coverage by one of several different
monolayers has minor effect on kG, reducing it by about
)t
50%. Fourth, kO for Ru(NH 3 3/+ 2 on GC, even with a
monolayer present, is within an order of magnitude of
kG on various metal surfaces. Overall, Ru(NH 3 3/+ 2 )t
kinetics are quite insensitive to the composition and
chemistry of the electrode material, provided it is a good
electronic conductor. With the exception of HOPG basal
plane, the variations in kG in Table 7 can be explained by
variations in tunneling distance caused by surface
642
tunneling:
monolayer
~
Ie
) +3
RuCNH 3 6
...
Ii RuCNH 3)6
1+2
~d-I
bridging:
/e(H,O)/3
e-
IL.
X.. p-Fe(H2 0)5+3
·H
~
Fe(Hp)6+2
Figure 5 Models for outer sphere (tunneling) and bridging
mechanisms. X denotes a surface functional group or site that
interacts with the redox system.
monolayers, whether intentional or adventitious. The fact
that a compact monolayer of nitrophenyl groups (for
example) has a minor effect on kO argues strongly against
a requirement for a specific surface interaction [38].
Marcus theory predicts a correlation of kO with the
homogeneous electron exchange rate, k exc . Such a corre-
lation is often frustrated by complications from work
terms, double-layer effects, etc., but has been observed
for certain systems. Ignoring many of the possible com-
plications' kO is approximated by 0.Q3 k~~~, and kO for
Ru(NH 3)t 3/+ Z from this relation is expected to be
1-2 cmls [23]. Although this prediction is likely to be
oversimplified, it does indicate afPr,0ximate agreement
of the observed kO for Ru(NH 3)t /+~ on spz carbon and
on metals with the homogeneous electron exchange rate.
A schematic of the tunneling mechanism is shown
in Fig. 5. Additional redox systems [38] exhibiting simi-
lar behavior are Ir Cl- Z/- 3, Co(phenanthroline)t 3/+ z,
Co(ethYlenediamine)t3~+z, and chlorpromazine+/o. As
noted in Sec.V A., electrostatic effects of surface charge
can alter the rates of such systems via Frumkin effects.
McCreery
Such effects are relatively small (factors of 2-3) for outer
sphere systems on polished GC [11] but can be much
larger when thick films or adsorption are involved.
C. Inner Sphere or Bridging Redox Systems
As noted earlier, electrocatalytic mechanisms come in
various forms but all share the property of lowering the
kinetic activation barrier through some sort of surface
interaction. In such a case, the observed kO will exceed
that of the uncatalyzed outer sphere process. The
tunneling rate discussed in Sec. V A. represents an
uncatalyzed rate that is affected by the distance between
the electrode and the redox center but not by any specific
chemical interaction. Should such an interaction occur
that promotes electron transfer, the observed rate exceeds
the outer sphere rate and the system is said to be
electrocatalytic. Electrocatalysis may occur by several
mechanisms, but all depend on some direct involvement
of the carbon surface.
An illustrative example for carbon electrodes is
Fe(HzO)t 3/+ Z in 0.2 M HCI0 4 in the absence ofCl- ion.
This system is slow for both homogeneous and hetero-
geneous electron transfer, because the Fe-O bond dis-
tance is quite different for Fe(II) and Fe(lII) and the
nuclear motion accompanying electron transfer results
in a high activation energy. Several rate constants for
Fe+ 3/+ Z are listed in Table 6. For carbon surfaces with
low O/C ratio, Fe+ 3/+ Z is slow, in the region of 10- 4 to
10- 5 cm/s. These values are similar to that observed on
gold when the Cl- concentration is low. Furthermore,
physi- and chemisorbed layers on GC also result in rate
constants below 10-4 cmls, implying that Fe+ 3/+ Z is
catalyzed by a surface site. Finally, reaction of surface
C=O groups with DNPH greatly inhibits kO for Fe+ 3/+ Z,
whereas adsorption of AQDS (which contains C=O
groups) increases kO.
These results indicate that the rates observed for
Fe+ 3/+ Z on gold and low-oxide GC are comparable and
probably represent the outer sphere (or "tunneling") rate.
This rate is within an orderofmagnitude ofthat observed
when surface sites are obscured by a chemi- or
physisorbed monolayer. The catalysis by oxides is
mediated by carbonyl groups, accounting for the
inhibition by DNPH and acceleration by oxidation and
AQDS adsorption. The mechanism of this catalysis is
not yet clearly defined but is likely to involve bridging of
the Fe(H zO)t 3/+ Z center to surface carbonyls [23,38],
illustrated in Fig. 5. This bridging apparently accelerates
the nuclear rearrangement required for electron transfer,
either by ligand substitution, hydrogen bonding, or an
"outer sphere" bridge. Although the mechanistic details
Electrochemical Properties of Carbon Surfaces 643

Table 6 Observed kO Values for Fet~/+3 in 0.2 M HCI0 4

kO (cm/s) kO, relative

Glassy carbon
PolishedGC 2.5xlO- 3 1.00
Fractured GC 2.3 xlO- 3 0.92
Reduced O/C (VHT) 1.4 x 10- 4 0.06
Nonspecific adsorber 9.1 xlO- s 0.04
Block -OH (DNBc)a 1.1 xlO- 3 0.44
Block -C=O (DNPH)a 1.6xlO- s 0.006
Nitrophenyl monolayer 7xlO- 6 0.003
Electrochemically oxidized 1.0 x 10- 2 4.0
AQDS modified 7.4xlO- 3 10
Gold electrode (CI- free)b 2.5xlO- s 0.005
Basal plane HOPG 1.4xlO- s 0.006

a GC surfaces following reactions of surface ~OH or C=O groups with DNBC or

DNPH.
b Adsorbed chloride appears to act as a bridge on Au elements and the observed kO is
quite dependent on trace CI- concentration. See Refs. 59 and 72.
Source: Refs. 23,38,59.

are not yet complete, it is clear that a surface carbonyl
group on the carbon surface provides an alternative faster
route that can operate in parallel with tunneling. When
even small amounts of surface carbonyls are present
(~I %), the bridging route becomes dominant. Chloride
ion at low concentration supports a similar catalytic
mechanism on a gold electrode, attributed to a bridging
chloride ion [59].
D. Redox Mediation by Surface Quinones
Ofthe many surface modifications developed to affect ET
rates on carbon electrodes, redox mediation by surface
quinones is of special interest. Both ortho and para
quinones are present on most carbon surfaces and may
be enriched by surface oxidation or other chemical modi-
fication [60,61]. Electrocatalysis by surface quinones
through redox mediation has been demonstrated forvari-
ous reactions, including ascorbic acid and NADH
oxidation [61]. Because the presence of some level of sur-
face quinones is difficult to avoid, there is always a possi-
bility that unintentional redox mediation can occur.
Surface quinones have also been associated with back-
ground current, particularly on intentionally oxidized
carbon electrodes [62,63].
E. Electrocatalysis at Modified Carbon
Surfaces
As noted earlier, a wide variety of chemical species have
been physi- and chemisorbed to carbon surfaces to
impart selectivity or catalytic activity. The chemical
mechanisms underlying the activity of these modified
surfaces are also quite numerous and in many cases
involve the carbon substrate only as a conductor of
electrons. The surface chemistry of the carbon may be
important in terms of the binding of the modifier, but
the carbon surface may not be directly involved in the
interaction ofthe adsorbed catalyst with the electroactive
species in solution. For example, catalysis of02 reduction
by adsorbed porphyrins on graphite depends mainly on
the porphyrin/02 interaction [40,41,64], and the nature
of the substrate appears to be unimportant provided it is
a conductor that is inert in the potential range involved.
Other than noting the wide use of carbon materials as
supports for catalytic surface modifications, it is beyond
the scope ofthis chapter to list or discuss the many modi-
fications of carbon surfaces directed toward
electrocatalysis.
F. Systematic Classification of Redox
Kinetics on Carbon Electrodes
It is clear from the discussion so far that many factors can
affect the electrochemical behavior of carbon electrodes.
In addition, redox systems vary tremendously in their
sensitivity to surface structure, ranging from systems such
as Ru(NH3)t3/+2, whose kO varies only slightly with
major changes in surface structure (Table 5), to systems
such as Fe+ 3/ +2, whose rate can vary by a factor of 10 3
depending on the presence of carbonyl groups (Table 6).
If one has a new redox system, how does one determine
644
its dependence on carbon surface condition? Is it a
tunneler, a bridger, etc., or does it depend on some other
electrocatalytic mechanism?
The diagram in Fig. 6 illustrates an approach to
determining which carbon surface properties affect
electron transfer kinetics for a given redox system [38].
Starting on the left side of the diagram, a series of sur-
face modifications are used to alter surface structure,
and then the effect on redox kinetics is observed. For
example, if addition of a physisorbed or chemisorbed
monolayer has little effect on the observed kinetics, the
redox system is not "surface sensitive" and is likel~ to
be an outer sphere "tunneler" such as Ru(NH3)t /+2.
If kG is significantly decreased by an intentional surface
monolayer, the redox mechanism appears to involve
some surface interaction. If the rate is greatly affected
by reducing the surface OIC ratio, then the mechanism
probably involves surface oxides. Several examples of
redox systems categorized according to these tests are
shown in Fig. 6 as well.
Fe 3+12+
EU 3+/2 +
Yes V+3+1+2
Oxide
Sensitive?
Fe(CN)6 3-/4-
Ascorbic Acid
Surface I I
Sensitive? I
Ru(NH 3 )6 3+/2 +
IrCI 62-/3-
No Co(phen h3+/2+
Figure 6 Decision tree for determining carbon surface effects on electron transfer kinetics. Several examples of systems conforming
to the scheme are listed. Tests of surface or oxide sensitivity are based on surface modification reactions. (From Ref. 38.)
McCreery
The diagram of Fig. 6 is certainly not complete but
does provide a framework to classify redox reactions on
carbon electrodes. There are likely to be additional
branches added to the decision tree, such as those related
to redox mediation, chemisorption to specific sites, etc.
After recalling Sec. I of this chapter, it is easy to appreci-
ate why so much variability has been observed with ET
kinetics at carbon electrodes. Not only do carbon surface
structures depend strongly on surface history, but redox
systems also vary greatly in their sensitivity to these sur-
face structures. If the mechanism of a particular redox
reaction or the surface structural factors affect kO have
been determined, the effect of carbon type and surface
history on redox reactivity can be predicted and in some
cases controlled.
G. Electrode Kinetics and B-Doped Diamond
ETreactions at diamond surfaces have attracted signifi-
cant recent interest, in part due to the rapid development
of CVD diamond film procedures [18,24,65-71]. A
C = 0 Sensitive? Fe 3+12+
EU 3+/2 +
V+3+1+2
C-OH Sensitive?
Yes Fe 3+/2 +
EU 3+/2 +
V+ 3+1+2
I Other
Fe(CN)6 3-/4 -
No Ascorbic Acid
Electrochemical Properties of Carbon Surfaces
Table 7 Observed kO Values for GC, HGC, and B-Doped Diamond
kO for Fe(CN)6 3/- 4
1 M KCI (cm/s)
GC, polished (clean) 0.06
GC, laser activated >0.5
GC, polished, aged a 0.003
B-doped diamond 0.02
HGC with boron 0.007
HGC without boron 0.008
" Entries from Ref. 71 were from electrodes exposed to lab air for at least several days.
related surface is the H-terminated GC electrode (HGC)
in which the surface carbon atoms are believed to be satu-
rated with hydrogen rather than oxides or unsatisfied
valences [71]. Diamond electrodes have sp3 hybridized
surface carbon atoms, with conductivity provided by
boron doping, whereas HGC has bulk conductivity equal
to GC but a C-H surface. Diamond is more inert than
GC in terms of oxidation and corrosion and may have
attractive mechanical and electrochemical properties
for industrial applications. As shown in Fig. 2, HGC
oxidizes very slowly in air and may be more stable than
GC for analytical applications. Swain and coworkers
[18,24,66] have shown that diamond electrodes have
lower background current than GC and remain active
for extended periods in air or in solution. In addition,
diamond provides an extended voltammetric potential
range, permitting electrochemical analyses of otherwise
intractable species.
Electrode kinetics at diamond and HGC have been
studied much less extensively than at other carbon elec-
trode materials, but some useful observations are
available. First, the bulk electronic properties of doped
diamond are generally similar to those of GC, although
some semiconductor behavior has been reported
[24,66,68]. For many outer sphere redox systems, such
as Ru(NH3)~3/+2 and IrCI 63/- 2, the kO values on
diamond are 1-2 orders of magnitude lower than those
on GC, but the voltammetric waves are well defined and
symmetric. Several kO values are listed in Table 7 for com-
parison. It is important to note that the HGC and
diamond values reported in Table 7 are from electrodes
aged in lab air for extended periods oftime. The diamond
and HGC surfaces appear to be relatively inert toward
impurity adsorption and retain ETreactivity longer than
"ordinary" GC [24].
At least on a preliminary basis, we conclude that
doped diamond and HGC behave qualitatively similarly
to GC for the "outer sphere" systems such as
645
kO )t
for Ru(NH 3 3/+ 2
I M KCI (cm/s) Reference
0.24 11,36
1.1 23,62
71
0.002 71
71
0.005 71
RU(NH3)~3/+2. This conclusion is reasonable if the elec-
trode material has sufficient conductivity and does not
exhibit semiconductor behavior. There are some indi-
cations that B-doped diamond behaves like a p-type
semiconductor at quite negative potentials, but this prop-
erty depends on doping level and preparation conditions.
To a first approximation, electron transfer for outer
sphere redox systems on diamond and HGC is similar
to but slower than that to clean Ge. A more precise com-
parison will depend on surface preparation conditions
of both diamond and GC electrodes.
When a surface interaction is involved, HGC or
diamond electrode behavior is quite different from that
of Ge. For example, Fe+ 3/+ 2 is much slower on diamond
or HGC than on GC [18,71], presumably due to the lack
of catalytic carbonyl groups. Halide oxidation is slow on
diamond compared with GC [68], as is electron transfer
to catechols, benzoquinone, or ascorbate [18,71]. These
reactions are all expected to involve catalysis by some sur-
face species that is absent on HGC or diamond. These
observations are quite consistent with the general elec-
trode kinetic scheme of Fig. 6. For the tunnelers that
require only a source or sink for electrons, diamond,
HGC, and GC are similar provided semiconductor
behavior is not involved. When an electrocatalytic route
is involved, surface chemistry can become a dominant
factor. Based on available results, HGC and diamond
can have quite different surfaces compared with GC and
redox systems sensitive to those differences behave
accordingly.
ACKNOWLEDGMENTS
I thank the National Science Foundation for support of
this work and the many coworkers cited in the references
for their scientific contributions. The efforts of Stacy
DuVall and Te. Kuo on the figures and Margaret Dodd
on preparing the manuscript are also appreciated.
646
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36
Bulk and Surface States of Reactive Oxide Films: An
Extended Semiconductor Model with Ti, Ni, and Fe as
Examples
Uwe Konig and Joachim Walter Schultze
Heinrich-Heine-Universitiit, Dusseldorf, Germany
ABSTRACT
The electronic properties ofoxide films can be described
by the semiconductor model in a first approximation.
Then, a homogeneous defect concentration N with a
defined energy level E is assumed. Due to amorphicity
and ionic conductivity of the films, additional defects
may be formed at the interfaces and migrate into the film,
thereby giving rise to complex dependencies ofthe defect
concentration on energy E, location x, and time t, N(E,
x, t). The changes in concentration will vary the reactiv-
ity ofthe films. The course of the related processes is fol-
lowed by i(t) and qf.!) transients, whereas the role of
defects is obtained by fast capacity measurements with
potentiostatic pulses. Under reasonable assumptions,
an evaluation based on the Schottky-Mott model yields
donor concentrations and properties ofthe surface states.
In special cases concentration profiles N~) can be also
derived. From the time dependence ofthe concentration
profile N~, t), the migration of defects can be described.
The oxide growth on passive iron is an example for
a reaction that strongly depends on the local defect
concentration. As a result, either field-dependent or
diffusion-limited oxide growth is observed. Intrinsic
redox reactions, for example within the passive films on
Ti and Ni, can also be followed. The redox process itself
is characterized by if.!) transients, whereas C(U) measure-
ments yield corresponding information ofthe migration
of protons. The formation of different types of surface
states is obtained during anodic oxygen evolution on Fe
and Ni in the dark and on Ti under illumination.
649
I. IN"rRODUC1"ION
A. Surface Reactions and Reactivity
Oxide films play an important role in electrochemical
energy conversion, electrocatalysis, corrosion protec-
tion, and electrochemical analysis and sensorics [1,2].
Their properties depend strongly on parameters such as
stoichiometry, film thickness d, electrode potential U,
and electrolyte composition Ci. The general properties
are determined by film formation, but redox processes
and modification by chemical or physical techniques
can decisively change the actual surface reactivity.
Especially in electrocatalysis, the reactivity of the sur-
face is important. It clearly represents a reaction rate but
may be vastly different for different reactions under con-
sideration. Figure 1shows a survey of possible reactions.
Oxide growth and corrosion are connected with ion
transfer reactions (ITR) at the metal-oxide and
oxide-electrolyte interfaces and within the oxide itself
(e.g., diffusion and migration of ions). ITR of other ions,
e.g., protons or chloride ions, take place either as electro-
sorption reactions within the double layer or as transport
reaction within the oxide (intercalation). For electron
transfer reactions (ETR), outer sphere and inner sphere
ETR have to be distinguished. They are coupled with elec-
tronic transport or ETR within the oxide, which can
prove to be rate determining. A reaction via surface states
must also be considered. Redox processes of the oxide
650 Konig and Schultze

II metal I I I oxide I I electrolyte I

ITR
M "+
Y
M,Oy I~ M "+
Y
corrosion
MytH I _____.L .~ MytH

MytH M,Oy 0 2' oxide formation sect. IV

e'
11
M,OyH H+ intercalation sect. V

J e ' I-.C Red ETR

outer sphere
Ox
2e-
H 20 sect. VI.A.
inner sphere
2h+
0.50 2 + 2H'

Red
e sect. VI.B.
via SS
Ox

-----
photo induced sect. VI.c.
O 2 + 2H+ 1

Figure 1 Schematic diagram of ITR and ETR at an oxide surface.

take place by a combination of ITR and ETR. Electronic
processes within the oxide, e.g., electron - hole pair gener-
ation by phonons or photons, may also be coupled with
ITR or ETR at the surface.
Although ITR depend mainly on the local field
strength, ETR are predominantly influenced by the dis-
tribution ofelectronic states in the electrolyte and within
the oxide. Therefore, typical ITR such as corrosion and
typical ETR such as oxygen or hydrogen evolution are
dominated by different parameters at the oxide surface.
The resulting different reactivity has been extensively dis-
cussed for the case of different grains of polycrystalline
titanium, where the reactivity for ETR and ITR was
shown to exhibit exactly opposite tendencies [3].
B. Semiconductor Model of Oxide Films:
Success and Limitations
Crystalline metal oxides may behave electronically as
metals, semiconductors, or insulators [4,5]. Because the
chemical similarity between crystalline bulk oxides and
amorphous oxide films gives rise to similar electronic
properties, many amorphous bulk oxides [4] or oxide
films [6] can be described successfully by the semicon-
ductor model. A wide variety of characteristics such
as band models, space charge layers, and photo-
electrochemical behavior can be described within the
framework of the semiconductor model. The correlation
between band edge energies and exchange current
Bulk and Surface States of Reactive Oxide Films
densities of outer sphere ETR is a good example for the
successful application of the semiconductor model to
oxides and oxide films [4,6]. However, the original semi-
conductor model can serve only as a first approximation
due to several reasons:
1. Oxide films are often amorphous or nanocrystalline.
In this case, the band gap Eg is not sharply defined.
At the band edges, localized states are formed
effectively causing a mobility gap.
2. Oxide films are often nonstoichiometric, and the
dopant levels are not as sharply defined as in the case
of bulk crystalline semiconductors.
3. The underlying metal is not in thermodynamic equi-
librium with the electrolyte leading to an inhomoge-
neous passive layer with a composition and structure
changing with distance x from the metal [7,8].
4. Surface states, e.g., states at the oxide-electrolyte
interface, are less reproducible and not as sharply
defined as for bulk crystalline semiconductors.
5. Many oxide films behave as mixed electronic/ionic
conductors. Oxide formation, redox processes, and
cathodic or anodic dissolution are typical examples
for reactions involving both ITR and ETR. Thus, they
do not behave as classic semiconductors, the compo-
sition of which remains unchanged under current
flow.
6. Intercalation of foreign ions may drastically change
the electronic properties, but this is not taken into
account in the first approximation.
In summary, it can be expected that the semiconductor
model is applicable to an experimental description of
oxide films in the steady state or at short time intervals
as long as all ITR can be neglected and the defect concen-
tration N{x) is constant throughout the layer. During elec-
trochemical experiments with reactive oxide films, ITR
will change the concentration within the film in depen-
dence on location and time, N{x, t). Due to different
defects, an energetic distribution N(E, x) may be formed.
Then, a dependence of the electronic structure on the
experimental conditions is to be expected and has to be
considered.
C. Nature of Defects and Electronic
Equilibrium
In oxide films on metals, a high defect concentration N
of 10 19 _10 21 cm- 3 has been found experimentally. N
depends strongly on the film thickness and polarization.
Defects can be caused by vacancies of oxygen, Va, or
metal, VM, or the corresponding interstitials, Mi l2 or
07-' Furthermore, intercalated foreign ions like H+
651
may form localized states within the mobility gap. Defects
within the oxide film can act either as electron donors or
acceptors. Finally, surface states at the oxide-electrolyte
interface have to be considered. They are due to adsorbed
species from the electrolyte, asymmetry of chemical
bonds (i.e., dangling bonds), or intermediates formed
during dissolution (e.g., radical in the case of Ge [9]). A
maximum surface concentration of N ss = 10 15 cm- 2 is
assumed corresponding to one monolayer. In summary,
different defect energy levels of donors, ED, acceptors
EA, and surface states Ess cause a defect distribution
N(E). Taking into account the migration of defects, the
complete function N(E, x, t) has to be considered.
The adjustment of the electronic equilibrium within
the oxide film depends on the rates ofthermal generation,
recombination, and elastic electron transfer processes
to neighboring electronic states. With increasing ener-
getic distance to the conduction band, generation
becomes slow or negligible. The elastic exchange with
neighboring electronic states given by the Gamov
formulae decreases with increasing local distance.
Therefore, the electronic equilibrium will be maintained
in thin semiconducting oxide films with low Eg values,
e.g., passive Fe and Ni. But for the valve metal films, e.g.,
passiveTi, electronic equilibrium cannot be maintained.
This is important for fast capacity measurements that
require an even faster electronic exchange via the conduc-
tion or valence band. The reaction rate of the surface
states, e.g., recombination, is very high and the electronic
equilibrium is usually established.
D. Evaluation of Reactive Defects
From the preceding statements it is obvious that the
electronic structure of reactive oxide films can be investi-
gated under defined conditions only. Because a strong
time dependence N{f) is expected, only ultrafast
measurements, e.g., pulse experiments, can reasonably
be applied for the investigation of the electronic proper-
ties of the oxide films [10]. Ifsuch methods are available,
the kinetics offormation and destruction of surface and
bulk defect states may be investigated.
An illustrative example shall be given here:
The time-consuming technique of electrochemical
impedance spectroscopy does not allow the record of
the potential dependent capacity qU) of reactive
films at constant film conditions [11]. In contrast to
that, the potentiostatic pulse experiment has been
proved as useful technique because 10 or more qU)
values maybe measured within 1 ms [12]. Thus, common
Schottky- Mott analysis becomes possible even in depen-
dence on polarisation time during fast oxide growth [13].
652 Konig and Schultze

Because of these difficulties and the corresponding
lack of time-resolved experimental data, the semicon-
ductor model of oxide films has up to now applied only
in the first approximation with the limitations mentioned
above.
E. Potential Distribution at the Interface
In the first approximation, the potential drops at the inter-
face t'1¢m/ox, within the oxide t'1¢ox, and in the Helmholtz
layer t'1¢HL are considered [14-16]. According to the
extended model, the contribution of surface states (SS)
has to be considered, too. In correspondence to the equiv-
alent circuit of semiconductor electrodes [17,18], t'1¢ss is
in series to t'1¢HL. This is in analogy to the concept of
Vetter and Schultze [19] for the anodic oxide growth on
noble metals with the separation of the Helmholtz layer
into an inner and an outer layer and the correspondent
potential drops t'1¢HL.o and t'1¢HL.i, where t'1¢ss is related
to t'1¢HLj and t'1¢HL to t'1¢HL.o. This is shown
schematically in Fig. 2 together with the resulting field
strength F = d¢/dx.
For most oxide films, the pH-dependence of charac-
teristic potentials is given by 60 mY/pH-unit. This is
caused by the adsorption equilibrium OH- {:} OH;ct in
the outer Helmholtz layer, i.e., t'1¢HL,o is fixed. On the
other hand, t'1¢HL.l may change in dependence on U and
the charging ofsurface states.
F. Objective: Analysis of Defect Formation
and Migration During Oxide Growth and
Redox Processes
The analysis of experimental data for well-known and
well-defined reactive oxide films during typical processes
is the major focus of this presentation. The processes dis-

I--- I IHelmholt:
I metal I oxide layer I electrolyte

~ d ox

-e- ~~m10x

~~ox = ~~sc

dox-d sc

~~HL1= ~~ss

~~HL,o = ~~HL

-'S x/om
u
~
~

x/om
Figure 2 Schematic diagram ofthe Galvani potential1J(;K) and local field strength F(;K) within the system metal- oxide-electrolyte.
Bulk and Surface States of Reactive Oxide Films
cussed here have to be controlled in dependence on time
and the electronic properties of the film. This requires
the recording of transients i =/( Up, t), q =/( Up, t),
C = (Up, t) and the potential dependence C(U) =/( Up,
t), where Up is the polarization potential offilm formation
or redox processes. These experimental data will be
analyzed with respect to
1. The formation of oxide films,
2. The formation ofspace charge layers during the oxide
growth and their influence on the reactivity,
3. The formation of surface states during various pro-
cesses,
4. The formation of defect states during intercalation
reactions.
The change of the oxide reactivity by the reactions
plotted out in Fig. I is presented in the section indicated
in the figure. First, we discuss the influence of the various
charge carriers on the properties ofthe unmodified oxide
layer on the oxide growth in Sec. IV. The subsequent Sec.
V is related to the intercalation of foreign ions during
the intrinsic redox process of an active oxide. Finally,
the modification of the oxide-electrolyte interface by
the formation and annihilation of surface states is
discussed in Sec.VI.
II. APPLICATION OF POTENTIOSTATIC
TRANSIENTS AND CAPACITY
MEASUREMENTS
A. Current and Charge Density'ft'ansients
The overall current density measured experimentally is
given by the sum of the reactions pointed out in Fig. 1:
i = i cap + iETR + ilTR (1)
The relevant ITR are the formation ofoxide films and
the migration of defects within these films that are com-
monly examined by transient methods [20,21]. The
transients have to be registered with a high dynamic
resolution immediately after the adjustment of the
potentiostatic control. This is mainly influenced by the
capabilities of the potentiostat and by the Helmholtz
capacity and the electrolyte resistance. For a layer with a
constant thickness, the attainment of the potentiostatic
control takes some flS. During oxide growth on a plain
metal electrode, it takes some ms due to the high reaction
rate involving a total charge ofsome m C cm -2. Therefore,
the period of registration is 1 f1S ::::: t::::: ks. From the analy-
sis of the resulting transients after the attainment of the
potentiostatic control, a separation of the reactions in
Eq. (l) is possible ifthey take place over different periods
653
of time [22-24]. The corresponding charges can then be
separated:
(2)
The separation of the spatial domains is not possible
since the i~) transients are related to the average trans-
port processes within the layer. Parallel processes or
inhomogeneities within the layer are very difficult to
examme.
B. Capacity and C(U) 'ft'ansients
Capacity transients C~) at a given potential reflect the
time dependence of the electronic properties within
the whole layer. The limits of this method are compar-
able with those discussed above for the i~) and q~)
experiments. Additional information about the charge
distribution can be achieved from the potential depen-
dence of the electrode capacity C(U), which is very
sensitive for changes in the charge concentration. If the
experiments are carried out fast enough, constant layer
properties can be maintained. Additional processes like
photo-induced reactions or incorporation of redox
species are comparably slow and can therefore be
neglected.
Special care is necessary for the analysis of the data.
Any presumptions have to be questioned carefully. In
the conventional interpretation, a C- 2 (U) plot is used
based on the classictheoryofMott [25] and Schottky [26]:
-2 2
C =D D
. o· ze·
N . (U - Ufb) (3)
From the gradient (dC- 2 ; d U), the defect density N
can be derived and the intercept with the potential axis
yields the flat band potential Ufb if the following
presumptions are assumed to be valid [27]:
1. The layer is at electronic equilibrium.
2. The potential drop at the interfaces is controlled by
the difference of the work functions of the related
phases.
3. A depletion layer is formed. The space charge layer is
exhausted of majority carriers (e.g., electrons in the
case of n-type semiconductors) and all defects are
ionized. As a consequence, the n-type donor level is
located above the Fermi level E F and the p-type
acceptor level is located beneath E F , respectively.
4. The energetic difference between the defects and the
band edges exceeds 3 kT, i.e., the extension of d sc is
larger than the Debye length.
654
5. The layer properties are homogeneous throughout
the layer and independent of the distance from the
oxide-electrolyte interface.
6. The potential drops at the interfaces are constant.
C. Extended Analysis ofC(U) Measurements
As shown above, the simple Schottky - Mott theory pre-
dicts straight lines in the C- 2 / U plot with a constant
intercept at Utb independent of time and polarization,
i.e., [d 2 ( C- 2 )/ dU 2 ] = 0. Experimentally, deviations from
the linearity are observed:
1. Deviations from linearity, i.e., [d 2 (C- 2 )/dU2t <0,
and negative slopes;
2. Shift of the intercept with the potential axis;
3. Influence of time.
These deviations are strongly connected with the
varying defect concentration N(E, x, t).
1. Deviations from Linearity
Deviations of the linearity are caused by either different
spatial N(x) or energetic distributions of the states N(E)
at the surface or within the layer [28,29]. A distinction is
usually not unambiguous. For example, a slope
dC- 2 / dU decreasing with increasing U may be caused
by either the exhaustion of the passive film for dsc >
dox [5], a defect concentration gradient decreasing
exponentially from the metal-oxide interface to the
oxide-electrolyte interface, dN(Y) /dx < 0, as it is often
assumed for passive films [30], or a contribution ofdeep
levels, i.e., a broader distribution function of the defects,
N(E). Then, the simple slope analysis I1C- 2 /11 U of
the overall lines yields the defect density at the
oxide-electrolyte interface and the lines are not sensitive
to the donor concentration within the oxide [31]. A nega-
tive slope is caused by, e.g., the charging ofdeep levels or
the formation of an inversion layer [5]. Further com-
plications arise, because the concentration gradient
°
dN(y)/dx> < may vary during redox reactions, e.g., by
intercalation of ions into the layer or surface reactions
[32]. The resulting change in slope depends on the nature
of the concentration gradient [33,34] caused by ion
migration or doping with foreign atoms. Examples are
discussed in Sec.Vand VI.
2. Shift of the Lines on the Potential Axis
A change in the bulk concentration ofthe charged defects
will lead to a change in E F and Utb, respectively, and this
is related to a shift ofthe C- 2 / Ulines on the potential axis.
An increase of the concentration gives rise to a cathodic
shift, whereas a decrease yields more anodic values of
Konig and Schultze
Utb according to Eq. (4), where Eq. (4a) describes the situ-
ation due to an energetic dispersion and Eq. (4b)
describes the shift of a spatial distribution:
I1U = kT . In(l + I1N(Ex )) (4a)
e N(Eo)
I1U = kT . In(l + I1N(X)) (4b)
e No
Surface reactions, on the other hand, will result in sur-
face states that give rise to a larger potential drop in the
oxide-electrolyte interface. Finally, Fermi-level pinning
will take place. The intercept with the U-axis varies
depending on the properties and number ofthe adsorbed
species within the Helmholtz layer [35]. Assuming
the states to be charged and a reasonable value of
2
CHL = 10 IlF cm- , a shift of about 0.1 V can be calcul-
ated [36] according to
ze· D· Do' N
11 U = -----=--- (5)
2· C~L
3. Frequency Dependence
The C(U) measurements are usually carried under
steady-state conditions, N(E, x) f= fit). Then, the fre-
quency dependence yields the rate of the charging of the
defects (localized states) and the recombination rates.
The levels of the localized states are located below the
Fermi level and act as deep levels NOL, leading to a fre-
quency dependence up to aboutI::::: 3 kHz [37,38].
But the frequency-dependent measurements also
include defect migration and will become time
dependent, N(E, x, t). To ensure constant properties and
composition, experiments have to be carried out with
extremely high time resolution starting at very short
periods of time. Because a frequency dependence exists
up to f::::: 3 kHz as mentioned above, a period of I ms for
one C(U) cycle is sufficient to provide constant layer
properties during the experiment.
4. Application and Analysis
1. Differentiation between local heterogeneities and
localized states in the mobility gap. A decrease of the
slope of the C- 2 ( U) lines with increasing potential,
[d 2 ( C- 2 )/ dU 2 ] < 0, can either be explained by a continu-
ous charging of localized states within the mobility gap
(energetic dispersion) [28] or an increasing concentration
ofdefects from the surface into the layer [39,40]. No separ-
ation is possible from the existing models and
experimental techniques.
l
 Bulk and Surface States of Reactive Oxide Films
2. Analysis ofconcentration gradients. An increase of
the slope C- 2 (U) lines, [d 2 (C- 2 )/dU2 ] > 0, on the other
hand, is readily explained by a defect concentration that
is decreasing with increasing distance from the surface.
Within a measuring period of 1 ms, the deep levels are
either in electronic equilibrium or can be neglected
altogether. Under these conditions, the local donor con-
centration, N(x), can be obtained from the gradient of a
C- 2 ( U) plot according to [26,39,41]
( N(x) = 2 . ( dU ) (6)
zeDoD sc dCs~ x
with the permittivity ofthe space charge layer DoD sc and
the charge of the defects, z = 1. Because the charge car-
riers will react within the Debye length of the space
charge layer located within the oxide film, the relevant
location is given by the extension ofthe space charge layer
at a given potential U according to
d _ Do' Dsc
sc - C (7)
sc
3. Analysis ofsurface states. The additional charge leads
to an increase of the electrode capacity by the additional
capacity Css. If the energy level Ess of the surface states
will be located near Ufb, Css will not dominate the overall
capacity and the surface states will lead to a shift of the
overall C- 2 / U line according to Eq. (5). A different situ-
ation can be observed if the distance of the energy level
of N ss from Ufb is large. Then, maxima in the C(U) plot
I
can be observed and the concentration can be derived
according to
Nss =~. JCssdU (8)
Based on the conditions discussed above, the distri-
bution of the charge carriers within the layer and on
the surface can be analyzed. Especially the time-
dependent depth profile can be described by
[dU/dC- 2 ]u =j(C-')u plots and is presented here for
various systems.
III. EXPERIMENTAL
A. Basic Pulse Program forTime-Dependent
Measurements
Various potentiostatic pulse programs were used to inves-
tigate both oxide formation and intercalation reactions,
respectively. For the latter type of experiment, the pulse
program applied is shown in Fig. 3. The experiment
started by polarization at the initial potential Uinit to
655
: formation: : oxidation reduction
Urad pre-
polarization
Up,a
Uinit
10s 10s
t
Figure 3 Experimental pulse program for potentiostatic
oxide layer formation, oxidation, and reduction.
ensure reproducible conditions for layer formation. Then,
the layer was formed at Uform within a formation time
tform. The subsequent polarization at Upre for a given
time t pre yields reproducible conditions for further
experiments. During the subsequent anodic pulse, the
oxidation process was examined at the oxidation poten-
tial Uox • Transients of the current density i =feu, t), the
electrode capacity C = feu, t), and the potential depen-
dence of the electrode capacity C(U) =feu, t) were
performed. After a certain time, the potential was
lowered again down to the reduction potential Ured to
study the reduction process.
B. Principles of C(f) and C( U, f)
Measurements
The measurements of the time-dependent electrode
capacity were also realized by a special program based
on potentiostatic pulses. The capacity is extracted from a
short potentiostatic pulse with an amplitude of
AU = 50 mVand a duration of At = 15-20 Jis. The related
capacitive charge is derived from the integrated
capacitive current density, i cap , according to Aqcap =
J icapdt. The capacity is then calculated accord-
ing to C = Aqcap/A U. The applicability of this method
depends on the absolute value of C, where InF:s
C:s 100 nF. The apparent surface has to be small
enough to facilitate capacitive charging within the
measuring period. On the other hand, it has to be large
enough to yield a detectable current density signal. For
this purpose, a fast rising potentiostat in combination
with a low resistance reference electrode has to be used.
Absolute values of the capacitive charge involved (about
1 nC) can be detected without difficulties resulting
in AC= InC/50 mV = 20 nF (e.g., 0.2 JiF cm- 2 for
A = 0.1 cm- 2).
656
Because i = icap + iF, the charge due to the faradayic
reactions /).qF must be small, e.g., less than 10% of the
capacitive charging /).qcap. Because the method depends
on the overall current density, it is important to analyze
the current components of any kind of side reactions
added to the capacitive charging during the duration of
the measurement. Current densities iF taking place
before the measurement are separated by a special sample
and hold device. Nevertheless, iF must be small enough.
The CCU) measurements at measuring potentials
U f- Uox f- U[orm were realized by a special staircase
pulse program shown in Fig. 4. One cycle with up to 12
values of C takes less than 1 ms and can conveniently be
carried out after a polarization time of t = 1 ms [42].
Every step represents one measuring potential U and
takes about 80 J1S to adjust potentiostatic control. The
capacity is derived from the superposition of the short
potentiostatic pulses as described above. The overall
staircase pulse program can be superimposed on any
potentiostatic polarisation potential.
The range of the measurement of the current density
depends on the rise time of the potentiostat. An special
system [43] supports the registration ofthe first value after
1 J1S. The registration of the electrode capacity depends
on the capacitive charging and a first reliable value can
be registered after 100 J1S (80 J1S adjustment of the
measuring potential Ustep and 20 J1S measuring pulse)
and the first CCU) cycle can be carried out after 1 ms.
c. Electrodes and Electrolytes
1. Nickel
The experiments were carried out with Ni wires
(A = 0.01 cm-z, purity 99.99%; Goodfellow). NaOH
1 M (pH 13.8) was used as electrolyte. An Hg/HgO/1 M
NaOH electrode was used as reference electrode. The
passive layer was formed by potentiodynamic cycling in
the potential range -0.2 V ~ U ~ 1.55 V with a scan rate
of dUidt = 20 mVis. The formation was carried out until
the potentiodynamic if U behavior became constant,
indicating complete formation. A layer thickness of
dox ::::; 3.5 nm was determined by ellipsometric measure-
ments at 632.5 nm. The redox measurements were
carried out in 0.1 M K 3/ 4[Fe(CN)6]/1 M NaOH.
2. Titanium
The experiments were carried out with both Ti wires
(A = 0.2 cm- 2, purity 99.6%, Goodfellow) and disc
electrodes (A = 0.2 cm- 2, purity 99.6%, Goodfellow).
H 2S04 0.5 M (pH 0.4) was used as electrolyte. An
Hg/Hg 2S04/O.5 M H2S04 electrode was used as refer-
ence electrode. The passive layer was formed by
Konig and Schultze
Up
I
1.3
~
1.2
1.1
0.9
0.8
0.7
o 100 200 300 400 500 600
t/ ~S
Figure 4 Experimental pulse program for the realization of
the C(U) experiments.
potentiostatic polarization at U[orm = 2 V (dox ::::;4 nm)
and 8 V (dox ::::;20 nm). The measurements under illumi-
nation were carried out using a l-kW Xe-lamp/
monochromator system. The electrode was illuminated
at), = 320 nm and P = 0.6 mW cm- z.
3. Iron
The experiments were carried out with Fe wires
(A = 0.06 cm -z, spectroscopical purity, Goodfellow).
The borate buffer electrolyte (pH 8.4) was prepared from
0.Q75 M NazB407 x lOHzO and 0.3 M H3B03 with 0.5 M
NaN03 as the supporting electrolyte. A hydrogen-loaded
Pd-wire with low resistance (typical R ::::; 100 Q) was used
as reference electrode.
All electrodes were embedded in an inert Polyester
resin and finally electropolished. All experiments were
carried out in typical electrochemical cells at T = 25 C. D
An Au-foil (A = 4 cm 2) was used as the counter electrode.
The electrolytes were prepared from analytical chemicals
and deionized water (system Millipore) and deaerated
by N 2 (99.999%).
The Hg reference electrodes were combined with an
impedance converter to minimize the electronic resist-
ance to less than 100 Q for ultrafast potential
adjustment. Unless otherwise stated, the potentials
given here refer to the hydrogen electrode in the same
solution (HESS).
Bulk and Surface States of Reactive Oxide Films
IV. INFLUENCE OF CHARGE CARRIER
DISTRIBUTION ON THE OXIDE GROWTH
The change in the potential distribution and related
field strength due to the variation in the concentration
and distribution of the charge carriers within the pass-
ive layers will influence the rate of migration and
diffusion, respectively. Furthermore, the ITR through
the oxide-electrolyte interface will determine the
amount of charge carriers within the surface layer.
Then, we have to discuss the influence on the rate
determining step.
Common models of the kinetics of passive layer for-
mation assume a rate determining ITR through the
metal-oxide interface [44] and the oxide-electrolyte
interface [19,45], respectively, or a field-assisted ion
transport within the layer itself [46,47]. As discussed
above, electronic equilibrium is assumed to be estab-
lished for good semiconductors like Fe or Ni but not in
the case of Ti. In the latter case, a frequency dependence
of the electrode impedance will be observed. Despite
the layer thickness of dox ~ 1-10 nm, a space charge will
be formed [5] that is usually neglected in the formation
kinetics.
The donor concentration obtained experimentally
amounts to N ~ 1020 cm -3. The corresponding extension
of the space charge layer reaches only 1-2 nm. These
°
results indicate a gradient dFldx > in the electric field
and an influence on the formation kinetics should be
likely. Additionally, the reactivity ofthe oxide-electrolyte
interface will be influenced, e.g., intrinsic redox pro-
cesses or anodic ETR such as 02 evolution [10,48,49]
A. Basic Kinetics of Oxide Growth Without
Space Charge
Common models are based on field induced transport
[Eq. (9)]. Under potentiostatic conditions and certain
assumptions, the inverse logarithmic law ofoxide growth
[Eq. (10)] can be derived:
i = io . exp( f3 . Fox)
Assuming a thickness controlled mechanism, the direct
logarithmic law [Eq. (11)] can be derived. It is assumed
that the electric field will remain constant and con-
sequently, liePox will increase and liePHL will decrease
during oxide growth [Eqn. (12)]. The decrease of the for-
mation current then can be explained by the number of
657
place exchange processes increasing with layer thickness
[e.g., 50, 51], an increasing structural order of the layer
[e.g., 52], or the number of interstitials [e.g., 53].
1
dox = const. - . ( f3 . Fox + 2.3log t) (11 )
c
i = i o . exp( f3 . Fox - c . d ox ) (12)
Again, certain assumptions have to be taken into
account:
1. The structure is independent of film thickness and
field strength.
2. No space charge is present.
3. The rate determining step remains unchanged.
4. The applied potential drop U - Utb is exclusively
located within the passive layer (liePox = U - Utb)
and liePox changes linearly between the metal-oxide
and oxide-electrolyte interfaces. This requires that
the potential drop within the Helmholtz layer liePHL
is either constant or negligible.
5. The ITR through the oxide-electrolyte interface is
not rate determining.
B. Influence of a Space Charge
Due to the amorphous character and nonstoichiometry
of real passive layers, a space charge region may be
established. The concentration of defects must be suf-
ficiently high (> 10 19 cm- 3) to generate space charge
effects within the thin passive layers. Different possi-
bilities have been described in various reviews [e.g., 50,
54-56]. The general description is based on the variation
of the field strength F(,<) by the local space charge density.
The main factors governing the local field strength are
the dielectric part Fdiel and the space charge part Fsc.
Fdiel at all locations x is given by the charged species
at the metal-oxide and oxide-electrolyte interface
assuming no charged components within the layer
according to Eq. (13) and describes the field strength
commonly discussed for layer formation:
(9)
x liePox
Fdiel =-d- (13)
ox
sc
F at the location x within the space charge layer
depends on the charge carrier concentration within the
layer and will be described by the Poisson equation where
°
x = is given by the beginning of the space charge layer
within the passive film:
x z·e·N 0
Fsc = D . D0 . xldsc (14)
658
The resulting local field strength at the location x is
given by superposition of all components:
Fl~cal = F;c + F dieJ
The average field Fox that governs the passivation pro-
cess is given by the integration of the local field strength
Fl~eal over the total layer thickness d ox :
ax
1
Fox = -d Jd
Fl~caldx
ox 0
The space charge can either be given by moving
species, M, or by immobile species that are part of the
layer structure, N, corresponding to the defect con-
centration. If both types are present, the resulting local
field strength is given by Eq. (17) according toYoung [57]:
x x 1 and finally the dielectric part will vanish. The resulting
FIoeal = Fdiel + 7J
.In(~ [M -(M-N). exp(-p. ;'·~o .NX)])
If the defect density N :::::: 1020 cm -3 is very high, a sep-
aration in immobile and mobile species is not possible.
Usually, only the immobile defects are taken into account
and Eq. (17) simplifies to Eq. (14).
The local field strength can be derived from the separ-
ation of the potential drop U - U/b that are determined
by the various types ofcharge carriers:
U - U/b = AcPox + AcPHL = AcPsc + AcPdiel + AcPHL
(18)
A separation is possible if the defect density is known.
Then, AcPsc at any location x can be calculated from the
Poisson equation. Again, x = 0 is given by the beginning
of the space charge layer within the passive film:
z·e·N .x2
AcPsc = 2 . D . Do
The dielectric part is given by the difference
AcPdiel = AcPox - AcPsc· AcPHL can be calculated accord-
ing to
1 1
AcPHL = qox . -C = (qsc + qdiel) . -C
HL HL
Konig and Schultze
From combination of Eq. (19) and Eq. (20), AcPox can
be calculated with the extension of the space charge layer
dsc:
(15)
dox
AcPox = . (CHL . AcPHL -z· e· N . dsc)+AcPsc
D ox ' Do
(21)
Taking Eqs. (19)-(21) into account, the separation of
the potential drop can be carried out by an iterative
(16) calculation. From the various potential drops, the local
field strengths are calculated.
If the defect concentration is small, the dielectric part
will dominate the potential drop, Fox remains constant
and the growth kinetics do not change. Ifthe carrier con-
centration within the film is sufficiently high, Fdiel
sc
decreases and a local field F will be generated. With
increasing layer thickness d ox , the overall potential drop
will be increasingly located within the space charge layer
shape of the potential drop AcP and the field strength
within the passive layer is shown in Fig. 2. The layer has
to be divided into the part near the oxide/electrolyte
where AcP is located and F sc increases linearly. In the part
(17) ofthe layer near the oxide-metal interface, dox··dsc , no
electric field is present.
If the field-assisted hopping in the space charge layer
remains the rate determining step, the model of Young
[57] can be applied, the field strength is given by Eqn. (16),
and the inverse logarithmic law will remain valid. If the
field-free part, docdsc becomes dominant, a change in
the rate-determining step to a diffusion controlled mech-
anism will take place [44,58] and the oxide growth will
now be described by the direct logarithmic law. The final
growth law results from the combination of the direct
and inverse logarithmic law [Eq. (22)]. The driving force
is given by the overall field strength within the space
charge layer according to Eq. (23). It is important to point
out that the field strength within the space charge layer
remains constant if the oxide growth is governed by
diffusion [13,59].
i = io . exp(p, F sc - c[dox - dscD (22)
(19)
SC
Fsc = d1 J'd Fi~ealdx = const. (23)
sc dox-dsc
Ofcourse, the reactivity ofthe overall system will be influ-
enced by the space charge. Any kind of reaction at the
oxide-electrolyte interface will be determined by the
(20)
space charge via Eqs. (15) and (18).
L
Bulk and Surface States of Reactive Oxide Films 659

c. Experimental Verification potentiostatic control

1. Simulation of Transients
(a) 2.2
The experimental verification of the model described
above is difficult. Therefore, an adequate analysis of the 2.0
transient data has to be developed. For this purpose, the 1.8
transients iq), qq), and cq) were recorded.
~ 1.6
The theoretical potential drops and resulting field -e-
strengths in dependence on log t are shown in Fig. 5 <:11.4
0..
based on the following parameters: concentration of 8 1.2
defects N = 1 X 10 20 cm- 3; dielectric number of the 't:l
~ 1.0
oxide D = 10; CHL = 40 IIF cm- 2 ; i1U = i1cPox = 2V
The growth factor c = 10 nm- 1 results from a fit of the '.....5 0.8
experimental data. The transport within the oxide layer 8. 0.6
is rate determining.
0.4
At t < 1 ms, no potentiostatic control is attained due to
the large initial faradaic charge q c::::: 1 mC cm- 2 and the 0.2
experimental current limitation to i = 10 A cm -2 of the
I
electronic circuit. After t = 300 lIS, a small linear (b)
increase of i1cPox takes place and the corresponding
i1cPHL decreases slightly up to t = 300 ms. Then, the
rate-determining step becomes independent of F and
";"
S
(.)
25 ~. l
I

~
~ 20 I
I HL
the overall potential drop is localized within the space ~

'0 I
...... I
charge layer. i1cPHL and i1cPox and F HL and Fox become I "'" F
constant after t = 300 ms. The absolute values of i1cPHL *~ .' I

\l
• I
15
and FHL depend on the value of CHL .
Figure 6 shows the simulated behavior of the layer
.sOIl
~
I::
10
/ F o, ~ F sc + F di• l
thickness (a) and the corresponding electrode capacity 1' ___
in dependence of log t (b) for various polarisation
potentials. The expected change in doxOog t) plot due to
the change in the growth law is not observed clearly. For
-'"
"'0

further interpretations, the analysis of the slope of the
lines ddox/d log t, yields a more useful indicator.
The electrode capacity, on the other hand, shows a sig-
nificant change in its time dependence. At small periods
oftime, C decreases with log t according to Eq. (10). Then,
Cbecomes constant when the thickness controlled mech-
anism takes place. Therefore, the experimental Cllog t
plot can be used to verifY the model.
2. Passive Layer Formation on Fe
Experiments on the passive layer formation on Fe
[13,60,61] in borate solution were carried out for
experimental verification [12,42]. The layers reach
thicknesses ofabout dox c::::: 1-4 nm. The applied potentials
are limited to 2 V due to the O 2 evolution. The trivalent
Fe-oxide films are nanocrystalline with a crystalline size
of 5 nm and oriented with the substrate [62]. The crystals
are formed by tetrahedral FeO~- and octahedral FeO~­
clusters. Cations occupy 12% ofthe octahedral interstitial
sites. The resulting band structure can be either calcul-
ated based on crystalline properties [63] or molecular
!.;:
Q.)
5
F diet
................ k'
o
-7 -6 -5 -4 -3 -2 -1 0 1 2 3
log(t1s)
Figure 5 Simulation of potential drops and corresponding
field strength in dependence on log t during a potentiostatic
polarization at U = 2 V for the transition from a
field-controlled mechanism to a thickness-controlled
mechanism. For details, see text.
orbitals [64]. Experimental verifications are realized by
ETR and capacity measurements [5]. The assumed
crystal structure based on Fe304 permits a continuous
change between the two-valent and three-valent oxide
[65].
The conduction and valence bands are formed by the
Fe-4s levels and the 0-2p levels, respectively. Different
localized states of Fe-3d levels are formed within the
mobility gap at low energies. Charge carriers within the
660 Konig and Schultze

potentiostatic control 40 i i i
:;;. Fe / pH 8.4

(a) 3
~s
30
Vro,m = 0.4 V(HESS)
~
2
U
20
I J:J F1-t=l
O.6V
s 10
-e..
-r5 o
> 1.2 V

1 -4 -3 -2 -1 0 2 3
log tis
do I ..........- .......-:
Figure 7 Electrode capacity C in dependence on log t during
oxide layer formation on Fe in borate buffer solution, pH 8.4,
at various formation potentials Uro rm .
(b)
15
capacity is reached after tform = 0.3 s for all potentials.
N
This behavior can be explained by a diffusion limited
's growth rate in terms of the above two-layer model.
~ 10
Figure 8 shows the influence of the growth rate as
~
U indicated by the slope (ddoxldlogt)( at a given
polarization time in dependence on the electrode
5 potential. The calculated behavior is shown in Fig. 8a
and the experimental results in Fig. 8b. For the
U - Ufb = 1.7 V simulation, the same data as in Fig. 5 are used. At longer
periods of time tform > 0.1 s, the lines agree quite well
o with the simulation. The deviation at short periods of
-6 -5 -4 -3 -2 -1 0 1 2 3 4 time can be explained by the lack of an adequate
crystallographic and band structure, respectively. Its for-
log(tis) mation requires at least a certain degree of crystallinity,
and this will take some time.
Figure 6 Simulation oflayer thickness and electrode capacity
Figure 9 shows the comparison of experimental
in dependence on log t based on the space charge model. Data 2
C- ( U) data with the simulated lines for Uform = 1.0,1.2,
as in Fig. 5.
and 1.5 V and the corresponding band structure after
tform = 100 s. Different charge carriers No, Nss, and
N m have been taken into account for the calculation [13].
oxide will be formed either by the interstitials, vacancies, The defect concentration No within the passive layer
or even stationary electronic donors and can be either decreases with Uform from No = 3.8 . 10 20 cm- 3 at 1.0 V
locally fixed or movable throughout the film. Surface up to No = 2.4 . 1020 cm- 3 at 1.5 V, which is due to an
states will be formed presumably by Fe-OR sites. increasing structural order with layer thickness [13]. It is
Figure 7 shows the time dependence of the electrode reflected by the increase of the slopes of the C- 2 ( U) lines
capacity during oxide formation at various potentials in the potential range Ufb SUS Ufb + 0.7 V.
Uform. At short polarization times t < 0.1 s, the capacity At higher potentials U> 0.7 V, the slope of the lines
decreases exponentially due to the growth and decreases. The absolute values decrease with Uform down
reorganization of the layer. A linear decrease of the lines to an almost constant value for Uform = 1.0 V. This cannot
according to Eq. (10) cannot be observed, but a constant be explained by either a concentration gradient or

L
 Bulk and Surface States of Reactive Oxide Films 661

(a) 1..,...-------,r---------....,
simulation
Fermi level
III
';IS E/eV
u 0.8

o~ 0.6
00
o
:§
~
0.4
8 0.1 s
'"0
'-""
'"0 0.2 Fe4s- I Fe(OH), Fe3d-levels
'-""
defects
levels I
-
,

(b)
CB
I donors
ND
surface
states
N ss
deep levels
N DL

';I 0.8
40rm = O.lso Fe/pH 8.4
S t = = 100s
~
u 0.04
U
S
-....
0.6 0 '-
~~-<r>~
0
fo

~
...... 0 0.03

- 00
0
'-....
0
"0
0
0.4
0.02
'"0 0.2
'-""
'"0
'-""
0.01

0.5 1 1.5
U rorrn N
Figure 8 Differential slope ddoxl d log [ in dependence on
Uform after different times [form for oxide formation on Fe in
borate buffer solution, pH 8.4. (a) Calculated data; (b) compari-
son ofcalculated and experimental data.
2
O......:J:i!:L-.......----L-.....,..-........--r--~
o U tb 0.5 1 1.5 2
UN(HESS)
Figure 9 Comparison of the calculated C- 2( U) plot (full
lines) with the experimental data (dots) during oxide formation
on Fe, pH 8.4, at various U form . The calculations are based on
the band model and charge carrier distribution pointed out in
the upper part ofthe picture. For details. see text.

localized states. Both would result in a continuous

decrease of the slope without reaching a constant value.
Furthermore, taking into account the behavior of the i(t)
and C(t) transient, it can be explained by interface states.
The surface states N ss are located 0.8 Vabove Ulb, which
corresponds to Uform = 1.0 V. At this potential, about
5% ofthe surface is covered with the states, correspond-
ing to N ss = 4 . 10 13 cm- 2 . With increasing Uform, the
concentration decreases down to I· 10 13 cm- 2 at
Uform = 1.5 V. In the potential range 0.7 V ~ U ~ 1.3 V,
the interface states govern the lines. At higher potentials,
deep Fe-3d levels will be charged and the lines will again
bend downward (NOL = 5· 1020 cm- 3).
The simulations on the basis of the results discussed
above are indicated by the lines. They agree very well with
the experimental data. These results together with the cal-
culations for layer formation (Fig. 8) will be conclusively
explained by the model described above.
3. Passive Layer Formation on Ni
A more pronounced effect has to be expected in the case
of a p-type passive layer like Ni oxide [59,66]. In this
system, a depletion layer is formed in cathodic direction,
whereas the passive layer formation requires anodic
potentials. Therefore, a determining space charge effect
occurs at potentials near U1b that corresponds to high
formation potentials.
As an example, in Fig. 10 the transients i(t), q(t), and C(t)
in dependence on log t during the passive layer formation
on a nickel electrode at various formation potentials
Uform are shown.
The transients i(t) decrease almost linearly after the
adjustment of the potentiostatic control with a gradient
of d log i/d log t ~ -1 independent of the potential. After
t ~ 3 s, side reactions like O 2 evolution and corrosion take
place and the gradient decreases. No change of the lines
662 Konig and Schultze

potentiostatic control
approach a constant value of C:::::10 !iF cm- 2 . This
0 behavior indicates the formation of a space charge layer,
,.... Utonn = 1.55V leading to a thickness-controlled mechanism at
-1
1
N

'su potentials Uform < Ufb. At Uform:::: Ufb, the lines are
-2 0.8V comparable, but the final value increases with Uform and
<
--~
:;::; -3
0.5V
the lines increase again with log t. A small increase of C
can already be observed at Uform = 1.0 V, indicating the
.9 ·4
influence of the flat band potential. The increase of the
-5 lines with log t is due to the increasing structural order
-6 of the layer and increasing amount of surface charge
8 according to the intrinsic oxidation of Ni-oxide.

6
N v. CHARGE CARRIER DISTRIBUTION DURING
'su INTRINSIC REDOX PROCESSES
~
4

--
""& A. Passive Films on Nickel
2 Besides the space charge effects during passive layer for-
mation (see Sec. IVC.3.), the passive films on nickel are
0 well known for their intrinsic redox process [32,68]. A
combination of electronic charging, intercalation of
100, 0 O.35V 0 protons, and structural changes takes place that changes
~ the charge distribution within the film. The passive layer
80
N

's consists of a double layer with an Ni-oxide at the

~ 60 1 •
O.7V
~ oxide-electrolyte interface [7].
U
40 ~ The reduced form behaves as a p-type semiconductor
~V
20
oIii i i i
-6 -5 -4 -3 -2 -1
log (tis)
Figure 10 Current density, corresponding charge density, and
electrode capacity during the passive layer formation on Ni at
various formation potentials in I M NaOH, pH 13.8.
can be observed at the reported flat band potential
Ufb::::: l.l V [67]. The corresponding charge density
increases almost linearly at any potential. icorr and i0 2 lead
to a faster increase of qat t::::3 s.
A more detailed picture is shown by the transients C(f).
At Uform = 0.35 V, a linear decrease with log t takes place.
The potential drop in the space charge layer is about
~1>sc = 0.75 V and the layer thickness is about
d ox ::::: 1 nm. Therefore, the oxide growth is controlled by
the high-field mechanism and ~1> extends over the whole
oxide. At Uform = 0.5 V (~1>sc::::: 0.6 V, d ox ::::: 1.3 nm) and
Uform = 0.7 V (~1>sc::::: 0.4 V, d ox ::::: 1.5 nm), the C(log t)
lines first decrease exponentially and subsequently
metal-oxide interface and a Ni-hydroxide at the
due to a small excess of oxygen. It is also assumed that
the conduction band is formed by the Ni-4 s levels and
i I I the valence band by 0-2p levels [69]. Due to the regular
o 2 octahedral symmetry of the crystal field, the 3d orbitals
will be splitted in eg and t2g orbitals. The t2g orbitals are
completely filled up in the case of the two-valent
Ni-oxide, and therefore the electronic conductivity is
poor (0'=3 x 10- 12 S/cm [70]). The distortion of
the crystal field symmetry of the NiOOH leads to
an additional splitting of the t2g-levels and to a higher
electronic conductivity of the trivalent Ni-oxide
(0' = 1 X 10- 4 S/cm [70]). Due to a small amount of
nonoxidized two-valent Ni, an n-type behavior is some-
times observed [69].
Due to the different reactivity of the various types of
Ni-oxides, the distribution of the active sites will vary
during the overall redox process [Eqn. (24)]. The
oxide-electrolyte interface will change due to H+ inter-
calation [Eqs. (25) and (26)].
NiOOH + H+ + e- ---+ Ni(OHh (24)
(Ni3+02-0H-)surface + H 20 + e----+
(NiH.20H-)surface+OH- (25)
 Bulk and Surface States of Reactive Oxide Films 663

Red1 Red2 Red3

(Ni 2+ ·20H-)surf + (Ni3+02-0H-)bulk -+ i_tO i _ t.o· 5 i _ r'
1
(Ni 2+ . 20H-hulk + (Ni3+02~OH-)surf (26) NiO" pH 13.8

- 0 1.55V--'+ O.5V
It has a strong influence on the O 2 evolution, which is
catalyzed by higher valence states of Ni [71]. Electronic
"I
E
-1
--
6'
cc
charging, H+ diffusion, and structural changes take place
in different time scales and influence each other. A separ-
ation is difficult and can only be achieved in the time
-
u
<C
::;:..
Cl
-2

-3
0

-1
E
3
0
()

-"
..2 -4 dlogi/dlogt = -0.5 3
domain. Due to the high conductivity of NiOOH, the
-5
reduction starts by changing the concentration of
charged species at the oxide-electrolyte interface. This -6 -2
concentration change is compensated by diffusion of ·6 -5 -4 -3 -2 -1 0 1
H+. For a detailed discussion, see Ref. 32 and 68. log (t."./s)

1. Charge Distribution During the Redox Process
During oxidation, the 02 evolution (anodic ETR)
dominates the overall current density, whereas the
kinetics during reduction can be examined with less inter-
ference by side reactions. As an example, Fig. 11 shows
the typical i{J) and q{J) curves recorded during reduction
at V red = 0.5 V The passive layer was oxidized first at
Vox = 1.55 V for tax = 100 s [32]. Three different time
domains can be distinguished.
1. Red1: The electrolyte resistance and the electronic
limitation (no potential control) lead to a constant
current density. Forty percent of the active Ni
atoms will be reduced (q::::;0.9 mC cm- 2, 100%:
q::::; 2.1 mC cm- 2). The conductivity is very high due
to the preceding oxidation. In the layer near the
metal- oxide interface, only electronic processes take
place. H+ intercalation for charge compensation take
place in a layer near the oxide-electrolyte interface.
2. Red2: The current density decreases with a gradient
of d log i/d log t::::; -0.5, indicating a rate-determin-
ing H+ diffusion (&j::::; 1.2 mC cm- 2). The resulting
1 total charge of q::::; 2.1 mC em-2 corresponds to
the amount ofactive charge carriers within the layer.
3. Red3: Further processes of restructuring or side
Figure 11 Transient of current density during reduction
(Ured = 0.5 V) of a passive Ni-oxide electrode in I M NaOH,
pH 13.8.
takes place. The lines show the typical behavior of a
p-type system. During oxidation, the gradient decreases
with lox, indicating an increasing defect concentration
from N A ::::;4 .10 20 cm- 3 after tax =10 ms Up to
N A::::; 1 . 1021 cm- 3 after tax = 10 s. During reduction, a
completely reversible behavior is observed.
The flat band potential Vfb::::; 1.1 Vas derived from the
intercept of the C- 2( V) lines with the potential axis is in
good agreement with values reported in the literature
[e.g., 67,72]. Due to the importance of the oxide-
electrolyte interface, a more detailed analysis of the lines
near the intercept with the V-axis is necessary. This yields
a significant tailing to higher potentials. From detailed
theoretical calculations and from published data [38], it
~
M-
(a)
14 ....---r-----;-;;-;-;--,-....--
(b)
---"""i"'ii'i!--,

reactions. The current density decreases with a gradi- '8 10

CJ
ent ofdlog i /dlog t::::; -1, indicating a field determined ~ 8
process.
~ 6
From the potentiostatic measurements, it is known =
;" 4
that electronic charging determines the period up to M

1-10 ms [32,68]. From C( V) measurements carried out 'u 2

Bee ~QQo
within this period, the distribution of the charge car- o +-,r-r~.,..,....,.._.__h-°T'°'_r_.c.......,._._~,.........-.-~,...,........_'_......__t
riers can be obtained. Figure 12 shows the simple 0.2 0.4 0.6 0.8 1.0 1.2 0.4 0.6 0.8 1.0 1.2 1.4
C- 2( V) relationship during oxidation at Vox = 1.3 V U (HESS) IV U(HESS) IV
(left) and subsequent reduction at Vred = 0.5 V One
measurement cycle qU) takes 1.6 ms. During this Figure 12 C- 2 ( U) during oxidation and reduction ofa passive
period, no significant change in the ionic structure Ni-oxide electrode in I M NaOH, pH 13.8.
664
can be concluded that the interface capacity CHL is nearly
the same as the capacity of the semiconducting phase
2
C sc . A value of about CHL::::; 15 ,uF cm- can be
estimated. According to Eq. (5), this leads to a shift of
the extrapolated intercept of the C- 2 ( U) lines of about
il¢::::;O.1 V in anodic direction. Therefore, U/b must be
corrected to U/b::::; 1.0 V This value corresponds to the
beginning of the oxidation observed experimentally and
can therefore be correlated directly with the formation
of an enrichment layer.
2. Interpretation
The relation ofthe ionic and electronic reactions strongly
influences the reactivity ofthe oxide-electrolyte interface
in the Ni - Ni-oxide system. During oxidation, the
activity of the interface at short periods of time is low
due to the poor electronic conductivity. The field-assisted
transport through the space charge layer determines the
rate during the overall reaction. At longer periods oftime,
additional charge carriers are formed and the extension
of the space charge layer decreases. The potential drop
moves toward the oxide-electrolyte interface, and finally
the charge transfer through the oxide-electrolyte
interface becomes rate determining. The oxidation
can already be observed at the flat band potential
U/b::::; 1.0 V Additional acceptors are formed at the met-
allic interface that move toward the oxide-electrolyte
interface during oxidation. A formation mechanism
involving holes via the valence band is likely [32].
During reduction, a high redox activity is expected due
to the high electronic conductivity. Reduction also starts
by charging 40% of the layer over a time interval of 100
,us. It is expected that reduction also starts at the
oxide-electrolyte interface. Then, the redox activity
decreases and diffusion of the H+ ions determines the
overall reaction. Ifall protons have moved out ofthe layer,
its electronic properties will again determine the con-
ductivity. The corresponding increase in space charge
layer extension can be followed by capacity transients.
B. Passive Titanium Oxide
Passive layers on titanium are among the most thoroughly
examined systems due to their high stability and wide
application [1,3]. Nevertheless, knowledge about surface
states and intercalation processes and about charge
mobility is still missing. The conduction and the valence
bands are formed by the 0-2p and Ti-3d levels,
respectively. The n-type character of passive Ti-oxide is
due to oxygen vacancies resulting in the formation of
Konig and Schultze
Ti3+ donors. Thin passive films are believed to be entirely
amorphous, whereas microcrystalline anatase [73]
and/or rutile are detected in thicker films [74,75].
Special interest is focused on the reduction ofTi-oxide
because the resulting MagneIli phases and other
suboxidesTin 0 2n - 1 (4:s n:S 28) behaves as metallic con-
ductors [76] due to the filling of the conduction band.
The reduction requires the intercalation of protons
similar to the processes within Ni-oxide. During these
processes, both donors, probablyTi3+ [77,78], and surface
states, probably OH-, are formed:
Ti0 2 + H+ + e- ~ TiOOH (27)
The reaction involves an ITR of H+ through the
oxide-electrolyte interface and the subsequent transport
within the film. At more cathodic potentials U < -0.2 V,
irreversible reactions take place and TiH species will be
produced with completely different properties [79].
A shift in U/b was detected for TiOOH species at the
oxide-electrolyte interface [80], indicating changes in
the surface charge. It is not known so far ifthe H+ species
are reduced first or iftheTi ions are reduced first and then
stabilised by the protons.
1. Transients of i(t) and C( U, t) and the Reversibilityof
the Redox Process
A passive film was formed at Uform = 2.0 V (dox ::::;4 nm).
Then, the intercalation process was investigated by
transients during oxidation at Uox :s Uform and reduction
at Ured :s 0 V (for the experimental program, see Fig. 3).
Figure 13 shows the transient iq) during oxidation at
Uox = 1.5 V and reduction at U red = 0 V and the cor-
responding charges. After capacitive charging, the
lines drop down almost linearly with a slope of d log if
dlog t = -1 without any significant structure. Avery small
capacitive charge of qeap::::; 10 ,uC cm- 2 can be derived.
No further reactions take place up to t::::; 10 ms. Then,
the charge increases almost linearly with log t up to
q::::; 15 ,uC cm ~2 after t = lOs. This is due to the slow inter-
calation reaction with an intercalation charge of
q::::; 5 ItC cm- 2 . At longer periods of time, side reactions
such as corrosion take place, the slope of the iq) lines
decreases and becomes nearly constant after t::::; 30 s.
Nevertheless, the overall charge involved is very small
q=IOO s: q::::;lOO,uC cm- 2).
The results are independent ofthe layer thickness [79],
and it can be assumed that the reaction takes place
in a limited part of the layer, presumably at the
oxide-electrolyte interface. This can be examined by
C(U) measurements. Figure 14 shows the resulting
C- 2 ( U) plots during reduction at U red = -0.1 V and
oxidation at Uox = 1.9 Vafter various polarization times.
 Bulk and Surface States of Reactive Oxide Films 665

2 With increasing polarization time, the lines shift to

-4 higher potentials without changing their slope. After
1
tred = 100 s, the gradient of the lines increases continu-
0 ously with U, [(dC- 2 /dU)/dU] > O. The reverse behavior
,....., -1 occurs during oxidation. As observed during reduction,
~
e(,J -2
no change in the lines take place up to t ox = 10 ms. Then,
< the lines become linear again. After t ox = 100 s, the slope
.....::::.
::::.
-3 return to the values of the lines before reduction.
OJ) OV -> U o.=1.5V Therefore, the overall redox process is fully reversible.
-4
oS Because the deviations of the lines are observed near
-5 the flat band potential, an increase of the carrier concen-
-6
tration near the oxide-electrolyte interface is assumed
to take place. These experimental results can be con-
-7 ..J.,."'T""T""'T""""T""T"""'T"""I"""T""T""" -"'-""'T"""'-"--ro'- -6 veniently explained only by the model described above.
-6 -5 -4 -3 -2 -1 0 1 2 3
2. Interpretation
log(tls)
The donor concentration depth profile will be derived
Figure 13 Current density and corresponding charge density
from the analysis ofthelines according to Eqs. (6) and (7).
during oxidation (Uox = 1.5 V) and reduction ( U red = 0 V) of a The reciprocal slope [dU / dC- 2] is proportional to the
passiveTi electrode, formed at Uform = 2 V in 0.5 M H 2 S0 4 . donor concentration and C- I reflects the extension of
the space charge layer. The resulting plot is shown in Fig.
15.
Up to tred = 10 ms, the donor distribution within the
The plots clearly show the expected n-type behavior. The layer is almost homogeneous (flat lines). Assuming a
lines show significant changes near to the flat band poten- dielectric number of 40, a donor concentration of
tial in both slope and intercept with the U axis. Up to a N;::;:,2.5 .10 19 cm- 3 is calculated. At longer periods of
reduction time tred = 10 ms, the C- 2( U) curves during time, N D increases near the oxide-electrolyte interface.
reduction are linear in the range 0 V ~ U:::: 0.5 v. At Within the layer, the concentration decreases
higher potentials, they bend downward. This can be inter- exponentially down to the value of the bulk within a few
i
1
preted by additional states within the band gap [e.g., 28]. nm (D = 40: d;::;:, 7 nm). The gradient increases with

(a) (b)

cathodic I Ured =-O.lV

0.14 0.14
anodic I UOx = 1.9V
0.12 0.12

~,-.. 0.10
tred=lms ~ tox =100 s 0.10 n,
~
e 0.08
(,J 0.08 ~ -'"
,-..

~
l")

....::::: 0.06 0.06 aN

"-'
N
'u 0.04 0.04
1 0.02 0.02

. 0.00 0.00
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
U(SHE)N U(SHE)N

1 !
Figure 14 C- 2 ( U) plots of a passive Ti electrode (Uform = 2 V) after various polarization times during cathodic polarization at
Ured = -0.1 V (a) and subsequent anodic polarization at Uox = 1.9 V (b).
666 Konig and Schultze

(a) (b)
dsdnm
o 2 4 6 8 10
70 I I I I I I I I 25

;;> 60
cathodic I U red = -O.lV anodic I U Ox = 1.9 V
"'*..... 20
'" 50
's ~

~ 40
15 l:.
=..
I-'

.-:- 30
S 10 e ~

~
~ 20
\ '"
5
~
....... 10 lOm~ ...:;.
o I Ims
i i ' I '
I _.. , I i i '
I0
0.0 0.1 0.2 0.0 0.1 0.2 0.3
Cl/[IlFcm-2rl Cl/[IlFcm-2rl

Figure 15 Analysis ofthe data of Fig. 14 according to Eq. (6): charge distribution within a passiveTi layer formed at Uform = 2 Vafter
various polarization times.

oxidation time from 10 20 /nm after tred = I ms up to the observed data in the transients (Fig. 13). The charging
4.5 . 1020 /nm after tred = 100 s. Then, the redox activity takes place within the first ps indicating the electronic
near the flat band potential increases and the surface character of the charge carriers.
begins to metalize. Differences in the electronic proper-
ties between different grains vanish [81].
Based on these data, theoretical calculations were car- 0.14 U red== -0, IV (intercalation)
ried out. Figure 16 shows the comparison of the calcul-
ated curves (full lines) with the experimental data 0.12
lines: simulation
during reduction (dots) after tred = 10 ms, 1 s, and 100 s. dots: experimental data
The following values were used for the simulation: ~,.-.. 0.10
No = 10 20 cm- 3 for the bulk; U/b =0.12 V, an
exponential increase of additional charge carriers Nss
'"'s
~ 0.08
from the bulk to the surface with 1020 cm -3 Inm forming
the surface charge. Ns s has to exceed No to show a ~
",'::::::: 0.06

l
detectable shift in the C- 2 ( U) lines. The bulk concen-
tration of No = 10 20 cm- 3 corresponds to a surface con- 'u
0.04
centration of N ss :::::: 2 . 10 13 cm- 2 or 2% ofa monolayer.
A monolayer corresponds to a bulk concentration 0.02
of Nss ::::::10 22 cm- 3 . The calculated lines fit the data
quite well and confirm the assumption of a concentra-
tion gradient near the oxide-electrolyte interface.
Furthermore, the calculations allow the estimation of a
maximum shift of the C- 2 ( U) lines of l\ U:::::: 1.5 Vdue to
the formation ofa monolayer of surface states.
From these data, a difference in the amount of
0.00 i ' I~ I
-0.4 -0.2 0.0 0.2
U(SHE)N
ii'

0.4

Figure 16 Comparison of simulation (full lines) and

I ;-~~
0.6 0.8
I
l
charge involved during oxidation and reduction of experimental data (dots) of C- 2 ( U) lines during reduction ofa
l\q:::::: 5 pC cm- 2 can be calculated that corresponds to Ti layer, Uform = 8 V, at Ured = 0 V
 Bulk and Surface States of Reactive Oxide Films 667

It is important to point out that the results indicate a
continuous change in the distribution and the concen-
tration of the charge carriers at polarization times
t ::::: 10 ms. Therefore, any experimental results over longer
periods of time refer to different surface properties.
VI. VARIATION OF THE REACTIVITY OF THE
INTERFACE OXIDE- ELECTROLYTE
Redox reactions taking place at the oxide-electrolyte
interface will change the local defect concentration and
will themselves be influenced vice versa by the change in
the distribution of the overall carriers. Besides the inter-
calation of protons into the passive layer and the charge
variation during the intrinsic redox process described
above, typical reactions changing the properties of the
interface are O 2 or H 2 evolution (see Fig. 1). Intermediate
products will be adsorbed and change the kinetics of the
charge transfer by the formation ofreactive surface states.
Further changes in reactivity can be induced by illumi-
nation thatyields additional charge carriers, which serves
to enlarge l1¢ss and reduces l1¢sc. Additionally, the
interface can be modified by the addition of conventional
redox systems like [Fe(CN)6]3-/4-.
A. O 2 Evolution at Passive Fe
Figure 17 shows the transient i(t) together with the density
of surface states N ss during the polarization of a passive
\ Fe electrode at Vox = 1.9 V in borate buffer. After
t ox ~ 300 /1S, i(t) becomes constant due to the dominating
O 2 evolution. A significant surface charge, on the other
hand, is first observed after about t ~ 10 ms. This is
derived from the C(U) measurements after various
periods of polarisation at Vox = 1.9 V shown in Fig. 18.
10
Fe - pH 8.4
Up to t ox = 10 ms, the lines still show the typical behavior
of the n-type oxide layer, indicating a dominating space
charge. At U> 1.7 V, the valence band or surface states
also contribute. After t ox = 100 ms, the capacity values
increase at U = 1.6 V, forming a maximum. It shifts to
lower potentials down to V ~ 1.25 Vafter t ox = 100 sand
increases from C ~ 18 /1F cm -2 after t ox = 10 ms up to
C ~ 25 {iF cm -2 after t ox = 100 s. No change in the lines
can be observed at potentials V < 0.6 V near the flat band
potential (Vfb ~0.2 V). The lines always show the
behavior for the n-type character. It is therefore apparent
that the passive layer will not be changed and that the
maximum describes additional charge carriers at the
oxide-electrolyte interface.
The maximum in Fig. 18 is assumed to reflect inter-
mediate states formed during the O 2 evolution, e.g.,
OH;d or O;d. Nss can be calculated according to Eq. (8).
The concentration increases almost linearly with log t
(Fig. 17). After t ox = 100 s, a coverage of about 10% is
reached. The O 2 evolution takes place already with 1%
coverage of those intermediates:
H 2 0 + (Fe - h+) =} Fe - OHad + H+
Fe - OH ad + (Fe - h+) =} Fe - Oad + H+ (28)
2Fe - Oad =} Fe + O 2
The surface states Ns s formed during the O 2 evolution
will be charged with increasing potential in the range of
35 . . . , . . . . . - - - - - - - - - - - - - - - - - ,
Fe! pH 8.4
Upre=1.0V
30
U ox=1.9V
25
~
E 20
(.)

~ 15
up. = l.OV 8

M
~
0 uo• = l.9V . Z U
eu Nss
6
"''"0-- 10
~ -1 ):l
<::. < 4 n
w
OJ)
3
..s2 N 5
-2
2
0
-3 0
0.5 1.0 1.5 2.0
0.0
-6 -5 -4 -3 -2 -1 0 2 3

I
!
!
log(t1s)

Figure 17 Transients of the current density and the surface

charge Nss during the 02 evolution at Vox = 1.9 Vat a passive
U(HESS)N

Figure 18 qU) measurements after various oxidation times

tox during the polarization at Vox = 1.9 VlHESS ofa passive Fe
Fe electrode (dox ~4 nm). electrode (dox ~4 nm) in borate buffer, pH 8.4.
668
0.6 V sUs 1.5 V No surface charge is present at
potentials Ufb sUs Ufb+0.5, and the space charge is
given by the donors only. If additional charged states are
present at the surface, the lines would be shifted to more
cathodic potentials due to the increase in A¢ss, which is
not observed. Furthermore, no species formed during
the reaction will move into the layer because this would
be reflected in the capacity values. The intermediate 0
species are located at the surface of the oxide.
B. O 2 Evolution and Additional Redox
Systems at Passive Hi
A different situation will occur for the O 2 evolution on
passive nickel. The reaction will be catalyzed by NiH
valent states at the surface. A concentration gradient will
be formed at the oxide-electrolyte interface due to the
de-intercalation ofH+ discussed in Sec.VA.
The higher valence states of Ni will form surface
states and govern the reactivity of the surface. Their for-
mation starts at the flat band potential Ufb ::::::1.0 V With
increasing Uox, the number of surface states will
increase, A¢ will be located increasingly in the
surface-near region, and the field strength will increase.
The electric field must be high enough to stabilize the
higher valence states; otherwise, the surface will be
again partially reduced and its reactivity decreases [32].
The addition of small amounts of a redox system will
stabilize the surface states [82-84] and reduce the over-
potential of the O 2 evolution. Figure 19 shows the cor-
responding Tafel plots of the O 2 evolution at a passive
Ni electrode in pure NaOH and with the addition of
1.25 . 1O- 5M Fe 2+/ 3+ and 1.25 . 10- 5 M [Fe(CN)6]3-/4-.
Both overpotential and even theTafel slope decrease from
b = 60 mV for the simple O 2 evolution up to b = 30 mV
with Fe 2+/ 3+ added.
Figure 20a shows the C(U) measurements at
Uox = 1.45 in 1 M NaOH (full lines) and with 0.1 M
K 3/ 4[Fe( CN)6] (indicated by "redox", dashed-dotted
lines) after tax = 1 ms and tax = 1 s.Without redox system,
the lines exhibit the typical p-type behavior. The values
up to C::::::70!iF cm- 2 above Ufb::::::1.0 V are due to
adsorption ofpresumably OH- species. At all potentials,
C increases from tax = 1 ms up to tax = I s, which can be
explained by the formation of surface states during 02
evolution. The lines with redox system added show an
increase in the C values in the range 0.6 V sUs 1.0 V
that is due to additional surface states formed by
[Fe(CN)d-/4-. Nevertheless, the absolute values also
increase at all potentials from tax = I ms up to tax = I s.
Therefore, two types of surface states will be formed
during O 2 evolution if a redox system is present. Both
Konig and Schultze
-3 -I [Fe(CN)i- l 4-
I 1.25*IO·~M
"I""'
S
u
~
~
.9
-4
b=60mV
1.50 1.55 1.60 1.65 1.70
U(HESS) IV
Figure 19 Tafel diagram of the current density vs. electrode
potential during the O 2 evolution at a Ni-oxide electrode in
presence of small concentration of redox systems.
enhance the surface activity but will not influence each
other. This can be explained by a small parallel coverage
of both types ofsurface states.
In contrast to the results on Fe, no maximum can be
observed. Therefore, the energetic level of the surface
states is located near Ufb of the Ni-oxide and the analysis
in terms ofa depth profile shown in Fig. 20byields further
information about their distribution. The charge carriers
are located within a very small region of about 2 nm at
the oxide-electrolyte interface. Their distribution is
dominated by the O 2 evolution, but the amount of charge
carriers is even higher in the presence ofthe redox system.
We therefore conclude that the addition of an active
redox system will change the amount of charge carriers
at the electrode surface. Even though the coverage is very
small, the activity of the passive layer will considerably
increase leading to an enhancement ofthe current density.
c. Photo-Induced Processes at Passive Ti
During illumination ofpassive titanium electrodes with a
sufficient energy, electron - hole pairs are formed within
the oxide. h+ migrate to the surface and will be discharged
by the formation of O 2 . During this process, the surface
reactivity and the concentration of N ss is changed.
The experiments were carried with a passive
I
film formed on a Ti electrode at U[orm = 8.0 V
(dox ::::::20 nm). The electrode was then prepolarized at
 Bulk and Surface States of Reactive Oxide Films 669

(a) (b)
300 ..,.....--.--------...,
70 VOX =1.45V VOX = 1.45V
60 >
*.......
f'l
f'l
~--ls/redox

·s CJ
200

20
lms I redox
-~

............

~~ 100
~ls

U
lms "C
.......
10
Is lms I redox
o +-"T""""-r--r--r---'1~""""--r"""T'"..,...-1 O+--..---r--.....,.---r-"""T'"--J
0.2 0.4 0.6 0.8 1.0 1.2 0.00 0.05 0.10
U(HESS)/V C-l/[f..LFcm-2rl
Figure 20 (a) C(U) behavior during the oxidation ofa passive Ni-electrode at Uox = 1.45 Vafter polarization times of tox = I ms and
I s in I M NaOH (pH 13.8) (full lines) and in I M NaOH/O.l M [Fe(CN)d-/ 4- (dashed-dotted lines). (b) Tentative analysis ofthe data
of a according to Eq. (6). The lines show the depth profile of the charge carriers described by the differential slope dU jdC- Z of the
C- z( U) plots. C- 1 is proportional to the extension ofthe space charge layer d sc .

1
U pre = Ured = 0 V. During the subsequent oxidation at
t;~
Uox = 2.0 V; both i(t) transients in the dark and under 0
illumination were examined (Fig. 21). The transient in
the dark shows the linear decrease with the well-known ,-... -1
slope of dlog i/dlog t ~ -I. Under illumination, the tran- ~
sient reveals a constant photo current density of S -2

-
CJ
i:::::: 0.1 rnA cm -z after tox :::::: 100 ms. Therefore, the
change in reactivity of the surface during illumination is
-<
;;;;
-3
clearly confirmed.
The change in the surface charge is reflected by the '='
charge detected during the backward polarization at
Ured = 0 V in the period 10 J..lS :s t :s 0.3 s. After the
oxidation at Uox = 2.0 V; the potential was lowered down
- ~ -4

-5
m = dlogildlogt

~5
to U red = 0 Vand the i(t) transient was registered with-
out illumination. Because no significant difference is -6 -1""".. .
observed between the transient during oxidation and
reduction (Fig. 13), only the reduction transient followed -6 -5 -4 -3 -2 -1 o 1
the oxidation under illumination is analyzed (Fig. 21). log (tis)
The value of ,1q~0.5 me cm- z derived thus is too
large for the reaction of states limited to the surface. The Figure 21 Current density transients during polarization ofa
sites have to be located within the layer, forming a gradient passive Ti electrode, Uform = 8 V: formation of surface states
as discussed above for the intercalation of protons (Sec. under illumination (320 nm,0.6 mW cm- z) and in the dark at
V.B.). In fact, it cannot be distinguished from the Uox = 2 Vand subsequent decomposition during polarization
transients i(t) alone if Nss will be formed or annihilated. at U red = 0 V without illumination.

1
I
r

1
670 Konig and Schultze

(a) (b) dsdnm

o 5 10 15 20
0.3 i i
OV(dark) -> Uox=2V (iIIJdark) 6
o ;;>
M *
,...., 15.0
dark, dark I- 5
o illuminated ~
~
,.-., =
tax 100s • e 10ms I 100s
~ 0.2

[4 ~=-
tJ

S ~
:::l 10.0
...... ~ ( 3
~ ..........
. ,...., '"
........ i
. ;t '\ 3.:..
N.......

'u
0.1
01
~
~:e
U
......
"'Cl
5.0
~~;::s~'\ _., 2

._ ...- i 1
illuminated, tax =100s
0.0
I~~
i i i ' 0.0 I , i , i , I 0
-0.2 0.0 0.2 0.4 0.6 0.8 no n2 n4 O~

U[SHE]N C- /[/-iFcm-2 1
1
r
Figure 22 (a) C- 2(U) plots during polarization at Uox = 2 Vofa passiveTi electrode, Uform = 8 V, with and without illumination. (b)
Analysis ofthe data from a: Depth profile ofthe charge carriers within a passiveTi-electrode.

This can be done by the examination of the C- 2 ( V) illumination. It must be assumed that the process is only
behavior. Figure 22a shows the C- 2 ( V) lines after partially reversible. Repeated polarization cycles will
tox = 10 ms and t ox = 100 s under illumination com- increase the intercalation depth of the 0 species and
pared with those in the dark during anodic polarization restructure the passive layer. A comparable situation is
at Vox = 2 V. The lines in the dark show the known shift known from the passive layer formation under potential
on the potential axis. Under illumination, the shift control. Although potentiostatic polarization reveals an
becomes smaller and the lines reveal a more linear
increase with a larger slope. This indicates that the charge
carriers effectively vanish during illumination. They will
be formed again during reduction at Ured = 0 V.
The analysis in terms ofa depth profile is shown in Fig.
I Ti02 ! I electrolyte
22b. The gradient vanishes during illumination and the d"x
states within the space charge layer also vanish. The

.
spatial region is given by the extension ofthe space charge --1• • • ~ _ o.so, +2H'

l
layer that is indicated by the increase at larger C- 1 values +--i I.
(about d sc ~ 12-16 nm). ........,• dsc 0
XPS examinations on Ti0 2 crystals indicate an o. - 11,0 +h+

oxidation of Ti 3+ sites to Ti4+ during photo-induced 02

, ~"
-n-o-.,n 0-8
evolution [85]. An insulating layer will be formed / 0,
irreversibly at the surface, leading to a decrease in the -@-n 0-0-8
I,
0/
photo activity of the crystal. Taking these results into "- "-
account, it must be assumed that the 0 vacancies will be -n-o-n
/ /
0-8

filled during the photo process. This reaction requires

the intercalation of 0 species into the layer.
0 I
•
A summary of the processes is given in Fig. 23 [79]. 0
species will be intercalated into the vacancies. Those near Figure 23 Schematic model of the activity of the system
the oxide-electrolyte interface will react during Ti/Ti -OX/02 under illumination.
"
 Bulk and Surface States of Reactive Oxide Films
amorphous oxide, a potentiodynamic formation wil1
establish a microcrystalIine oxide with distinguishable
grain properties. Furthermore, the formation of per-
oxides have to be taken into account [86].
VII. SUMMARY
Even though the semiconductor model can be success-
ful1y applied to passive layers under stationary con-
ditions, it has to be extended for reactive oxide films.
Charge carriers are formed during intrinsic and extrinsic
redox processes and their concentration varies with time,
resulting in a complex dependence N(E, x, t).
Because the properties will change very fast, the
measurements have to be carried out as fast as possible.
It is known from frequency-dependent measurements
that charging effects of the defects wil1 only take place at
times longer than 1 ms. Shorter periods wil1 reflect elec-
tronic charging only. This can be observed especial1y
1 during the redox process ofNi-oxide.
Time-dependent C(U) measurements reveal distri-
bution profiles of the charge carriers. If the gradient of
the C- 2 / U lines increases with U, [d 2 ( C- 2 )/ d U 2] > 0, a
depth profile can be derived. If the gradient decreases
i Elsevier Sci. Pub!. 1980.
with U[d 2 ( C- 2 )/dU2 ] < 0, either energetic dispersion or
spatial distribution are possible and cannot be separated.
A simple situation occurs if the carrier concentration
remains constant throughout the layer, Nf,x) = const. A
+ smal1 concentration of charge carriers does not change
the almost linear potential drop f..¢sc = f..¢ox throughout
the oxide layer. If the carrier concentration is high
enough, the potential drop wil1 be located within the
space charge layer that takes only a part ofthe oxide layer
at the electrolyte-oxide interface. Then, no potential
drop is located near the metal-oxide interface any more.
If the rate-determining step changes from the field
assisted hopping within d sc to the diffusion limited trans-
port within dox - d sc , the formation kinetics will change
to a thickness controlled mechanism.
The formation of charge carriers at the oxide surface
will localize the potential drop at the oxide-electrolyte
interface. Surface states formed during polarization and
remaining at the oxide-electrolyte interface will be
charged and do not change the bulk properties as it is
demonstrated for O 2 evolution at Fe-oxide (Sec.YLA.).
A different situation occurs if a redox system is
adsorbed at the surface or if the surface is changed dur-
ing the process. In the case of Ni, surface states wil1 be
1 formed by adsorption of active species like Fe2+/3+ or
[Fe( CNh]3-/4-. These states wil1 further enhance surface
reactions like O 2 evolution by catalysis (Sec.YLB.).
671
During intrinsic redox processes, ions wil1 move in
and out of the layer. A typical process is the intercalation
of protons forming concentration gradients N(x) moving
from the oxide-electrolyte interface into the layer. The
charge distribution N(x) will change the potential distri-
bution and the local field strength. It has to be assumed
that the activity of the layer wil1 show spatial variations
both normal and lateral to the surface.
Another important process is the photo-induced
intercalation via vacancies or interstitials. The concen-
tration gradients N(x) then flatten and the overal1 proper-
ties equilibrate. This effect has been demonstrated for
Ti-oxide (Sec.YLC).
ACKNOWLEDGMENT
We thank the Arbeitsgemeinschaft Elektrochemischer
Forschungsinstitutionen, AGEF, eY, and the Forsch-
ungszentrum Jiilich for financial support of this work.
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r
 37
Solid-State Voltammetry
Pawel J. Kulesza and Marcin A. Malik
University of Warsaw, Warsaw, Poland
ABSTRACT
Basic principles of electrochemical measurements of
solid, rigid, and semirigid (nonfluid) systems performed
in the absence ofliquid electrolyte phase typically at room
temperatures are discussed. Special attention has been
paid to the discussion of the mechanisms of charge
propagation, including bulk charge transport and
interfacial electron transfer. The theory is supported with
the examples of representative systems such as solid
solutions, organic polymers, redox melts, inorganic
mixed-valence materials, sol-gel processed structures,
and materials containing catalytically reactive centers.
The emphasis is also on experimental requirements,
and configurations of common cells for solid-state
voltammetry are provided. Application of micro-
dimensional electrodes, including ultramicrodisk elec-
1 trodes and interdigitated arrays, has led to the
improvement in the quality ofsolid-state electrochemical
I data and has provided new diagnostic and analytical
possibilities. Possible applications of the area are
mentioned.
1 I. INTRODUCTION
There is no precise meaning of the term solid-state elec-
trochemistry; it is defined and used rather loosely. If one
1 refers to aims and scope of a new Journal of Solid State
Electrochemistry published by Springer-Verlag [1], the
subject becomes very diverse because it covers very wide
range of topics related to the electrochemistry of solid
phases. In this context, solid-state aspects of electro-
1 chemistry would include, in addition to ion and electron
transport in solid materials and polymers, such areas
673
as electrocatalysis, photoelectrochemistry, corrosion,
batteries, galvanic metal plating, sensors, and many
other scientific and technological developments. In this
chapter, we focus on the new emerging area of solid-state
electrochemistry in the absence of bulk liquid phase that
deals with voltammetric and related studies of systems
existing in rigid or semirigid (nonfluid) forms at room
(ambient) temperatures. Therefore, we used in the title
the word "voltammetry" rather than "electrochemistry."
The other fields are not covered systematically herein
because their general scopes are of secondary interest to
our objectives. Nevertheless, we often refer to various
concepts that have been developed to explain behavior
of electrodes modified with polymer films exposed to
liquid-supporting electrolytes. Throughout this chapter,
attention is given to some thermodynamic and kinetic
properties that allow description of charge transport in
solid systems.
Historically, the progress ofelectrochemical studies of
solids was made possible because ofthe existence of solid
electrolytes, and it concerned the problems of energy
storage and production [2]. In solid ionic conductors,
the passage of current involves charged atoms (ions),
and it is accompanied by mass transport. The examples
of solid conductors [2-6] that have ionic conductivity as
high as that in concentrated liquid electrolytes [7-9] or
molten salts [10] are known. Most of these solid electro-
lytes with very high ionic conductivity are high tempera-
ture systems. More recently, it has become possible to
apply conventional electrochemical methods to the inves-
tigations of thin, three-dimensional, polymeric films of
organic and inorganic materials that are either exposed
674
to liquid-supporting electrolytes (modified electrodes) or
studied in the absence of liquid phase at room (or
comparable) temperatures [11-14]. R. W Murray and his
coworkers at University of North Carolina were the first
to introduce the term solid-state electrochemistry
(voltammetry) in its present meaning, and they signifi-
cantly contributed to the theory and understanding of
charge propagation in redox conducting polymers. P. 1.
Kulesza et al. at University of Warsaw demonstrated and
described solid-state voltammetric measurements of
bulk inorganic materials and powders. Credit should be
given to 1. A. Cox of Miami University, Oxford (Ohio,
U.S.A.) for his contributions leading to novel
amperometric sensors for gases, particularly with the
use of sol-gel processed materials. Direct and indirect
contributions to the area, originating from various
research groups headed by M. B. Armand, A. 1. Bard, L.
R. Faulkner, C. R. Martin, 1. G. Osteryoung, D. R.
Rosseinsky, R. M. Wightman, and M. S. Wrighton, are
obvious from the references cited here.
The applicable solid material is bifunctional in nature
because it serves as electrolyte medium and contains
electroactive centers. The applicable system's redox
centers are typically macroscopically immobile, and the
transport of electrons, which is based on hopping
(self-exchange), can be coupled to the displacement of
counterions. Thus, the overall charge propagation can
be formally made equivalent, as in the case ofelectrodes
modified with thin redox polymer films [13,15-19], to the
mechanism of diffusional mass transfer with the same
diffusion coefficient for both oxidized and reduced
states. This effective diffusive mechanism is sometimes
called redox conduction [15,18,19]. Although in the
case of modified electrodes the charge-compensating
counterions originate from an infinite external source,
the liquid-supporting electrolyte, the systems to be inves-
tigated for solid-state measurements in the absence of
bulk liquid phase are expected to contain not only the
redox centers, which are highly concentrated and
typically immobile [19-21] but also a sufficiently large
"ionic budget" [20] of mobile structural counterions.
Typical materials for solid-state voltammetry include
electroactive organic polymers consisting of fixed
molecular redox sites and mixed-valence ionically
conducting inorganic compounds. Various geometries
of measurement cells, particularly those utilizing
microdimensional electrodes, have been proposed to deal
with relatively slow (in comparison with conventional sol-
ution measurements) dynamics of charge transport
characteristic of rigid and semirigid media. Common
electroanalytical methodology has been successfully
extended to solid-state electrochemical measurements.
Kulesza and Malik
Thus, analytical characterization of materials, esti-
mation of electron transfer rates, and determination of
analytes using amperometric sensing have become
feasible. Measurements of reaction rates and thermo-
dynamic parameters permit the kinetic and mechanistic
analysis of processes. These processes may include
diffusional charge propagation in solid and semirigid
materials, diffusion-controlled solid-state reactions,
and phase boundary reactions at solid-solid and
gas-solid interfaces.
II. GENERAL CONSIDERATIONS: DEFINITION
AN D CLASSIFICATION
Solid-state voltammetry significantly differs from any
conventional electrochemical approach because in the
case ofa solid-state measurement there is no contact with
any electrolyte solution, either liquid or solid. A rigid or
semirigid material to be investigated serves generally as
both "electrolyte" and "electroactive species." The system
can be exposed to the atmosphere of inert gas, vapors of
water or a pure organic solvent [19-23], or, sometimes,
to reactive gaseous analytes [24,25].
It is useful to classifY materials into several categories
according to their chemical structure and possible modes
of charge propagation. The major classes of applicable
materials include polymer-attached redox molecules
and redox ions that are exchanged into ionomer polymers
[19,20,26], ionicallyconducting mixed-valence inorganic
solids [21,22], redox melts [27], and systems consisting
ofredox species that are dissolved in an ionic polymer sol-
vent or solid electrolyte [28]. As far as organic polymeric
and inorganic polynuclear systems are concerned, they
typically contain three-dimensionally distributed highly
concentrated redox centers between which fast electron
self-exchange (hopping) is feasible [19-22]. Although
these redox centers may have short range of mobility
about equilibrium position, they are classically fixed
and macroscopically immobile. Consequently, electron
hopping and ion displacement is required for redox
polymeric materials [11,18] to be electroactive. In the case
of systems composed of redox species dissolved in an t
ionic polymer solvent or solid electrolyte, a greater role t
of physical diffusion in the mechanism of charge trans-
port is expected. This is also true for materials prepared
by sol-gel processes [29]. They resemble rigid molecular
sieves in terms of their structure, but they have character-
istics of aqueous solutions because they are capable of
trapping electroactive substances and mobile ions within
their pore water islands. In such systems, redox centers
are not immobilized and, from mechanistic point ofview,
their physical diffusion would have to be coupled to elec- ,..
 Solid-State Voltammetry
tron self-exchange [30]. In any case, to provide charge bal-
ance during electron transfers and to support diffusive
transport of electrons and to minimize ohmic effects,
the material must host a sizeable population of mobile
counterions. By analogy to conventional electro-
chemistry, they serve the same purpose as ions in
liquid-supporting electrolytes.
Solid-state voltammetry experiments, where there
are no electrolyte solutions, can be performed on thin
monolithic films, true multilayer films (e.g., bilayer
films), and on bulk solids. Electrochemical responses
of the solid films, which are from hundred nanometers
to a few micrometers thick, usually show thin-layer-like
behavior characteristic of polymer-modified electrodes
exposed to liquid electrolytes. In the case of bulk solids,
a model of semi-infinite effective diffusion may be
operative; under certain conditions, conventional
solution-type voltammograms can be developed.
III. MEASUREMENT CELLS
The general problem in the construction ofelectrochemi-
cal cells for solid-state voltammetry was the necessity to
deal with the relatively high ohmic drops and poor ionic
conductivities of rigid and semirigid media relative to
those characteristic of liquid electrolytes. Consequently,
many cell arrangements, in which electrodes were placed
~
as close as possible, were designed for materials typically
in a form of thin films or layers. The most successful
setups, having various geometries, utilized micro-
dimensional electrodes [20-23,30-36], and they often
~I were miniaturized systems [17,19,20,24-26,37]. Appli-
cation of ultramicroelectrodes permitted successful
investigation ofbulk materials.
An important problem in solid-state voltammetry is
selection of a stable nonblocking reference electrode. A
common quasi-reference electrode is fabricated from
silver disk or wire, which is ultimately covered with
Ag 2 o. Such reference system fails if there is a chemical
interaction of silver with the investigated material that
results in the formation of blocking film. This situation
occurred in studies of transition metal hexacyan-
oferrates [38]. Electrode substrates covered with
mixed-valence cyanoruthenate [39] and AgI or CuI [28]
also were used as quasi-reference systems. They operate
most reliably in the cells utilizing microdimensional
working electrodes.
The selection of a reference system is simplified for
solids prepared by sol-gel chemistry at room temperature.
These materials contain chlorides in dried gel and aque-
675
ous microphases or residual water in sufficient amounts
so that a conventional Ag/AgCl reference can function
as in aqueous solutions [14].
The simplest cells for solid-state voltammetry were
designed in two-electrode sandwich configurations, and
they did not require any reference electrodes [40-43]. In
the case of a closed sandwich design (Fig. lA), potential
differences polarized two opposing plane parallel elec-
trodes in opposite directions [41,43]. The solid sample
was placed between the electrodes; such a setup was suit-
able for the investigation of thin films and bulk materials,
e.g., pressed powders. An alternative solution was to fab-
ricate an open-face sandwich on a glass slide (Fig. lB)
[24,40]. In the latter case, gold was evaporated in a
manner that produces a gap of d = 25-100 ,urn between
two Cr-anchored Au layers [24]. The gap and the gold
electrodes were covered with the polymeric material
to be investigated. Such two-electrode sandwich cells
were operating in a manner analogous to classic
biamperometry in which potential differences were
applied to two identical electrodes and scanned linearly
with time. Any nonohmic (faradaic) current flow was
accompanied by simultaneous redox processes occur-
ring at the interfaces formed by the opposing electrodes.
The interdigitated array (IDA) electrode systems
[19,31,44-46] are related to the sandwich and the
paired-band electrode designs [47]. Voltammetric
measurements utilizing sandwich geometries and IDA
systems [15,17,19,31,39,40,43,48] often have been used
to inspect the dynamics of charge propagation in
mixed-valence electron-hopping materials. The IDA
(Fig. lC) is a microlithographically defined array of
parallel microband gold or platinum "fingers"
(electrodes) supported on a silicon/silicon oxide wafer
surface [19]. A typical IDA has from 10 to 15 finger elec-
trodes that are separated by gaps (d) equal to 1-15 ,urn.
The sample is in the form ofa coating over the entire IDA.
The IDA may be used in a sandwich configuration as
the polymeric film (thickness, t) is placed in the gap
(which is also defined by the finger's height, h; e.g., equal
to 0.1 ,urn) between the two parallel precisely separated,
opposing electrodes. In addition to diagnostic
capabilities, it is noteworthy that both open-face
sandwiches and IDAs can be exposed easily to the sur-
rounding gaseous atmosphere and applied for solid-state
electrochemical sensing ofcertain gaseous components.
Avery useful sandwich geometry (Fig. ID) can be fab-
ricated by evaporation of a gold layer (e.g., 30 nm) onto
the entire plane of a thin film of a sample that was pre-
viously deposited on a gold or platinum substrate [18,19].
Contact to the overlaid gold electrode, which is porous,
can be provided through metallic platinum. Although
 f.
Kulesza and Malik ~
676

A electrode substrate B ~
t
e.g glassy carbon
gap

investigated
material disk gold
electrodes h
electrode
tygon
tubing

glass slide

ga'i investigated
material
~.L.

fingers
(e.g. Pt)

D cross-sectional view

investigated
film

layer of
porous
gold

epoxy
holder

Figure 1 Configurations of common sandwich and related cells for solid-state voltammetry. (A) A simple two-electrode sandwich
design, (B) open-sandwich design, (C) an interdigitated array (IDA), and (D) a system sandwiching a polymer film between a disk,
or microdisk, electrode (e.g., Pt, Au) and a vapor-deposited porous gold (to which electrical contact is provided through another Pt elec-
trode).

two-electrode monitoring of the current-potential
responses does not require a liquid electrolyte, a compar-
able liquid-phase experiment can be done because the
electrolyte ions can freely pass through the porous gold
layer. If the film requires preconditioning to obtain the
desired oxidation state, a preliminary liquid-phase exper-
iment (e.g., in four electrode mode [19]) is possible. The
general advantage of such a design, as well as of IDAs
and open-face sandwiches, is that the experiments can
be conducted with comparable ease in the presence
or absence of a liquid electrolyte, in contact with a
pure solvent, or in contact with an inert solvent vapor
that may contain electrochemically reactive gas
[24,25,31,39,49,50].
Solid-State VoItammetry
The development of ultramicroelectrode based tech-
niques [33,51-56] has led to an improvement in the quality
of solid-state voltammetrie data and to new diagnostic
and analytical possibilities [20-23,30,32,34-36]. One of
the most useful properties of ultramicroelectrodes is,
in addition to their compact size and utility in
characterization ofsmall samples, that they are much less
susceptible to distortion caused by uncompensated
resistance because the small currents make ohmic
drops negligible. Further, ultramicroelectrodes have per-
mitted kinetic measurements using cyclic voltam-
metry as fast scan rates as a result of their much
smaller uncompensated resistance and low background
(capacitance) currents.
A microcell for the investigation ofpolymer films (e.g.,
50.um thick) was designed in three-electrode mode
[31,35,36] where the electrodes, namely a central working
electrode (e.g., Pt disk of 10 .urn diameter), auxiliary, and
reference electrodes (e.g., in a form of tips of larger Pt
and Ag wires), were placed in a common plane (Fig. 2A).
The investigated film was cast onto the planar microcell
in a manner as to contact all three electrodes. To keep
the uncompensated resistance as small as possible,
care must be exercised to position the working
ultramicroelectrode as close as possible to Ag reference.
Such a cell can be easily operated in the absence or
presence of liquid electrolyte phase and in the atmos-
phere ofsolvent vapors or gaseous reactants.
For studies of bulk materials (e.g., single crystals of
heteropoly tungstic acids), another three-electrode
design (Fig. 2B) was proposed [21,32]. A 1O-.um carbon
fiber disk (working electrode) was positioned opposite
to the reference that itself was surrounded by a relatively
large graphite ring as a counter electrode. Initially, a
gel-type dry-contact Ag/AgCI reference was used [21],
but in subsequent studies [32] it was replaced with an Ag
disk reference electrode. Similar, but two-electrode,
designs (Fig. 2C) also were used for the investigation of
both bulk materials and thin solid films [22,23,34]. They
used an ultramicrodisk working electrode that typically
faced a large surface area (0.5-1 cm 2) electrode made
from glassy carbon or a metal such as Ag or Pt. Currents
flowing through the latter had very low densities in com-
parison with the relatively high density currents appear-
ing at the tip of an microelectrode. Consequently, the
large surface area electrode served not only as a counter
but also as a quasi-reference because it held a constant
potential (although one without any thermodynamic
meaning). The concept of such quasi-reference electrode
goes back to classic polarography with a mercury
pool electrode [22,23]. If the investigated material is
neither too large (thick) nor too poorly conducting,
677
the uncompensated resistance in voltammetry at a
disk-shaped ultramicroelectrode is dominated by the
resistance near the electrode surface; it is equal to 0" /4nr
(where 0" is the material's specific resistance) [21,33].Thus,
the performance of a two-electrode cell utilizing an
ultramicro working electrode is often not worse than that
of the analogous three-electrode design.
Three-electrode geometries, which used conventional
size electrodes, have been considered for the investigation
of powdered materials [42,49]. Ultramicroelectrodes are
usually too small to deal with such grain-type systems as
powders. Nevertheless, the size of working electrode
(glassy carbon rod; diameter, I mm) was much smaller
than that of counter electrode (platinum-sheet disk;
diameter, 2 cm) [49]. The same concept may be applied
to a two-electrode design on the condition that the refer-
ence system is nonblocking and the ohmic effects do not
complicate voltammetric responses.
IV. REPRESENTATIVE MATERIALS FOR
SOLID-STATE VOLTAMMETRY
A. Solid Solutions
An important class of electroactive polymers of interest
to solid-state voltammetry involves dissolution of the
redox species (neutral or ionic salt) into the polymer.
Examples of redox species include ferrocene, metal-
lotetraphenyl-porphyrins, metal polypiridine and
[Os(phenhf+ (phen = phenanthroline) complexes, and
tetracyanoquinodimethane [31,35,36,57,58]. They were
dissolved in thin films of the ionically conducting poly-
mer electrolyte formed by a metal salt (e.g., lithium
triflate (LiCF 3S0 3» in a solvating polymer, usually
poly(ethylene oxide) (PEO) [59,60]. Polymer electro-
lytes cover a wide variety of materials in which ions
exist and are mobile in the absence of any solvent or
low-molecular-weight plasticizer. Ionic motion does
not correspond to a net displacement of the
macromolecule. The materials are often cross-linked,
and the materials are bound together to form a single
three-dimensional network. The studies have yielded
values of such physicochemical parameters as homo-
geneous and heterogeneous electron transfer rates and
formal potentials. In addition, the characterization of
dynamics of diffusional mass transport and axial
coordination reactions in these polymers have been
performed. Electrochemical reactions in polymer
electrolytes can often be compared with those occur-
ring in conventional liquid electrolytes and
polyelectrolytes [61,62].
678 Kulesza and Malik

A B
working
microelectrode
auxiliary
electrode
(e.g. Pt)

I. I pJ microelectrode

investigated
1!!ii!Io.. " investigated material
film
epoxy

~",~epoxy
holder
counter electrode reference
(glassy carbon ring) electrode (Ag)

glass'body
of microelectrode

c
teflon
holder

I. I pJ microelectrode

investigated
material
I
large surface
area electrode

Figure 2 Typical ultramicroelectrode based cells used in solid-state voltammetry. (A) A planar three-electrodeconfiguni'tion. (B) a
three-electrode geometry in which the working ultramicrodisk electrode opposing reference and counter ele(;trodes.,and. (C) a
two-electrode design utilizing large surface area counter/semireference electrode.

B. Organic Polymers [19,20,40,77,78] or by electrochemical polymerization

Organic polymers can function as the host matrix for
redox centers [35,36,57,63-68] or as the electroactive
matrices themselves [50,69-73]. Most systems have
used ionically conducting polymers to serve as the
electrolyte medium and as the host for analyte. Rep-
resentative examples include the systems based on
PEO matrix that contains dissolved metal salts
[36,74,75] and the films of Nafion polymer [76]. Redox
polymers have been fabricated with electroactive sites
included within the main polymer chain of the polymer
of such moieties as pyrrole and vinyl groups attached
to electroactive species [19,20,79]. These systems com-
prise mixed-valence films. Studies have centered on
measurements of electron hopping and transfer rates
and, the state of solvation of the film [50,72,80] and
they have been performed under conditions that allow
[19,80,81] or preclude [19,72,82] the development of con-
centration gradients of reduced (electron donor) and
oxidized (electron acceptor) sites in the film bulk.
Another example concerns a conducting polymer, for
which the current-potential curves of electrochemically
Solid-State Voltammetry
doped poly(benzimidazobenzophenantroline) [40] can,
depending on the choice of environment, satisfY criteria
commonly associated either with redox conductivity
or electronic conductivity.
c. Redox Melts
It has been recently established [83-86] that amorphous
highly viscous redox melts or molten salts can be pro-
duced by combining such room temperature liquids as
oligomeric polyether chains of appropriate length with
redox molecular or ionic materials that are normally
crystalline at room temperature. The voltammetric
measurements ofpolyether-tailed cobalt bipyridine com-
plexes relied on the intrinsic ionic conductivity of highly
mobile CIO" counterions in the melt [86] because electro-
lytes like LiCI0 4 readily dissolve in polyethers. The
observed changes in the physical diffusion of cobalt
bipyridine complex and in the rate of electron
self-exchange between mixed-valence cobalt(II,I) sites
were associated with coordination effect between Li+ cat-
ion and polyether leading to chain cross-linking and a
decrease in chain segmental mobility motion. Redox
melts provide a novel environment to study the electron
transfer dynamics because physical mobility of redox
centers is greatly reduced but the overall charge propa-
gation is enhanced by electron hopping. In another study
[85], solvent dynamics control of heterogeneous electron
transfers of cobalt(III,II)-tris(bipyridine) complexes
was postulated. A redox melt was also investigated in such
a way as to make the effective diffusion of a bulky metal
complex on the "molecule-scale," i.e., confined to dis-
tances comparable to its own dimensions [27]. From a fun-
damental viewpoint, it is noteworthy that determination
of rates of "molecule-scale near-surface" transport may
permit probing interfacial potential distributions and
structural reorganizations that are occurring on a micro-
scopic scale relative to the bulk material.
D. Inorganic Mixed-Valence Materials
Investigation of mixed-valence inorganic systems
initially focused on Prussian blue (PB). The elec-
tron-hopping conductivity of PB was studied using vol-
tammetry on films over interdigitated array electrodes
in the presence and absence ofa contacting solution [87].
The rate constant for electron self-exchange between
hexacyanoferrate (III,II) sites in the system's lattice
was found to be significantly greater than the analogous
rate constant for the homogeneous solution reaction.
The so-called "insoluble" PB, FelIl[FeIl(CN)6h·nH20,
cannot show any ionic conductivity due to the
absence of structural K + IOns, the "soluble"
679
form, KFe III [Fe II (CN)6]' nH 20, is characterized by
fairly high ionic mobility of hydrated potassium counter-
ions even under solvent free conditions. Redox processes
can be observed with "soluble" PB and related
FeIII-substituted metal hexacyanoferrates III the
absence ofliquid electrolyte [23,41,42,87-93].
A simple two-electrode cell was proposed and
applied to monitoring current-potential curves of
KFe III [Fe II (CN)6]' nH 20 powder sandwiched between
two opposing electrodes [41]. The existence or possibility
of generation of mixed-valence sites, in addition to the
presence of some solvent (structural or adsorbed water),
was suggested as a requirement for the development of
appreciable voltammetric currents at room temperature
[41,88,89]. Despite the granular nature of the sample that
leads to some irreproducibility, useful electrochemical
data were obtained. The possibility of in situ Fourier
transform infrared/ATR spectroelectrochemical study
ofPB in the solid-state was also demonstrated [43].
Voltammetry or related methods can be used to the
study of inorganic oxides, polyoxometallates, and trans-
ition metal salts [21,22,39,49,94-97]. For example, the
reversible oxidation of VIV to VV in VOS0 4 . 3H 20 and
VOS0 4 . 5H 20 powders was studied using carbon fiber
electrodes [22]. Some attentionwas paid to the importance
ofthe content ofwater ofhydration (rather than adsorbed
water) in the material. Whereas voltammetric responses
ofhydrated VOS0 4 could be easily recorded, after vacuum
drying ofthe system, no redox activity was found.
The tetragonal heteropoly-12-tungstic acid single
crystals, which are protonically conducting well-defined
solids, have been shown to be very attractive model
systems for fundamental and electroanalytical char-
acterization of bulk materials in the solid state
[21,32,34,94,95]. The rigid polytungstate array has vari-
ous accessible oxidation states, and, while in the
mixed-valent WV1,v state, fast electron transport is
possible. The exceptionally mobile protons within the
hydrated three-dimensional structure permitthe electron
transfers to be readily coupled to the counterion
displacement. Absolute analytical approaches, which
allow estimation ofboth the effective diffusion coefficient
(Deff) and the concentration of redox sites (Co), were
proposed. The measurements of Deff and Co were a direct
result of the ability to perform voltammetric or potential
step experiments at ultramicroelectrodes in the limiting
time regimes where two distinct (linear and spherical)
diffusional patterns were followed. Indirectly, such
physicochemical parameters as the crystal's density and
the unit cell parameter were also estimated [21,34].
Fast-scan cyclic voltammetric measurements at
ultramicrodisk electrodes permitted addressing the
680
dynamics of heterogeneous (intrinsic) electron transfers
at the interfaces formed by carbon fiber substrates and
WVI.V sites in the crystals [21,32].
E. Sol-Gel Processed Materials
Materials prepared by the sol-gel process [29] have
characteristics of both aqueous solutions (in term of
mobility of substances in the pore water) and rigid mol-
ecular sieves (in terms of their structure). Such solid
matrices are synthetically simple, and their sorption
capabilities are quite general. In particular, they show
high sorption capacities for electroactive substances and
electrolyte ions. Consequently, the resulting semirigid
systems may be studied by voltammetry in the absence
of contacting liquid electrolyte phase. It was demon-
strated that silica obtained by sol-gel chemistry served
as an attractive host matrix for encapsulation of ferro-
cene [98] or heteropolyacids of tungsten [99,100]. In the
latter case, the effective diffusion coefficient
(D e ff=3xlO- 7 cm 2 S-I) was found to be larger than
expected for a solid electrolyte. Such behavior suggests
an important role ofresidual water existing in the systems'
pores. Further, templating of the internal structure of
silica by macrosystems such as micelles was postulated
for silica gels obtained in the presence of a surfactant
(Triton X-114). Consequently, the pores containing
hetrepolytungstic acid were fairly sizable, and the result-
ing Deff's were larger (2 x 10- 7 to 3 X 10- 6 cm2 s-l) when
compared with those determined for gels fabricated in
the absence of the surfactant (2-7 x 10- 8 cm 2 s-I) [99].
Heteropolytungstic acid that is immobilized in silica
retains the voltammetric characteristics that it has in a
liquid phase [99,100]. Electrochemistry studies of solids
prepared by sol-gel processes has been reviewed recently
[101,102].
F. Materials Containing Reactive Centers
Electrocatalytic processes at conventional modified
electrodes, i.e., at thin reactive films exposed to liquid
supporting electrolytes, have been intensely studied for
the last two decades [11,13,15-17]. Such systems, with a
three-dimensional distribution of catalytic (reactive)
centers, can possess both the experimental advantages
of typical heterogenous catalysts and the reactivity or
selectivity of the homogeneous analogs. In the most
advanced illustrations ofpotent electrocatalysis at modi-
fied electrodes, the active film contains, in addition to
efficient catalyst sites, redox mediators or other effective
distributors of charge. Consequently, electrons can be
carried rapidly to and from reactive centers. In principle,
Kulesza and Malik
the attractiveness ofsuch systems shall be retained during
solid-state electrochemical experiments (in the absence
of liquid electrolyte phase) that involve catalytic
oxidation or reduction of gaseous reactants. Having in
mind theory and diagnostic experiments developed for
electrocatalytic modified electrodes [103-105], the
dynamics of a catalytic system operating under
solid-state voltammetric conditions is expected to be
controlled primarily by charge propagation within the
reactive film and/or the catalytic reaction at the
film - gaseous reactant interphase or within the film.
Other factors, such as transport of a gaseous reactant in
air or in the film, the heterogeneous electron transfer at
the underlying electrode substrate are likely to be rela-
tively fast. One of the most important conflicts in these
systems concerns the need to distribute electrons (charge)
rapidly in the catalytic material vs. the need for the struc-
ture to engage effectively in fast and specific redox chem-
istry with gaseous substrate. The latter process implies
the existence of reactive sites in the material and the
necessity of a specific chemical reaction, typically
involving 0 and/or H transfers, to occur. To meet this
requirement, exposure to humid atmosphere or supply
of water vapor may have to be necessary. Under suf-
ficiently dry conditions, significant decomposition of
the material's hydration (solvation) structure would take
place, and this phenomenon would lead to irreproducible
and unreliable results. These problems are typically
resolved with the use of microdimensional working elec-
trodes where only small fractions of the reactive material
are electrolyzed.
Advances in the area of solid-state electrocatalytic
reactions seem to be of the primary importance to the
development ofnovel methods for amperometric sensing
of gaseous analytes. In this context, voltammetric
characterization of a frozen eutectic mixture [106] and
the amperometric detection of gas phase species with
the use of a cell, in which a microdimensional indicator
electrode (ca. 1 Jim diameter) was separated from an
auxiliary/quasi-reference electrode by a ring of glass or
epoxy [107], should be mentioned. In another example,
solid-state electrocatalytic oxidation of isopropanal at a
zeolite containing UO~+ was observed [81]. Cyclic
voltammetry was also used to study the catalytic
electroreduction ofoxygen at porous platinum electrodes
of the type used in fuel cells [108]. Interdigitated
microelectrode arrays coated with films prepared by a
sol-gel process that hosted sulfite oxidase and cofactor
were suggested as a design of an amperometric sensor
for S02 [98]. Thin films of ruthenium oxide cross-linked
and anchored by cyanoruthenates (covering the
open-face sandwich) and the analogous membrane-
Solid-State Voltammetry
impregnated systems were demonstrated to show
solid-state electrocatalytic activity toward oxidation of
methanol vapors [24]. The analytical sensing of methanol
and certain N -nitrosamines in the gas phase was possible
with the use ofa set of interdigitated array ofPt electrodes
that was coated with Nafion and thin films of a catalyst
based on ruthenium oxide [25]. It is noteworthy that both
solid-state extraction and electrocatalytic oxidation were
involved in the development of the signal in this design
of an amperometric sensor for gases. In another report
[39], an interdigitated microelectrode coated (by a sol-gel
process) withaglassypolymerofV 205 was demonstrated
to serve as a solid electrolyte for voltammetric studies in
the absence of bulk liquid phase. The redox behavior
of iron(II) 1,1O-phenantroline immobilized therein
occurred at virtually the same potential as in the conven-
tional solution-phase experiment at a Pt working
electrode. Indirect evidence for the electrocatalytic
oxidation of ammonia at Pt that was modified with a
polymeric ruthenium oxide catalyst also was presented.
The study of solid-state voltammetry of ammonia was
extended to a description of an amperometric sensor
[109]. More details about the development of
amperometric sensors designed for use in the absence
of liquid electrolyte phase can be found in the recent
review [110].
v. MECHANISMS OF CHARGE PROPAGATION
In solid-state electrochemistry, depending on the
experimental conditions (e.g., type of polymeric
material, nature and concentration of redox centers,
mobility and availability of counterions), the overall
transport process can be controlled by a variety of
phenomena such as electron hopping rate, counterion
migration and ion-pairing, coupling of physical
diffusion, and electron hopping [19,20]. Because the
applicable materials are typically rigid or semirigid
(nonfluid) systems, physical diffusion of redox centers,
segmental motion of polymer chains, and polymer
diffusion can often be neglected. Regardless the actual
mechanism, the situation is advantageous when the over-
all rate of charge transport in the investigated material
obeys Fick's law ofdiffusion; then it can be characterized
by an observable parameter defined as the apparent or
effective diffusion coefficient, D app or Derr.When the elec-
tron self-exchange rate, rather than the mobility of
charge-compensating ions, is the kinetically limiting
factor, it is plausible to describe currents arising from
electron hopping in terms ofa Fickian model with equiv-
alent electron diffusion coefficients, De.
681
A. Bulk Charge Propagation
Several theoretical treatments have related such a macro-
scopic property as De to site-to-site electron exchange rate
constant (k ex ) [19,111-114]:
(1)
where C T is the total concentration of redox sites, e
stands for a geometric factor that in the case of
three-dimensional electron hopping becomes equal to ~
and b is the distance between the redox sites at the time
ofelectron transfer that is usually estimated as the average
intersite distance, (C T N A )-1/3, with N A as Avogadro's
number.
It comes from Eq. (1) that both the density of the redox
centers (CT ) and the rate constant for electron
self-exchange (keJ must be large enough to develop a
diffusion-controlled current. The actual site densities
are between 0.5 and 4.5 mol dm-\ and the average site
spacings are from 0.4 to 1.8 nm for the typical undiluted
organic redox polymers, melts, polymeric (solid)
solutions of electroactive species [19,20,26,27,31], and
model inorganic mixed-valence polynuclear materials
[21,32,87,94]. The respective parameters may be different
in the case ofthe materials prepared by the sol-gel process
[30] and the simple redox molecule solutes dissolved in
rigid polymer solvents [20]. These systems are likely to
propagate charge according to different mechanisms that
involve coupling of physical diffusion and electron
hopping.
The coupling of physical diffusion and electron
self-exchange was initially developed to describe electron
self-exchange reactions in solutions of redox ions [20].
The experimental diffusion rate, D app , was found to be
dependent on the physical diffusion, D phys , and the effec-
tive electron transfer rate constant, kapp, as follows:
(2)
This equation shall be used together with the following
relations:
l/kapp = l/k ex + l/kd (2a)
and
(2b)
where k d is the diffusion-controlled rate constant. In
liquid solutions, where physical diffusion is relatively fast,
i.e., on the level from 10- 6 to 10- 5 cm 2 S-l, electron
self-exchange does not contribute significantly to
the overall transport [D app in Eq. (2)]. The same obser-
vation seems to apply to sol-gel processed systems that
682 Kulesza and Malik

]O~~H o

o o
i1E
Figure 3 The current responses (vs. the potential differences, i1E between electrodes) obtained with the use of sandwich-type con-
figurations. Development of (A) the steady-state limiting current in the case of a thin film, (B) steady-state voltammetric peaks sym-
metrical around i1E = 0 V (dotted line marks initial potential scan) for thick films or pressed powders (bulk materials), and (C)
exponential dependence when voltage, rather than concentration, gradients are generated (e.g., in the case of insufficient mobility or
population of counterions).

(though dry and similar to ionically conducting molecu-
lar sieves in terms of their structure) have characteristics
resembling aqueous solution in terms of mobility of sub-
stances in the pore water [29]. The situation is different
in the case of redox species dissolved in polymers where
rates of physical diffusion are much smaller. When elec-
tron self-exchange between the redox sites is fast, i.e., kex
is high, the D app values are expected to be enhanced by
electron hopping mechanism. Though separating elec-
tron and diffusion rates is not generally straightforward,
certain experimental approaches for redox monomers
have been described [19]. They rely on the so-called
Dahms- Ruff relation [113] which in its corrected form
[20] is as follows:
D app = Dphys + De = D phys + k ex 15 2 C T /6 (2c)
In both organic redox polymers and inorganic
polynuclear materials, the mixed-valence sites typically
differ in oxidation state by one electron and, therefore at
least one state must be ionic.To preserve electroneutrality,
the electron transport must be accompanied by the
unimpeded motion of charge-compensating, structural,
or interstitial counterions. These counterions are
typically small hydrated cations (H+, K+, Na+) or anions
(Cl-, ClOi, BFi). Their population must be high, and
they must have good diffusive mobility within the
material's structure [19-23]. In many cases, the overall
kinetics is controlled by counterion diffusion in the
material rather than by electron motion [19,20,22]. Then,
it is more appropriate to describe diffusional charge
transport in terms of Deff or D app instead of De [Eq. (1)].
The actual extent of displacement of counterions
during individual electron hops is a subject of con-
troversy. It is commonly accepted that transient electro-
chemical experiments like cyclic voltammetry require
"macroscopic" motion of counter ions [13,19]. If the
current-potential experiment is performed in a sandwich
configuration and the steady-state limiting current (ilim
occurs (i.e., when the concentration gradients are
maximized and are equal to C T / d, where d is the
thickness of the sandwiched mixed-valence film), it is
believed that the current flow would not require signifi-
cant displacement of counterions, and therefore only
"microscopic" motion of ions is postulated [19,20].
Because, in the latter case, the electron hopping event is
primarily related to the electron dynamics, steady-state
rather than transient experiments are recommended for
studies aimed at determination of the electron hopping
rate. A relevant relationship is Fick's first law as applied
to the steady-state limiting current (Fig. 3A) [26,40]:
ilim = nFACTDe/d (3)
where A is the cross-sectional area of the sandwiched
film, and nand Fhave their usual significance. It has been
found that both him and De are maximized when the
material is in the 1 : 1mixed-valence state, i.e., it contains
equal amounts of reduced (electron donor) and oxidized
(electron acceptor) sites [19,20]. It also should be recalled
that although "microscopic" counterion motion influ-
ences the electron transfer to a lesser extent than does
"macroscopic" counterion diffusion, some migration
effects may still appear in the microscopic case [115].
Use of Eq. (3) generally requires thin films [20]. For a
given experimental time, t, this thickness must not exceed
the diffusion layer thickness, (2D e t)1/2. Such limitation
has applied, for example, to the powders of transition
metal hexacyanoferrates that were pressed between two
Solid-State Voltammetry
sandwich-forming electrodes [41,88,89]. The resulting
steady-state current-potential responses were in a form
of symmetrical peaks around 0 V (Fig. 3B).
An extreme situation can be imagined where popu-
lation of counterions is low or they are immobile on the
experimental time scale [19]. In these cases, the mass
transport (hopping) of electrons cannot be supported
with ionic motion and the development of electrolytically
generated concentration gradients is precluded [26,40].
The current developed with such mixed-valence
materials is exponentially related to the applied voltage
(Fig. 3C), but not small voltage gradients it can be
linearized [82,116]. Within this linear regime, the electri-
cal (molecular) conductivity, (J, can be related to the
electron-self exchange dynamics [19] and expressed in
terms of the electron diffusion as
(4)
where p is the fitting parameter (ideally equal to 1), and
CR and Co represent concentrations of reduced and
oxidized sites, respectively. A similar theoretical
approach has been proposed for dielectrics doped with
electron donors and acceptors. The electron diffusion
coefficients (De) in Eq. (3) and (4) are expected to have
different values.
The measurement approaches described above allow
probing of environmental effects (roles of structural
counterions, solvent vapors, and/or liquid electrolyte
microphases) on solid-state electron transfer rates
[19,20,26,40]. Under certain conditions, solid-state
electroanalytical measurements often permit separation
of ionic conductivity from mixed-valence electronic
transport [19,20].
B. Interfacial Electron 'ft'ansfer
Solid-state electrochemical approaches can be used
to estimate the standard (intrinsic) heterogeneous rate
for the electron transfer at the interface formed by an
investigated solid and a surface of the microdimensional
working electrode [21,32,83,85,117,118]. Cyclic volt-
ammetry can be used on condition that the electrode pro-
cess is controlled simultaneously by effective diffusion
(linear) and interfacial electron transfer. In other words,
sufficiently fast scan rates are applied to make the
diffusion-controlled system show some irreversibility. i.e.,
behave quasi-reversibly.
The basic kinetic equation in the Nicholson method
takes a simplified form in solid-state voltammetry
[21,23] :
'P = ko/[DeffJrv(nF /RT)]1/2 (5)
683
because the D eff has the same values for the oxidized and
reduced species and the transfer coefficient disappears.
The standard heterogeneous rate constant, ko, is cor-
related with a peak separation dependent kinetic
parameter, 'P, as described and tabulated elsewhere [7,9].
Care must be exercised to keep the uncompensated resist-
ance small enough to make potential drops negligible.
When uncompensated potential is not reduced to
zero, positive feedback (electronic compensation) can
effectively reduce it further [117]. The Nicholson approach
has been successfully used to determine heterogeneous
rate constants at the interfaces formed with heteropoly
tungstic acid single crystals [21,32], redox melts [83,85],
and redox-conducting polymers [117-119]. An alternate
method makes use of steady-state voltammograms at an
ultramicrodisk electrode for the measurement of the
standard heterogeneous rate constant of ferrocene and
its derivatives in polyelectrolytes [120,121]. The theory
and equations have been developed previously for
quasi-reversible redox reactions in solutions [122]. The
actual measurements require the availability of a set of
electrodes with different radii and the accurate potential
measurements. Further, it is often difficult to obtain
steady-state plateau currents in the solids having low
diffusion coefficients (see Sec.VI). AC impedance at an
ultramicroelectrode has also proved to be a powerful tool
to study readox reactions (Fe2+/3+ couple) in solid poly-
mer systems (long-chain solid polyethers) characterized
by low ionic conductivities and diffusion coefficients
[123]. In general, heterogeneous electron transfer rates
are smaller in rigid and semirigid media compared
with monomeric fluids [120] and concentrated solutions
[32].
VI. NATURE OF ELECTROCHEMICAL
RESPONSES
With transient electrochemical measurements in
solid-state systems, the ultimate goal is to have the situ-
ation where regardless of the details of the charge propa-
gation mechanism, the overall mass transport is
diffusional and related to apparent (effective) diffusion
coefficient, Dapp (D eff ). By analogy to experiments of
polymer modified electrodes [8,11,13,124,125], it is
important to distinguish between the semi-infinite
diffusion and thin-layer-like cases. The diagnostic cri-
terion applicable to a thin-layer system is that for a given
experimental time, t, the diffusion layer thickness
(2D app t)1/2, is smaller than the material thickness, d. At
the semi-infinite linear diffusion limit, (2D app t)1/2 « d,
voltammetric peak shows the classic diffusive tail (Fig.
4A), and the peak current, i p , depends linearly on square
684 Kulesza and Malik

c
-
c:
~:::J 0 o o
U

Ef Ef Ef
Potential

Figure 4 Voltammetric current-potential responses characteristic of (A) bulk system (semi-infinite linear diffusion), (B) thin-layer
type behavior, and (C) intermediate situation (between cases A and B).

root of scan rate, V 1/ 2 , according to the Randles- Sevcik dimensionless time parameter r=4D app t/r 2, where r is
dependence [7,8]: the electrode radius. Iffor the fast scan rate (short time)
experiments, where r«l, the diffusion field is small com-
i p = 2.69 x 1Q5 n3/2 AD app 1/2C 1 2
ov / (6) pared with the electrode radius, here, the charge propa-
gation mechanism will follow the pattern predicted
where Co stands for the concentration of mixed-valence
for linear (planar) diffusion perpendicular to elec-
sites that either already exist or can be electrolytically gen-
trode surface. The result is a typical peak-shaped
erated within the material. At the thin-layer limit,
voltammogram with a diffusional tail (Fig. SA). On the
(2D app t)I/2 » d; now, the shape of voltammetric peaks
other hand, large values of r, which correspond to the
is more Gaussain type, and i p depends linearly on v. The
slow scan rate (long time) experiment, may cause the
latter situation is rare in solid-state voltammetry, and
hemispherical diffusion layer to greatly exceed the size
intermediate voltammetric patterns are often observed
of the electrode; here, spherical (radial) diffusion
(Fig. 4C). In the above discussion, it is assumed that elec-
becomes predominant. In the limit, this situation pro-
trodes have conventional, rather than micro, sizes.
duces a sigmoidal steady-state voltammogram (Fig. 5B).
An important characteristics of the ultramicro-
Currents generated at ultramicroelectrodes are depen-
electrode-based-state voltammetric measurements of
dent on their geometry. For a disk-shaped microelectrode,
certain bulk redox-conducting materials is that by
the limiting plateau current is as follows:
analogy to classic solution experiments, the nature of
mass transport may depend on the time domain
[33,126,127] or, more precisely, on the value of the ilim = 4nFrD app Co (7)

B
-e
c:
...:::J
U

Ef
o -- Ef
Potential

Figure 5 Ultramicroelectrode based solid-state voltammetric responses of a bulk material obtained in two (short and long) time
regimes, i.e., at sufficiently (A) fast and (B) slow scan rates.
Solid-State VoItammetry 685

contribution from •• "2

radial diffusion" ~ 3b

Possible~
...
C
t
kinetic
CD ohmic/migration
•
. - / _ ...1
• • ... ...:
... 'I'
~ limitations •• ' " I

~::::::J limitation ca
.c ",.,f.
•
I
I

o o ". ... ideal case

"./ (linear diffusion)
...... /
_ (. : .steady state o ~~
A
(//IJ

,. ,. radial diffusion ~~~~------ kinetic limitation

,. ~~ 3a B
00 V
1
V
2
V
3 o
Square root of scan rate Square root of time
Figure 6 Characteristic responses in diagnostic experiments at ultramicroelectrodes. (A) Voltammetric peak current plots ys. square
root of scan rate and (B) chronocoulometric charge dependencies on square root of time.

An important analytical case is that ofa material with
properties that are amenable to an experimental time
domain that includes both limits of the linear diffusion
and the spherical transport. By performing cyclic
voltammetric or potential step experiments at each limit,
data are generated that permit calculation ofthe concen-
tration of mixed-valence redox centers, Co, and the
apparent (effective) diffusion coefficient, D app (Deff) for
charge propagation in the material [21,30,32,34]. It is
noteworthy that this approach is designed for bulk
materials; that is, for a given experimental time, t, the
thickness of the material must exceed the diffusion layer
thickness (2D app t)I/2. In addition, it is expected that the
systems are characterized by fast dynamics of charge
propagation. For materials that have a rather low D app
(e.g., below 10- 10 cm 2 S-I, impractically slow scan rates
or extraordinary small ultramicroelectrodes are required
for radial diffusion (T » 1).
It is assumed above that the redox reactions are
electrochemically reversible and, under conditions of
ultramicroelectrode based voltammetric experiments,
there are no significant migration and ohmic limitations.
It has been recognized that such problems could appear,
particularly, at shorter time scales or even at very low cur-
rent [117]. Obviously, they will complicate interpretation
ofvoltammetric experiments in the solid state. Hence, it
is crucial to perform diagnostic experiments, which
include the plotting of dependencies of i p on vl / 2 (or v),
before any conclusions about the model of charge propa-
gation are made. For example, a linear portion of
i p - v I /2 dependence extrapolated to a zero intercept (Fig.
6A) is consistent with the linear diffusion regime. In other
words, voltammetric peak currents can be described in
terms of Randles-Sevcik dependence [Eq. (6)] in the
range ofscan rates from V2 to V3 in Fig. 6A. At sufficiently
slow scan rates (below VI in Fig. 6A), when voltammetric
currents become independent of scan rate, steady-state
plateau currents are developed [Eq. (7)], and such
behavior is indicative of the predominantly spherical
(radial) mass transport to the electrode surface. At fast
scan rates (larger than V3 in Fig 6A), kinetic limitations
may appear, and the overall description ofvoltammetric
peak currents becomes more complex [7,9]. Another diag-
nostic experiment can be performed by plotting chrono-
coulometric charge (Q) vs. t l / 2 responses (Fig. 6B). In the
ideal case (Fig. 6B, curve 1), i.e., in the absence ofohmic/
migration effects, slow interfacial electron transfer and
with the linear diffusion as a predominant charge trans-
port mechanism, the dependence of Q on t l / 2 can be
described in terms of integrated Cottrell equation [7,9]:
(8)
where the parameters either have been discussed above
or have their usual significance. Such behavior requires
application of a sufficiently short potential pulse [21].
If there were any contribution from radial diffusion (Fig.
6B, curve 2) or possible ohmic/migration limitations
(portion 3b of curve 3), a positive deviation from linear-
ity would be observed. A kinetic limitation would lead
to sizeable negative intercept (portion 3a of curve 3) [7].
The pattern ofradial diffusion transport can be easily
diagnosed using the double potential-step long-pulse
chronoamperometric experiment [21]. Although the
forward potential-step features a steady-state current
686
~2!
...
I\..------..,
~
o 0
If
forward step . reverse step
1-0 - - - - - - - - .... ~ - - - - - - - - ....
o Time
Figure 7 Diagnosis of radial (spherical) diffusional charge
propagation using long-pulse ultramicroelectrode based
ch ronoamperometry.
response, during the reverse pulse, the current decays
rapidly to zero (Fig. 7) because the electrolysis products
diffuse away from the surface of an ultram icroelectrode.
VII. CONCLUDING REMARKS
In summary, solid-state voltammetry provides a route to
characterization (in the absence of contact with liquid
electrolyte phase) of rigid and semirigid materials that
are redox conducting. The candidate systems are ionically
conducting, and they contain redox centers between
which electron hopping is typically operative. Some new
approaches to characterization of novel materials,
especially of those of low ionic conductivity, have been
stimulated by the development of ultramicroelectrodes.
Potential applications are expected in such diverse areas
as charge storage in batteries and redox supercapacitors
[128], electrochromism [129], electrosynthesis [98], mol-
ecular electronics [17,67,130-132], characterization of
mixed-valent ionically conducting materials [20-22],
and the development of novel amperometric sensors for
gases where the measurement concept is based on
electrocatalysis at the gas-solid interface [24,25,98]. In
the latter case, a material is tailored to provide the reactive
medium and to facilitate the delivery of charge from the
electrode to an external (gaseous) reactant, e.g., to permit
the electrocatalytic sensing of a gaseous analyte at the
gas- solid interface. Alternatively, the materials can be
designed for the purpose of studying the heterogeneous
and homogeneous electron-transfer dynamics or to deter-
mine the concentration of redox centers. From materials
chemistry viewpoint, it is noteworthy that a single mater-
ial can exhibit characteristics normally associated with
both electronic and redox modes ofconductivity, and the
transformation from one characteristic to another may
be a matter of ionic mobility, solvent dynamics control of
electron transfers, and chemical nature ofthe system.
Kulesza and Malik
Further progress in the area of materials are expected
aiming at fabrication of systems that are independent of
the humidity and showing fast dynamics ofcharge propa-
gation. Recent advances in inorganic materials prepared
by sol-gel processes, electronically conducting polymers,
and organic conductors are promising. A new synthetic
route to room temperature redox melts of ionic subs-
tances, based on using polyether-tailed counterions, can
be challenging and applicable to many redox moieties
[133]. From fundamental viewpoint, systems character-
ized by very slow diffusion rates (on the "molecule scale")
are of importance as well. Much research is still needed
to achieve a detailed understanding oftransport phenom-
ena occurring in polymer films and in bulk solids in the
absence ofliquid electrolyte phase. In addition, there are
uncertainties about the structure and properties of
interphase regions where changes in the morphology can
be caused by the potential and potential-induced pro-
cesses (e.g., displacement of ions and solvent molecules,
structural reorganization).
An important issue is the determination and the
meaning of diffusion coefficients measured experimen-
tally using different techniques. In this context, appli-
cation of methods that may provide separately
information about the dynamics of the electronic and
ionic charge transport processes would be helpful.
Impedance spectroscopy, which allows the simultaneous
determination of the heterogeneous rate constant and
charge transport diffusion coefficient, is likely to become
a powerful tool for studies of rigid and semirigid
materials. It can be expected that new spectroscopic
and spectroelectrochemical methods for the in situ
characterization of the electrode-electrolyte interfaces
[117] will provide additional means for investigating of
the interphase regions in solid-state electrochemistry.
ACKNOWLEDGMENTS
Supported by State Committee for Scientific Research
(KBN), Poland, under Grant No. 3T09A 09313 and by
the Ministry of National Education, Poland, under the
Contract No. BST-592/l/98 administered by University
of Warsaw. We appreciate helpful discussions with
Professors James A. Cox (Miami University, Oxford,
Ohio, U. S.A.) andZbigniewGalus (University ofWarsaw).
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38
Conducting Polymer Films as Electrodes
Judith F. Rubinson and Harry B. Mark, Jr.
University ofCincinnati, Cincinnati, Ohio
ABSTRACT
There has been a great deal of interest in the modification
of electrode surfaces with polymeric materials to impart
properties as resistance to corrosion, resistance to fouling
by reaction products, and better interaction between
solution species and the electrode surface. Over the last
several years, investigations have shown that conducting
polymers themselves can function as electrodes. The con-
ductivities of these polymers vary over several orders of
magnitude, depending on the monomer and synthetic
method chosen. Here we describe some of the methods
used to produce conducting polymers, the techniques
used to investigate their properties, and some of the
analytical applications found for them.
I. INTRODUCTION
A. Conducting Polymers vs. Redox Polymers
Over the last several years, there has been a great deal of
interest in the modification of electrode surfaces with
polymeric materials to impart such properties as resist-
ance to corrosion, resistance to fouling by reaction pro-
ducts, and better interaction between solution species
and the electrode surface. Here we describe the synthesis,
the characterization, and the electroanalytical and
electrocatalytic applications ofelectrodes whose surfaces
are made up of conducting polymer films. Although
some of these applications have involved inclusion of
redox active groups or copolymerization ofa conducting
and a redox polymer, conducting polymer electrodes
constitute a class in and of themselves-one where the
689
polymer film itself is a conductor, as opposed a
nonconducting material such as a self-assembled
monolayer of alkanethiol or an ionic polymer such as
Nafion. The conductivity ofthese materials ranges widely,
depending on structure and on synthetic method.
Although most of the polymers synthesized to date have
conductivities in the range of 10- 2 to 10-4 S cm -1, there
have been reports of some polymers with conductivities
as high as 104 S cm -1 (the same order of magnitude as
the conductivities ofcopper and silver). These are in sharp
contrast to the conductivities of insulators, which are in
the range of 10- 10 Scm-I. The names and structures of
some of the conducting films that have been synthesized
are included in Table 1. Ofthese, polyaniline, polypyrrole,
and polythiophene-along with their derivatives-have
been by far the most widely investigated.
B. Solitons, Polarons, and Bipolarons-What
Is the Basis of Conduction?
Given that chemists, materials engineers, and physicists
(among others) have all been involved in synthesizing
and characterizing these conductive polymers, it is
worthwhile to attempt a translation of some of the
language used by the various groups to characterize the
modes of conduction in the polymers. Perhaps the first
point to make is that unlike three-dimensional solid con-
ductors (or semiconductors), these polymers are
extremely anisotropic. Also, when we talk about conduc-
tion bands and valence bands for conducting polymers,
the energy boundaries ofthese "bands"are not as sharply
690
Table 1 Structures of Some Conducting Polymers Used as Electrodes
Polyparaphenylene
Polyaniline
--tot
{--0-4
Poly-o-anisidine
~t
Polythiophene
• The linkages between repeating units are through substitutents on the periphery ofthe macrocycle.
defined and the electronic states responsible for conduc-
tion are not delocalized over the entire extent of the poly-
mer film.
As seen in Fig. 1, the type ofcharge carriers involved in
conduction depends on the nature of the polymer itself.
In the case of the polymers shown in Table 1, the charge
carriers are in semilocalized nondegenerate states
created between the filled valence band (from the highest
occupied molecular orbitals, HOMOs) and the unoc-
cupied band (from the lowest unoccupied molecular
orbitals, LUMOs). The terms polaron and bipolaron cor-
Rubinson and Mark
Polypyrrole
Substituted
m
dibenzotetraaza[14]annulenes
n
Substituted porphyrins'
~
Substituted
phthalocyanines'
respond to the radical cation and dication, respectively
[1]. Bipolarons result from polarons on two adjacent units.
Their spins tend to pair to produce a site with a + 2 charge
and a spin of zero. These sites store charge.
Charge carriers can result either from doping (and
transferring an electron to the dopant) or from oxidation
ofthe polymer. Often more than one type ofcharge carrier
can be involved, depending on the oxidation state of the
polymer or the type of defect that leads to conduction.
Polarons and electron hopping between adjacent defects
have both been proposed as charge carriers in the
Conducting Polymer Films as Electrodes
~conduction band
0 A.. .
A • • • • • A •• ~ -+-
Soliton
~ Valence band
Polaron
Bipolaron
r::===-:Yconduction band
~ Valence band
Polaron Bipolaron
Figure 1 Energy levels and modes of conduction in con-
ducting polymers, (a) Solutions in polyacetylene; (b) polaron
and bipolaron formation in polyaromatic systems. (From Ref. 1.)
polypyrrole family of conductors. This type of charge
transport is also fairly well accepted in explaining trans-
port in other polymers containing aromatic units such as
polyphenylene, polyaniline, and the polythiophenes [2,3].
The role of the heteroatom in polythiophene and poly-
pyrrole is still not fully understood, but it seems likely that
thep lone pair does interact with theextendedpisystem [3].
II. SYNTHESIS
Conducting polymer films have been prepared on elec-
trode surfaces by a number of different routes. However,
the route most often chosen is electrochemical
polymerization from a solution on the order of
0.01-0.1 M in monomer or oligomer. Nonaqueous
solvents such as acetonitrile, methylene chloride, or in
some cases propylene carbonate are used for the synthesis
of polythiophene, poly-p-phenylene, and polypyrrole,
whereas polyaniline can be prepared in either
nonaqueous or in acidic aqueous media. A more exotic
example is that of the electro-oxidation of benzene in
AIC1}/N-butylpyridinium chloride [4] to produce
poly-p -phenylene.
691
Monomer oxidation
X EIllP
O
~ A Oxidize·
Resonance forms
\) . ....--_. 6 . .--_. o·
+0 + +
Chain propagation
Figure 2 Mechanism of polymerization for monomers such
as thiophene and pyrrole. (From Ref. 5.)
As illustrated for the polyheterolene in Fig. 2, the con-
ducting polymer is formed by an ECE mechanism where,
after oxidation of the monomer, the actual coupling step
is chemical. Thus, long chains are favored at high
monomer concentrations [5]. Such a mechanism has also
been proposed for p-o-anisidine [6] and is widely
accepted as the mechanism for the formation of other
conducting polymers.
Monomer or oligomer concentration and solvent are
not the only variables to be optimized for electrosynthesis
of the polymer film. Other parameters include the back-
ground electrolyte, temperature, and mode of oxidation
(coulostatic, potentiostatic, voltage pulse, or sawtooth
wave). This last parameter has been shown to have a pro-
found effect on the morphology of the polymer film. For
example, when a double potential step protocol is used
for deposition of poly(thiophene-3-acetic acid), the
polymerization takes place in discrete two-dimensional
layers [7].
692 Rubinson and Mark

In some cases the substrate on which the film is the electrochemical characteristics of conducting
deposited also has an effect on its properties. For polymers. The goal is to tailor their behavior based on
example, poly-o-anisidine has been shown to exhibit such parameters as synthetic method, substrates for
very different polymer fiber structures depending on deposition, and conditions during electrochemical
the conductivity of the substrate on which it is formed applications. A brief discussion of the types of measure-
and on the number of nucleation sites on which the poly- ments that have been done is presented next, along with
mer is deposited [6]. Another example of this depen- brief descriptions of some of the less commonly used
dence on substrate occurs with polyaniline deposition. methods.
If aniline is electropolymerized onto a surface already
covered with a polyaniline layer, the process is
autocatalytic-deposition takes place well negative of A. Conductivity/Resistivity Measurements
the oxidation potential for aniline [8,9].
One of the most reliable methods for determining the
Early studies were based on the use of inert substrate
conductivity of a conducting polymer film is the use of a
materials such as platinum or glassy carbon. These inert
four-point probe [20,21]. As pictured in Fig. 3, the appar-
substrates continue to be used most often; however, depo-
atus consists of four tips about 1 mm apart in a straight
sition on more active metals such as molybdenum [10],
line that projects down from a stage that can be raised
nickel [10], aluminum [11,12], titanium [12], brass [12],
and lowered. A current from a high impedance source is
zinc [13] and iron [14,15], and also on stainless steel [10,16]
supplied through the probes at the outside and a voltage
have recently been investigated. At the potentials used
measurement is made across the two probes that are at
during deposition, the substrate tends to oxidize and
distances Xl and X2 from the positive tip from the current
interfacial layers are formed containing oxidized metal
source. The potential is then measured between the two
species [10,14,15] and decomposition products from the
inner tips. For a film of thickness t« s, the distance
solvent and background electrolyte [14]. In addition,
between the inner and outer probes, the resistivity of the
deposition on semiconductors such as indium tin oxide
film is defined as
(ITO), tin oxide, or fluoride-doped tin oxide can be car-
ried out if a transparent substrate is desired.
A novel electrolysis of monomer in a flowing stream nt
P = In2
(V)
I
has been used to create fibers of poly-3-methylthiophene.
The shapes and diameters of the fibers can both be con- We know the current, I, and can obtain (or at least
trolled by varying the fluid flow pattern [17]. approximate) a value for t. By measuring the potential V,
The preparation of conducting polymer electrodes we can then calculate p and its reciprocal, the con-
does not have to take place by electropolymerization of ductivity. The only drawback to this type of measurement
the monomer onto a conducting substrate. Solid-state is that it is important to avoid deformation of the film
polymerization of phenylene oligomers in the presence when lowering the tips onto the film surface.
of arsenic pentafluoride provides films that show very
high conductivities, with terphenyl producing the most
highly conductive product [18]. One novel approach is to
carry out a solution polymerization by oxidation with
FeCb or 12 to produce a soluble oligomer, followed by
adsorption onto a conducting substrate. This latter
method has been used to produce monolayer films
of polyoctylthiophene. Gold was sputtered onto a
single-crystal silicon surface. Because of the interaction -I + +1
between the sulfur and the gold atoms, a flat, highly I-S
ordered, self-assembled monolayer of the polyoctyl- Xl X2 0= X Polymer
thiophene results on the surface of the gold when it is , / '(Thickness = t)
immersed into the polyoctylthiophene solution [19].
-0---- Substrate

III. CHARACTERIZATION
Figure 3 A four-point probe for measuring small resistances.
A number of different techniques have been used in the This arrangement of probes eliminates any contribution to the
attempt to develop predictive capability with respect to measurement ofthe resistance from the probes themselves.
Conducting Polymer Films as Electrodes
If it is possible to produce freestanding films, an easier
method can be used. In this case, gold or some other metal
is deposited by cold vapor deposition onto both sides of
the film and then its resistance can be measured using a
conventional two-probe method. On the other hand, this
method assumes that there are no pores in the film into
which the gold deposits, providing a metallic conduction
path.
B. Scanning Electron and High Magnification
Optical Microscopy
Scanning electron and high magnification optical
microscopy are invaluable in characterizing the
morphology of conductive polymer films [22,23]. These
two techniques can provide evidence regarding
uniformity of the film thickness, presence (or absence)
of pores at the resolution provided by the microscope,
and how these vary with polymerization conditions.
Shown in Fig. 4 is a scanning electron micrograph of a
film of polyphenylene on ITO. It is easy to see the
"bumpy" surface of the polythiophene on the ITO. On
the scale shown, each of the small features is about
0.1-0.3 ,um in length. This type of rough surface is fairly
typical for conductive polymers. Early in the poly-
merization, nucleation occurs at sites on the surface.
Over time growth occurs on and around these isolated
sites and eventually they coalesce to form what appears
to be a pore-free layer.
Figure 5 shows a photomicrograph of poly-
3-methylthiophene on platinum. At the magnification
used (500 x), the surface seems much flatter than that
Figure 4 Scanning electron micrograph ofpoly-p-phenylene
on ITO. Polymer grown from 0.01 M dibromo-l,4-biphenyl in
THF/HMPT + 0.03 M LiCl0 4 . (From Ref. 22.)
693
Figure 5 Photomicrograph of poly-3-methylthiophene on
platinum. Polymer grown for 20 s at 1.7 V vs. Ag/AgCl in
0.075 M monomer. Supporting electrolyte: 0.05 M TBATFB
in acetonitrile. T = -20°e. (From Ref. 23.)
seen for the polyphenylene on ITO we saw in Fig. 4. The
fuzzy edge of the dark portion shows that small fibers
extend out across the intersection between the con-
ducting substrate electrode and its insulating sheath.This
type of "edge effect" can be minimized if conditions are
manipulated to optimize the synthesis. There seems, as
in Fig. 4, to be no pores present on this electrode. This is
not to say that pores with diameters on the order of tens
of nanometers or even tortuous channels are not present.
However, the combination of such results with electro-
chemical characterization can provide evidence for com-
plete coverage.
c. ScanninglUnneling Microscopy
Scanning tunneling microscopy involves the relationship
between the tunneling current between a submicroscopic
tip and the height ofthe tip above the surface to be probed
[24,25]. With an operating voltage on the order of
millivolts to about a volt, the tunneling current will be
on the order of nanoamps for a separation of a few
nanometers. A distance change on the order of an A
results in a dramatic change (about an order of
magnitude) in the tunneling current. This means that as
the tip is rastered along the x and y directions, variations
in the topology of the surface produce changes in the
tunneling current. Measurements can be made at con-
stant height (in which case the tip mount is designed to
be fixed in the z direction and the current changes) or at
constant current (where the height is adjusted by a
feedback circuit).
694
Figure 6 Scanning tunneling micrograph of polythiophene.
Note the stripes and dots corresponding to localized ordering
of chains. (From Ref. 27.)
Due to the fact that conducting polymer films (and
their substrates) are not generally flat on the submicron
level, scanning tunneling microscopy requires that the
film be deposited on a well-defined substrate surface or
that only a small nearly atomically flat area be
investigated. In such cases, it is possible to detect changes
in film thickness on the order ofa few nanometers [26,27]
and to map surface morphology with nanometer res-
olution. For example, a scanning tunneling micrograph
ofpolythiophene on ITO can be seen in Fig. 6. As can be
seen from the scale indicated on the micrograph, we are
looking at features 10 to 100 times smaller than those seen
in the optical and scanning electron micrographs in Figs.
4 and 5. In other words, we are approaching the scale of
individual molecular chains. The pattern ofordered white
stripes and dots corresponds to local areas where the
chains are closely aligned.
Scanning tunneling microscopy carried out on poly-
(pyrrole) has been used to support transmission electron
microscopy and x-ray results that suggest these polymers
adopt a helical structure [3]
D. Spectroscopic Characterization
1. Infrared
Vibrational spectroscopy has been used both in transmit-
tance mode for freestanding films and in reflectance
modes [28], but reflectance has been especially useful
because it can be carried out while the film is in place on
the substrate. Normally, the surfaces ofconducting poly-
mer electrodes are "rough" in the sense of reflection of
light. For this reason, diffuse reflectance or attenuated
total reflection has been used more often than specular
Rubinson and Mark
J
<.l
IR
I~ I
<~~ --'
800 1200 1600 2000 2400 2800
Wavenumber. em-'
Figure 7 Raman and FTIR spectra of poly-3-methyl-
thiophene in its neutral form. (From Ref. 29.)
reflectance. An infrared (IR) spectrum of regioregular
polyoctylthiophene on ITO is shown in Fig. 7 [29]. The
simplest application ofIR spectroscopy would be to look
for the presence of specific vibrations that confirm that
a polymer has been immobilized on the surface. However,
the relative intensity of characteristic vibrations can be
used for such purposes as obtaining average chain
lengths. For example, for polyphenylene, the aromatic
stretching vibrations would occur at slightly different fre-
quencies for terminal and internal aromatic rings. Ifwe
know the extinction coefficients for each type of
vibration, we can obtain an approximation of their rela-
tive populations.
2. Raman Spectroscopy
Raman spectroscopy and microspectroscopy [12,29]
hold much promise for characterization of conducting
polymer films. It can be used to provide qualitative infor-
mation in the same ways described above for IR.
However, it can provide one additional piece ofevidence
for determining chain length. As the chain length
becomes greater, the resonance frequency decreases.
Therefore, resonance occurs at a progressively lower fre-
quencies (longer wavelengths) as the chains lengthen.
The only drawback is the laser intensity used in some
Raman instruments means that cooling of the sample
may be necessary in some applications.
3. Absorption and Fluorescence in the UV-vis
Region
A number of derivatives of polyphenylene have been
shown to exhibit electroluminescent behavior. Diff-
erential UV-vis spectrometry has been used to good effect
to investigate the changes in the luminescence output as
Conducting Polymer Films as Electrodes 695

a function ofdopant level, temperature, and applied volt- 10

S2s
age [30]. These studies were carried out with films 9
deposited on an [TO substrate and thus were conducted 8
in transmission mode. (Combination of UV-visible 7
spectrometry with electrochemical characterization is
6
discussed in sec. E.3. below).
Fluorescence spectrometry has also been used to
characterize poly-p-phenylene on quartz [31], but
5
4
) \
\~
3
perhaps its greatest utility is yet to come-fluorescence
2 'vJy+J
microscopy should have the capability to investigate con-
ducting polymer films in terms of mapping electroactive 1

sites on the surface. In this technique, the electro- 0

chemiluminescence from a reaction on the surface of 239 237 235 233 231 229 227 225
the electrode can be detected, causing sites where the Binding energy I eY
redox process occurs to show up as bright spots on a
map of the surface [32]. Correlation of these results with Figure 8 High resolution XPS spectrum of poly-3-methyl-
other surface characterization techniques would provide thiophene grown on Mo. Polymerization conditions: 90 s at
evidence about how morphology or presence of specific 1.8 V vs. Ag/AgCI, 0.1 M TBATFB in acetonitrile, 0.05 M
functional groups influence the electrochemical charac- 3-methylthiophene. MgKcaadiation,300 W;45 takeoffangle.
G

teristics of the polymer film. (From Ref. 10.)

4. X-Ray Photoelectron Spectroscopy (XPS)

XPS, also called electron spectroscopy for chemical
analysis or ESCA, can be used to analyze the surface (the
top 2-5 nm) of films. XPS relies on the ejection of elec-
trons from the valence levels of atoms by bombarding
the sample with x-rays of a given energy. Conservation
of energy dictates that the energy of the incident x-rays
hI' must show up in the sum of the binding energy (BE)
and the kinetic energy (KE) of the ejected electron and
a contribution from the work function (W) of the sample.
Expressed mathematically,
hI' = BE+ KE+W
Because hI' is known because of the source used and the
contribution of the work function can be found by
calibrating with a known energy (such as the C-ls peak),
the identity of the species present can be determined
based on where peaks occur in a binding (or kinetic)
energy plot. The plot in Fig. 8 shows the molybdenum 3d
and sulfur 2s binding energy region for a polythiophene
film produced on a molybdenum substrate electrode.
Depending on the valence state of the molybdenum and
the atoms to which it is bound, the binding energy of
the 3d s/ 2 and 3d 3/ 2 electrons will vary. This spectrum
indicates that both Mo(O) and Mo(VI) are present in the
film.
The intensity of peaks in conjunction with response
factors for the transitions can be used to determine the
atom ratio of the species present. This technique has
proven very effective for analysis of films containing met-
allic species, such as those produced on active metal
substrates [10,33]. Depth profiling, carried out by chang-
ing the incident angle of the incoming x-rays, has been
used to provide insight into the variation in composition
of the film as a function of distance from the outside of
the film or from the surface of the metal substrate [10].
Transport of ReOi ions through a P3MT film has also
been studied using XPS, and the results provided evi-
dence that although spontaneous ion exchange was very
slow (days), active transport by means of varying the
potential through one polymer redox cycle (which took
about 25 s) resulted in complete depletion ofthe ion from
the film [34].
5. Electron Paramagnetic Resonance (EPR)
The population ofspins in these conducting polymers is a
function of dopant level and oxidation state. As such, it
is useful for optimizing the conductivity ofpolymer films.
The correlation of integrated EPR signal and the number
of unpaired spins makes it a perfect tool for investigation
of variations in spin population with synthetic method
and experimental conditions during use of the polymer
electrode [35].
E. Electrochemical Characterization
1. Cyclic Voltammetry
The most straightforward use of cyclic voltammetry is
investigation of the redox properties of the film in the
absence of redox-active solutes. Properties such as
switching potentials between ionic and neutral forms,
useful potential windows for solution processes, and
696 Rubinson and Mark

200 F platinum or glassy carbon has been extensively used to

100
~ characterize the electron transfer processes at the
polymer electrode. Shown in Fig. 10 is a comparison of
the voltammograms in phosphate buffer (pH 7.4)
0 for dopamine and p-aminophenol at poly-3-methyl-
<::l.
thiophene and at platinum. Note the changes in EO' for
- -100 their redox processes and also the enhancement of their
reversibility. The decrease in peak separation indicates
-200 that the couples are now more electrochemically
reversible, whereas the fact that the peak currents are
-300 -..,.-,---,--,----,--..,.---1
1 - 1- - . ,- - , _ , - - - . - - . - - - . - - , _ , - - - . - - , - - . ,
more nearly equal is indicative of increased chemical
0.4 0.2 0.0 -0.2 -0.4 -0.8 -0.8 -1 .0 -1 .2 -1 .4 reversibility [39]. Pretreatment of glassy carbon or
E/VVB.SCE pyrolytic graphic surfaces has been shown to result in
the same types of improvement in electrode behavior.
Figure 9 Cyclic voltammogram ofa 0.15 -/lm polypyrrole film However, the effects are, as a whole, neither as dramatic
in 0.2 M Et 4 NBF4 in acetonitrile. Scan rate: 20 mY S-I. - - , nor as long-lived.
before treatment with NaOH; "', after treatment with NaOH. A detailed investigation ofthe scan rate dependency of
(From Ref. 36.) the cyclic voltammograms for catechol, dopamine,
ascorbic acid, and p-aminophenol at poly-3-methyl-
thiophene has shown that the apparent diffusion constant
breakdown potentials can be found from such studies. For for these species ranges from 10-6 to 10- 7 cm 2 s-I.These
example, shown in Fig. 9 are the cyclic voltammograms values are 10 3 to 109 times the diffusion rates normally
for BF4-doped polypyrrole and OH--doped poly-
pyrrole. The redox processes on the scan toward more
positive potentials corresponds to the oxidation and
anion doping of the polymer, whereas the peaks on
the reverse scan correspond to the reduction of the poly-
mer back to its neutral form, which is concommitant
with undoping. The reduction reaction for the
hydroxide-doped form takes place at a more negative
potential, thus extending the useful window for the poly-
mer beyond the usual 0-1.0 V (vs. SCE)-the currents I 20 IJA
are <200 pA down to -1.0 V. The conducting polymer
electrode is now useful for monitoring redox processes
at negative potentials [36].
The width of the potential window for untreated
polypyrrole is fairly typical ofthese conducting polymers.
Two notable exceptions are polyphenylene, for which
the currents from background processes do not become
large until outside the range of -1.5 V to + 1.0 V vs. SCE
in acetonitrile [37], and for poly(dibenzotetraaza-
[14]annulene), which in acetonitrile or methylene chlor-
ide (0.1 M NH 4 PF 6 as background electrolyte) shows
minimal background currents from about +0.5 to -1.5 V
vs SCE [38]. The broadness of the peaks is also typical I I I I I I I i I I I I I I I I I I I I I
and results in part from the fact that variations in chain 0.8 0.7 0.8 0.5 0.4 0.3 0.2 0.1 0.0 -0.1 -0.2
lengths within the film result in a range of redox E (V VB AglAgQ)
potentials, with longer chains normally switching at less
positive potentials. Figure 10 Cyclic voltammograms for 5 mM dopamine
Comparison of the cyclic voltammetric behavior of (upper curves) and p-aminophenol (lower curves) at Pt ( ... )
solution species under a given set of experimental con- and at P3MT (--) electrodes. Background electrolyte: 0.1 M
ditions at conducting polymer electrodes with that at H 2S0 4. (From Ref. 39.)
Conducting Polymer Films as Electrodes
seen for diffusion ofredox species through polymers; they
are much closer to those seen for solution species, which
are on the order of 10- 6 to 10-9 . This finding, in combi-
nation with the lack of EO' dependence on the substrate
electrode used for polymerization, suggests that the elec-
tron transfer takes place near or at the polymer-solution
interface [40]. This piece of evidence would seem to
exclude the possibility that the redox active substance
must diffuse along pores and then be reduced at the sur-
face of the substrate, as was first believed. Diffusion con-
stants have been measured within the film, using
poly-3-methylthiophene into which ferricyanide has been
incorporated, and apparent diffusion constants are more
characteristic ofdiffusion through polymers [41].
2. AC Impedance Spectroscopy
Variations in the impedance ofconducting polymer elec-
trodes with frequency can be used to characterize the
types of charge transport operating at different applied
potentials [42,43]. In this technique, a small-amplitude
AC potential is superimposed on top of a fixed applied
(DC) potential. The alternating current that flows is
shifted by a given phase angle at a given frequency. The
impedance of the system (I1E/11 i) can be visualized in
terms of an equivalent circuit like that shown in Fig. 11.
The elements included in such circuits might correspond
to contributions from the resistance of the electrolyte in
the cell, the double-layer capacitance, polarization
resistance, charge transfer resistance, and a component
called a Warburg impedance that reflects the effects of
diffusion. The impedance ofthe circuit will be comprised
ofa real and an imaginary component.
A plot of the imaginary component value vs. the real
component (a Nyquist plot) of the impedance for the
simple circuit shown in Fig. 11 is shown in Fig. 12. The
semicircle on the left ofthe plot (high frequency) is typical
Zp
Figure 11 A circuit representing the contributions of the
resistance of the electrolyte (Rd the capacitance due to the
double layer (CoL), the resistance corresponding to charge
transfer (RCT), the Warburg impedance (Zw), and the
impedance due to the polymer (Zp).
697
>-
~
Cll
c:
"61
Cll
.1;
N
OL...JL- _
o
Zreal
Figure 12 The general shape ofthe impedance plotthat would
result from the equivalent circuit of Fig. 11. The leftmost
intersection of the semicircle with the real axis indicates the
overall resistance of the solution + the polymer film.
for a capacitor in parallel with a resistor, whereas the line
at 45° is characteristic of the diffusion component of the
circuit. (If the frequency is low enough, it will eventually
turn back toward the origin.)
Apparent diffusion constants for charge transport in
polypyrrole have been found to be on the order of
10-9 cm 2 S-I, based on ac impedance data. These
experiments, carried out in the "insulator" regime for
the polymer, have also provided insight into the mode of
conduction in the insulator region. The results suggest
that polypyrrole's behavior in the insulating region
closely resembles that of a redox polymer, where charge
transport takes place by electron self-exchange [44].There
is, in addition, a large contribution from ion transport
due to the electrolyte solution trapped in the polymer.This
dual mode of conduction is also apparent in impedance
results carried out using freestanding films ofpolypyrrole
[45]. Impedance spectroscopy has also been used to
investigate the composite layer between bulk aluminum
and polypyrrole when pyrrole is electropolymerized
on aluminum [11].
Monitoring the polymerization of poly-octyl-
thiophene using impedance spectrometry provides clear
evidence of a transition from tunneling to conduction
through the polymer as the polymerization process pro-
ceeds [18].
3. Scanning Electrochemical Microscopy (SECM)
Unlike other scanning probe microscopic methods,
which give little insight into the electrochemistry at the
electrode surface, SECM can be used to map variations
in electrochemical behavior as a function of the presence
of specific functional groups or morphology [46-49].
698 Rubinson and Mark

The physical setup is much like that in scanning

tunneling microscopy, except that the tip and/or substrate
o I _______________
fO
are connected through a potentiostat or bipotentiostat -1~- J 20

to auxiliary and reference electrodes. Also, the current

~ .)
<C
measured at the tip is not a tunneling current but a current 10 "
c
due to solution redox processes. The resolution is limited
by the tip size and the distance between the tip and the sur-
- r·'
i
:;
.....
~
~

"
" ~
face being investigated (the smaller the tip and/or the ·3
~i
Q.
i=
closer the tip is to the surface being investigated, the -10

smaller the area "seen" at any given time.) Commercial

-4

LJ
instrumentation can provide resolutions on the order -20

of I to 10 ,um, although under ideal conditions (atomic-

ally flat surface, research grade instruments, and
electrogenerated nanotips), resolution on the order of a
few nanometers has been accomplished. The areas that
can be mapped are limited primariIy by the time required
for data acquisition and the area that is flat enough to
avoid running the tip into a substrate "cliff:'
In generation/collection mode, the potential at the
polymer electrode to be investigated and the tip potential
are set by a biopotentiostat. The potentials are chosen to
give oxidation at one electrode and reduction of the
oxidation product at the other. For example, say that the
polymer electrode potential is set to give reduction of a
solution species. The tip is moved over the surface of the
conducting polymer and when over sites at which
reduction place an increase in current is seen at the tip
due to reoxidation. The resolution of this type of exper-
iment can be enhanced ifthe species produced at the poly-
mer surface is not chemically stable, because it would
decompose before diffusing very far from its point of ori-
gin [32]. Another way in which this dual working elec-
trode system can be used is in monitoring the release of
redox active species from the substrate. An example of
the use of this technique is seen the Fig. 13 [46]. Bromide
is released from a polypyrrole film as the potential is
swept toward more negative potentials, and dissolved
oxygen mediates its oxidation to Br2. A plot of potential
vs. current at the tip clearly shows the release of Be on
the scan toward negative potentials and the reuptake of
the Br- as the potential is scanned in the opposite
direction.
In the feedback mode, the potential of the conducting
polymer electrode is set by a redox couple in solution
(heavily weighted toward either oxidized or reduced
species) and the tip potential is set by the potentiostat.
Changes in the tip current can be used to indicate the
presence of conducting vs. insulating regions. Two
important factors result from the close approach of the
tip to the substrate. First, diffusion is hindered between
the tip and the substrate because they are within less than
a micron of each other. This means that when above an
-51 I I I til -30
0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8
Esubstrllte I V Vs seE
Figure 13 Release and uptake ofBr- from a polypyrrole elec-
trode as a function of potential. "', Substrate current; - -
tip current. (From Ref. 46.)
insulator the tip current will drop due to decreased mass
transport to the surface. Second, because the area
beneath the electrode is usually extremely small com-
pared with the total area of the polymer electrode and
the potential of the polymer is set by the redox couple in
solution, the potential at the polymer surface will be suf-
ficient to reoxidize (or rereduce) the product formed at
the tip and an oxidation-reduction cycle is set up that
leads to an increase in current over the level seen when
diffusion is not hindered. In this way, the conductivity of
the polymer film can be monitored as the tip is rastered
over the surface. This mode has been used to obtain a
profile of the conductivity of a platinum electrode onto
half of which a poly-p-phenylene film had been
electropolymerized. As seen in Fig. 14, as the tip scans
first across the insulating tubing around the outside there
is only a small current measured at the tip. As the tip
passes over the unmodified platinum surface and sub-
sequently the polymer film, the current first sharply
increases, then decreases t.o an intermediate level. As
t.he tip then begins to travel across the insulator, the cur-
rent again drops sharply. Note that this is a relatively low
resolution scan (about 10-20 ,urn based on the tip size
and the distance from the substrate) compared with the
scale ofthe experiments described above. The single scan
also covers a much larger distance (about 2 mm) com-
pared with micron scale of a typical SECM experiment.
4. Spectroscopy + Electrochemistry
Two different approaches to combining UV-vis
spectroscopy with electrochemistry have proven useful
in the study of conducting polymers. The first is tra-
r
Conducting Polymer Films as Electrodes 699

290
0.28
Platinum
"~
::J
270 0.27 • •
~ 250 PPP-Pl
0.26 • •
E 230 •
c:
~
210
.." 0.25
•
"
::J

'0
190
170 ..
c:
of
0.24
0.23
•
.. 150 :i:
-5> 130
.a
« 0.22 •
~
::J
110
90
0.21 •
"0 Insulating sheath
0.20 • •
lIJ
.a 70 Insulating sheoth
• • •
«
50 L...J~~--.J._-'-""""'~~"""""~.J........o-'-~""""'--'--~""""'-'--" 0.19 t • •
o 20 40 60 60 1 00 1 20 1 40 1 60 1 80 200 220 240 0.18 I I I I I I I
Distance (0.01 mm steps) -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
(a)
E (V vs AQ/ AQel)
Figure 14 Scanning electrochemical micrograph ofa Pt elec-
trode onto half of which a PPP film was deposited. Electrolyte: 0.0 0
0.01 M ferrocene carboxylic acid in pH 4.5 acetate buffer.
-0.1 ~..
ditional spectroelectrochemistry, where the change in the 001 " ....
« -0.2 .~
concentration ratio of the reduced and oxidized forms a.
«
of the polymer are monitored by spectroscopy as the
~
lIJ
>
applied potential is changed. The second has been ~ -0.3
w ......~
dubbed "spectrocyclic voltammetry" [9,50]. In this
technique, the absorbance at a given wavelength is moni- -0.4
~
tored as the applied potential is scanned in a linear
fashion. -0.5 I
-3 -2 -1 0 2
Spectroelectrochemistry has been used to find both (b) In {(A-Aox)/(Arod-A)}
the n and EO' values corresponding to the production of
polarons and bipolarons. The technique is based on the
Figure 15 Determination of 11 for the oxidation ofpolypyrrole
Nernst equation (and thus assumes that the redox process by spectroelectrochemistry. (a) Absorbance at 380 nm for an
is electrochemically reversible). The absorbance will Sn02/PPy-MoS~--M003 electrode as a function of potential
change for the system as the potential is changed accord- in aqueous 0.1 M KCl. (b) Based on the data in (a), 11 = 0.27.
ingto (From Ref. 51.)

E = EO' _ RT In A - A ox
nF A red - A
where Eis the applied potential, EO' is the formal potential
for the process, A is the observed absorbance, and A red
and A ox are the absorbances of the fully reduced and the
fully oxidized species, respectively. A plot of Evs. the value
of the log term yields a plot with a slope of RT/nF and
an intercept of EO'. This procedure is illustrated in Fig. 15.
This technique has also been used to find the n values
for a number of thiophenes and for polypyrrole. For
polypyrrole, the n values for production of polarons and
bipolarons both were found to be around 0.25, whereas
the £0' values were -0.26 and 0.07 V vs. Ag/AgCl,
respectively [51]. For the polythiophene family of poly-
mers, the n values ranged from 0.21 to 0.52, and the EO'
values ranged from 0.43 to 0.85 V vs. Ag/AgCl. For
poly-3-methylthiophene itself, the n-values were OJ and
0.62 V, respectively [52].
Variations in absorbance during a linear voltage
scan can be recorded directly, producing a trace that
looks much like a cyclic voltammogram. In Fig. 16, the
absorbance due to the dication form of polyaniline
and oligomers of the starting material (N-phenyl-
p-phenylenediamine) is monitored as a function of
potential. As the potential is swept from 0.8 to 0.0 V vs.
Ag/AgCl (the dotted line), the absorbance decreases
(shown in the figure as the positive direction) and it
increases as the potential is swept back toward +0.8 V.
5. Variation in Potential Combined with Other
Techniques
Changes in mass can be followed as potential is varied by
simultaneous use of an electrochemical quartz
microbalance [53]. This technique can be used to look at
the incorporation of a dopant into the film because the
mass of the polymer will change.
700
0.01 Absorbance Units
~'\
I 1 I 1 1 I 1 1
0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Figure 16 Variation in absorbance of aniline at 740 nm as a
function ofpotential. (From Ref. 9.)
IV. ANALYTICAL APPLICATIONS
Application of these polymer electrodes to analytical
problems has shown that they can greatly enhance the
sensitivity or selectivity of electrochemical detection of a
variety ofanalytes. Table 2 and the following section sum-
marize some ofthe analytical applications that have been
reported along with figures of merit for their use.
A. Gas Sensors
Detection of volatile compounds based on changes in a
conducting polymer electrode has formed the basis for a
number of applications. These changes can take the form
of alterations in ac impedance spectra, dc conductivity,
potential, or bulk acoustic wave properties.
One ofthe earliest gas sensors was based on the poten-
tial response ofa conducting polymer and involved a film
of polypyrrole on a metal field-effect transitor [54]. Since
that time, efforts directed toward the development of
"electronic nose" devices has spurred the development
of a number ofgas sensors based on conducting polymer
electrodes. Correlation of the changes in resistance of a
polypyrrole film and the response of an electrochemical
quartz microbalance has shown that conducting polymer
electrodes can be used to detect the presence and concen-
tration of water, methanol, methylene chloride, and a
number ofaromatic hydrocarbons that must be regulated
in the workplace [55]. An ac impedance "fingerprint"
has been shown to be a viable method for the simul-
taneous determination of a number of species such as
methanol, acetone, and ethylacetate [56]. Its most
impressive characteristic is its short response time: about
20 s. Although slower (response time 4 min), a much
simpler dc device based on a polyaniline film has been
used to detect the ammonia content offertilizers [57].
Rubinson and Mark
B. Ion-Selective Electrodes
Conducting polymer ion-selective electrodes have been
developed both for anions and for cations. Anion
selective membranes have been developed for the detec-
tion of most halides and pseudohalides [39,58,59]. These
tend to exhibit selectivities that depend on the size of
the ion in solution compared with the dopant ion during
polymerization. The ion-selective electrodes developed
for the determination of cations generally incorporate
a complexing agent in the structure of the monomer or
rely on trapping complexing agent in the film during
0.0
polymerization [60-62]. These complexing agents can
be used to tailor the polymer electrode for enhanced
selectivity [60] or in the case of very stable metal
complex formation can be used for preconcentration
[61].
C. Biological Molecules
Due to the fact that the response of conducting polymer
electrodes is less likely to be degraded by fouling from
matrix organic components or from products of organic
redox processes at the electrode, these electrodes have
been extensively investigated for the determination of
biological molecules. Electrodes where the conducting
polymer is the electron transfer site and ones where
mediators or enzymatic reagents have been incorporated
during polymerization have been developed [63-65].
Incorporation of enzymes into a conducting polymer
film (as opposed to incorporation into a polyelectrolyte
or insulating polymer film) leads to better physical (and
often chemical) stability of the enzyme. In addition,
charge transport is enhanced. When electropolymer-
ization is carried out on a metered droplet of monomer-
enzyme solution, the amount of enzyme is precisely
known, and thus studies can even be done ofdry electrode
activity compared with solution activity [66].
Poly-3-methylthiophene electrodes, as well as those
utilizing other conducting polymers, have been shown
to exhibit decreased overpotentials and enhancement
of the reversibility of the redox processes involving
catecholamines [67]. For P3MT, these advantages are
maintained even in the presence of such matrix com-
ponents as albumin, hemoglobin, and surfactants such
as Triton. Detection limits of 10- 8 to 10- 9 M have been
shown for some of these species. The differences in
redox potential and reversibility for the various mol-
ecules of interest in neurotransmitter research also pre-
sents the possibilities of selective detection [21,64,68]
or simultaneous detection using scanning techniques
[39].
Conducting Polymer Films as Electrodes 701

Table 2 Analytical Applications of Conducting Polymer Electrodes

Analyte Polymer Detection range Mode Reference

Alcohols (vapor-phase) Polypyrrole 0.1 ppm d electronic 54

work function
Ammonia Polyaniline 10-4 to 10- 5 M Conductivity 57
Glucose Polythianaphthene+ 10- 5 to 10- 3 M Amperometric 95
glucose oxidase
Polypyrrole 1-5 mM Amperometric 69
Polyaniline 2-30 mM Potentiometric 74
(with AC current
applied)
Inorganic anions Poly (R-pyrrole) 10- 3 M FIA IAmperometric 96
Polypyrrole+dyes 10- 4 to 10- 5 M HPLC/Pulsed
amperometric 97
Poly(methylpyrrole) I 10- 5 M Potentiometric 59
P3MT
Inorganic cations Polypyrrole+ 10-4 to 10- 5 M HPLC/Pulsed 56
organic dyes amperometric
Potentiometric 97
MeOH, acetone, ethyl Poly-N-(2-pyridyl)-pyrrole 100 ppm AC conductivity 56
acetate (vapor phase)
Monosaccharides Poly (R-pyrrole)+ 10- 3 M Amperometric 66
oxidase enzymes
Neurotransmitters P3MT 10- 8 to 10-9 M HPLCI 98
Amperometric
Penicillin Polypyrrole+ 10- 3 M Amperometric 73
penicillinase
Phenols, acetaminophen P3MT 10-4 M Amperometric 99
Propylgallate P3MT 10- 6 M CV 100
Proteins Polypyrrole 10- 7 to 10- 9 M FIA/Pulse 101
amperometric
Quinones, anthracene, Polyethylene oxide+ Quinones: ng (neat) SFC/average 102
ferrocene Ru(bipy)~+ Anthracene, current over
ferrocene: JJg (neat) CV scan

Another area of intense interest is the detection of
glucose, with the eventual goal of in vivo detection and
incorporation of the electrode into a feedback device for
the release ofinsulin for diabetic patients. The conducting
polymer electrodes developed so far have incorporated
glucose oxidase into the polymer. They are thus used
much like the electrodes already in use, which are based
on a carbon fiber electrode plus a membrane containing
the oxidase [63,65,69].
The role of the heteroatom in the detection of these
molecules is still controversial. However, it has been
shown that the redox behavior of catechol at poly-
3-methylthiophene is severely affected by treatment of
the electrode with molybdenum-containing species. The
fact that this deleterious effect does not extend to outer
sphere redox processes such as ferro/ferricyanide
suggests an intimate interaction between the heteroatom
and the catechol functionalities of the neurotransmitters
[40].
D. Microelectrodes/Microarrays
Possible applications for in vivo detection and for
on-line detection have spurred several efforts to produced
microelectrodes and microarrays with conducting poly-
mer electrode surfaces [70-72]. As a result, micro-
electrodes and/or microarrays have been used in both
amperometric [39] and resistometric/conductimetric
[67-77] modes ofdetection.
Microelectrodes in and of themselves benefit from the
advantages of better mass transport (thus attaining
steady-state behavior more quickly) and of diminished
702 Rubinson and Mark

potential drops due to solution resistance. These lead to 80 .r-------------------,

faster stable response and lower detection limits that are
crucial for the construction of biosensors and of
detectors for HPLC and flow injection analysis (FIA). 70 Norepinephrine
Conducting polymer microelectrodes with entrapped
enzymes or cofactors enjoy two additional advantages.
First, the enzyme is immobilized only at the actual elec- 60
trode surface and is not "wasted" on the nonconducting
parts of the assembly where it would not be able to L-dopa
undergo repetitive turnover between its reduced and 50
oxidized states. Second, in contrast to entrapment in
monolayers or very thin films, the conducting polymer
can be thicker and thus include more enzyme. Such an c( 40
c:
entrapment technique has been used as the basis of a ::::::
microelectrode for the detection of glucose [68]. Epinephrine
Crucial to reproducible behavior of these micro- 30
electrodes (both with and without trapped enzymes or
cofactors) is the morphology of the conducting polymer
film. As was the case for larger electrodes, the concen- 20
trations of electrolyte and monomer, the temperature,
and the polymerization electrode used during production
of the film all have an effect. An additional consideration 10
for microelectrodes and microarrays is the growth of the
film beyond the boundary of the electrode on which the
film is deposited. For microelectrodes in amperometric o
or potentiometric devices, growth beyond the perimeter
of the actual electrode surface often leads to physical
instability. For microarrays, overlap of polymer from
o 2 4 6 8 10 12 14 16 18 20

adjacent microelectrodes creates one large working elec- Time/min

trode surface or, in the case ofa working and an auxiliary
electrode, a short circuit. In addition, it has been shown
that the separation/radius ratio has a profound effect on
the steady-state behavior of microarrays~as the ratio
increases, the approach to steady-state behavior is
hastened. One systematic approach to optimization of
growth conditions is that of fractional factorial design
used for production of poly-3-methylthiophene elec-
trodes [21].
On the other hand, growth of polymer to connect two
adjacent microelectrodes can be exploited for resisto-
metric/conductometric devices. Resistance changes in a
conducting polymer film between two microelectrodes
is the basis for most of the "electronic nose" devices on
the market today [76]. These devices, generally based on
principle component analysis of the responses from sev-
eral sensors in an array, have helped to provide
fingerprints for flavors and aromas for the flavor industry
and are being investigated for diagnostic applications
based on body odor fingerprints. Microarrays are ideal
for these applications because various "pieces" of the
fingerprint need to be obtained over a very short distance
both physically and temporally.
Figure 17 Amperometric detection of catecholamines at a
P3MTelectrode after separation by HPLC. (From Ref. 64.)
E. HPLC/FIA Detection
Both macro- and microelectrodes with conducting poly-
mer surfaces have been used for detection in flowing
streams. Perhaps the most effort has gone into
amperometric detection of catecholamines and of
glucose. Shown in Fig. 17 is an example of the detection
of catecholamines. The analytes were detected in this
study at levels of 0.001-0.1 x 10-6 M.
Although the detection of biological molecules has
probably spawned the most reports in the literature, the
detection of ions has also been an area of great interest.
Conductometric anion detectors have been fabricated
using poly-3-methylthiophene macroelectrodes [39],
which can detect ions in the millimolar range, and a
pulsed conductometric system has been constructed
based on polypyrrole that is capable of detecting ions at
ppm concentrations [77].
Conducting Polymer Films as Electrodes
Incorporation of microarrays into detectors presents
the possibility of simultaneous multianalyte detection.
This can be accomplished by means of either different
polymers on different sensors (as is the case with the elec-
tronic nose) or by using different applied potentials at
two or more electrode of the same type of conducting
polymer. For example, a dual-band electrode has been
fabricated based on the difference in the reversibility of
the redox processes for catecholamines and ascorbic acid
[70]. Because the catecholamines are much more
reversible, the first electrode is set at a potential that
oxidizes both the catecholamines and the ascorbic
acid, whereas the second is set to re-reduce the
catecholamines. In this way, the signals are not swamped
by that from ascorbic acid.
Returning to the theme of conductometric/
resistometric devices, changes in resistance of polymer
electrodes have been used in sensors for a broad range of
analytes. For example, they have been used in sensors
ranging from ones for penicillin [73] to glucose [74] to
the components that give beer its characteristic flavor
[75].
V. ELECTROCATALYSIS AND OTHER
APPLICATIONS
The electrocatalytic applications ofconducting polymer
electrodes have not been explored to a large extent at this
time, although there are a few reports of the use of both
modified and unmodified conducting polymer
electrodes. The oxidations of methanol and other Cl
compounds have been shown to be catalyzed at
polypyrrole electrodes into which have been incorpor-
ated highly dispersed platinum and ruthenium
microparticles [78], whereas the reduction of CO 2 and
O 2 has been shown to be catalyzed at a number of
electrodes containing polymerized Ni(II) complexes.
The ligands involved in these Ni(II) complexes are
those that can stabilize low oxidation states, such
as porphyrins [79,80], phthalocyanines [81], or dibenzo-
tetraaza[14]annulenes [38]. CO 2 reduction has also been
shown to be catalyzed at a polyaniline/Prussion Blue
electrode [82,83].
Recently, an alternative view of the acceleration of
reactions at conducting polymer electrodes has surfaced,
based on evidence that indicates that the rates of redox
reactions are not actually accelerated but that the poly-
mer serves to prevent surface effects of the underlying
substrate electrode [84].
Although outside the scope of this chapter, several
other areas have benefitted from the advent of conducting
polymer electrodes: electroremediation [85], electro-
703
chromatography [3,86,87], electrochromic devices
[30,88], light-emitting diode fabrication [89,90],
substrates for the deposition ofcopper and nickel metallic
films [91], and the assembly of lightweight batteries
[92,93], among others [94].
VI. CONCLUSIONS
Two very general conclusions can be drawn from the
above discussions. One involves the "naming" oforganic
conducting polymer electrodes. In most of the literature
cited in this chapter, the authors refer to their electrodes
as "polymer-modified" electrodes. We believe this is a
misnomer. In general, the electrochemical responses
and characteristics of these materials is independent of
the nature of the conducting support on which they are
electrodeposited or otherwise mounted. In reality, con-
ducting organic polymers represent a new class of elec-
trode materials.
Second, this chapter shows that over a relatively short
period of time, a wide variety of polymer electrode types
and applications have been developed. Given the
creativity exhibited by synthetic organic chemists in
developing new nomomers, oligomers, and substituted
monomers there would appear to be unlimited possi-
bilities for the development of electrodes optimized for
specific applications.
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39
Photoelectrochemistryof Nanostructured Semiconductors:
The Case of Anatase Ti0 2
Jan Augustynski
University ofGeneva, Geneva, Switzerland
ABSTRACT
During recent 10 years, the interest in characterization of
colloidal semiconductor films, focused initially on the
observation ofthe quantum size effect, extended to more
general aspects of their photoelectrochemical behavior.
These include, in particular, the mechanism of charge
separation in such networks of nanoparticles and the
way by which charge carriers are transported across the
films. In this chapter, an apparently anomalous photo-
electrochemical behavior of titanium dioxide films com-
posed of ca. 30 nm in diameter or larger nanoparticles
is delineated. It is shown, among others, that nanoporous
rutile Ti0 2 films exhibit much lower activity toward
photooxidation ofsmall organic molecules than the films
composed of anatase nanoparticles of similar size. The
maximum of the spectral photoresponse of the anatase
Ti0 2 films, with thicknesses ranging from less than
I JIm to ca. 45 11m, is located close to 300 nm corre-
sponding to a short (few tens nm) penetration depth of
the incident light. In addition, the nanoporous anatase
films with thicknesses exceeding by 2-3 orders of
magnitude the actual light penetration depth preserve
excellent photocurrent-voltage characteristics. This is
also the case for the nonannealed anatase films formed
by electrophoretic deposition. The unusual behavior of
the nanocrystalline anatase films is considered in terms
of the self-doping induced by the passage of the
photocurrent through the film, leading to the Mott
transition in the shallow donor level of anatase. This
results in a sharp rise in the electrical conductivity of the
film. The self-doping mechanism is proposed to account
707
equally for the electron transport through the
dye-sensitized nanostructured anatase electrodes used
in liquid-junction photovoltaic cells.
I. INTRODUCTION
There is currently large interest in the photophysical and
photocatalytic properties ofmesoporous nanocrystalline
semiconductor films. Several important advances in the
fields of (photo)electrochemical energy conversion and
storage, optoelectronics, photocatalysis, and others rely,
in fact, on the use of thin films of this kind [1-8]. Such
nanostructured films consist of a network of colloidal
semiconductor particles, with diameters in the range of
a few to several tens of nanometers, interconnected more
or less closely and penetrated by the electrolyte. Due to
their large extent of porosity, the nanostructured films
can easily be modified over the entire surface area, with
sensitizers (dyes), metals, or other semiconductors.
The initial interest in the colloidal semiconductor
films was associated with the investigation of quantum
size effect. This kind of deviation from the properties (in
particular optical) of the bulk semiconductor was first
observed for an ultrathin film composed of isolated CdS
nanoparticles [9] and then for various colloids dispersed
in a liquid or glass. In such so-called quantum dots, with
dimensions (usually less than 5 nm in diameter) smaller
than the lowest exciton diameter in the corresponding
bulk material, the confinement ofcharges leads to the for-
mation of discrete electronic states and to the
708
accompanying blue shift of the absorption edge [10]. A
large number of colloidal semiconductors exhibiting
quantum size effect have been characterized, in par-
ticular, cadmium, lead, mercury, and zinc chalcogenides
and also some oxides, such as ZnO and W0 3 [11,12]. Sur-
prisingly enough, their special optical properties are pre-
served when the quantum size particles are deposited on
a conducting substrate to form a relatively thick (several
hundred nanometers) film. This is the case especially for
deposits obtained at relatively low temperature, which
achieve the compromise between the confinement of
charges typical of the isolated quantum dots, on the one
hand, and a sizeable electrical conductivity, on the other.
Such a dual behavior is apparently due to the existence
of an ultrathin passive layer around the particles. In fact,
when the as-prepared colloidal films are subjected to
annealing at increasingly higher temperatures, the
absorption edge is observed to shift progressively to
larger wavelengths and to reach finally the value charac-
teristic of the bulk material [11,12].
The occurrence of the quantum size effects in the
colloidal films composed of electrically wired
nanoparticles is not the only apparent anomaly exhibited
by these semiconductor networks. Equally unexpected
is the fact that such films, used as photoelectrodes
in liquid junction cells, frequently yield large photo-
currents, equivalent in some cases to quantum
efficiencies close to 100%. Even if the efficiency of poly-
crystalline photoelectrochemical (liquid junction) cells
is, in general, much less affected by the size of crystallites
than that of solid-state photovoltaic cells, the multiplica-
tion of grain boundaries in the colloidal films should
normally result, in both cases, in high recombination
losses. However, a comparative study conducted using
nanosized CdS deposits demonstrated a striking differ-
ence between the behavior of solid-state and liquid elec-
trolyte junctions involving such films [13], pointing at
the essential role played by the redox species present in
the solution. Recognizing that the small size of the
particles forming the films, unable to sustain significant
electric field in their bulk, impeded formation ofan effec-
tive space charge layer, Hodes et al. [13,14] suggested that
the separation ofcharges occurred directly at the particle
surface through the transfer to the solution species. It is
to be noted that such a mode of operation is typical of
illuminated semiconductor particles dispersed in a sol-
ution rather than ofa compact material. In the latter case,
the distribution ofcharges at the interface between a bulk
semiconductor and an electrolyte (considered as a kind
of the Schottky junction) results in the formation of the
space charge layer within the semiconductor. Electrons
and holes present in or entering the space charge layer
Augustynski
are separated by the electric field. In semiconductors with
large dielectric constant and low doping levels, the width
ofthe space charge layer may exceed 100 nm. In addition
to the questions regarding the exact mechanism of charge
separation in nanostructured semiconductor films,
related to the absence of the conventional space charge
layer, also the way by which the charge carriers are trans-
ported across such films to be collected at the back
contact requires clarification. A plausible model of
charge transport has, in particular, to conciliate
steep photocurrent-voltage (iph - E) characteristics,
frequently observed for the nanostructured semi-
conductor-electrolyte junctions, with the low conduc-
tivity exhibited by such films in the absence of
illumination. In this connection, particularly intriguing
is the behavior of the nanostructured films composed of
anatase Ti0 2 particles with diameters ranging from ca.
10 to 30 nm and thicknesses reaching several tens of
microns that still maintain high quantum efficiencies
and excellent iph - E characteristics [15].
The mode of operation of nanostructured anatase
films is attracting large interest [16] since their successful
application in dye-sensitized liquid junction solar cells
[1,17]. It was in an attempt to increase the surface area of
dye-sensitized electrodes over which the preadsorbed
dye molecules may capt incident photons that O'Regan
and Gratzel [1,17] used colloidal anataseTi0 2 films com-
posed ofa large number of interconnected nanoparticles
(ca. 15 nm in diameter) stacked on a conducting glass
support. It has been estimated that such a network of
nanoparticles produces a 1000-fold enhancement of the
real surface area [6]. Despite the low doping level and
poor conductivity of the anatase particles, the solar cells
based on relatively thick (ca. 10 {lm) Ti0 2 films of this
kind exhibit excellent photocurrent-voltage character-
istics with fill factors exceeding 0.7 [1]. Such cells using
Ru II (2,2'-bipyridyl-4,4' dicarboxylateh (NCSh as a
senstizer and an 1-/13 redox couple already demon-
strated conversion efficiencies close to 10% [18]. Various
studies conducted with other dye-sensitized nano-
crystalline semiconductor materials (Sn02, ZnO) [19,20]
did not equal, for the moment, the excellent character-
istics ofthe anatase based cells.
Besides nanocrystalline solar cells, other important
applications of Ti0 2 are in the field of photocatalysis, in
particular, the photocatalytic degradation of pollutants
present in water or in air [21,22]. Unlike in the former
case, the latter applications involve irradiation of the
semiconductor with near-UV light ofenergy higher than
the bandgap energy (3.05 eV for the anatase form ofTi0 2).
Although it can absorb only a weak portion of the solar
light, Ti0 2 presents a series of unique advantages as a
Nanostructured Semiconductors
photocatalyst. These include its high stability (virtual
absence of photocorrosion for a large range ofpH), con-
venient position of its band edges (allowing simultaneous
occurrence of photooxidation reactions and of oxygen
reduction), and its high activity toward oxidation of a
large variety oforganic compounds (especially in the ana-
tase form). The photocatalysts usually being used in the
form of nanosized powders suspended in the solution
or immobilized on a support, investigation of film
photoelectrodes composed of such nanoparticles allows
a direct insight into the kinetics of both cathodic and
photoanodic reactions.
In this chapter, photoelectrochemical properties of
nanostructured anatase and rutile Ti0 2 films under the
bandgap UV illumination are discussed on the basis of
recent results obtained in the author's laboratory. The
unusual behavior of the anatase films is pointed out and
explained in terms ofa self-doping model.
II. PREPARATION OF THE
NANOSTRUCTURED FILMS
A handful of nanostructured film fabrication methods
are available, depending on the film material. Thus, the
frequently investigated nanocrystalline CdS and CdSe
films, exhibiting quantum size effect, are often obtained
by electrodeposition or chemical deposition [12]. The size
of the resulting colloidal particles forming such film
is, in general, strongly influenced by the deposition
temperature (lower the temperature, smaller the
nanoparticles). The most common substrates for thin film
semiconductor electrodes are conducting glass (for
example, glass coated with a 500- to 1000-nm thick layer
of Sb- or F-doped Sn02) and various metals (titanium,
gold, etc.). The former substrate offers the possibility to
illuminate the semiconductor films from both the front
and the back side.
Awidely used deposition method involves preparation
of a colloidal suspension of the semiconductor material
(for example, by using controlled hydrolysis-in the case
of an oxide semiconductor) and its subsequent appli-
cation onto the substrate, layer by layer. Each layer is
dried or annealed to improve the cohesion of the film.
When several microns-thick films are required, the indi-
vidual layers are kept at about 0.5 /lm to avoid deep cracks
within the film. A detailed example ofsuch a preparation
procedure may be found in Ref. I for the case of a
nanocrystallineTi0 2 film. The experiments described in
the present chapter were in most cases performed using
Ti0 2 films prepared from commercial photocatalysts:
P25 ca. 75% anatase/25'Yo rutile (Degussa), A-HRS
anatase and R-SM2 rutile (both from Tioxide).
709
A suspension oftheTi0 2 powder in DMF-containing
dissolved poly(vinylidenefluoride), PVDF (typical com-
position: I g P25 and 0.4 g PVDF per 20 cm 3 DMF)
was applied to the substrate, dried in air for 30 min at
25°C and then for 40 min at 100°C to evaporate the
solvent, and finally annealed for I h at 450°C [23]. The
support consisted of an F-doped Sn02 film (0.5 /lm
thick) deposited on glass (Libbey Owens Ford,
10 n/square). Thicker films were formed by multiple
application (until 50 times) and heat treatment of a
standard, less than I /lm-thick, layer.
In Fig. la-d are displayed typical SEM images of the
nanostructured Ti0 2 films. Parts a and b of Fig. I rep-
resent a top view and Fig. Ie shows a cross-sectional view
of a ca. 0.6-/lm-thick film composed of P25 particles.
Aggregates of partly fused particles are separated by
nanopores of different sizes. For comparison purposes,
the films formed by electrophoretic deposition of P25
particles were also used. The deposits were obtained from
a suspension of 0.5 g of P25 powder in 10 cm 3 of
demineralized water. For example, a voltage of 4 V
applied for 20 s between an Sn02/glass cathode and a
Pt counterelectrode yielded a ca. 15-/lm thick deposit.
Freshly formed films were first dried and then heated for
I h at 450°C in air.
III. PHOTOELECTROCHEMICAL BEHAVIOR
OF NANOSIZED Ti0 2 FILMS
A. Photocurrent-Voltage Characteristics
The unsual feature of the nanostructured anatase Ti0 2
photoelectrodes consists in an unprecedented sensitivity
of the delivered photocurrent to the nature of the hole
scavenger (electron donor) present in the solution. Such
a behavior is illustrated in Fig. 2 showing photo-
current-voltage (iph - E) characteristics of a Ti0 2 film,
composed of P25 nanoparticles, recorded in the back-
ground electrolyte (O.lM HCl04) alone and with
additions of methanol or formic acid. Although the typi-
cal saturation photocurrent attained in the presence of
HCOOH in the solution is about 20 times larger than that
corresponding to the photooxidation of water (curve a),
it is still twice as large as the photocurrent observed in
the solution containing CH 30H (curve b). As a rule, an
increase in the photocurrent was accompanied by a nega-
tive shift of its onset potential, E ph . A similar shift of E ph
has previously been observed for the bulk polycrystalline
anatase photoelectrodes after addition to the solution of
the species undergoing preferential photooxidation with
respect to water [24,25]. However, in the case of the bulk
710 Augustynski

(a) (b)

(e) (d)

Figure 1 Scanning electron micrographs of a particulateTiOz (P25) film showing surface view (a, b) and cross-sectional views (c, d)
ofa I-layer (c) and 3-layers (d) deposit. Magnification: (a) 140,OOOx, (b) 70,OOOx, (c) 93,333 x, and (d) 14,OOOx.

samples, the associated increase of the photocurrent
(attributable essentially to the partial occurrence of the
photocurrent doubling) does not exceed 20~30%.
The unusually strong influence of the nature of the
electron donor upon the amount of the photocurrent
(observed until now only in the case ofparticulate anatase
films) [23,26] is in agreement with the conclusion of
Hodes et al. [14], following their study of colloidal CdS
and CdSe films, indicating that in such systems, charge
separation occurs by differing rates of electron and hole
transfer into solution. This is in fact the case for formic
acid and methanol undergoing rapid charge transfer at
the anatase surface leading, in both cases, to CO 2 as a
final product. Importantly, the intermediates HCOO',
respectively, CH 3 0' are oxidized even easier than the
starting reactants (both are able to inject electrons into
the conduction band of Ti0 2) and the reduction of CO 2
at the surface of Ti0 2 is a slow process. The situation is
totally different for the photooxidation ofwater at anatase
Ti0 2, producing in the first-step Tis-O' radical species
Tis - 0- + h+ -+ Tis - O· (1)
or, depending on the solution pH
Tis - OH + h-t -+ Tis - O· +H+ (2)
Nanostructured Semiconductors
10.,---------------------,
(e)
9
8
7 of the observed quantum yield with increasing film
N 6
E
u (b)
<{ 5
E in terms of recombination losses at crystal boundaries
.~ 4
3 thicker than the penetration depth of the incident light.
2
(a)
-0.2 o 0.2 0.4 0.6 0.8 1.2
E/Vvs RHE
Figure 2 Photocurrent-potential curves for a TiO z electrode
consisting of three successive layers of P25 nanoparticles,
recorded in 0.1 M HCI0 4 (a), 0.1 M HCI0 4/0.1 M MeOH (b),
and 0.1 M HCI04/0.1 M HCOOH (c) under the full output
illumination ofa 150-W xenon lamp [15].
whereTis denotes titanium ions in the surface. These rad-
ical species are expected to act as effective recombination
centres for the conduction band electrons [25,27].
The hole-electron recombination at the nano-
structured anatase films proceeds, apparently, quite
effectively because it is not possible to detect, using cyclic
voltammetry, any significant amount of the surface per-
oxides. In contrast, the bulk anatase samples, subjected
to a similar anodic bias, become covered with ca. a
monolayer of peroxo species easily monitored
electrochemically [27]. It is to be noted that curve a in
Fig. 2, illustrating the photogeneration ofoxygen, reflects
the general behavior, at the particulate anatase films, of
reversible redox couples where the initial hole transfer
leads to the formation of an easily reducible species
(which can be either the final product or an intermediate
of the photooxidation reaction). In fact, photo-
current-voltage characteristics similar to curve a in Fig.
2 are also obtained in the case of photooxidation of both
hydroquinone and iodide ions.
B. Quantum Efficiencies of the Photocurrent
Although the highly selective behavior of the nano-
structured anatase films toward the photooxidation of
various species in the solution is essentially consistent
with the model proposed by Hodes et al. [14], this is not
the case for other features exhibited by these anatase
711
samples. The measurements performed using colloidal
CdS and CdSe films showed that their spectral responses
were strongly affected by the thickness of the semicon-
ductor layer. The general trend was toward the decrease
thickness, accompanied by a red shift of the maximum
photoresponse [14]. These observations were explained
occurring in the semiconductor films significantly
The authors predicted also, in such a case, resistance
losses leading to a deteriorated i ph - E behavior.
Assuming that the transport of most charge carriers in a
nanostructured semiconductor film takes place via
diffusion, Sodergren et al. [28] derived a relationship for
the spectral response of the photocurrent as a function
of the film thickness. According to this model, for the
films with thicknesses, d, exceeding the diffusion length
of electrons, L, the quantum efficiency of the
photocurrent should reach a maximum when
a. = lid (3)
a. being the optical absorption coefficient in the
nanostructured semiconductor. Consequently, the maxi-
mum is expected to be shifted toward the band edge with
the thickness of the anatase film increasing from ca. 1 to
more than 40 flm. However, the results of measurements
carried out with nanostructured P25 films of various
thicknesses (ranging from ca. 1 to 45 flm) [15] apparently
do not follow predictions of the above model. Figure 3A
displays photon-to-current efficiency vs. potential plots
for a ca. 2.5-flm-thick film illuminated with 300-nm,
respectively, 380-nm wavelengths, obtained in 0.1 M aq.
HCI04 with and without addition offormic acid. Despite
the fact that the 300 nm light is absorbed very close to
the outer film - electrolyte interface, much farer from the
back contact than the 380-nm light, the short wavelength
photocurrent yield is almost three times larger than that
for the 380-nm illumination. The optical penetration
depths (a.-I), for 300 and 380 nm wavelengths in rutile,
based on the absorption spectrum given by Eagles [29],
are oflO nm, respectively 1 flffi. Taking into account that
anatase films formed by sputtering exhibit somewhat
lower absorbance than similar rutile films [30] and
assuming that the porosity of the 2.5-flm-thick anatase
film is close to 60%, one can estimate the actual
penetration depths for 300 and 380 nm light to be of the
order of 30 nm, respectively, 3 flm. Consequently, the
highest photocurrent efficiencies represented in Fig. 3A
correspond to the situation where the hole-electron pairs
are generated in an extremely thin outer portion of the
712 Augustynski

120 TiA\-------------------.-
'(A) , 20 which are apparently inconsistent with the eXlstmg
b models for photocurrent generation in nanocrystalline
100
semiconductor films, suggest that the electrons flowing
15
80
to the back contact suffer, in fact, recombination
a principally inside the illuminated portion of the film.
~ ~
~ 60 10 ~ Larger the illuminated region ofthe film, where the holes
~ ~ are photogenerated, traversed by the electrons, smaller
40 b' the actual maximum photocurrentyield. This view is con-
5 sistent with the characteristic shape of the spectral
20
...--
a' photoresponses shown in Fig. 4, which will be examined
o I -,"- ( I I I I I 1 0 more in detail later. Photocurrent efficiency vs. potential
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1 12 (IPCE-E) plots recorded for a much thicker (ca. 10 ,urn)
EV vs RHE anatase film, represented in Fig. 3B, follow the same
trend, with the maximum efficiencies for both the 300-
140 '(8) b 10 and 380-nm illumination increasing markedly with
120 respect to those for the ca. 2.5-,um-thick film. Such an
a T 8
increase is easier to understand in the case of the longer
100
wavelength illumination where the 380-nm light could
~ 80 6 '# eventually not be completely absorbed within the
LJ.J LJ.J
() ()
a. 2.5-,um-thick film. Although the latter argument obvi-
~ 60 b' 4 -
ously does not hold for the shorter (i.e., 300 nm) wave-
40 a' length illumination, the corresponding data in Fig. 3B
2 support a virtual absence of recombination in the
20
unilluminated region of the film. Further increase of the
01 rr r I I I I I 10 Ti0 2 film thickness (until ca. 45 ,urn) did not produce sig-
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2
nificant changes in the amount of the photocurrent
EVvs RHE
observed in the solution containing formic acid (Fig. 3C).
It is to be noted that despite the light absorption taking
140 I(C) F • "'" I 10 place at a very large distance from the back contact, the
b
120 photocurrent rises steeply to reach a maximum
8
100 a corresponding, for A= 300 nm, to the quantum yield of
about 140% (due, in part, to the occurrence of the
~ 80 6 ?f2.
LJ.J LJ.J photocurrent doubling mechanism) [31]. This indicates,
()
~ 60
b'
4
a:- in addition to a small extent of recombination, quite low
resistive losses across the film. Although significantly
40
a'
2
different, the saturation photocurrents for both the
20 thinner and the thickest Ti0 2 film examined in this
study are, in fact, attained under practically identical
oI ~I II I I I I I 1 0
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2
bias.
E Vvs RHE The above described behavior of the nanostructured
anatase films is observed in all cases in which solution
Figure 3 Photocurrentefficiency (IPCE)-potential curves for contains an efficient scavenger of the photogenerated
the nanostructured anatase (P25) films ofvarious thicknesses, holes, such as formic and oxalic acid or methanol.
2.5-tlm (A), lO-tlm (B), and 45-tlm-thick (C), illuminated with However, for the photooxidation reactions involving
300 nm (a, b) and 380 nm (ai, b') monochromatic light in 0.1 M large extent of recombination, an increase in the film
HCI0 4 (a, a') and 0.1 M HCI0 4 (0.1 M HCOOH (b, b') [15). thickness causes an opposite effect, i.e., a decrease of the
photocurrent, although the quantum yields correspond-
ing to short wavelength illumination remain still higher
Ti0 2 films, ca. 2.5 ,urn far from the back contact. On the than those observed at longer wavelengths. This kind of
other hand, the corresponding quantum yields decrease behavior is represented by IPCE-E and IPCE-A plots for
significantly in the case where light (A = 380 nm) the photooxidation ofwater shown in Fig. 3, respectively,
penetrates more or less the whole film. These results, Fig. 4.

L
Nanostructured Semiconductors 713

(A)100 c. Spectral Photoresponses

90 In Fig. 4A-C are displayed spectral photocurrent
b
80 responses for the nanostructured anatase films of differ-
70 ent thicknesses, corresponding to the photooxidation of
formic acid, methanol, and water. In the first two cases,
.rJ.l
:!? 60
the plots exhibit a pronounced maximum at ca. 300 nm
u 50 irrespective the actual thickness ofthe film. These results
e: 40 are again at variance with the predictions ofthe "electron
30 diffusion model" of charge carrier transport in
20 semiconducting nanostructured films [28], according to
which the maximum of the spectral photoresponse is
10
expected to be red-shifted with increasing the film
0 thickness [cf. Eq. (3)]. The actual dependence of the
250 300 350 400 450
photoresponse on the film thickness is clearly affected
Wavelength (nm) by the nature ofthe hole scavenger present in the solution.
Thus, for rapid (and irreversible) photooxidation
(8) 160
reactions, the quantum efficiency of the photocurrent
140 increases with increasing the film thickness (until ca.
10 Ilm) over the entire range of wavelengths. In the case
120 of photooxidation of water, leading to the formation of
c
100 readily reducible Tis-O' species, the IPCE values at
0~ shorter wavelengths follow an opposite tendency,
UJ 80
() decreasing moderately for thicker films. An abrupt
Q: decrease of the quantum yield for the 2.5-llm-thick film
60
(more rapid than for the thicker films), observed for the
40 wavelengths larger than 360 nm (Fig. 4C) is explained
20 by the optical penetration depth exceeding the thickness
oftheTi0 2 film.
0 Various series of measurements performed with the
250 300 350 400 450 nanostructured Ti0 2 films deposited from the dis-
Wavelength (nm) persions containing the PVDF binder were duplicated
using films formed by electrophoresis of a suspension of
(C)20
P25 particles in pure water. The obtained results
18 (including the amount of the photocurrent) were closely
16 similar to those shown in Figs. 2-4 [15].
14 a
D. Effect of Light Intensity
0~
12 b
UJ 10 c The data displayed in Figs. 3 and 4 reflect the
()
Q: photocurrent response of nanostructured anatase films
8
to low intensity illumination generated through the
6 monochromator. Additional measurements, performed
4 using argon-ion laser light (334, 351.1, and 363.8 nm emi-
2 ssion lines) revealed that the actual relationship between
0 the film thickness and the amount of the photocurrent
250 300 350 400 is, in fact, strongly affected by the light intensity. As shown
in Fig. 5, plot b, under 300-mW illumination (focused
Wavelength (nm)
on 0.28 cm 2 of the film surface), the maximum
Figure 4 Spectral photoresponses for the nanostructured photocurrents measured in solution of formic acid are
anatase (P25) films: 2.5-flm (a), lO-flm (b), and 45-flm-thick (c), almost independent on the film thickness for the films
recorded in 0.1 M HCI0 4 /0.1 M MeOH (A), 0.1 M HCI04 1 consisting of 3 to 12 consecutive layers with thicknesses
0.1 M HCOOH (B), 0.1 M HCI04 (C) [15]. ranging from 2.5 to 10 Ilm. However, thinner films, such
714 Augustynski

20 (a) 2

-----
-------
b 18

08+ 16 1.5
N
. 14
'5
"Eu «
"Eu 06 . 12 E
1

.~
« 10 ~
E
__"5. 0.4 8 -..ffi. 0.5

0.2 4 20 40 60 80 100
% Transmission
2

0 0 (b)16 , ~
2 4 6 8 10 12 14
Nb. layers 14

12
Figure 5 Variation of the saturation photocurrent of the ':' 10
nanostructured anatase (P2S) films as a function of the film 5
thickness, recorded in 0.1 M HCI0 4 /0.1 M HCOOH, using ~ 8
the full outputofa argon-ion laser (334, 3S1.1, and 363.8 nm lines) .~ 6

corresponding to 300 mW/O.28 cm 2 (plot b) and illuminated 4

through a 0.6% neutral filter (plot a) [IS].
2

as I pm thick, delivered much lower photocurrents. These 20 40 60 80 100

results are closely similar to those previously reported
for the nanostructured anatase films exposed to a 0.1 M
NaOH/O.1 M CH 30H solution and illuminated with the
full output ofa 150-W xenon lamp [26].
Importantly, when the full output of the argon-ion
laser was replaced by a strongly attenuated illumina-
tion (using a 0.006 transmission filter), the observed
photocurrents showed again a substantial increase with
increasing the film thickness (cf. plot a in Fig. 5). Thus,
the pronounced dependence of the photocurrent on the
film thickness, extending to thicknesses of ca. 10 lIm,
appears as a typical feature ofthe nanostructured anatase
films subjected to a low intensity illumination.
In Fig. 6 are shown the maximum photocurrents
(corresponding to the plateau of the iph - E curve)
plotted against the light (334-363.8 nm) intensity.
Although in the case of photooxidation of water, the
photocurrent is linear with light intensity (Fig. 6a), the
photocurrents recorded in the solution containing formic
acid strongly deviate from linearity (Fig. 6b), due appar-
ently to the rate-limiting diffusion and/or adsorption of
HCOOH within the Ti0 2 film. Accordingly, it is the
relationship between the amount of the photocurrent
and the film thickness observed under low intensity
illumination, i.e., in the absence of the effects related to
the transport and adsorption of reactants, which is to be
considered as typical of the behavior of nanostructured
anatase photoelectrodes.
% Transmission
Figure 6 Saturation photocurrents for a 2.S-,um-thick
nanostructured anatase (P2S) film plotted as a function oflight
intensity in 0.1 M HCI0 4 (a) and 0.1 M HCI0 4 /0.1 M HCOOH
(b); full output illumination corresponding to 300 mWI
0.28 cm 2 ofargon-ion laser light (334, 3S1.1, and 363.8 nm) [IS].
E. Comparison Between Anatase and Rutile
Almost all studies devoted previously to the photo-
electrochemical characterization of nanostructuredTiO z
films are in fact concerned with the anatase form of this
semiconductor. It is useful to recall, in this connection,
that aqueous suspensions of the rutile photocatalyst
exhibit, in general, lower or even much lower activity
than similar anatase samples [32-35]. To compare
photoelectrochemical behavior of nanostructured films
including two different forms of TiO z, anatase and rutile
powders with similar mean diameters ofl50 nm, respect-
ively 210 nm, have been chosen. As shown by scanning
electron micrographs in Fig. 7, both films exhibit almost
identical morphologies. Photocurrent vs. potential
curves, recorded in the supporting electrolyte and after
addition of methanol, respectively, formic acid to the
solution, fully confirmed striking difference in
photoactivity between the two forms of TiO z. As shown
in Fig. 8A and B, the photocurrents observed for the rutile
Nanostructured Semiconductors 715

(a) (b)

Figure 7 Scanning electron micrographs showing surface views ofparticuiateTi0 2 films consisting ofrutile (R-SM2) (a) and anatase
(A-HRS) (b). Magnification 76,666x [15].

film are, in fact, 30 to 50 times lower than those for the
anatase counterpart. Such a behavior, which is in con-
trast with that of the corresponding bulk films exhibiting
comparable photoelectrochemical activities [31], point
at the essential role played in the case of the
nanostructured films by the interfacial kinetics.
On the other hand, the comparison of the iph - E
curves in Fig. 8B with those displayed in Fig. 2, recorded
for the film of similar thickness composed of much
smaller P25 particles, shows significant difference both
in the amount of the photocurrent and in the shape of
the curves. Poorer photocurrent-voltage characteristics

0.1 3
(A) (8)
0.09
2.5
0.08

0.07
2
"I 006 "I
E
u
E
u
<t: 005 <t: 1.5 b
E E
.E- 0.04 ..ffi.

0.03

0.02
0.5
a
0.01

0
-0.4 -02 0 0.2 0.4 0.6 0.8 1.2 -02 o 0.2 0.4 0.6 0.8 12
E IVvs RHE E IV vs RHE

Figure 8 Photocurrent-potential curves forTi0 2 rutile (R-SM2) (a) and Ti0 2 anatase (A-HRS) (b) nanostructuredfilms consisting of
three consecutive layers, recorded in 0.1 M HCl0 4 (a), 0.1 M HCl0 4 /0.l M MeOH (b), and 0.1 M HCl0 4 /0.l M HCOOH (c), under
the full output illumination ofa 150-W xenon lamp [15].
716
of the film formed from the larger anatase particles may
be due to larger recombination losses and higher contact
resistance.
F. Particular Electrical Properties of Anatase
When considering largely differing photoelectro-
chemical behavior of nanostructured anatase and rutile
films, it is important to recall that also physical properties
of these two forms of Ti0 2 are far from being identical.
Recent studies of polycrystalline films of anatase and
rutile [30] (and ofthe anatase single crystal [36]) revealed
in particular important differences in their electrical pro-
perties. In the case ofanatase films submitted to thermal
treatment in vacuum, with donor concentrations
approaching 10 19 cm- 3 , the authors found evidence for
a Mott (insulator-metal) transition occurring in a donor
band ofthe semiconductor. This finding is consistent with
the electrical resistivity of the anatase films strongly
decreasing after the vacuum treatment and becoming
practically independent on the temperature. The
Hall-effect measurements performed with these films
showed a maximum in the Hall constant with decreasing
temperature, indicative of a transition in the conduction
mechanism [30]. None of these effects was observed for
the rutile films with high carrier concentration
(>10 19 cm- 3), exhibiting a less pronounced decrease in
resistivity following the thermal treatment in vacuum.
An important conclusion drawn by Tang et al. [30]
from the results of their resistivity and Hall-effect
measurements is that the insulator-metal transition
occurs in a donor band ofthe reduced anatase films. This
is supported by the fact that both the corresponding
resistivity against temperature and Hall constant vs. tem-
perature plots remain flat down to low temperatures at
which the population ofelectrons in the conduction band
of anatase falls to a low level. As postulated by these
authors [30], the conduction via the donor band of doped
anatase remains still the dominant process at room
temperature. The absence of the Mott transition in the
donor band of heavily doped rutile is to be assigned to a
small Bohr radius (aH) of the donor state, comparable
with the interionic distance in the rutile lattice. In con-
trast, the donor radius aH in anatase, deduced byTang et
al. on the basis of the critical donor concentration for
the Mott transition, is almost six times larger. The large
donor radius in anatase is the consequence of a small
electron effective mass m* '" Imo, 20 times smaller than
that in rutile.
It is useful to recall, in this connection, a large
improvement in the photocurrent-voltage characteristics
of the anatase films, deposited on titanium by a sol-gel
Augustynski
method, induced by a high temperature (>500°C) treat-
ment in argon [31,37]. Diffusion of Ti atoms from the
support into the film creates a profile of donor con-
centration, sufficient to allow the insulator-metal
transition in a more or less large portion ofthe film adjac-
ent to the back contact. This is, however, not the case for
the nanostructured films consisting normally of poorly
doped anatase particles. The estimated donor concen-
trations in such films, of about ND = 10 17 cm- 3 [17,38],
are in fact almost two orders of magnitude lower than
the critical value of ND for which the Mott transition is
expected to take place. It is interesting to note, in this con-
nection, that the additional thermal treatment in argon
performed with the first version of nanostructured ana-
tase films used in the dye-sensitized cells [17] was rapidly
abandoned [I].
IV. SELF-DOPING OF NANOSIZED ANATASE
FILMS UNDER THE FLOW OF THE
CURRENT
Clearly, the central question to be answered is how
an initially poorly conducting network of anatase
nanoparticles allows excellent photocurrent-voltage
characteristics either in a dye-sensitized liquid-junction
solar cell or under direct band gap (and, more especially,
the short wavelength) illumination in the presence of a
suitable hole scavenger. A possible explanation is that an
adjustment in the electron population within the donor
band of anatase occurs at the initial stages of the film
illumination, before the steady-state photocurrent is
attained. Once reached the critical carrier concentration
close to 10 19 cm- 3 , the unilluminated (and probably also
the weakly illuminated) region of the anatase film
exposed to a UV light undergo the Mott transition
accompanied by a more than hundredfold increase in
conductivity.
Although in the case of a bulk anatase electrode the
compensation of an excess of negative charge would
require a simultaneous injection into the solid phase of
protons or alkali cations, the situation is totally different
for the nanostructured anatase film, with pores filled with
the electrolyte, exhibiting an exceptionally high surface
to volume ratio. Assuming that roughly two thirds ofthe
total surface area ("'55 m 2 . g-l) of the P25 particles is
actually in contact with the electrolyte, we can estimate
that the electrochemically active surface area of the
nanostructured film is of the order of 1.5 X 10 6 cm 2 per
cm 3 of the solid phase. This implies that a negligible
adjustment, ca. 6x 10 12 ions· cm- 2 (or I ion per 15 nm 2)
in the concentration of cations in the Helmholtz layer
suffices for compensating an excess charge carrier con-
 Nanostructured Semiconductors
50
40
'i 30
~
c.
a
20 r--···-W.'._&~.~._._._ ... _~-_.~
Light on
·
,·
..,
10 ,
· . ,
-\. "l
0 The authors noted that their results could be interpreted
0 10 20
Time (5)
Figure 9 Photocurrent vs. time curves recorded for a 0,6-~m
(a) and a 13-~m-thick (b) nanostructured anatase (P25) film,
in 0.1 M HCI0 4 /0.1 M MeOH, at 0.8 V vs. RHE, under a
320-nm monochromatic light [40].
centration of 10 19 cm- 3 within the P25 nanoparticles.
The above value is to be compared with a typical variation
in the surface-charge density of an oxide with pH of the
solution, which is ofabout 5 pC . cm- 2 per ~pH = 1[39],
i.e., five times larger.
The explanation involving an insulator-metal
transition occurring in the network of anatase nano-
particles spontaneously, under an anodic photocurrent
flowing across the film, is supported by a series of
additional observations. In Fig. 9 (curve b) is shown a
slow photocurrent transient following the illumination
of a l5-pm-thick nanostructured anatase film with a
monochromatic 320-nm light. The slow rise of
the photocurrent to reach the steady-state value
(corresponding to the plateau in Fig. 3) may be due to
the charging of the relatively thick unilluminated portion
of the film by the photogenerated electrons. As a matter
of fact, in a similar experiment performed with a much
thinner (ca. I-pm-thick) film, the steady-state
photocurrent was attained after only a short delay (Fig.
9, curve a). Also, a second consecutive illumination of
the l5-pm-thick film resulted in an almost direct rise of
the photocurrent [40].
Salafsky et al. [41] recently described time-resolved
microwave conductivity measurements performed with
dye-sensitized, 1O-pm-thick nanostructured anatase
films. The illumination of the sample with continuous
white light of 100 mW . cm -2 was accompanied by a sig-
nificant increase in the conductivity extending over a
period of several seconds (in fact, the conductivity was
still rising when, after a 6-s illumination period, the light
717
was turned off). Importantly, when the film was
Light off illuminated with less intense light, the observed
microwave conductivity was much (more than 10 times)
lower. These resul ts establish a direct connection between
charging ofthe nanostructured film through the electrons
injected to the conduction band of anatase by the
photoexcited dye, on the one hand, and the rise in the film
conductivity, on the other.
Cao et al. [42] reached, in fact, a similar conclusion on
the basis oftheir measurements oftransient photocurrent
response of dye-sensitized nanocristalline anatase cell.
30 40 in terms of the "electron diffusion model" [28] only by
assuming that the diffusion coefficient for electrons
within the film depends on the intensity of the incident
light. To explain the fact that the observed rise time of
the photocurrent became shorter with increasing light
intensity, Cao et al. supposed the diffusion coefficient
for electrons being proportional to the electron concen-
tration within the nanostructured film. Again, these
results are consistent with the initial build-up of the elec-
tron concentration in the particulate anatase film, after
switching on the light, leading to an increased con-
ductivity. It is to be noted, in this connection, that the
photocharging of small semiconductor particles,
deposited on an insulating support or in the form ofa sus-
pension in an aqueous electrolyte, has been reported pre-
viously to produce the shift of the absorption edge
toward shorter wavelengths (the so-called Burnstein
shift) [43]. This effect was assigned to a shift of the Fermi
level into the conduction band of the semiconductor due
to the increased electron concentration within the
nanoparticles. Interestingly, in the case when the
irradiated dispersion of a CdS colloid contained an
efficient hole scavenger and no other electron acceptor
than water molecules (i.e., a situation similar to that of
the nanostructured anatase film illuminated in a
deaerated solution offormic acid), the relaxation of the
colloid in the dark, to a nondegenerate state, was quite
slow taking several seconds.
The preparation of the nanostructured semi-
conducting oxide films involves, in general, a high tem-
perature (:::400°C) annealing, intended to produce
partial sintering of the nanoparticles and to establish
among them an electrical contact [17]. However, recent
experiments with electrophoretically deposited P25 films
demonstrated that the films simply dried at room tem-
perature behaved essentially in a similar way as the
annealed samples [44]. In particular, the shapes of the
spectral photoresponses of a film dried at 25°C and of a
film annealed at 400°C were practically identical (cf.
Fig. 10). Considering that for the 300-nm illumination,
718
140
120
100
~
0 80
w efficiency of the photooxidation reaction involving
()
a.. 60
40
20
0 under identical illumination conditions (Fig. II b) showed
250 300 350 400 450
Wavelength (nm)
Figure 10 Spectral photoresponses for the nanostructured
anatase (P25) films obtained by electrophoretic deposition
without final heat treatment (a) and after annealing at 400°C (b),
recorded in 0.1 M HCl0 4 /O.l M HCOOH [15].
the optical penetration depth, IX-I, is two orders of
magnitude lower than the film thickness, one cannot
invoke the presence of in situ photoexcited electrons [42]
to explain the apparent low resistance of the contact
regions among nonannealed nanoparticles. It is import-
ant to realize that in the absence ofcharging (self-doping),
such a network of nanoparticles maintained together by
the van der Waals~ London interactions can be expected
to exhibit much higher resistance than a similar film con-
sisting of partly sintered particles. This is related to the
presence of more numerous trap sites in the contact
regions, able to deplete the nanoparticles offree carriers
below the original 10 17 -cm- 3 level. This problem has
been discussed in detail in the context of Hall-effect
measurements performed with bulk polycrystalline
semiconductor samples consisting of small crystallites,
i.e., including large area of grain boundaries [30,45]. The
situation is completely changed as a consequence of film
charging, due to the trap filling and to the increase of the
carrier concentration leading to a decreased barrier
height between nanoparticles. It is to be noted, in this
connection, that once reached the critical carrier con-
centration corresponding to the Mott transition,
No~1019 cm- 3 , the depletion layer will become
Augustynski
relatively thin in comparison with the size, ca. 25 nm,
of nanoparticles. Using e = 31 as the static dielectric
constant of anatase [30], one obtains in such a case the
Debye length, Lo = (eeokT/ Noe 2)1/2, close to 2 nm.
In this connection, it is useful to mention also a series
ofexperiments giving an insight into the potential distri-
bution within the illuminated nanostructured anatase
films subjected to an anodic bias [46]. Numerous
attempts to determine for such films the faradaic
formic acid, using gas chromatographic analyses, gave
systematically values between 130 and 140%.
Such results were obtained under continuous air
bubbling through the solution (cf. Fig. lla); however,
under nitrogen bubbling, the observed faradaic
efficiencies were close to 100%. Subsequent determi-
nation of the amount of CO 2 formed at open circuit,
that the "excess" faradaic yields determined under anodic
bias were, in fact, due to the simultaneous occurrence of
the "open-circuit process." The latter involves, coupled,
the hole scavenging
HCOOH + 2h+ -+ C02 + 2H+ (4)
and the electron scavenging reaction
1/202 + 2e- + 2H+ -+ H20 (5)
As reaction (5) requires potentials close to (or more nega-
tive than) 0 V vs. RHE, the fact that the open-circuit pro-
cess remains practically unaffected by the anodic bias
indicates that the actual potential of the illuminated
region of the nanostructured film should be closer to the
flat-band potential rather than to the positive potential
applied to the back contact.
v. CONCLUSIONS
Several aspects of the photoelectrochemical behavior of
the nanostructured anatase films appear anomalous in
the light of previously proposed models describing the
charge carrier transport in such networks of semicon-
ductor particles. This concerns, in particular, the fact that
the films with thicknesses largely (by at least two orders
of magnitude) exceeding the penetration depth of the
incident UV light exhibit excellent photocurrent-voltage
characteristics consistent with quite small resistance
losses. This is the case even for electrophoretically
deposited films that did not undergo any annealing.
An alternative explanation of the behavior of
nanostructured anatase Ti0 2 films, both under the band
gap UV illumination and in the dye-sensitized con-
 Nanostructured Semiconductors 719

14o,-------------------, 3 1400 ~----------------__,

(a) (b)

120 i"- 1200

2.5
f
'$.
f
ti 100 f
_ 1000
z I 2 E
UJ a.
U 80 I .9:
u:: I Corrected efficiency "5 c:
0
800
tt I 1.5 « :g
U 60 ,:
I E (5
> 600
~
UJ
I:
I: 0

\-
~
~
40

20
':
0.5
U
400
N2 J Air

200

O+--~f--'---+--_+_--+__-___l--__+O

o 100 200 300 400 500 600

/1
O¥----+--+----+--+----+--+--~
TIME (min) o 200 400 600 800 1000 1200 1400
TIME (min)

Figure 11 (a) Faradaic efficiency and saturation photocurrent, fora nanostructured anatase (P25) film (ca. 2.5 tim thick) polarized at
0.35 V vs. RHE, plotted against time. Air saturated 0.1 M HCI0 4 /0.1 M HCOOH solution: illumination with a 150-W xenon lamp
through a 320-nm cutofffilter (b). Amount of C02 evolved at the same P25 Ti0 2 film at open-circuit: other conditions as in (a) [46].

figuration, under white light illumination is proposed in
terms of the self-doping occurring at the initial stages of
the photocurrent flow across the film. The transient
1 charging of the film continues until the critical electron
concentration in the donor level of anatase (ca.
10 19 cm -3) allowing the insulator-metal (Mott) transition
is reached. This transition is accompanied by an import-
ant increase in the electrical conductivity ofanatase.
The proposed mechanism of self-doping constitutes
an unique feature of nanoporous semiconductor
networks, penetrated by the electrolyte, which offer the
possibility of excess charge compensation by an adjust-
ment of the cation concentration in the Helmholtz layer.
In the case of 25 nm in diameter P25 particles, the
increase of the surface concentration of monovalent cat-
ions required to compensate a 10 19 -cm- 3 excess of elec-
trons within the nanoparticles is of the order of only 1
ion per 15 nm 2 .
For relatively thick anatase films illuminated with the
band gap UV light, the proposed occurrence of the
insulator-metal transition, as a consequence of the
t self-doping of nanoparticles, provides actually a means
to extend the back contact close to the illuminated region
that the charge recombination takes place principally
within and close to the illuminated portion of the film.
The fact, established through the experiments performed
in the presence of formic acid, that the open-circuit
activity of a nanostructured anatase film persists, irres-
pective the applied positive (anodic) bias of more than
0.7 V, indicates that the actual potential of the
illuminated region of the film remains close to the
flat-band value. Although the potential distribution
across the film is, for the moment, not completely clear,
one can assume the potential across the illuminated
portion of the film to become increasingly more positive
with decreasing the amount of the absorbed photons
and the accompanying excess of photogenerated
electrons.
ACKNOWLEDGMENTS
I thank Drs. Axel Wahl, Martine Ulmann, and Annick
Carroy for their contributions to the work related in this
chapter. I am grateful to the Swiss National Science
Foundation for research support.

of the film. Such an explanation is consistent with the

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of the nanostructured anatase electrodes are practically
unaffected by the thickness of the films being used.
High IPCE values observed for the films illuminated
with short wavelengths of the incident light (character-
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,
l
 40
Semiconductor Nanocomposite Films for
Photoelectrochemical Applications
Krishnan Rajeshwar and Norma R. de Tacconi
~. University ofTexas at Arlington, Arlington, Texas
\
ABSTRACT
This chapter focuses on the materials aspects of
photoelectrochemistry and particularly on the evolution
in the use as photoanodes, of single crystals, poly-
crystalline films, nanocrystalline films, and nano-
crystalline composites comprising of semiconductor
particles dispersed in a continuous matrix medium.
Occlusion electrodeposition is described as a versatile
method for preparing these nanocomposite films. The
important and varied roles that the matrix components
play in dictating the photoelectrochemical behavior of
the resultant nanocomposite assemblies are also
highlighted. Finally, cofunctional film architectures
wherein the matrix component is chosen to enhance
the adsorption cross-section of a targeted substrate
candidate are also described. Such strategies provide
an avenue for improving quantum yields in photo-
catalytic reactions.
I. INTRODUCTION
The field of photoelectrochemistry can be considered to
..- be truly born with Becquerel's classical experiments
\
more than 100 years ago [1]. There was intense activity
thereafter in the 1950s and 1960s in the electrochemistry
ofsemiconductor materials, undoubtedly driven by poss-
ible applications in the electronics industry [2-5]. Mod-
ern photoelectrochemistry came into prominence with
the experiments of Fujishima and coworkers [6-8]
showing that solar energy could be used to split water into
H2 and 02. This field literally exploded thereafter [9,10],
721
and the growth spurt was only slowed in the late 1980s
with a drop in oil prices and declining interest in solar
energy conversion. There is renewed interest now in
environmentally benign methods for energy production
and consumption. Photoelectrochemical methods are
also showing promise in the treatment of hazardous
wastes and for maintaining the quality of indoor air and
water streams [11,12].
From a materials perspective, the field has evolved
from the use of semiconductor single crystals to poly-
crystalline thin films and very recently to nanostructured
films [13,14]. Single crystals, although clearly impractical
from a technology perspective, did serve to form the foun-
dation for many experimental and theoretical studies in
the field in the 1970s and 1980s [10]. Polycrystalline films
further promoted this development and brought the field
closer to practical implementation. Interestingly, the
use of polycrystalline semiconductor films also aided in
further fundamental understanding of interfacial
phenomena, particularly those related to surface
recombination and surface state passivation. The advent
of the dye-sensitized Ti0 2 solar cell [15] opened the door
to nanostructured, semiconductor films [13,14,16]. Inter-
estingly, these developments appear to have paralleled
corresponding advances in the semiconductor and metal
colloid chemistry communities.
Even further down the "family tree" ofsemiconductor
electrode materials for photoelectrochemical applic-
ations are matrix/semiconductor nanocomposites, i.e.,
nanocrystalline films comprising of semiconductor
particles that are dispersed in a nonphotoactive continu-
722
ous matrix. Examples of matrix candidates are metals
and polymers. Traditionally, metal islands have been
incorporated on semiconductor photoelectrode surfaces
to improve the catalytic activity of the latter [10]. Inter-
estingly, unusual photoeffects were observed by Nakato
et al. for such "composite" electrodes [17-19] and were
attributed to the surface band-energy ofthe semiconduc-
tor at the metal-covered parts being different from that
at the "naked" regions. Metal-filmed semiconductor elec-
trodes have also been used in photoelectrochemical cells
[20], and this "heterojunction photoelectrode" approach
was later extended to the use of films such as tin-doped
indium oxide [21] and Sn02 [22]. This chapter builds on
this early corpus of work and focuses on new data for
composite films containing nano-sized semiconductor
particles dispersed in them. Table 1 illustrates that the
matrix component in such "nanocomposites" could be
either a metal or an insulator. Other materials such as
carbon black and organic polymers can also be used as
the matrix hosts for the semiconductor particles. In what
follows, we focus in particular on the varied role that the
matrix component plays in dictating the (photo) electro-
chemical behavior of the semiconductor particles in the
film.
In concluding this introductory section, it is
interesting to reflect on another paradigm shift that has
occurred in the science and technology of semiconductor
materials for solar energy conversion and specifically
for photovoltaic applications. The conventional wisdom
in these applications has been to secure film growth con-
ditions such that large crystallites approaching
single-crystal dimensions are obtained. For newer
devices based on nanostructured electrodes and dye-
sensitized photoelectrochemical cells, however, quite
different criteria must be established in terms of "ideal"
attributes for the thin film morphology. Transposing the
lessons learned from semiconductor colloids, for
example, a smaller particle size translates to better quan-
tum efficiencies! Further, we are only just beginning to
learn about the role ofthe film pore structure and electro-
lyte accessibility in terms of controlling the charge
transfer efficacy of the overall thin film structure. Clearly,
Table 1 Candidates for the Matrix (Continuous Phase)
Component in a Semiconductor Nanocomposite Film
Type of material Example(s)
Metal Nickel
Insulator Silica
Organic polymer Polypyrrole, polyaniline
Miscellaneous Carbon black
Rajeshwar and de Tacconi
designing a semiconductor thin film structure for
majority-carrier transfer requires a different set of rules
from those related to the more classical minority-carrier
device architecture.
II. SEMICONDUCTOR (PHOTO)
ELECTROCHEMISTRY: A PRIMER
Concepts related to bonding and electronic carriers in
semiconductor materials-particularly from a chemist's
perspective-have been discussed by other authors [23].
There are also many books on the fundamental principles
of semiconductor electrochemistry and photoelectro-
chemistry [24-28]. Therefore, only a brief discussion is
given below as a prelude to the theme of this chapter,
namely, nanocomposite semiconductor films.
Consider an n-type semiconductor in contact with a
redox electrolyte in the dark.When it is polarized positive
(i.e., "reverse-biased" in semiconductor physics par-
lance), no (anodic) current flows because there are no
minority carriers (holes) in the dark. On the other hand,
when the potential is moved systematically more negative
(relative to the "rest" condition), the current increases
exponentially because of the transport of electrons from
the semiconductor phase to the electrolyte (cathodic
direction).
When the electrode is irradiated with photons
exceeding the band-gap of the semiconductor, electron-
hole pairs are generated. A fraction of these are separated
by the built-in field and the applied bias, and the
minority-carrier current flow in the reverse bias regime
is greatly enhanced. Figure 1 contains a schematic dia-
gram of the dark and light current-voltage curves that
can be voltammetrically generated for an n-type
semiconductor-electrolyte junction. The plateau regime
in the reverse-bias direction is limited only by the avail-
able photon flux. Charge transfer kinetics manifest
mainly at potentials near the photocurrent onset and the
rising portion thereafter.
The forward-bias regime is not expected to be mark-
edly altered by electrode illumination in this simplified
model. However, "crossover" effects are often seen in this
l
regime, particularly for polycrystalline films but also for
single crystals [29-35]. Simply put, there is an excess
cathodic current flow under illumination relative to the
dark situation (Fig. 2). Although many explanations have
been forwarded to explain this anomaly [33-35], the most
tenable appears to be related to the electrostatics across
the semiconductor-liquid junction being modified by
illumination. In other words, the band-edge positions of
the semiconductor surface are no longer "pinned."
Semiconductor Nanocomposite Films 723

light, 12 (>1))
light
u light, I) u
:.e0 :a0
§ §

..... .....
=
Q)
0 =
Q)
0
dark

~ dark ~
U U
u u
:a0 :a0
..s:::: ..s::::
~ ~
u u

< ) < >

Voltage Voltage

Figure 1 Schematic diagram of the current-voltage curves in Figure 2 The "crossover" effect illustrating excess current
the dark and under illumination for a semiconductor-liquid flow under illumination in the forward bias regime for an
junction. An n-type semiconductor is assumed and I) and 12 n-type semiconductor-liquid junction.
are the incident light intensities.

Important parameters related to the carrier-flow
dynamics are the minority-carrier diffusion length, the
depletion layer width, and the penetration depth of the
excitation light within the semiconductor phase [36,37].
The kinetics of charge transfer at semiconductor-liquid
interface have also been discussed by other authors
[38-40] relative to the corresponding behavior of
metal-electrolyte junctions and semiconductor/metal
contacts.
Relative to single crystals, the behavior of poly-
crystalline films is considerably more complex because
ofthe presence ofdefects and grain boundaries.The treat-
ment of the interfacial electrostatics also presents new
challenges, and models leading to Mott-Schottky analy-
ses of the capacitance-voltage behavior have only limited
validity. Nanocrystalline semiconductor films compris-
ing of particles often smaller than the depletion layer
dimensions present an added level of complexity. The
reader is referred to several recent discussions on the
behavior of such films from a photoelectrochemical
perspective [13,14,16].
Finally, a few comments on the analytical aspects are
also in order before closing this section. In addition to
the usual methods for the study of metal electrodes [41],
light can be used as an added perturbation variable [42].
Thus, voltammetry can be performed with simultaneous
irradiation of the semiconductor surface. A particularly
useful approach is to chop the light while slowly scanning
the potential. In this manner, both the dark and light
behavior can be simultaneously studied. Alternatively,
lock-in detection can be used synchronously with a
chopper, especially when the photocurrent signals are
rather weak. The photocurrent can be also measured as
a function of wavelength at fixed potentials, a technique
known as photocurrent spectroscopy [36,37]. Simul-
taneous voltammetry-electrochemical quartz crystal
microgravimetry (EQCM) measurements have proven
to be extremely useful in the study ofsemiconductor elec-
trodes [43-45]. These experiments when combined with
coulometric data offer quantitative insights into the
behavior of semiconductor-liquid junctions. When
performed in conjunction with photoexcitation of the
semiconductor film, EQCM affords quantitative assess-
ment of reaction stoichiometry, stabilization efficiency,
etc [46]. The reader is referred to the original literature
for further details.
Spatial effects in the photoelectrochemical behavior of
semiconductor electrodes have been relatively less
explored to date. Photoelectrochemical microscopy [47],
a technique in which a laser beam is rastered across a
724 Rajeshwar and de Tacconi

semiconductor surface in contact with an electrolyte,
reveals "hot spots," wherein the kinetics of minority car-
rier transfer and thus the measured photocurrent are sig-
nificantly higher than in other regions of the
photoelectrode surface. Visualization of
electrochemically active surface sites has also been
accomplished more recently on Ti/Ti0 2 film electrodes
[48,49] using scanning electrochemical microscopy [50].
III. PREPARATION OF SEMICONDUCTOR
NANOCOMPOSITE FILMS
Occlusion electrodedeposition [51] is a versatile method
for the preparation of semiconductor nanocomposite
films as demonstrated in this laboratory [52,53]. A
schematic diagram of this electrosynthesis approach is
contained in Fig. 3. For our initial experiments, we used
Ti0 2 as the test semiconductor and nickel as the matrix
component, respectively. Thus, the targeted particles
(Ti02 in this case) to be immobilized onto a support elec-
trode (Au in this case) are first loaded in an
electrodeposition "bath" containing a suitable metal ion
(e.g., Ni2+). The deposition potential (or current) is then
controlled to be in the regime wherein the process
Ni2+ +2e- ---+ Ni takes place. TheTi0 2 particles are main-
tained in suspension in the bath by magnetic stirring.
The metal matrix assimilates the inert particles during
its growth to afford the nanocomposite in film form (Fig.
3). This strategy has previously been used by the ceramic
community for the fabrication of "electrocomposites."
[54]
Several variables have been identified [53] that control
the extent ofassimilation oftheTi02 particles into the for-
ming nickel matrix; these are listed in Table 2. The effects
of Ti0 2 solution dose and the deposition potential are
illustrated in Figs. 4 and 5, respectively. These are assessed
by examining the voltammograms of the resultant films
under chopped light illumination (see Sec. II above) while
Table 2 Variables Controlling the Extent
of Ti0 2 Particle Uptake in the NilTi0 2
Nanocomposite Filma
Number Variable
I Initial dose ofTi0 2 in the bath
2 Deposition potential
3 Bath pH
4 Bath temperature
5 Bath hydrodynamics

.. . a See also Ref. 53.

- •
+
+

•
• .. •.. .,.'
• • • .,
•.
.. +

•
+
Nil'

"•
•
+
• ., •
•
+

Semiconductor particle
• .
Figure 3 Schematic diagram ofthe occlusion electrodeposition process and the resultant nanocompositefilm product with Ni/Ti0 2
as an example.
Semiconductor Nanocomposite Films
"'0
(a) 0 M TlOz (pure Ni)
-4.1 ·lUI 04.4 04.2 0 0.2 0.4 0.8 0.1
Potential I V vs. AglAgCI
Figure 4 Effect of TiO z dose in the initial deposition bath on
the photoactivity ofthe resultant Ni/TiO z nanocomposite films
in 0.1 M KN0 3 . (From Ref. 53.)
slowlyscanning from -0.8 to 1.0 V (vs. Ag/AgClreference)
in 0.1 M KN03 [53]. Under these conditions, the TiO z
particles are the only photoactive components in the
nanocomposite films and the nickel matrix is photo-
electrochemically "silent." Thus, a 0.8 M TiO z solution
dose and a deposition potential of -0.8 V were found to
be optimal for securing maximal photoactivity in the film
[53]. Too high a TiO z solution dose inhibits the transport
of TiO z particles to the cathode surface. Similarly, too
low (i.e., negative) a deposition potential results in a
deleteriously fast rate of nickel deposition with a con-
sequent inefficiency in the extent ofTiO z particle uptake.
725
(C)Ed=-l.O~
(b) Ed. -0.9 V ~
(SlEd-ad
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8
Potential I V vs. AglAgCI
Figure 5 Effect of deposition potential (Ed vs. Ag/AgCl
reference) on the photoactivity of the resultant Ni/TiO z
nanocomposite films in 0.1 M KN0 3 . The TiO z dose in the
deposition bath was 0.4 M. (From Ref. 53.)
The influence of the other variables in Table 2 can be
similarly rationalized. However, the effect of solution
pH is particularly interesting and illustrates the electro-
phoretic component in the occlusion electrodeposition
mechanism. Figure 6 contains similar data as in Figs. 4
and 5 but illustrates the effect of the deposition bath pH
instead [53]. The extent of incorporation of the TiO z
particles is seen to diminish at pH values both lower and
higher than ca. 5. At low pH, TiO z occlusion is adversely
affected by hydrogen evolution at the cathode surface.
The point ofzero charge (PZC) ofTiO z is ca. 6.0 [55].
At bath pH values higher than this value, the TiO z
particles will be negatively charged and will be
electrostatically repelled from the cathode surface. This
would explain the progressively lowered photoactivity of
the films electrosynthesized from baths of pH greater
than ~5.0. An added factor in this trend is the fact that
nickel deposition proceeds faster at pH values greater
than ~5. As noted earlier, too high a deposition rate of
726 Rajeshwar and de Tacconi

medium ionic strength. Electrophoretic measurements

(a) pH= 1
~Innnnnn~ under illumination of the Ti0 2 particles, i.e., "photo-

~
electrophoretic" experiments [56;57], have shown a par-
ticle mobility shift consistent with the buildup of
negative charge on theTiO 2surface on irradiation [58,59].
(b) pH= 2
Thus, the occlusion efficiency should be reduced under
bath illumination with UV light. Such experiments are
in progress. A high medium ionic strength should ameli-
(c) pH= 3
.~ orate this radiation effect by electrostatic screening.
It is worth noting that the occlusion electrodeposition
approach is also amenable to the growth of polymer/
semiconductor nanocomposite films (Table 1). Thus,
(d) pH= 4 organic (conducting) polymers such as polypyrrole or
polyaniline can be chosen as the matrix component. In
..--. this case, the deposition bath containing the precursor
1 monomer (pyrrole or aniline, respectively) is dosed with

i
; :,
c.>
~ requisite amounts ofnanosized semiconductor particles
to be occluded. Contrasting with the Ni/Ti0 2 case, a
positive potential is applied to anodically grow the poly-
mer matrix. Polypyrrole/Ti0 2, polypyrrole/W03, poly-
(e) pH= 5
aniline/W0 3, and polypyrrole/CdS nanocomposite
films have been grown in this manner [60-64].
In the case of polymeric matrices, chemical poly-
merization reactions can also be used instead of the
electrosynthesis route. Thus, oxidants such as FeCl) or
(NH4hS20g can be added to the solution ofthe monomer
that is dosed with semiconductor particles. We have dis-
cussed the analytical aspects of the films derived from
the chemical route elsewhere [65].
The chemical route, especially sol-gel chemistry, is
useful for the synthesis ofboth the dispersed and the con-
tinuous phases in the nanocompositefilm. Sol-gel science
begins with the chemistry of metal alkoxides [66,67].
I.-
Silicon alkoxides have been particularly well studied,
l driven largely by the applications of silica in catalysis
and in separation science. The sol-gel process involves
-0.8 -0.8 -0.4 -0.2 0 0.2 0.4 0.6 0.8
the hydrolysis and polycondensation of metal alkoxides
Potential, V VS. AglAgCI
to form macromolecular oxide networks. Although
colloidal gels derived from silica have been the most
Figure 6 As in Figs. 4 and 5 but illustrating the effect of depo-
extensively studied systems to date, titanium alkoxides
sition bath pH. TheTiO z dose and the deposition potential were
have also received much attention [14]. Accordingly,
0.4 M and -0.8V, respectively. (From Ref. 53.)
Si0 2/Ti0 2, AI 20 3/Ti0 2, zeolite/Ti0 2, carbon black/
Ti0 2, and other nanocompositefilms have been prepared
the matrix component would be deleterious to particle by the sol-gel route [68-73].We further discuss these films
uptake. The (favorable) electrostatic effects at pH <PZC in Sec. VII within the context of cofunctional
in the acidic pH range are undoubtedly overshadowed photocatalyst assemblies.
by the HER as discussed earlier.
If the electrophoretic picture for the occlusion process
IV. PHOTOELECTROCHEMISTRY OF Ni/Ti0 2
is correct, then any perturbation that modulates the par-
AND Ni/CdS NANOCOMPOSITE FILMS
ticle surface charge or "screens" it ought to bring about a
corresponding change in the extent of Ti0 2 particle Figure 7 contains representative "photovoltammo-
occlusion. Two such variables are UV irradiation and grams," i.e., voltammograms obtained under simul-
Semiconductor Nan9composite Films 727

taneous irradiation of the semiconductor nano-

composite film for Nil CdS (Fig. 7A) and Ni/Ti0 2 (Fig.
7B), respectively, in 1.5 M Na2S03 [74]. In the former case,
the "dark" and "light" profiles obtained under constant
(vis-a.-vis interrupted) illumination are also shown for
comparison. We return to the small peak seen for the
Ni/CdS case (Fig. 7A) later. But the first point to note is
that the current-voltage profiles in the dark and under
illumination are surprisingly well behaved for both
systems. This was the serendipitous aspect of our early
work on this topic. Thus, the nickel matrix did not short
circuit each semiconductor cluster and thus the overall
electrode. Evidence for such adverse effects of metal
islands or ions on the photoactivity ofUV-irradiatedTi0 2
already exists in the literature [75,76]. For example, at high -0.8 -0.' -0.4 -0.2 0.2
levels ofCu 2+ or Fe 2+, the following sequence ofreactions
was found to occur [75,76]:

(1) (B)

l o.
2 /IA
(2)

or

Cu2+ + 2e- ----+ Cuo

Cuo + 2h+ ----+ Cu2+
Thus, the Fe 2+ /3 + and CuO /2 + redox couples simply act as
mediators for e- - h+ pair recombination. In our NiiTi02
nanocomposite case, initial hole attack on the nickel
regions followed by redeposition ofthe nickel would lead
to the same consequence of no net photocurrent.
The overall similarity in the current-voltage behavior
of n-type semiconductor photanodes (prepared from
thin films or single crystals) (see, e.g., Fig. 1) and our
nanocomposite films (additionally containing nickel) is
intriguing, particularly when considering the almost cer-
tain absence of (minority-carrier) depletion layers [77]
in the latter. In fact, the voltammograms shown in Fig. 7
(and in Figs. 4-6 earlier) for these nanocomposite films
are not strikingly different from those obtained for
nanocrystalline films prepared, for example, by sol-gel
methods (see below). However, this similarity at first
glance can be misleading because there are important
effects introduced by the presence of nickel in the
nanocomposite film matrix. These effects in fact consti-
tute the theme of this chapter.
-0.' :0.4 .0.2 0 0.2
Potential I V VI Ag I Agel
(3)
Figure 7 (A) Photocurrent-potential scans under interrupted
(curve b) and constant (curve c) irradiation of an Ni/CdS
nanocomposite film in 1.5 M Na ZS03. A dark current scan in
the same electrolyte is also shown for comparison (curve a).
(B) As in (A) for an Ni/TiO z film but shown only forthe chopped
illumination condition. (From Ref. 74.)
Returning to the origin of the small peak on the
forward (positive) going cycle for the Ni/CdS film in Fig.
7A, we see that this peak also appears in the Ni/Ti0 2 case,
albeit at much higher light fluxes (Fig. 8). The
photocurrents in the Ni/CdS case also increase with suc-
cessive cycles with the rate of increase ultimately slowing
down [74]. It is also interesting that the peak does not
manifest itself on the return cycle, both in the Nil CdS
(Fig. 7A) and in the Ni/Ti0 2 (Fig. 8d) cases. All these data
in conjunction with x-ray photoelectron spectroscopy
evidence [74] are consistent with the fact that a Ni(OHh
passivation layer forms on the nanocomposite film
surface. This then provides a logical explanation for the
rather unique behavior ofthe nickel-containing semicon-
ductor nanocomposite films relative to the copper and
728 Rajeshwar and de Tacconi

(d) (d) -lJ

15~ p --
15~
(e)

(e)
(b) ./
15~ c.

(a) ~

(b)
r
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2

I~1
Potential I V

Figure 9 Cyclic voltammograms in 1.5 M Na2S03 for (a)

Ni/Ti0 2 and (b-d) Ni film electrodes. (From Ref. 74.)

(a) the nickel component. These results are for the sulfite
I 1 J.1A

(""~
•1.0 .0.' .0.'
•
.0.4
.
.0.2 •o
Pot.ntJall V va Ag I AgCl
Figure 8 As in Fig. 7B but illustrating the dependence of the
photovoltammogram profiles on the incident light flux: (a) 2.2,
(b) 5.6, and (c) 60.6mW/cm 2, respectively. The scans were
positive-going (from -I.OV) in all the cases except in (d) where
the return scan is shown at 60.6mW/cm 2. (From Ref. 74.)
iron systems discussed earlier. Simply put, if the kinetics
ofthe electron and hole pathways are vastly different, then
a net photocurrent will be observed [78].
Further experiments with other metal-borne Ti0 2
films (e.g., Au, Ag, Cu) ought to confirm the veracity of
our current mechanistic picture; these are in progress in
our laboratory.
Comparing the Ni ITi0 2 and Ni ICdSfilms themselves,
the presence of Ti0 2 particles appears to stabilize the
nickel matrix against corrosion [74]. Figure 9contains vol-
tammetry data, shedding further light on the behavior of
(pH 9) medium [74]. Figure 9a shows a voltammogram
(now in the dark) for an Ni/Ti0 2 film in this medium.
Significantly, the voltammogram is featureless, under-
lining the excellent stability ofthe nickel matrix.
0.2
Consider the corresponding profiles in Figs. 9b-d for
a nickel film electrode. As long as the negative limit is kept
positive ofca. -0.8 V, only a trace of the nickel corrosion
feature at approximately -0.3 V is evident. The manifes-
tation ofthe nickel corrosion-passivation layer is brought
out in the voltammogram in Fig. 9d. The anodic peak that
appears in Fig. 9 corresponds to the one seen earlier for
the nanocomposite film cases in Fig. 7A and 8. Inter-
estingly, in the dark, the nickel is stable against corrosion
in both the Ni/CdS (Fig. 7A) and Ni/Ti0 2 (Fig. 9a) cases.
However, the latter is intrinsically more stable under
irradiation relative to the Ni/CdS case. Obviously, the
stability of the semiconductor particles themselves
against photocorrosion is an important factor here, and
CdS is known to be photoelectrochemically much less
stable than Ti0 2 in aqueous media [79,80].
The data in the next two sections pertain to the
Ni/Ti0 2 nanocomposite system. The next section exam-
ines the photoelectrochemical behavior in the presence
of organic substrates. Section VI describes chemical
modification schemes for the parent NilTi0 2 films. The
Semiconductor Nanocomposite Films
final section reverts to a general discussion on
cofunctional photocatalyst assemblies comprising of
Ti0 2 as the dispersed phase.
v. PHOTOCURRENT ENHANCEMENT IN THE
PRESENCE OF ORGANIC SUBSTRATES
This section concerns the photocurrent enhancement
observed for semiconductor electrodes in the presence
ofcertain multiequivalentredoxsystems [24,25].The term
"current doubling" has been used for this phenomenon,
but as also pointed out by other authors [81,82], this ter-
minology perhaps is misleading because photocurrent
enhancement by a factor of2 is usually not observed. The
classical model for the current doubling phenomenon is
as follows:
hv>Eg
n-type semiconductor --~ e- + h+ (la)
R· -~R+ + ecb (5)
In the above scheme, R is a multiequivalent reducing
agent, and reaction 5 represents the injection of an elec-
tron into the semiconductor conduction band. Thus,
according to the classical scheme, absorption ofa photon
results in two charge carriers. However, as pointed out
earlier, values of 2 are rarely ever observed (see below).
For the purpose of this discussion, we define a photo-
current enhancement factor, F, as the ratio of the photo-
currents observed in the presence and absence of the
organic ("current-doubling") additive in the electrolyte.
The photocurrents are normally measured in the satu-
ration (photon-flux limited) regime of the iph -E curve.
Remarkably high values of F(as high as 5.5) have been
observed by us for Ni/Ti0 2 nanocomposite films in the
presence of formate anions [83]. The first instance for
the observation of anomalously high Fvalues appears to
have been for the germanium-electrolyte interface [84].
Factors as high as 4 were also reported for the photo-
dissolution of Si in fluoride media [85-87]. However,
factors lower than 2 are more typical.
Figure 10 compares the behavior of our nano-
composite Ni/Ti0 2 films with their nanocrystalline
counterparts (i.e., films containing no nickel) with and
without formate in the 0.1 M NaN0 3 medium [83]. Values
for F consistently lower than 2 were observed for us for
the latter. On the other hand, values as high as 5.5 are
observed when there is interspersed nickel between the
photocatalyst sites, as in our Ni/Ti0 2 nanocomposite
729
films (Fig. 10). The value of F is also seen to depend on
the initial Ti0 2 content of the bath used to prepare the
nanocomposite films (Fig. 11) [83]. Interestingly, the F
values start to progressively diminish as the initially
anatase-rich P-25 Ti0 2 particles are thermally converted
to the rutile phase (Fig. 12). It is rather striking that the
pure rutile phase shows no photocurrent enhancement
at all (i.e., F = 1, Fig. 12).
It is also important to note that the Fvalue does not dip
much below the theoretical yield of 2 even under the
"adverse" experimental conditions of high Ti0 2 10adings
of the nickel electrodeposition bath (see Fig. 11). We
attribute the behavior in Figs. 10-12 to a synergistic effect
involving the Ni and Ti0 2 components in our
nanocomposite films as illustrated in Fig. 13. The organic
substrate is shown in this scheme to adsorb strongly on
nickel sites. There is literature precedent for the proclivity
offormate ions to adsorb on the Ni surface [e.g., 88-90].
Thus, the hole pathway [Eq. (4)] is turned "on" in our
Ni/Ti0 2 nanocomposite films. This formate photo-
oxidation pathway would be especially favored by the
co-occluded nickel- Ti0 2 clusters in our nanocomposite
films as illustrated in Fig. 13.
In the absence of the organic additive, the holes are
channeled toward reaction 4 and subsequent steps lead-
ing to the net 4e- photogeneration of O 2 according to
the scheme described by other authors [91]:
(6)
(6a)
This is a relatively inefficient process in our Ni/Ti0 2
films. Presumably, the deposition conditions represented
by intermediate values of the deposition time and low
Ti0 2 loading facilitate optimal formation of Ni - Ti0 2
clusters ofthe sort shown in Fig. 13. This in turn facilitates
initial adsorption and direct photooxidation of the
organic substrate as illustrated in this mechanistic
scheme.
Finally, the above mechanistic scheme also offers a
logical explanation for the values of F < 2 typically
observed for Ti0 2 and other semiconductor photo-
electrodes. If the substrate photooxidation occurs via a
mediated pathway
HCOO- +·OH -----+ HCOO· + OH- (7)
then the F value is dictated by the fraction of ·OH that
oxidize the organic substrate [Eq. (7)] vis-a-vis those that
participate in the O 2 photogeneration pathway.
In summation, the site proximity effect facilitated by
Ni- Ti0 2 clusters for both substrate adsorption and
730 Rajeshwar and de Tacconi

(a) (b)

1 4
!1A

Il~

~~.I
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 ~ ~ ~ M U U ~ ~ ~
Potential I V VB. AgIAgel Potential I V VB. AglAgO

Figure 10 Photovoltammograms (as in Fig. 7B) for Ni/Ti0 2 (a) and Ti02 (b) in 0.1 M NaN0 3 with (top) and without (bottom) 0.01 M
HCOONa. The Ti0 2 nanocrystalline film in b was prepared by a sol-gel method. Note the change in current scales in the two frames
in each of the two sets ofdata in a and b, respectively. (From Ref. 83.)

photo-oxidation (Fig. 13) is believed to underpin the high
values for F observed for the Ni/Ti0 2 nanocomposite
films. We return to the issue ofcofunctional photocatalyst
assemblies in a subsequent section below. Suffice here to
pointout that the present data on Ni ITi0 2 nanocomposite
photoelectrodes also constitute a strategic first step
toward tuning photocatalyst morphology to favor a tar-
geted reaction pathway (e.g., the photogeneration of
organic radicals). They also suggest the virtue of synthetic
strategies affording nanoscopically ordered and spatially
separated arrays of photocatalyst sites within an inert
matrix. Such studies are presently in progress in this
laboratory.
VI. CHEMICAL MODIFICATION OF Ni/Ti0 2
NANOCOMPOSITE FILMS
The nickel component in the Ni/Ti0 2 nanocomposite
film is amenable to surface derivatization to afford nickel
hexacyanoferrate (NHF) redox centers within the film
[92,93]. The resultant matrix containing these redox
centers and semiconductor (Ti0 2) particles presents
interesting opportunities for exploring photoinduced
charge transfer. Such films exhibit "bipolar" photo-
electrochemical behavior as shown in Fig. 14. In this
bipolar behavior, the carrier transit direction at the semi-
conductor film-solution interface and the rear (ohmic)
contact is reversed. Simply put, hole transfer nominally
expected for an n-type semiconductor at the former is
replaced by electron transfer to the electrolyte.
Two types of derivatived NilTi0 2 films were grown:
Type I films were obtained by voltammetric cycling of
Ni/Ti0 2 nanocomposite film in 0.01 M K3Fe(CNh +
0.1 M NaN03 [94]. Type II films were potentiostatically
grown (0.7 V, 5 min) on a nickel film surface in a 0.01 M
K3Fe(CN)6 solution loaded with 0.8 M Ti0 2 (Degussa
P25) particles. Figure 14a and b provide a direct compari-
son of the photoelectrochemical behavior of a Ni/Ti0 2
Semiconductor Nanocomposite Films 731

3 . 0 . . . . - - - - - - - - - - - - - -.....

® Ni clusters

Figure 13 Schematic representation of the adsorption of for-

mate ions on the nickel clusters and photoprocesses at the
l.S,L.-_---l_ _.....J.._ _--'-_ _....L.._---"
Ni/Ti0 2 nanocomposite film-solution interface. (From Ref.
0.0 0.2 0.4 0.6 0.8 1.0 83.)
(TiOz11 M
Figure 11 The dependence ofthe photocurrent enhancement
factor, F (see text), on the initial Ti0 2 content of the bath used This behavior of the type I film can be rationalized as
to prepare the Ni/Ti0 2 nanocomposite films. (From Ref. 83.) follows by first noting that the observed photocurrents
are anodic in polarity; i.e., the minority carriers (holes)
are driven to the film -solution interface and the majority
carriers move to the film bulk under the imposed electric
anatase .... F = 5.5
field gradient. Thus, in the parent Ni/Ti0 2 case, the nickel
matrix acts as an efficient sink for the photogenerated

..
::> electrons fromTi0 2• On the other hand, in the derivatized
«
600·C F = 5.4 case, the NHF surrounding the Ti0 2 islands does not
~
'iii have this capacity with the iron redox centers being con-
l:
....l:CIl 650·C .. F=4.3
fined to the +2 state. The consequence is facile e- -h+
pair recombination as diagnosed by the spiked nature of
the photocurrent transients at potentials below ca. 0040
F = 2.9 V (i.e., the onset ofthe NHF II --* III transition).
At higher potentials, the (oxidized) NHFredox centers
can now drain the photogenerated electrons from the
F =1.0 adjacent Ti0 2 before these electrons recombine with the
holes. The net result is an improved quantum yield and
300 400 500 600 700 800 900
higher photocurrents for the derivatized films relative to
wavelength Icm- 1
the parent NilTi0 2 case(cf. Fig.14a and b). In both cases,
we presume that the photogenerated holes oxidize either
Figure 12 Dependence of F on the rutile content of the the surface hydroxyl groups on theTi0 2 particles or water
Ni/Ti0 2 films. In each case, the Ti0 2 particles used to prepare itself.
the films were thermally converted at progressively higher tem- Type II films preparedbyderivatizinganickel electrode
peratures (as shown) for 2h. The rutile contentofthe film in each in situ with both NHF and Ti0 2 exhibited more unusual
case is indicated by the corresponding laser Raman bands. photoelectrochemical behavior in 0.1 M NaN0 3 [94]. Fig-
ure 14c contains linear sweep voltammetric data under
chopped illumination of the derivatized film. The
film before (Fig. 14a) and after (Fig. 14b) electrochemical photocurrent transients are now cathodic in polarity and
derivatization with NHF. Again, chopped illumination gradually decay in amplitude as the potential is swept to
was used in both cases. This comparison underlines two the NHF II --* III redox regime. Thereafter, the transients
points: the photoactivity of the derivatized Ni/Ti0 2 is revert to the usual anodic polarity, and the "normal"
appreciable only after the NHF II --* III redox transition S-shape envelope typical of n-type photoelectrodes (see
unlike in the parent nanocomposite case and the Fig. 1). At potentials below the NHF II--*III redox
photocurrent in the saturation region for the derivatized transition, the photogenerated holes from Ti0 2 are more
film exceeds that in the parent Ni/Ti0 2 case.
732 Rajeshwar and de Tacconi

the saturation anodic photocurrent for the type II film is

(a) not "sensitized" (relative to the parent Ni/TiO z film) like
in the type I case discussed earlier. This trend is consistent
1
0 .5 fJA with the carrier transit model for type I vs. type II film
behavior presented above.
The difference in the photoelectrochemical behavior
of the two types of derivatized films is reproducible and
underlines the sensitivity ofthe microenvironment within
the nanocomposite films to their preparation history.
(b) The "bipolar" nature of the photocurrents from type II
films is particularly noteworthy. These results are import-
ant in that they demonstrate that quantum yields in a par-

1
0 .5 fJA
ticulate or nanocrystalline photoelectrochemical system
can be improved by intimately contacting the semicon-
ductor particles with a molecular redox system in a
"nanocomposite" film configuration. In this regard, the
chemically modified Ni/TiO z film provides a useful

~
framework for exploring charge transfer processes at
semiconductor/molecular solid contacts. Also, carrier
transit to the semiconductor-liquid boundary can be
modulated by controlling the microenvironment within
(c) nanocomposite photoelectrodes. Even bipolar behavior
can be obtained for a given photoelectrode in the same
electrolyte.
1
0 .2 fJA Electrochromic films that change color in response
to electrical perturbation have attracted consider-
able recent interest stemming from potential applic-

~
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8
Potential/ V VI. Ag/AgC'
Figure 14 Photovoltammograms (as in Fig. 7B) for (a)
Ni/TiO z, (b) Ni/TiOz derivatized with NHF (type I film, see
text), and (c) Ni derivatized with NHF+TiO z (type II film).
(From Ref. 94.)
efficiently transferred to the (reduced) NHF sites than to
the film/solution boundary as in the type lease (Fig.l4b).
We presume that the photogenerated electrons fromTiO z
now move to this boundary and reduce incipient electron
acceptor agents such as residual Oz present in solution.
This carrier transit behavior is presumably facilitated by
the absence ofNi/TiO z contacts in the type II films unlike
in their type Icounterparts [94]. As the electric field gradi-
ent is increased and potentials in the NHF II ~ III redox
regime are accessed, electron transfer ensues from TiO z
to the (oxidized) NHF sites, and holes are driven in the
film -solution boundary as before. Interestingly, note that
ations in "smart" windows, displays, automobile rear-
view mirrors, and the like [95,96]. Their photo-
electrochromic counterparts have been less widely
explored to date. In the photoelectrochromic approach,
the coloration ~ bleaching transition is triggered by
initial optical excitation of a semiconductor followed by
electron transfer to the chromic component (usually a
dye) in the device. The reverse (bleached ~ colored state)
sequence occurs in the dark. An example ofthis approach
is based in the TiOz-methylene blue (MB) interface. On
UVexcitation of TiO z, the initially blue MB dye is tran-
sformed to the colorless leuco state. The color is restored
when the excitation light is turned off[97].
The chemically modified Ni/TiO z films described
above form the basis for an alternative approach to an
integrated photoelectrochromic device wherein the
active components (semiconductor and the dye) are con-
fined within a solid film [98]. We were thus able to show
that optical transitions (and thus color changes) in the
NHF component can be instigated by initial photo-
excitation of the TiO z particle followed by electron
transfer from it to the adjacent (oxidized) NHF sites
within the film (Fig. 15). Concomitantly, the initially yel-
low film turns blue. This photoelectrochromic transition
occurs at open circuit (i.e., is thermodynamically
Semiconductor Nanocomposite Films 733

NiFe(CN) 6 1-/2- 1.6

[) 0 1.2
bIl

~
hv
NiFe(CN) 61-/2-
« CIl
CJ
s::

2 .
0
III
.c 0.8
III
.c
3 «

0.4

Figure 15 Energy diagram for electron transfer from

photoexcited Ti0 2 particles to the NHFredox centers within a
chemically modified Ni/Ti0 2 film. (From Ref. 98.)
0.0 L......---L_........._ .......- - - J _........_...L..._'-----L_.......----l

350 450 550 650 760 850

spontaneous, Fig. 15) as long as hole scavengers (e.g., wavelength I nm
methanol) are present as illustrated in Fig. 15. The reverse
transition (blue--*yellow) can be accomplished (in the Figure 16 Diffuse reflectance spectroscopy data illustrating
dark) by electrochemically reoxidizing the Fe(II) sites the photoelectrochromic transition in a chemically modified
within the NHF component of the film (see below). Ni/Ti0 2 film. Spectra a and b refer to before and after
Proof-of-concept is contained in the data in Fig. 16. photoexcitation of the Ti0 2 particles, respectively. (From
The diffuse-reflectance spectra are shown before and Ref. 98.)
after photoexcitation of the Ti0 2 component in the film
at open circuit and are corrected for the background
This concept has been realized by immobilizing Ti0 2
absorption of Ti0 2• The two spectra correspond to the
particles in a high surface-area support phase (Table 3).
oxidized and reduced redox states of NHF, respectively,
Obviously, this idea has been pervasive in the gas-phase
or equivalently, to the two colored states of the
catalysis field. Thus, it is not surprising that such
photoelectrochromic device. The transition between the
cofunctional assemblies have been tested for gas-phase
two states is stable and reversible. In the particular exper-
photocatalytic reactions also [69].
iments in Fig. 16, methanol was used as the hole scavenger
The rate constants for solution phase reactions using
[98]. The reverse transition in the dark can be induced
such assemblies show a volcano-like profile, two
by pulsing the film from open circuit to O.7V for a few min-
examples of which are shown in Fig. 17 [70,71]. Thus, at
utes to reoxidize the Fe(II) sites within the NHF
component.

Table 3 Examples of Supports

VII. COFUNCTIONAL PHOTOCATALYST in Cofunctional Photocatalyst
ASSEMBLIES Assemblies a
One approach for improving quantum yields at particu- Support References
late semiconductor-solution interfaces is to facilitate
rapid scavenging of the photogenerated holes via Silica 70-72
Alumina 70,72
adsorbed reductants andlor oxidized intermediates. This
Zeolites 69,70
can be accomplished by incorporating more effective
Activated carbon 68,70,73
adsorption sites than Ti0 2 (for example) on the film Mordenite 70
surface. However, such sites must be near the Ti0 2 sites, Ferrierite 70
so that hydroxyl radicals [see Eqs. (6) and (6a)] can reach
them quickly before quantum yield-diminishing re- a Ti0 2 was the photocatalyst in all
combination reactions. these cases.
734 Rajeshwar and de Tacconi

0.1

000 ~ (a)

/ \ C> 400
0.06 N-
E
I
~a
0.04

0.02
«
~
Q)
() 200
-:c:: 0 20 40 60 80 100 .{g
-
E
C
os
enc::
n02 content I wt % ~
Cf)

0 005
<J

'"
Cii
a: 0.04 I (b)

II o 100
Percentage of Ti0 2
0.03
Figure 18 Variation of surface area with the composition ofa
0.02 cofunctional Ti0 2 /zeolite photocatalyst assembly. The surface
i area ofmordenite is also shown for comparison. (From Ref. 69.)
0.01

0
0 20 40 60 60 100 Finally, our Ni/Ti0 2 nanocomposite films are also
% Silica cofunctional in the sense that nickel provides the adsorp-
tion sites for the reductant andlor the oxidized
Figure 17 First-order rate constants for the photocatalytic intermediate(s) (see Fig. 13). We have seen earlier that
decomposition of propionaldehyde (a) and rhodamine 6G (b) binding radical intermediates to the film surface
vs. the composition of the nanocomposite film assembly. facilitates electron injection into the film and conse-
Mordenite and silica were used as the support phases for the quently high photocurrent enhancements.
experiments corresponding to a and b, respectively. (From Refs.
70 and 71.)

VIII. CONCLUDING REMARKS

low support loadings, the rate constants are low because
of inefficient adsorption of the substrate resulting from
the low surface area (Fig. 18). On the other hand, at very
high support loadings, the photocatalyst sites are too far
separated from one another. In this regime, surface
mobility plays a limiting role in the reaction rate [70,71].
The influence of the support phase itself has been
emphasized by other authors [70]. Thus, the adsorption
constants (K ad ) of a range of adsorbents with
propionaldehyde as a substrate were correlated with the
corresponding photocatalytic rate constants [71]. Once
again, a volcano plot was obtained, signifYing that
supports with too low or too high Kad values were
ineffective. The parallel here with the heterogeneous
gas-phase catalysis findings [99] is noteworthy.
Unfortunately, however, the Kad values obviously are
substrate specific so that generalizations cannot be made
as to the virtues of a particular kind of support for
cofunctional photocatalyst assemblies.
This chapter has attempted to highlight the important
and varied roles that the matrix components play in
semiconductor nanocomposite films for photoelectro-
chemistry applications. The virtues of the occlusion
electrodeposition approach for preparing these films
have been discussed as are experimental methods for
characterizing them. In some instances (e.g., nicke!),
the matrix also provides a template for subsequent
chemical modification of the initially prepared
nanocomposite film. Cofunctional assemblies built
from these interesting materials also provide an avenue
for improving quantum yields in photocatalytic
reactions. However, application possibilities related to
other fields, for example, sensors, remain to be tested.
Thus, it is our hope that the above discussion will
perhaps sow the seeds for discovering these and other
use opportunities in the future for semiconductor
nanocomposite films in general.
Semiconductor Nanocomposite Films 735

ACKNOWLEDGMENTS 25. SR Morrison. Electrochemistry at Semiconductor and

Oxidized Metal Electrodes. New York and London:
The work in our laboratory described herein represents Plenum, 1980.
the collected efforts of our talented students, including 26. SJ Fonash. Solar Cell Device Physics. San Diego:
Mai Zhou, Willy W-Y. Lin, Hongjen Wenren, Darrell Academic, 1981.
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41
Electronic and Morphological Structures of Semiconductor
Electrodes
Kohei Uosaki, Michio Koinuma, and Shen Ye
Hokkaido University, Sapporo, Japan
ABSTRACT
After a brief description of the electronic structure at
semiconductor-electrolyte interface is given, in situ
determinations of electronic and morphological struc-
tures as semiconductor electrodes by electrochemical
tunneling spectroscopy (ETS) and atomic force
microscopy (AFM), respectively, are described. In situ
ETS is applied top- and n-GaAs electrodes in HCI0 4 sol-
ution and results at n-GaAs electrode are analyzed
semiquantitatively. In situ electrochemical AFM shows
that an atomically ordered structure ofp-lnSe surface is
lost when positive potential is applied as resul t of anodic
decomposition (lnSe+H 2 0_Se+lnOH 2 ++H+ +3e-).
An atomically ordered structure is, however, recovered
if negative potential is applied because the deposited Se
is removed reductively at negative potentials (Se+
H+ +2e- _ HSe-). In situ electrochemical AFM is also
applied to investigate the surface structure of p-GaAs.
The atomically ordered GaAs (100)-(1 xl) structure is
observed in electrolyte solutions in contrast to the results
in vacuum where the surface is reconstructed, showing
the important roles of ions. Electrochemical deposition
ofCu on p-GaAs(lOO) surface is strongly affected by sur-
face defects, applied potential, and the concentration of
Cu 2 + ion in solution. Atomically resolved Cu(lll)-(1 xl)
structure is observed on top ofthe Cu deposits, but GaAs
(100)-(1 xl) structure is still observed other portions of
the surface, suggesting the weak interaction between the
substrate (GaAs) and Cu.
737
I. INTRODUCTION
The first report on the electrochemistry of semiconduc-
tors was published in 1955 by Brattain and Garrett [1],
who examined the electrochemical properties of germ-
anium. The history of semiconductor photoelectro-
chemistry, however, started over 100 years ago when
Becquerel [2] found that an electric current flowed if one
of the electrodes immersed in a dilute acid was
illuminated by light. Although the concept of semicon-
ductor did not exist at that time, it is now clear that the
electrodes he used had semiconductor properties. Since
the publication of Brattain and Garrett, the knowledge
of semiconductor electrochemistry has grown steadily,
and several reviews and books on this subject appeared
by the early 1970s [3-10]. More significant progress in
semiconductor electrochemistry has been achieved since
the 1970s triggered by the publication of Fujishima and
Honda [11], who reported that water can be decomposed
to hydrogen and oxygen under illumination using a
Ti0 2 /electrolyte solution/metal cell, and the first oil
crisis that took place just after their publication.
Photoelectrochemical energy conversion using semicon-
ductor electrodes attracted many research groups as one
possible means of converting solar energy to chemical
energy, hydrogen, and/or electricity. As a result of
intensive research for more than two decades, not
only has the photoelectrochemical conversion efficiency
increased and the application of semiconductor elec-
trodes widened but also the understanding ofthe electro-
chemical properties of semiconductors has progressed
738
quite significantly. Electrochemistry ofsemiconductors is
important not only for solar energy conversion but also
for the wet processing of semiconductor surfaces such
as etching and metal deposition [12-16].
To understand the mechanism of the electrochemical
and photoelectrochemical reactions, in situ information
on electronic and morphological structures of semicon-
ductor electrode surfaces with atomic resolution is
essential.
In this article, after a brief description of the
semiconductor-electrolyte interface, in situ determin-
ations of electronic and morphological structures at
semiconductor electrodes by electrochemical tunneling
spectroscopy and atomic force microscopy, respectively,
are described.
II. ELECTRONIC STRUCTURE OF
SEMICONDUCTOR- ELECTROLYTE
INTERFACES
When a semiconductor is in contact with an electrolyte
solution and they are in equilibrium, the electrochemical
potentials ofthe two phases should be equal. The electro-
chemical potentials ofthe semiconductor and the electro-
lyte solution are represented by the Fermi level and the
redox potential, respectively. Because the Fermi levels of
n- and p-type semiconductors are situated just below
the bottom of the conduction band and just above the
top of the valence band, respectively, and the redox
potentials of most commonly used electrolytes are found
between the bottom of the conduction band and above
the top of the valence band, i.e., within the energy gap,
electrons should be transferred from the n-type semicon-
Semiconductor Solution Semiconductor
Ec _ -...::J" n-l-
Ef
E c .s;c_ _ --=::
- --Ox/ Red
Ef
Ev - -
Ev
(a)
Figure I Energydiagrams at an n-type semiconductor- electrolyte interface in (a) equilibrium, (b) under forward bias, and (c) under
reverse bias in an ideal situation. Ec and Ev are the energy of the conduction and valence band, respectively, Er is the Fermi level,
and Ox/Red represents the redox potential.
Uosaki et aI.
ductor to the solution and from the solution to the p-type
semiconductor upon contact for equilibrium to be estab-
lished between the two phases. Because of the relatively
low free carrier density in semiconductors, the excess
charge should be compensated by the ionization of
donors for n-type or acceptors for p-type semi-
conductors. Thus, the energy bands are bent up at
n- and down at p-type semiconductor-electrolyte
interfaces.
Figure 1 shows the energy band diagram of an n-type
semiconductor -electrolyte interface in equilibrium (a),
under forward bias (b), and under reverse bias (c) in an
ideal situation [17]. In equilibrium, as a result ofelectron
transfer from the n-type semiconductor to the solution,
the energy bands are bent up as mentioned above. In the
band bending region, free (majority) carriers, electrons
for an n-type semiconductor and holes of a p-type
semiconductor, are depleted, and the region is called
the space charge (depletion) region or layer. The existence
ofthe space charge region is the origin ofmany interesting
characteristics of semiconductor electrodes.
When an external potential is applied, the position of
the Fermi level of the semiconductor relative to the sol-
ution redox potential changes, but the band edge energy
stays constant and only the amount of band bending is
affected.When the potential of the n-type semiconductor
is made negative relative to the equilibrium potential,
electrons are transferred from the semiconductor to the
solution and cathodic current flows (Fig. Ib). I( the rate
of electrochemical reaction at the surface!'is sI6w,'elec-
trons are accumulated near the'stifface;iihd'ilnac'cumu-
lation layer is formed. On the othyr. h~hd,\ylH::n the
potential of the n-type semiconductor is made positive
Solution Semiconductor Solution
-Ox/Red Ec~ -Ox/ Red
Ef -
Ev
(b) (c)
Electronic and Morphological Structures of Semiconductor Electrodes 739

relative to equilibrium potential, electrons cannot be 1.5 r - - - - - - - - - - - - - - - - _

transferred from the solution to the semiconductor due
to the existence of the space charge region and no
anodic current flows (Fig. Ie). At a p-type semi-
conductor-electrolyte interface, similar arguments are
valid and anodic current flows under positive ~O.5 )

!
polarization, but no cathodic current flows under nega-
tive polarization. Thus, rectification is expected at the
semiconductor-electrolyte interface. ~
°l:-......- -........==.......- - - - - -lI i...--
Figure 2 shows current-potential relations of the (a) p-
[18] and (b) n-GaAs [19] electrodes in 10 mM Hel in the 8 -o·~'-::.8,----.L..---O=-".::-6---l-_-=oL.4,----.L..--,-O=-".2=---l..-,----O~--L----,,-JO.2
dark. As described above, whereas a large cathodic cur-
(a) Potential IV vs. Ag/AgCI
rent and a negligible anodic current were observed at
n-GaAs, a large anodic current was observed but only a C\l
2.0 r----------------,
small cathodic current flowed at p-GaAs electrode. The E
u
cathodic current corresponds to hydrogen evolution and c< 1.0
the anodic current to GaAs dissolution. E
The potential distribution within the semiconductor
can be calculated by solving the Poisson equation as ->.
'00 0

I
c
(l)

with the boundary conditions V(O) = VIb and V(oo) = V,

(1)
-
0
c
....
(l)
....
~
-1.0
()
where Vex), VIb, and Vare the potential of the semicon-
-2.0 L..L._ _........_ _~"'---..&....--~
ductor at x from the semiconductor surface, the flat band -1.5 -1.0 -0.5 0
potential and the electrode potential of the semiconduc- (b) Potential I V vs. Ag/AgCI
tor electrode, respectively, with respect to a common ref-
erence electrode, eo is the dielectric constant of vacuum,
Figure 2 Current-potential relations of (a) p- and (b)
e is the relative dielectric constant of the semiconductor, n-GaAs electrodes in 10 mM HCI solution in the dark.
e is the elementary charge, and N is the concentration of
the donor (No) for an n-type or the acceptor (NA) for a
p-type semiconductor. The thickness of the space charge III. INVESTIGATION OF THE ELECTRONIC
region, W is then given approximately by STRUCTURE AT SEMICONDUCTOR-
ELECTROLYTE INTERFACES BY
W = (2eoeA¢scl e N)1/2 (2) ELECTROCHEMICAL TUNNELING
SPECTROSCOPY
where A¢sc is the potential drop within the semiconduc-
tor and is given by VIb - V. If the reverse bias of an n-type As mentioned above, information on the electronic struc-
semiconductor is increased significantly, the Fermi level ture of semiconductor-electrolyte interfaces such as the
becomes closer to the valence band than to the conduc- band position, band bending, and the position and the
tion band at the surface, and the surface concentration density ofthe surface states is very important in semicon-
of holes (the minority carrier) exceeds that of electrons ductor electrochemistry. Many techniques have been
(the majority carrier) at the surface. This situation is developed to obtain such information. We have demon-
called inversion. strated that photoluminescence (PL) and electro-
One must note that the situation shown by Fig. 1is an luminescence (EL) measurements are useful to obtain
ideal case where the surface state density is low and the such information and to understand the photoelectro-
carrier density is not too high. If either the surface state chemical processes at semiconductor electrodes. For
density [20] or the carrier density [21] is high, an appreci- example, PL measurements were used to determine the
able portion of the potential drop occurs within the thickness of the space charge region and the surface
Helmholtz layer, i.e., the electrolyte side of the interface. recombination rate at bare and Pt modified p-GaAs elec-
In an extreme case, all of the potential drop occurs within trode [22] and to detect the formation ofthe accumulation
the Helmholtz layer. This situation is often called Fermi layer at n-GaAs [23]. EL measurements were used to
level pinning [20]. prove the formation of the inversion layer at p-GaAs [24]
740
and the existence of the intermediate adsorbed hydrogen
at p-GaAs surface [25].
These techniques and most surface science techniques
such as low energy electron diffraction (LEEO), x-ray
photoelectron spectroscopy (XPS), and infrared spectro-
scopy (IR) can, however, provide only information
averaged over a wide region ofthe surface and are not suit-
able for studying the properties of a local surface region
(~nm). The scanning tunneling microscope (STM),
invented by Binnigand Rohrer in 1982 [26,27], can provide
information on a solid surface with very high spatial resol-
ution because the tunneling current flows through a region
ofonly several square nm. STM has now become a routine
technique for obtaining information on the morph-
ological structure of solid surfaces on an atomic scale in
ultrahigh vacuum (UHV), in air, or even in electrolyte
solution. Many books and reviews on the application and
theory ofthe STM are available [28-34].
Because the tunneling current depends on the overlap
between the wave functions ofthe sample and the tip and
is proportional to the local density of states (LOOS) of
the sample ifan s-wave (free electron) metal is used as a tip,
STM can provide not only topographic information on
the surface but also information on an electronic structure
of the sample surface at an atomic scale (scanning
tunneling spectroscopy [STS]). In fact, the STM was
initially designed for this purpose [26]. STS has been suc-
cessfully applied for the studies of electronic structures
ofmetals and semiconductors in UHV [35-44] and in air
[45-49]. Hamers et al. [35,36] reported an atomically
resolved electronic structure of an Si(1ll) (7x7) surface
obtained by STS measurement in UHV for the first time.
In addition to a conventional image, they mapped out
the complete electronic structure ofan Si(111) (7 x 7) unit
cell. The results are in good agreement with previous
results obtained by spectroscopic measurement ofa large
area such as ultraviolet photoemission spectroscopy and
inverse photoemission spectroscopy. Fan and Bard [45]
carried out a tunneling spectroscopy (TS) measurement
on an n-FeS2(00 I) semiconductor in air. They observed a
peak at 1.6 eV from the Fermi level in the normalized
conductance spectrum that is attributed to the valence
level consisting mainlyofFe3dt2g states ofthe sample.
STS measurement is expected to provide valuable in-
formation on the local electronic structure ofa substrate
also in electrolyte solution. Reports of electrochemical
STS or even TS study on electrodes in electrolyte solution
are, however, still very limited. Itaya and Tomita [50,51]
reported that the STM measurement of Ti0 2 and ZnO
electrodes can be possible only when the electrode poten-
tia
is more negative than Vto, i.e., in the forward bias
region. The tip clashed with the electrode surface when
Uosaki et aI.
the electrode was in a depletion condition.We have shown
that information on the electronic structure ofa semicon-
ductor surface can be obtained by measuring the tip cur-
rent as a function of the potential of the semiconductor
electrode in solution with the feedback circuit of the
STM active. We called this method tip-current vol-
tammetry (TCV) [52-55]. Because the distance between
the tip and the sample varies with potential and the tip
touches the surface of a semiconductor electrode in the
depletion region, TCV does not provide quantitative
information on the electronic structure of a semi-
conductor-electrolyte interface.
We have developed a more appropriate technique,
electrochemical tunneling spectroscopy, in which the
tunneling current (iT) is measured as a function of the
potential of semiconductor electrodes under a constant
sample-tip distance at a given tip potential and have
already applied the technique to n-GaAs and p-GaAs
electrodes in detail [56].
Figure 3 shows typical iT-V relations at (a)
n-GaAs(lOO) (Si doped: N D = 0.84x10 18 cm- 3) and (b)
p-GaAs(IOO) (Zn doped: NA = 1.01 xlO 18 cm- 3 ) elec-
trodes in 2 mM HCI0 4 solution. The tip, a simply cut Pt
wire insulated with apiezon wax, was allowed to approach
the sample surface by keeping the sample potential in
the forward bias region (-0.54 V for n-GaAs in Fig. 3a
and +0.47 V for p-GaAs in Fig. 3b and the tip potential
in the double-layer region of pte+0.24 V in Fig. 3a and
+0.37 V in Fig. 3b). Preset tunneling currents for n-GaAs
and p-GaAs were 5 and 8 nA, respectively. Once a
tunneling state was achieved under an ordinary STM
feedback control mode, the STM was switched into the
external control mode, i.e., feed back control inactive,
and the potential of the GaAs electrode was swept while
the tip potential and the tip-sample distance were kept
constant. The scan rate was ca. 0.1 Vis.
In both cases, the tunneling current decreased quickly
as the forward bias decreased and only very small
tunneling current flowed at potentials more positive than
ca. -0.35 Vat the n-GaAs electrode (Fig. 3a) and more
negative than +0.3 Vat the p-GaAs electrode (Fig. 3b).
The tunneling current in a reverse direction was observed
at n-GaAs electrode at a much more positive potential
region, ca. greater than +2 V, (Fig. 3a) and at the p-GaAs
electrode at a much more negative potential region, ca.
less than -0.1 V (Fig. 3b).
A. Qualitative Description of the 'lUnneling
Behavior of GaAs Electrodes in
Electrolyte Solution
The iT-Vreiations ofGaAs electrodes can be explained by
considering the potential dependent band bending of
f Electronic and Morphological Structures of Semiconductor Electrodes 741

from the sample to the tip was denoted as the cathodic

0 tunneling current and from the tip to the sample as the
~ anodic tunneling current. As the potential is swept posi-
--
U
.....
l:l
11)
t::
;:l

bD
-2

~~
11 Ia~rd~
tively in external control mode, the Fermi level of n-GaAs
is lowered and the electron concentration at the n-GaAs
surface is decreased, leading to a rapid decrease in the
cathodic tunneling current from n-GaAs to the tip (Fig.

~
;§11)
3). The tunneling current decreases to zero near the Vfb
§ -4 Dqtlctlolll
and no current is expected to flow at potentials more posi-
~ Aa:umw.ado.
tive than Vfb as experimentally observed because a space
charge layer is formed within the semiconductor in this
-6 potential region ("depletion" region). The space charge
-1 4
layer can be considered as an extra barrier to the electron
(a) tunneling from n-GaAs to the tip. The tunneling barrier
becomes thicker as the reverse bias increases.
!l
Anodic tunneling current was observed, however, as
the potential became much more positive (more than
~ 6 +2.5 V), although it was much smaller than the cathodic
--
.....
p
11)
1-< 4
tunneling current observed in the forward bias region
(Fig. 3a). As mentioned above, the space charge layer,
1-<

8 which blocks the tunneling ofelectrons, becomes thicker

bn
2 in the potential region much more positive than Vfb . The
.S
'0 -<;-
P
l:l
0
~ reverse bias condition and the barrier to electron
-2
-0.4 -0.2 0 0.2
(b)
Electrode Potential / V V5.
Figure 3 Typical ir-Vrelations at (a) n-GaAs(lOO) (Si doped:
N D =0.84 x 1018 cm -3) and (b) p-GaAs(IOO) (Zn doped:
NA = 1.01 x 1018 cm -3) electrodes in 2 mM HCl0 4 solution.
Tip (a simply cut Pt wire) potential was kept in the double layer
region of Pt (+0.24 V in a and +0.37 V in b). Preset tunneling
currents for n-GaAs and p-GaAs were 5 and 8 nA, respectively.
the semiconductor electrode described in the previous
section (Fig. 1) and the relative positions of the Fermi
levels ofthe tip and semiconductor. The energy diagrams
for an n-GaAs-solution-tip interface in various poten-
tial regions are also shown in Fig. 3a to describe the iT-V
relation.
When the potential of the n-GaAs electrode is more
negative than the Vfb , the n-GaAs electrode is under an
"accumulation" condition and sufficient carriers
(electrons) exist at the semiconductor surface. If the tip
approaches the n-GaAs surface under this condition with
the feedback circuit active, electrons can tunnel from the
n-GaAs to the tip because the Fermi level of the n-GaAs
is higher than that of the tip and the preset cathodic
tunneling current flows. In this article, electron tunneling
Fermi level of the semiconductor electrode, however,
becomes lower than that of the tip under a very large
tunneling from the tip to the sample becomes thinner as
the potential becomes more positive. Thus, electrons are
0.4 0.6
expected to tunnel from the tip to the unoccupied state of
RHE the conduction band in the n-GaAs electrode. A larger
anodic tunneling current was observed at an electrode
with a higher doping density and with a more negative tip
potential. The effect of carrier density is reasonable
because a semiconductor of higher density has a thinner
space charge layer at a given electrode potential [see Eq.
(2)].The effect ofthe tip potential is explained later. It must
be mentioned here that an oxide layer may be formed on
the n-GaAs surface at a very positive potential and the
nature ofthe n-GaAs surface should be changed by the for-
mation of the oxide layer. Thus, a quantitative treatment
ofthe anodic tunneling current is rather difficult.
A similar qualitative interpretation can be given for
the iT-Vrelation ofp-GaAs shown in Fig. 3b except for
the facts that the space charge layer is formed in the
anodic potential region and hole is the majority carrier.
B. Semiquantitative Analysis of the
'lUnneling Behavior of n-GaAs in the
Forward Bias Region
The tunneling current between a sample and an s-wave tip
is often approximately given by [29, 30]
(3)
742 Uosaki et al.

(a) --.------- (b) ~ __

where Ps(O, Ef) represents the surface LDOS near the
Fermi level of the sample (Er), dVand x are the bias and <Po
<P;
the distance between the sample and the tip, and KO is
~~-L---:$---1j~:v~)
Eo J Jo
the decay constant that is given by c-------- Er

•
J7.... -E,
KO = (2n/h)(2m4»1/2 (4)

where h is the Planck constant, m is the mass of an

n-GaAs n-GaAs Tip
electron, and 4> is the mean barrier height. Unfortunately,
however, this equation is applicable only to the situation
where dV is very small and therefore is not suitable for (c) (d) ~ __
the analyses ofthe present results because the bias is more
than a few hundred mV
The net flux of the tunneling electron from a substrate
to a tip, iT, can be given by
Er
Ed...'< I , ~
fT = fS-+T - fT-+S (5) E;
E~
where fS-+ T and iT-+s are the flux of the tunneling elec- n-GaAs Tip n-GaAs Tip
tron from the substrate to the tip and that from the tip to
the substrate, respectively. When the bias between the Figure 4 Energy diagrams for the n-GaAs-electrolyte-tip
substrate and the tip is zero, no net tunneling current flows interface when the potentials of (a) both n-GaAs and the tip
as are at Vfb , (b) the tip is more positive than Vfb while keeping
n-GaAs at Vfb , (c) n-GaAs is more negative and the tip is more
fS-+ T = fT-+s = fo (6) positive than Vfb, and (d) n-GaAs is much more positive than
Vfb. See the details in the text.
where fo is the flux of tunneling electron flowing in both
directions at zero bias. Simmons [57] derived a general-
ized expression for the bias dependence of iT for the elec- from n-GaAs to the tip becomes 4>~, which is smaller than
tron tunneling between similar electrodes for an 4>0 by [e( V1b- VTip)]/2. On the other hand, the barrier
arbitrary barrier by treating both fS-+T and iT-+s and height for the electron tunneling from the tip to n-GaAs
has shown that an expression similar to Eq. (3) can be becomes 4>0 + [e( Vtb - VTip)] /2. Thus, iT is given by
deduced for low bias limit. He further applied the formula
for a rectangular barrier for low, intermediate, and high fT =fS-+T - fT-+S
bias cases. We modified his treatment so that it can be oc{4>~ exp( -2Ks-+TX)} (8)
applied to the semiconductor-electrolyte-tip interface.
Figure 4a shows an energy diagram for
- {[4>~ + e(Vtb - hip)] exp[-2KT-+SX]}
n-GaAs-electrolyte- tip interface when the potentials where
of both n-GaAs and the tip are at Vtb, where Ec and E v
are the energy of the conduction and valence band, KS-+T = (2n/h)(2m4>~)1/2 (9)
respectively, and 4>0 is the barrier height for electron
tunneling. E c is assumed to be equal to Er in the semicon-
ductor bulk. In this case no net tunneling current flows KT-+S = (2n/h){2m[4>~ + e(Vtb - VTip)]}1/2 (10)
because the bias between n-GaAs and the tip is zero,
Because we consider only the situation where bias is inter-
although electrons tunnel between n-GaAs and the tip
mediate and Vtb is more negative than VTip (Fig. 4b), the
in both directions at same rate, fo. In this case, fo can be
absolute value of the second term in Eq. (8) is much
given by
smaller than the first term. Furthermore, there is no
fo oc4>o exp( -2Kox) (7) unoccupied electronic level in GaAs for the electron
tunneling from the tip to n-GaAs because the Fermi level
and 4> in Eq. (4) should be replaced by 4>0. of the tip is within the forbidden band of n-GaAs. Thus,
When the tip potential is made more positive than Vtb the second term can be ignored.
while keeping the potential ofn-GaAs at Vtb as shown If the potential of an n-GaAs electrode is made more
in Fig. 4b, the barrier height for the electron tunneling negative than the flat band potential by (V - Vtb), the bar-
Electronic and Morphological Structures of Semiconductor Electrodes 743

rier height for the electron tunneling from n-GaAs to the 10

tip decreases by e( VID - V), but that for the electron "?·o· •
tunneling from the tip to n-GaAs does not change (Fig. ~ -<~oo·.
4c). This is because the band edges of the conduction ---t:l "
"
0
0 • (b)
" •
and valence bands of n-GaAs are assumed to be pinned is
;::l "
o 0 • •
o o ••
with respect to the vacuum level and a potential drop u
(0) 0 •
l)l) o
occurs solely within n-GaAs. [41]. One must note, .::1 '.
<3 0.1 "
however, that this assumption is not valid in certain cases t:l
t:l
such as high carrier density or high surface state density ~ (0)
as mentioned before. The second term ofEq. (8) can also
0.01 L.......L .1...-_ _- - ' -_ _----L. "'----'
be ignored in this case. Thus, Eq. (8) can be written for this -0.45 -0.4 -0.35 -0.3 -0.25
situation as Electrode Potential / V vs. RHE
IT = I s--+T - I T--+ S
Figure 5 Log(ir) - Vrelations ofn-GaAswith doping levels
c::::::IS--+TCX:{cP~ - e(VID - V)}exp(-2Ks--+TX) of (a) 0.84 x 10 18 cm- 3 and (b) 2.48 x 10 18 cm- 3 . Surface elec-
(11) tron concentrations of these electrodes calculated by using Eq.
(14) are also shown in the figure by solid (0.84 x 10 18 cm- 3)
where and broken (2.48 x 10 18 cm- 3) lines.
I I
KS--+T = (2n/h){2m[cPo - e(V ID - V)]}2 (12)
In the above treatment, the tunneling current is con- of higher doping density shows a higher surface electron
sidered to be affected by potential only through the poten- concentration at a given potential but the slopes of the
tial dependence of the barrier height. Because the log(n s (V)) - V relations are the same. The slopes of the
surface concentration ofelectron also varies with poten- log(h) - V relation for the two samples are also very
tial quite significantly in the present case, the potential similar. The slopes of the log(n s (V)) - V relations are,
dependence of the surface electron concentration should however, larger than those of the log(h) - Vrelations.
be taken into account and h should be given by We have assumed so far that all the potential drop
occurs within the n-GaAs electrode, but it is known that
h cx:n s ( V){ cP~ - e(VID - V)} exp(-2Ks--+T x) (13)
some of the potential drop also occurs in the Helmholtz
where ns (V) is the surface electron concentration at a layer when the carrier density [21] or the surface state den-
given potential, V, and is approximately given by sity [20] is high as mentioned before. This makes the slope
of the log(n s (V)) - Vand therefore of the log(h) - V
ns(V) = noexp[e(VID - V)/k7l (14) relations small. This should be at least a part of the
reasons for the discrepancy between the slopes of the
where no is the electron concentration in the bulk of the
log(n s (V) - V relation and that of the log(h) - V
n-type semiconductor (noC:::::: N D ). Thus, Eq. (12) becomes
relations.
hcx:{noexp[e(V1D - V)/kT]} x The slopes of log(h) - V relations depended on the tip
(15) potential. The more positive the tip potential, the smaller
(cP~ - e(VID - V)}exp(- 2Ks--+TX) the slope. Because the potential dependence of surface
This equation suggests that the tunneling current changes electron concentrations should not be affected by the tip
exponentially with potential when the term (VID - V) potential, the tip-potential-dependent slope means that
the presence of the tip near the semiconductor electrode
does not vary too much. Figure 5 is the replot ofthe result
of Fig. 3a and that of n-GaAs of higher carrier density affects the potential distribution at the semiconductor-
(No = 2.48 xlO- 18 cm -3), i.e., the potential dependence
electrolyte interface or the electrode-electrolyte inter-
of the log of the tunneling current for n-GaAs electrodes face in general.
of two different doping densities (ND =0.84xlO 18 cm- 3
and 2.48 x 10 18 cm- 3). It is clear that the tunneling current
c. Semiquantitative Analysis of the
1Unneling Behavior of n-GaAs in a Very
actually varies exponentially with potential as expected
Positive Potential Region
from Eq. (15). The surface electron concentrations of the
two samples are calculated using Eq. (14) and are also As discussed before, when the potential of n-GaAs
plotted as a function ofthe potential in Fig. 5.The n-GaAs became very positive, a small amount of tunneling cur-
744 Uosaki et al.

rent flowed from the tip to the n-GaAs electrode. The -1 r '- - - - - - - - - - - - - - - ,

~
energy diagram for this situation is shown in Fig. 4d. TiP Potential
The barrier shape at the interface does not change if one vi o . .. ·+0.16 V
> ····+0.36 V
assumes all potential drops within the semiconductor as ;>
mentioned before. In this case, however, in addition to --
(;/
'.0 /:;.V=3.5 V
····+0.56 V

the tunneling barrier at the n-GaAs-electrolyte-tip ~ 2

interface in the forward bias region discussed above, the ~
space charge layer formed within the n-GaAs electrode -8 3r-'+' ___
should be considered as an extra barrier to electron ~.,
tunneling from the tip to the conduction band. It is P3 4 I I I I I I
obvious from Fig. 4d that the second term is dominant 80 60 40 20 o
in Eq. (5) because (V - VTip ) is fairly large and there is no (a)
vacant state in the tip at Er of n-GaAs under the present
condition. ~ -0.4
Vlb~
As described above, the space charge layer formed
~ -0.2
within n-GaAs in the reverse bias region acts as an extra ;>
barrier to the electron tunneling from the tip to n-GaAs. -- 0
3 5.6nm .··3.2n Tip Potential
The thickness and the height of the space charge layer
affects the tunneling probability in the reverse bias region.
<:i
.9 0.2 7.9nm ...
t.:'< __ ~
4.6nm
_ +0.16 V
o
The degree of the tunneling process through the extra A.
~ 0.4 IO.3nm •• '
t-:·~·~ -
6.0nm
~ _ +0.36 V
barrier (space charge layer) can be evaluated by
calculating the transmission coefficient through the ~
~ 0.6
~.~.~. - - - - - - ¥ - - - - - - - - - - - - -,-
+0.56 V
barrier. The potential distribution within the semi- ~ _~_~':;-_~I_L.t~I-_l.l--LI_~,
I v
12 10 8 6 4 2 0
conductor can be calculated by solving the Poisson
(b) Distance from the Surface / nm
equation [Eq. (1)] as mentioned before. As an example,
the energy diagrams of the conduction band of n-GaAs
Figure 6 Calculated conduction posItIOn in the space
of two doping densities (No =0.84xlO I8 cm- 3 , solid
charge region in n-GaAs with two doping densities
line; 2.48xlO 18 cm- 3 , dotted line) were calculated for (ND = 0.84 X ]018 cm- 3 , solid line; 2.48 x ]018 cm- 3 , dotted
V = +3.1 V using Eq. (1) with Vfb = -0.34 V and are line) as a function ofdistance from the surface using Eq. (I) with
shown in Fig. 6a. The tip potentials of 0.1, 0.3, and 0.5 V V/b = -0.34 Vand V = +3.16 V (.<1V = 3.50 V). The tip poten-
are also indicated in the figure to show the effect of the tials of 0.16, 0.36, and 0.56 V are also indicated in the figure.
tip potential on the effective width ofthe tunneling barrier The energy diagrams were enlarged for the region near the
within the semiconductor. The energy diagrams were Fermi level of the tip in b.
enlarged for the region near the Fermi level of the tip in
Fig. 6b. Figure 6 clearly shows that the n-GaAs with the
higher doping density has a thinner space charge layer at
a given tip potential. The transmission coefficient The values of k t can be calculated using Eq. (16) with
through the space charge layer for the electron tunneling the values of the thickness of the space charge layer for
from the tip to the conduction band of n-GaAs, k(, various tip potentials. The calculated values for the two
depends on the thickness of the space charge layer at the doping densities clearly show that the higher the doping
energy of the Er of the tip, d( VTip), and the energy differ- density, the larger the k t because the barrier width is
ence between the Er of the tip and bottom of the conduc- thinner. Although this result is in agreement with the
tion band at the surface, which is equal to e( VTip - Vfb). experimental results [56] qualitatively, the calculated
The following Gamaw-Jeffreys equation can be used effect of doping density on k t is much larger than the
for the calculation of k t [58] experimentally observed effect on ir. Whereas calculated
kt for No =2.48xlO I8 cm- 3 , is 10 5 times of that for
No = 0.84x 10 18 cm- 3 , iT for the former was only about
k t = exp{(8nd( VTip)/3h)[2me(VTip - Vfb)]} (16) four times ofthat for the latter in the case ofa tip potential
of +0.16 V.
Here the barrier shape was assumed to be a triangle as a The calculation using Eq. (16) also shows that kt
first approximation. This assumption is reasonable as increases as the tip potential becomes more negative
shown in Fig. 6b. and the sample potential became more positive as
Electronic and Morphological Structures of Semiconductor Electrodes
experimentally observed. The values of k(, however,
depended on the potential of n-GaAs and the tip
potential more significantly than those of iT. For
example, iT ofn-GaAs at +2 V increased ca. one order
of magnitude by changing the tip potential from +0.56
to +0.36 V, but k t increased more than six orders of
magnitude for the same change. Similarly, the
tunneling current increased about five times as the
potential changed from +2 to + 3 V with a given tip
potential of +0.16 V, whereas the calculated k t is
expected to increase ca. 30 times under the same con-
ditions. The effect of the tip potential on the tunneling
current can be explained by considering the thickness
of the space charge layer at the energy of the tunneling
electron, i.e., the Fermi level of the tip. Because the
thickness of the tunneling barrier within the space
charge layer is thinner when the tip potential is more
negative (Fig. 6), the tunneling probability from the
tip to the n-GaAs electrode through the space charge
layer should be higher at a more positive tip potential,
i.e., at higher energy. As the potential becomes more
positive, the difference between Vtb and V increases,
leading to a decrease in the thickness of the space
charge layer at the tip potential d( VTip) and therefore
an increase in k t .
Several reasons should be considered for the discrep-
ancy between the potential dependence of k t and that of
iT. One important reason is that the tunneling barrier
consists not only of the space charge layer of n-GaAs
but also of the barrier between the n-GaAs surface and
the tip, which is considered to be the only barrier to the
electron tunneling in the forward bias region in the
preceding section. Thus, the potential dependence of k t
is not necessarily that of iT.
A more important reason seems to be, however, the
existence of the surface states and impurity levels of
n-GaAs. If one looks at the energy diagram shown
in Fig. 6, the thickness of the space charge layer at
the tip potential d( VTip) is far too thick for electron
tunneling to take place with reasonable tunneling
probability without considering the resonance
tunneling through these states. The importance of
the surface state on the tunneling behavior is clearly
demonstrated by experimental results in which the
anodic tunneling current flowed more easily at an
n-GaAs electrode treated with Ru than at the etched
GaAs electrode by the sulfur-treated n-GaAs elec-
trode behaved as an ideal semiconductor, and
tunneling current was observed only in the
"accumulation" region. The Ru and S treatments have
been known to increase and decrease, respectively,
the surface state density.
745
IV. ELECTROCHEMICAL ATOMIC FORCE
MICROSCOPE OBSERVATION OF THE
MORPHOLOGICAL STRUCTURE OF
SEMICONDUCTOR ELECTRODES
The STM has now become a popular tool for imaging
electrode surfaces in situ with atomic resolution and has
been proved to be a very useful aid in understanding the
fundamentals of electrode processes [32,33]. This tech-
nique has, however, some limitations. Because STM uses
a tunneling current as a probe, only the surface of con-
ducting materials can be imaged. Thus, STM measure-
ment of semiconductor electrodes is not possible under
reverse bias because of the existence of a space charge
layer as described in the previous section. On the other
hand, atomic force microscope (AFM) measurements
can be carried out over a wide potential region even where
a space charge layer within a semiconductor or insulating
oxide layer on the surface is formed because it is not affec-
ted by the sample conductivity. Furthermore, electro-
chemical processes on the tip, which may cause serious
problems in the STM measurements in electrolyte
solutions, can be avoided in the AFM measurements. It
has already been applied for the in situ imaging of elec-
trode surface [59-61]. Thus, although several papers on
STM observation of semiconductor electrode have been
published [50,51,54,62-74], here we concentrate on sev-
eral examples that demonstrate the usefulness of AFM
for the in situ monitoring of the morphological structure
of a semiconductor electrode with atomic resolution.
A. In Situ Real-Time Monitoring of the
Surface Structure of a p-lnSe Electrode
During Electrochemical Reaction
InSe is a III-VI layered compound semiconductor and
has interesting properties, including strong conductivity
anisotropy, [75,76] high photosensivity with an optimum
energy gap for solar energy conversion (1.3 eV) [77,78],
and the predicted high electrochemical stability of the
van derWaals face [79]. Because ofthese properties, InSe
has been considered a good candidate for
photoelectrodes [80-83]. We have shown the importance
of surface conditions with respect to photoelectro-
chemical properties using a laser spot scanning
microscope with micron resolution [84,85]. Here we
applied AFM to obtain information on the surface struc-
ture of InSe in solution under potential control with
atomic resolution [86].
Figure 7 shows an AFM image ofp-InSe obtained in
pure water. The image obtained in water is essentially
the same as that obtained in air [87]. The topmost atoms
show a hexagonal structure with a nearest-neighbor dis-
746 Uosaki et al.

5.0

'2.5

0.40 nm

o 2.5
o
5.0 nm
(b)
0.126-nm
0.310 nm
0.126~
0.282~
~

.In
t:m!hIS
@e

Figure 7 An atomically resolved AFM image of the van der

Waals face of p-InSe (ca. 0.1 % Zn doping) obtained in pure
water.

tance of 0.40 ± 0.03 nm. The dominant structure ofInSe

crystals grown by the Bridgman method is rhombohedral
as shown in Fig. 8 [88,89], which suggests that Se forms
the topmost layer of a hexagonal arrangement with a
nearest-neighbor distance of 0.400 nm. The results of
AFM measurements (Fig. 7) are in good agreement with Figure 8 (a) The atomic arrangement of the topmost and
the surface structure expected from Fig. 8. A higher resol- second layers ofthe van der Waals face ofInSe. (b) The stacking
ution image showed that In was also observed in the sequence ofInSe in the rhombohedral structure.
second layer. AFM imaging in liquid has two advantages:
the repulsive force of the tip in water (ca. 10- 9 N) is lower
than that in air (ca. 10- 8 N) by an order of magnitude '" 80 r '- - - - - - - - - - - - - -

. Y' /d
because ofthe absence ofcapillary forces and the reduced
van der Waals interaction [90-92] and the surface con- u 60

~ 40
l
tamination is greatly reduced because the surface is
covered with pure water. Actually, the atomic image was
more stable in water (more than 10 min) than in air (a
few minutes).
-
>.
.~ 20 ~ .. , .'
,
-
Figure 9 shows a typical cyclic voltammogram of a
p-InSe electrode in 10 mM Na2S04 solution in the dark
(sweep rate, 15 mV/s). The open-circuit potential was ca.
Q)
"0
~
~ -20
0
7a
. -'-
(f)•. ' . '
-~~ .•.....
.

-0.5 V vs. Ag/AgCl. The anodic current was larger than

....
;:j
-
U _40L-.l....--...L...--....L--...J......-.....L--.......L...---'---.J
the cathodic current. Under illumination, a significant -1.0 -0.8 -0.6 -0.4 -0.2 0 0.2
cathodic photocurrent due to hydrogen generation flowed Potential / V vs. AgIAgel
at potentials more negative than ca. -1.0 V No illumi-
nation effect was observed for the anodic current. These Figure 9 Typical cyclic voitammogram of the p-InSe elec-
results confirm that the material is a p-type trode in 10 mM Na ZS04 solution in the dark (sweep rate,
semiconductor. 15 mV/s).

....
Electronic and Morphological Structures of Semiconductor Electrodes
Figure 10 shows the AFM images obtained
sequentially when the potential was scanned from -1.0
to +0.2 Vand back again at a rate of IS mYls. All images
shown in Fig. 10 were obtained while the tip was scanned
from the top to the bottom. It took 11 s to capture one
image and therefore the potential differed by 0.15 V
between the top and the bottom of the image. In a rela-
tively negative potential region (less than -0.5 V), the
atomic image was clearly resolved (Fig. lOa). The image
is essentially the same as those obtained in air and in
water (cf. Fig. 7). This result suggests that the surface is
stable under these conditions.When the potential became
more positive than -0.5 V, the atomic image became less
clear (Fig. IOb). The more positive the potential, the larger
the nonatomically resolved area (Fig. lOc and d). The
atomic image was completely lost at potentials more posi-
tive than 0 V (Fig. IOd). The atomic image was partly
recovered when the potential was scanned from positive
to negative and became more negative than -0.7 V (Fig.
lOe) and was completely recovered if the potential was
kept at -0.8 V for I min (Fig. 1Of). These results suggest
-1.CN -0.50
- -......-0.83 0.33
-0.16 +0.17
+0.01
-0.61
-0.78
Figure 10 AFM images of the p-InSe electrode in to mM
Na2S04. (a-e) Images were obtained sequentially while the
potential was scanned from -1.0 to +0.2 Vand back again at a
rate of 15 mYls. (f) Image was taken 1 min after the potential
was kept at -0.8 V.
747
that InSe is decomposed and an amorphous layer is
formed on the surface when anodically oxidized.
However, the amorphous layer can be removed at nega-
tive potentials and an ordered surface of one layer below
appears.
If the potential was kept at +0.5 V for 2 min and then
pulsed to -1.0 V, the atomic image was never recovered,
suggesting that once the amorphous layer on the surface
becomes too thick, it cannot be completely removed even
ifthe potential is kept negative for a long time. The surface
looked brown after the potential was kept positive for a
long time.
These results can be explained by assuming that the
anodic process is the decomposition of InSe to selenium
and hydroxylated indium ion: [93,94]
InSe + H20 ~ Se + InOH 2+ + H+ + 3e-
Because InOH 2+ is soluble but Se is insoluble in the
solution, Se is left on the InSe surface and forms an
amorphous layer upon oxidation. This should explain
why the atomic image was lost at positive potentials. The
deposited Se is removed reductively at negative potentials
(Se+H+ +2e- ~ HSe-) [89] when the Se layer is not too
thick. In this case, the atomically ordered van der Waals
face appears, and an atomically resolved AFM image
can be obtained at negative potentials. If the Se layer is
too thick, total removal of Se by electrochemical
reduction must be difficult because the layer is porous
and has low conductivity.
AFM images of atomic resolution with a hexagonal
structure was also observed under potential control in
2 mM HCI0 4 solution.
B. Atomically Resolved Structure of
GaAs(100) Surface in Electrolyte
Solutions Obtained by Electrochemical
AFM
GaAs is one of the most attractive semiconductor
materials to be used in various electronic devices and in
dry/wet solar cells. Thus, many papers on the electro-
chemical behavior of GaAs in the dark and under illumi-
nation have been published, [22,95-99] but in situ
observation of the GaAs surface structure on an atomic
scale is rather limited. In this section, we use an in situ
electrochemical AFM for the investigation ofthe surface
structure of a p-GaAs(100) face in HCI solution and
showed that the atomic arrangement of the (100)-(1 xl)
structure is observed on the surface but the surface struc-
ture is changed ifGaAs( 100) is kept at open circuit poten-
tial or anodically polarized.
748
The current-potential relation of a p-GaAs electrode
in 10 mM HCl in the dark is already shown in Fig. 2.
Anodic current corresponding to the GaAs dissolution
was observed at potentials more positive that +0.15 V
vs. Ag/AgCl. Significant cathodic current due to
hydrogen evolution flowed at potentials more negative
than about -0.9 V When the electrode was kept at open
circuit potential (~O.O 1 V) or at a potential where a small
anodic current flowed in 10 mM HCl solution, truncated
pyramids ofrelatively uniform size (50-100 nm square)
were formed on the surface as shown in Fig. lla (top view)
and b (cross-sectional view). This structure was stable in
HCl solution at 0 V where almost no current flowed for
a long period of time (more than 30 min). A truncated
pyramidal structure was formed only at open circuit
potential or when the anodic current flowed, possibly
due to anodic dissolution of the GaAs electrode in HCl,
nm
10..,...,- - - - - - - - - - - - - - - - - ,
(b)
I nm
-100\: .1 1 1 400
Figure 11 An AFM image (400 x 400 nm) of the
p-GaAs(IOO) surface obtained at 0 V vs. Ag/AgCl in 10 mM
HCl after the anodic potential was applied. (a) Top view and
(b) cross-sectional view.
Uosaki et al.
which proceeds most selectively at the (lll) face. The
formation of the pyramids at open circuit suggests the
flow of anodic current compensated by the cathodic
photocurrent. The electrochemically formed planes had
an angle ofabout 40-50° with respect to the (100) surface
and seemed to correspond to the Ga{Ill} crystallo-
graphic planes that form an angle of 54.7 0 with respect
to the (100) surface. The etching proceeds up to the
Ga{lll} planes because the As {11l} planes are very
active compared with the Ga{III } planes [10 0-102]. The
shapes and sizes ofthe truncated pyramids were strongly
dependent on the experimental conditions, such as HCl
concentration and temperature.
The above result shows that the usual practice of
characterizing the quality of the semiconductor surface,
i.e., to record cyclic voltammogram, damages the surface
if the potential was scanned to the value more positive
than the open circuit potential.
Although the atomic arrangement was not observed in
air because the GaAs surface was covered with native
oxide, it was observed when the electrode was immersed
in electrolyte solution and a negative potential was
applied. Figure 12 shows typical atomically resolved
AFM images of a p-type GaAs(100) electrode obtained
in HCl solution with a two-dimensional Fourier trans-
form spectrum. The AFM image was captured near the
open circuit potential, i.e., at 0 V, after the electrode was
kept at -0.8 V for about 10 min to remove the oxide layer
reductively and is shown without any filtering. The AFM
image and 2D Fourier transform spectrum show that the
atomic structure is of nearly fourfold symmetry with a
nearest-neighbor distance of about 0040 nm, which is in
good agreement with the value of the GaAs (100)-(1 xl)
Figure 12 (a) An atomically resolved AFM image of the
p-GaAs(100) electrode surface in 10 mM HCl obtained at 0 V
vs. Ag/AgCl, showing the GaAs(IOO)-(l xl) structure. The
image was not filtered. (b) Two-dimensional Fourier spectrum
of a.
Electronic and Morphological Structures of Semiconductor Electrodes
structure [103]. Thus, the GaAs(100)-(1 xl) structure is
exposed in HCl solution. This is in contrast with the fact
that the GaAs(100) surface forms reconstructed struc-
tures such as (2x4) and c(4x4) under UHV condition
because ofthe existence ofthe danglingbondin the (1 xl)
structure [104,105]. The atomic images are clearer near
the open circuit potential than in a more cathodic poten-
tial region. The x-ray Photoelectron (XP) spectrum shows
that the Ga/As ratio is higher and the Cl peak is stronger
in samples that were removed from the cell after a positive
potential was applied than in samples without anodic
treatment. Thus, we speculate that the topmost atoms
are Ga and the (1 xl) structures is stabilized by the
termination of the dangling bond by Cl (Cn.
An atomic arrangement showing the GaAs(100)-
(1 xl) structure was also observed in H 2S04 solution
[106]. The atomic images were, however, obtained more
clearly at a more cathodic potential region that is close
to the potential of H 2 evolution than at potentials near
the open circuit potential. The atomic arrangement was
very clear at -0.75 V but became less clear at -004 V. It
was hardly observed at +0.1 V, which is very close to the
open-circuit potential. This result suggests that SO~­
ion cannot stabilize the (100)-(1 xl) structure by
terminating the dangling bonds ofthe GaAs(100) surface
but the GaAs(100)-(1 xl) structure is stabilized in the
cathodic potential region as a result of termination of
the dangling bond by H (H+). Yao et al. [73] also observed
the (1 xl) structure at n-GaAs(100) in H 2S04 solution in
the cathodic potential region using electrochemical
STM and proposed that the termination of the dangling
bond by hydrogen is responsible for the (1 xl) structure.
To claritY the role of the adsorbed ions/atoms on the
GaAs surface, the surface was treated with S, which is
known to decrease the surface state density as described
in the preceding section [107,108]. Atomic images of the
p-GaAs(100) surface were observed in Na2S solution
over a very wide potential region where almost no current
flowed, i.e., between the onset potential ofhydrogen evol-
ution (-0.7 V) and anodic dissolution (+0.05 V). Figure
13 shows (a) the current-potential relation and (b)
atomically resolved AFM images at various potentials
ofa p-GaAs(100) electrode in 2 mM Na 2S solution. All
AFM images obtained in Na2S solution showed an ident-
ical structure regardless of the electrode potential. The
structure showed fourfold symmetry with a nearest-
neighbor distance ofabout 0040 nm. The atomic distance
and the directions ofthe atom rows were the same as those
obtained in 10 mM H 2S0 4 solution at -0.8 V before the
solution was replaced by 2 mM Na 2S solution. Thus, it
is clear that the p-GaAs(100) surface has the (1 xl) struc-
ture in Na 2S solution. This is again in contrast with the
749
r,
(a) ~ 12.---------------,
<:E 0.8
.~04
~= a
<:
~ .0·$L.,8-.....,.0l..:.6-.....,.0L.,4-.....,.0l..:.2,....--0~---::0"::.2--::04
::l •
(b) u Po~~ntial/ V vs. Ag/AgCI
10
5 5
a a
o 5 10 a 5 10 a 5
Figure 13 (a) Cyclic voHammogram and (b) atomically
resolved AFM images of the p-GaAs(IOO) electrode in 2 mM
NazS solution at various potentials indicated by arrows in a.
result obtained under UHV. Sulfur atoms are adsorbed
on the GaAs(100) surface and form a (2 xl) adlayer when
the GaAs(100) surface was exposed to H2S gas in the
UHV chamber [109]. Once the GaAs(100) surface was
treated in Na2S solution, the atomic arrangement of the
GaAs(100)-(1 xl) structure was observed easily over a
wide potential region even in H2S04 solution. These
results should be related to the fact that the GaAs elec-
trode shows ideal characteristics ofa semiconductor elec-
trode if the surface is treated with sulfur as described
before.
c. Electrodeposition of Cu on GaAs(100)
Surface
Electrochemical deposition is a simple and popular
method to form thin films on conducting and
semiconducting surfaces. Although numerous papers
on the electrochemical deposition on metals have been
published, [110-113] only a very limited number of studies
has dealt with the electrodeposition of metal on semi-
conductor surfaces despite its technical significance
[114-118]. In this section, we monitored the electrochemi-
cal deposition of Cu on the p-GaAs(100) surfaces with
atomic resolution using an in situ electrochemical AFM.
The effects of surface defects, applied potential, and the
concentration of Cu2+ ion in solution on how the Cu
deposition took place were studied visually [119-121].
Figure 14 shows the current-potential relation of a
p-GaAs(100) electrode in 9 mM HCl+l mM CuClz sol-
ution [119]. Cu deposition took place at potentials more
negative than -0.1 V and anodic stripping peaks were
observed at +0.01 and +0.09 V. How the electro-
750 Uosaki et al.

C)J
E 2.0 deposition of Cu proceeded was strongly dependent on
C? the structure ofthe substrate as has been known for a long
~ 1.5 time. Figures 15 and 16 show a series of AFM images

-'w
~ 1.0
taken before (a) and during (b-f) the bulk deposition of
Cu in 9 mM HCl+l mM CuClz solution on a
p-GaAs(lOO) surface of relatively flat structure and with
c
anodically preformed truncated pyramidal structures,
~ 0.5
+-< respectively [119]. The potential was stepped from +0.1
c to -0.15 Vat the time indicated by a thick arrow in Fig.
....::::l~ 0
15b. Figure 15b clearly shows that immediately after the
() -0.5 I ! , , J ! I I I
potential was stepped to -0.15 V, a large number of small
-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 grains were generated with a spacing of several tens of
Potential / V vs. Ag/AgCI nm. These initial deposits of Cu on the surface seemed
to act as effective nucleation centers and the initial growth
Figure 14 Cyclic voltammogram of the p-GaAs(IOO) elec- of these grains seemed to be three dimensional. AFM
trode in 9 mM HCI + I mM CuCh solution. images were continuously captured at -0.15 Vand are

50

1.0
50
Ot--
o
J(f) -Ii
nm I.
100
1.0 •
50

0..... -j
o i

Figure 15 Sequentially obtained AFM images ofp-GaAs in the relatively flat region in 9 mM HCI+I mM CuCIz solution (a) at
+0.1 V vs. Ag/AgCI, (b) while the potential was pulsed to -0.15 V, (c-e) at -0.15 V, and (f) while the potential was pulsed back to the
initial potential (+ 0.1 V). Time after the application of - 0.15 V was (c) 4 s, (d) 12 s. (e) 20 s, and (f) 74 s at the beginning of imaging.
Thick arrows indicate the onset of deposition and stripping. Arrows beside the figure indicate the scan direction of the tip.
Electronic and Morphological Structures of Semiconductor Electrodes 751

50
0
0
(elj 0.5

nm
1.d OO 1.0
50
0
0

nm
(flj 0.5

1.dOO
50 50
0
0 0.5

Figure 16 Sequentially obtained AFM images of the p-GaAs surface with preformed truncated pyramidal structures in 9 mM
HCI + I mM CuCh solution (a) at + 0.1 V vs. Ag/AgCI, (b) while the potential was pulsed to -0.15 V, (c-e) at -0.15 V, and (f) while
the potential was pulsed back to the initial potential (+0.1 V). Time after the application of -0.15 V was (c) 3 s, (d) II s, (e) 19 s, and
(f) 204 s at the beginning of imaging. Thick arrows indicate the onset of deposition and stripping. Arrows beside the figure indicate
the scan direction of the tip.

shown in Figs. 15c-e. As time progressed, the grains ofCu
overlapped with each other and finally truncated pyrami-
dal structures of relatively uniformed size were formed
(Fig. 15e). Upon stepping the potential back to +0.1 Vas
indicated by a thick arrow in Fig. 15f, Cu deposits were
removed immediately within the time domain of the
AFM measurement and the surface was returned to a
state similar to that before the Cu deposition (Fig. 15f).
Totally different time sequences were observed for the
electrodeposition of Cu on GaAs(lOO) with truncated
pyramidal structures (Fig. 16a) as shown in Fig. 16b-e.
As soon as the potential was stepped to the bulk depo-
sition region (-0.15 V), indicated by a thick arrow in Fig.
16b, the electrochemical deposition of Cu started to
occur along the preformed structure (Fig. 16b). Grains
observed in Fig. 15 were not seen in this image. The
truncated pyramids grew with the progress of the depo-
sition mainly in a vertical direction. Thus, the Cu depo-
sition process seemed to occur predominantly on the
defect.
The effect ofthe applied cathodic potential on the way
how the Cu electrodeposition proceeded was investigated
on the flat p-GaAs(lOO) surface in 10 mM H2S04 +
CUS04 solution.When the electrode potential was pulsed
to -0.05 V, which is almost equal to the onset potential
of the bulk Cu deposition, a small number of large
clusters of Cu was formed on the surface. As the applied
potential became more negative, the number of Cu
752 Uosaki et a1.

clusters increased but the size of each cluster decreased.
Cu clusters were not observed on the GaAs(lOO) surface
when -0.4 V was applied. In this case, Cu deposition
seemed to occur on the whole GaAs(lOO) surface almost
uniformly. These results show that we were able to control
the size and the numbers of the Cu clusters formed on
the GaAs(lOO) surface by adjusting the applied over-
potentials. The Cu clusters grew in size with time but the
total number of Cu clusters was constant from the initial
stage of the deposition. These results confirm that the
initial deposits of Cu on the surface acted as effective
nucleation centers. The size and numbers of Cu clusters
were also influenced by the concentration of Cu2+ ion.
Figure 17a shows an AFM image of a p-GaAs(lOO)
surface with a small number of Cu deposits in 1 mM
CuS04+10 mM H2S04 solution at -0.2 V. Islands of
relatively uniform size were located on the GaAs surface.
High-resolution AFM images of the surface of the top
of a Cu island and the portion between the Cu islands
are shown in Fig.17b and c, respectively. Figure 17b shows
that the topmost atoms have a hexagonal structure with
a nearest-neighbor distance of 0.26 ± 0.04 nm, which is
almost equal to the known lattice constant (0.256 nm)
of bulk Cu in the (lll) basal plane. Thus, Cu deposits
seemed to have a closely packed structure. On the other
hand, the atomic arrangement of a square lattice with an
atomic distance of about 0.4 nm corresponding to the
underlying structure of the GaAs(lOO)-(l xl) structure
was observed in the region between Cu deposits (Fig. 17c).
The direction of the atom rows of the Cu(lll) structure
on the top of each Cu cluster was different. This result
suggests that the bulk deposition of Cu on a GaAs(lOO)
surface proceeded without strong influence of the
orientation of the underlying GaAs(lOO) surface. This
was confirmed by an AFM image on an atomic scale
obtained at the boundary region between two Cu deposits
(Fig. 18) [120]. Both sides of the boundary region show
closely packed hexagonal structures corresponding to
the Cu(111) lattice but with different atomic orientation,
10.0
8.0
6.0
4.0

10.0 2.0
7.5

5.0
I"
0 2.0 4.0 6.0 8.0 10.8 nm
(a) - .- 2.5

(b)
50
·10.0

7.5

5.0

2.5

o
o 2.5 5.0 7.5 10.0 nm

Figure 17 (a) An AFM image (l xl Jim) of the p-GaAs(lOO)
surface with small number of Cu islands in 10 mM
H2S04 + 1 mM CUS04 solution. Atomically resolved AFM
images of (b) the top ofa Cu deposit and (c) the portion between
Cu deposits with the two-dimensional Fourier spectrum as
insets.
Figure 18 (a) An atomically resolved AFM image of the
boundary region of two domains of the eu deposits on the
p-GaAs(lOO) surface obtained at -0.3 V vs. Ag/AgCI in 10 mM
H 2S0 4 + 1 mM CUS04 solution. (b) Schematically drawn
atomic arrangement for the boundary region indicated by a
white square in a.
Electronic and Morphological Structures of Semiconductor Electrodes
and the atoms were less ordered at the boundary region.
The atomic arrangements of Fig. 18a are schematically
shown in Fig. 18b as a guide. The angles between two atom
rows of the Cu(lll) lattice at the boundary regions had
no regularity. Thus, the direction ofthe atom rows seemed
to be determined at he initial stage ofbulk Cu deposition.
V. CONCLUSIONS
A semiconductor-solution interface has a unique prop-
erty because the Fermi level of a semiconductor, and
therefore the band bending within the semiconductor
can be controlled externally. Electrochemical tunnel-
ing spectroscopy was introduced as a novel technique
to characterize the electronic structure at semi-
conductor-electrolyte interfaces. AFM investigations
clearly showed that a very clean and atomically ordered
surface ofa semiconductor can be exposed in electrolyte
solution if the semiconductor is treated properly and is
kept within a certain potential region.
ACKNOWLEDGMENT
Supported in part by a Grant-in-Aid for Scientific
Research on Priority Area of "Electrochemistry of
Ordered Interfaces" (No. 09237101) from the Ministry
of Education, Science, Sports and Culture, Japan.
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42
Epitaxial Compound Electrodeposition
Travis L. Wade, Thomas A. Sorenson, and John L. Stickney
University ofGeorgia, Athens, Georgia
ABSTRACT
This chapter concerns the electrodeposition of com-
pound semiconductors. That compound semiconduc-
tors can be electrodeposited is well known. Questions
being addressed by this group concern the limits to
compound electrodeposit quality that can be achieved.
Can epitaxial deposits be formed? Under what conditions
can they be formed, and with what types and numbers of
defects? This chapter briefly describes a number of
compound electrodeposition methodologies that have
been used to form devices, such as high-efficiency
photovoltaics. The chapter then elaborates on the method
of electrochemical atomic layer epitaxy (ALE). Electro-
chemical ALE is based on the use of surface limited elec-
trochemical reactions, known as underpotential
deposits (UPD), to form atomic layers of the elements
making up a compound, individually, in a cycle. Each
cycle ofdeposition forms a monolayer of the compound,
and the number of cycles determines the deposit
thickness. In principle, using surface limit reactions to
form eachatomiclayer should prevent three-dimensional
growth and promote epitaxy. Thin films have been formed
using this technique in an automated electrochemical
thin-layer flow cell system. Electrochemical ALE is,
presently, a relatively slower methodology, and there are
a number of automation issues to be resolved, some of
which are discussed in this chapter. One of the main
reasons for studying electrochemical ALE, however, is
that it results in the deconvolution of compound
electrodeposition into a series of individually tractable
steps, studies of which should benefit understanding of
the limits and mechanisms of compound
electrodeposition in general. Studies of these steps have
been pursued using surface-sensitive spectroscopes and
scanning probe techniques.
757
I. INTRODUCTION
Electrodeposition was one of the first methods used for
the formation of thin film materials, the chromium
electroplating of car bumpers being a classic example.
More recently, the most important area for thin film
growth is in the formation of electronic and
optoelectronic devices. The basic structures of these
devices consist ofa sequence ofthin layers of metals and
semiconductors.
The definition ofepitaxy varies greatly from source to
source, but for the purposes of this article, the following
general description is offered: "Epitaxy means that the
crystallographic order of the film is being significantly
influenced by that of the substrate as a result of some
degree of matching between the two along the interface"
[1].
The epitaxial formation of metals electrochemically
has been studied for a number of years [2-5] and is cur-
rentlyan important research area. However, the epitaxial
formation of metal thin films, although possibly
desirable, is not generally required in device structures,
as most metal films are used as current carriers and their
structure is only of secondary importance. On the other
hand, the structures of semiconducting thin films are
generally of foremost importance. That is, for a
semiconducting laser to work correctly, the layers must
be crystalline and, generally, be deposited epitaxially.
Small amounts of stress can shift the luminescent
properties, and small numbers of defects can provide
recombination centers that ruin a device's efficiency and
provide pathways for degradation. On the other hand,
there are a number of high-quality devices constructed
758
with polycrystalline materials, photovoltaics, for
instance.
For the above reasons, and lack of space, this chapter
will not cover metal epitaxy but is limited to studies of
compound electrodeposition. To further limit the scope
of this chapter, only non-oxide compounds are consid-
ered. The conditions and methodologies for electro-
depositing oxides are generally different from those used
to deposit other compounds. In addition, a description
of the electrochemical formation of thin oxide films
would require discussion of the vast area of corrosion.
Presently, epitaxial thin film deposits of compound
semiconductors are made using techniques such as mol-
ecular beam epitaxy (MBE) [6-9] and vapor phase
epitaxy (VPE) [10-12]. MBE involves deposition in an
ultrahigh vacuum (UHV) environment, where beams
of atoms, ions, or molecular precursors are impinged,
line of sight, on a heated substrate. The growth rate is
controlled by the reactant fluxes to the surface and the
temperature of the substrate. In VPE, an off-shoot of
the general technique of chemical vapor deposition,
pressures in the viscous flow regime are used. The sys-
tems still run under vacuum; however, the gas flows
can be modeled as fluids, between roughly 10- 3 Torr
and atmospheric pressure. Again, the fluxes of precursor
gases and the temperatures of the substrates control
growth.
In the formation ofdevice structures with thin films of
compound semiconductors, a host of materials issues
come up in the design and execution [13]. One primary
issue is the lattice match. In general, different compounds
have different lattice constants, and epitaxy depends on
the minimization of this mismatch. If compounds are to
deposit epitaxially, the misfit must be accommodated. If
the mismatch is low and the deposit thin, it may form
epitaxially with only a small amount of strain at the
interface. However, as the thickness grows, so does the
strain, until it is sufficient to overcome the strengths of
chemical bonds, resulting in the formation of dis-
locations. This point is generally referred to as the critical
thickness [14,15].
There are a number of compounds where close lattice
matches exist, for example, ZnSe on GaAs and HgTe
and CdTe on InSb. However, mismatches can still be sig-
nificant at the 0.1 % level, in some cases. One solution to
dealing with these small differences is to form an alloy
by adding a small amount of a third element. There are a
number of good examples of this, for instance, the com-
pound Hg1-xCd xTe (MCT) is used in the formation of
high-quality IR detectors, among other things. It is
frequently grown on Cd.96Zn.o4Te because the lattice
mismatch with CdTe is too large. Even with a good lattice
Wade et at.
match, problems with differences in thermal expansion
coefficients (TEC) are frequently encountered. If devices
were formed at the temperature for which they are to be
used, this might not be a problem, but most are formed
at elevated temperature, using MBE or VPE, where
matchingTECs is critical.
The main question in this group is: can epitaxial
thin films of compound semiconductors be formed
electrochemically. As mentioned above, the epitaxial
electrodeposition of metals has been investigated and
shown in a number of systems [2-5]; however, elemental
electrodeposition is fundamentally different from for-
ming a compound: compounds have stoichiometry.
Where electrodeposition of a metal usually involves
reduction of a cationic precursor, the mechanisms for
electrochemical compound formation are generally
more complex, and some are discussed below.
Benefits expected from the development of electro-
chemical methodologies for compound semiconductor
formation include the relatively low temperatures used
to form deposits. MatchingTECs would not be a problem
if the deposits are formed at or near room temperature.
In addition, most devices are formed with multiple thin
films of different compounds, and they are increasingly
composed for superlattice structures where thin films of
multiple compounds are alternated with a very short
periodicity. When higher temperatures are used, adjac-
ent layers can interdiffuse. The sharpness of the interface
between layers is an important factor in determining
device function, in some cases. Room temperature device
formation should eliminate most interdiffusion
problems. Other expected benefits from an electrochemi-
cal methodology are that deposits can be formed under
conditions very close to equilibrium, which is generally
not the case with VPE and MBE. The wastestreams from
electrochemical processes can be relatively simple and
easy to deal with. However, the most important benefit
to be had from developing an electrodeposition method-
ology for compound thin film formation is that it should
be orthogonal to the heat-based film formation tech-
niques of MBE and VPE.
The downsides to using an electrodeposition method-
ology are that deposits must be formed on conductive
substrates andin a condensed medium (solvent). The con-
ductivity, and/or type of conductivity, required in a
substrate is a function of the deposition methodology
used, and the limits are not yet clear. As for the use of a
condensed medium, the problems do not appear
insurmountable, given that high-quality thin films are
formed using liquid-phase epitaxy, where a melt of the
elemental reactants is used to form thin films [16]. In
addition, ultra-large-scale integration processing of Si
 Epitaxial Compound Electrodeposition
chips is replete with polishing, etching, and washing steps
in which condensed solvents are used. The highest purity
1 water in the world is produced by the semiconductor
industry. As for the purity of electrochemical reactants,
a purity equivalent to that presently used in gas- and
vacuum-based deposition techniques can easily be had.
The actual concentrations ofreactant ions (ions per cm3)
and proportional concentrations ofimpurities in an elec-
trochemical deposition process are very similar to those
used in gas- or vacuum-based techniques. Presently, the
use of large concentrations of supporting electrolyte
offers the largest challenge, although the concentration
needed is a function of the cell design and with optimal
placement of the auxiliary electrode, very low concen-
trations can be used.
There are hundreds of studies reported and reviewed
in the literature ofthe electrochemical formation of com-
pound semiconductors [17-22]. Most of those studies
have been concerned with II-VI compounds, although
some studies of III-V, IV-VI and chalcopyrite compounds
have also been reported. The overwhelming majority of
compound electrodeposition studies has resulted in the
formation of polycrystalline deposits. The extent of
epitaxy was determined in only a handful of studies.
Single crystalline substrates were seldom used. Most of
the previous work in compound electrodeposition was
carried out with the intent of forming photovoltaics or
photoelectrochemical cells, and some high-efficiency
devices were produced on polycrystalline substrates.
There is, however, a lackofinformation on the conditions
that might lead to the formation of epitaxial deposits,
and so the question can be raised: Is there anything
inherent about electrochemical deposition method-
ologies that precludes the formation ofepitaxial deposits,
given an adequate substrate, lattice match and high purity
reactants?
There are a few basic methodologies that have been
used in the vast majority of compound semiconductor
electrodeposition studies [17-22]. One of the earliest
methods used is referred to here as the precipitation
method, which is based on electrogenerating one of the
components at the substrate surface, which then react
with a species in solution to form the compound [23-25].
The classic example is to use a Cd electrode and anodize
it in the presence of a sulfide solution. CdS then
precipitates on the surface to form a thin film of the
semiconductor. That the deposit is formed by precipi-
tation suggests a low probability of forming an epitaxial
deposit. In addition, the thickness is limited by mass
transfer to or from the substrate surface through the
growing film. The mechanism is similar to passive film
formation in corrosion.
759
The method most practiced was originally
performed by Gobrect et al. [26] in the early 1960s
and developed by Panicku et al. [27] to deposit CdTe
and by Hodes et al. [28] to deposit CdSe in the
mid-1970s. The method involves the use of oxidized pre-
cursors of both group II and VI elements. That is,
Cd+ 2 and tellurite (HTeO{) or selenite (HSe0 3) ions
were reduced simultaneously from the same solution.
This method is referred to here as codeposition. Gen-
erally, a large excess of the group II ion (Cd 2+ in most
studies) was used, whereas the chalcogenide concen-
tration was kept low as a limiting reagent. The potential
maintained for deposition of the chalcogenide was
negative enough for bulk Te formation (an
overpotential) yet positive enough to prevent bulk
deposition of Cd. Thus, Cd was only deposited at an
underpotential, on previously deposited Te. Under-
potential deposition (UPD) is a phenomenon, where
the first atomic layer of one element deposits on a
second element at a potential before, under, that
necessary to deposit the element on itself [29-32]. The
driving force for UPD is the free energy of formation
of a surface compound. By using a potential where only
UPD of Cd occurs, the stoichiometry of the deposit
was regulated. Historically, deposits formed in this
manner have had less than ideal morphology and struc-
ture being described as "cauliflower-like" [33] in some
cases. Recent reports by Lincot et al. [34] have
indicated that epitaxial deposits can be formed using
this method if the deposition is controlled at a potential
just before that needed to form bulk Cd and if adequate
quality single crystalline substrates are used.
There are a number of "hybrid methods" used to form
compounds, where at least one step in the thin film forma-
tion process is electrochemical in nature. A patent by
Kapur et al. [35] serves as a good example. In that
method, ,um-thick films of each element were electro-
deposited sequentially on the substrate. This elemental
sandwich was then annealed, resulting in the inter-
diffusion of the components and their reaction to form
the compound. Other hybrid methods include where
electrochemically deposited layers were annealed in an
atmosphere of a gaseous precursor for another element
to form the compound, for example: a CuIn alloy was
first electrochemically deposited and then annealed in
the presence of H2Se gas to give a thin film of CuInSe2
[36]. Wade et al. [37] developed a method of electro-
chemically generating precursors of III-V compounds,
AIN and GaN, which they subsequently convert to the
compounds by calcination. Electrophoretic deposition
[38], before calcination, can be used to form thin films
with these precursors [39].
760
A number of variations on the above methods have
been tried, including the use of nonaqueous solvents
[40-43] and various deposition potential sequences
[44-48]. In addition, different precursors have been
investigated, for example elemental Se [26], Se02 [26],
SeSO~- [49], SeCN- [50] and H2Se [51] have all been
used as sources of Se in compound electrodeposition
procedures.
Another related methodology is chemical-bath depo-
sition (CBO), a type of electroless plating, where sol-
utions are used but the reducing agents are chemical
rather than electrodes [52-55]. Most of the chemistry
and the techniques used in CBO are closely related to
the electrochemical systems mentioned above.
II. ELECTROCHEMICAL ALE
The remainder of this chapter is devoted to a particular
methodology that is under development in this [22,56-58]
and a number of other laboratories [59-63], referred to
as electrochemical atomic layer epitaxy (electrochemical
ALE or ECALE). It is an electrochemical method for for-
ming thin films of compound semiconductors by dep-
ositing them one atomic layer at a time. That is, the
deposition process is decomposed into a series of inde-
pendent steps, which can be studied individually.
ALE [64-68] is a thin film formation technique that
has been around since the mid 1970s and is based on the
use of surface-limited reactions to form individual
atomic layers of the elements making up a compound.
The surface-limited reactions are used in a cycle, where
each cycle results in the formation of a monolayer of the
compound. By limiting depositions to single atomic
layers, no three-dimensional growth is promoted and
epitaxial deposits should result. Historically, the vast
majority of these studies have involved the use of MBE
or VPE methodologies.
By combining atomic-layer formation via UPO with
the principle of ALE, electrochemical ALE was created
[57,69] most work on electrochemical ALE has been on
the II-VI compounds, especially the cadmium-based
compounds CdTe, CdSe, and CdS [22,56-61,69-83].
Research into the nature of electrochemical ALE has
essentially divided into atomic-level studies ofthe forma-
tion of the first few monolayers of a compound
[59-62,72,73,76,77,79,80,84,85] and studies of the
structure, morphology, and composition of thin films
formed using electrochemical ALE [56,70,74]. Unlike
the methodologies briefly described above, no devices
have as yet been produced using electrochemical ALE.
Wade et a1.
A. Atomic Layer Studies
Studies ofthe formation ofthe first atomic layer are equiv-
alent to studies ofthe UPO ofthe elementon the substrate.
Presently, most of the work has been performed on Au
substrates, as they are relatively well understood, inert,
and reusable. The UPO of Cd [86-93] has been studied,
and some scanning probe work has recently been pub-
lished [94]. There are considerably fewer studies of the
structures formed by Zn UPO [95,96], and studies of
chalcogenide atomic layers are limited as well. In
atomic-level studies of electrochemical ALE by this
group, chalcogenide atomic layers have, in general, been
deposited first, due to their increased stability over the
corresponding group II atomic layers. The chalcogenide
atomic layers have then been used as substrates in the for-
mation ofatomic layers of the group II element. Recently,
however, Gichuhi et al. [97] suggested that better deposits
of CdS may result if a full monolayer of Cd is first
deposited on the surface before the first atomic layer ofa
chalcogenide.
The surface chemistry of atomic layers of chalco-
genides formed using UPO has proven to be diverse and
interesting [79,80,98-102]. The lowest coverage structures
(between 0.2 and 0.3 monolayers [ML]) are usually simple
arrays of independent atoms. As the coverages are
increased, as atoms are pushed together, they start to
form chains, clusters, and rings. For instance, eight
membered rings have been observed to form in atomic
layers of selenium [99,100] and sulfur [103,104] on Au
surfaces. One characteristic of chalcogenide UPO
appears to be slow deposition kinetics, under the con-
ditions being used, with some peaks corresponding to
the formation of atomic layers [98-100] actually appear-
ing at overpotentials rather than underpotentials. A
consequence of the slow deposition kinetics is a lack of
deposit homogeneity, given that for a particular depo-
sition time and potential, several structures may exist
simultaneously on the surface.
Figure 1displays the voltammetry for deposition of Te
from a solution containing 0.25 mM HTeOi on an
Au(lll) electrode. Figure 2 is a low energy electron
diffraction (LEEO) pattern taken after emersion of the
electrode at 0.19 V [102], just after the first UPO feature
in Fig. lao The hexagonal symmetry of the LEEO pattern
is clearly visible. The integral beams, corresponding to
the Au(lll) substrate, are not visible at the energy used
in Fig. 2 but consist of a hexagon of spots rotated by 30°
from the clusters ofspots in the figure, just outside the dis-
played area. The visible spot clusters are grouped around
positions characteristic of a (~3 x ~3)R30° pattern. In
the case of a simple (~3x~3)R30° pattern, however,
 Epitaxial Compound Electrodeposition 761

(a) (b)

~f------j'-----~----A""-=::::::::==-----1
:::J
u
10 !JA

-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4

+ 10~ Potential (V YS. Ag/AgCl (3M»
E
~f----_L""7"-=~~----:::====:::===~ (c)
u

+
\ c
~
:::J
U
10 !JA

-0.2 0.0 0.2 0.4 0.6 0.8 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4
Potential (V vs. AgiAgel (3M)) Potential (V YS. Ag/AgCl (3M»

Figure 1 Cyclic voltammograms oftellurium and cadmium deposition on Au(lll). Scan rate, 5 mY/so (a) 0.25 mM HTeOi /20 mM
H2S04 (pH 2.1). (b) 20 mM CdS0 4120 mM H 2S0 4 (pH 2.1) on 0.5 monolayerTe on Au(lll). (c) 20 mM CdS0 4120 mM H 2S0 4 on
clean Au(lll).

six single spots would be visible around the central specu-
lar beam. In Fig. 2, a hexagon of spots is visible, where
the single ..}3 spots would be, in what has been referred
to as a split-spot pattern. However, another way to
characterize this pattern is to notice that the individual
spots are aligned in the same direction as the integral
beams, in the n-by direction, and that the distance
between the spots is one twelfth that between integral
beams, suggesting a (12 x 12) unit cell. Most beams that
should be present in a full (12 x 12) pattern are missing. It
is likely that a lot of the 12 x 12 spots were of a relatively
low intensity, given the large size of the unit cell and the
diffraction conditions. The ..}3 symmetry of the surface
was so strong that it accentuated only those (12 x 12) spots
near the ..}3 positions.
Figure 3 is an in situ STM image oftheTe structure cor-
responding to the surface that produced the pattern in
Fig. 2. The structure has a large periodicity (12 x 12) unit
cell, delineated by darker lines, running through the
image. However, within each (12 x 12) unit cell, the atoms
appear in a hexagonal arrangement with spacings con-
sistent with a (..}3 x ..}3)R30° array and in good agree-
ment with the ex situ LEED image (Fig. 2). A structure
proposed to account for the coverages determined
electrochemically, the LEED patterns and the STM
images, is shown in Fig. 4. The nature of the dark lines,
the (12 x 12) periodicity, is currently under discussion. A
structure previously proposed by this group based on
phase boundaries between different ..}3 domains
[102,105] appears unrealistic after closer inspection, as
the lines ofTe atoms would shift at the phase boundaries,
which they do not appear to do. A different structure has
been proposed by Hayden et al. [62], suggesting a higher
coverage of Te than the one third expected in a simple
762
Figure 2 LEED pattern taken for an Au(lll) electrode. on
which about one third ML of Te has been deposited. Only
fractional order beams shown, with clusters of spots near the
..)3 positions. 19.6 eY.
(.j3 x .j3)R30° structure. Higher coverageTe structures,
with a very similar appearance, have been observed under
some conditions by this group. At present it appears that
a sequence ofsimilar structures are formed as a function
ofcoverage. The origin ofthe darker lines is still not clear,
however. There is some evidence that a reconstruction
in the Au surface may be responsible, and the structure
proposed in Fig. 4 suggests that, however, it is still under
study. A more likely explanation is that the dark lines are
the result of a moire pattern, a mismatch between the
substrate and the Te atomic layer.
Given that ordered epitaxial atomic layers ofTe can be
formed, the second step in the formation ofa monolayer
of CdTe is deposition of a Cd atomic layer on top [79,80].
Figure lb is the voltammetry for Cd deposition on a
Te-coated Au(lll) surface (Fig. 4). For comparison, Fig.
Ie is the equivalent voltammetry for Cd deposition on
Wade et al.
0.3 ...
15.0 0.1 ...
10.0 0.0 ...
5.0
o
o 5.0 10.0 15.0
....
Figure 3 Height mode in situ STM image of the one third
coverage Au(l1l)(l2 x 12)-Te in 0.25 mM HTeOi (pH 2.1) at a
potential of 0.2 Y. Imaging parameters: Vbias = -24.4 mY,
setpoint: 5.00 nA.
Figure 4 Proposed structure of Au(1ll)(l2 x l2)-Te. The
structure is based on reconstruction of the Au surface, where
rows of atoms are removed and triangles of the resulting atoms
center themselves in the resulting space. Te atoms form a rela-
tively homogeneous ..)3 over the whole surface.
the Au( Ill) electrode, without Te. A single underpotential
deposition feature is observed in each (Fig. lb and c).
The differences are that Cd deposition on clean Au
appears more reversible, starting sooner, and results in a
very low broad peak, compared with that on theTe atomic
layer. Small amounts of Cd are deposited at significantly
more positive potentials on the clean Au surface than on
the Te-coated surface, suggesting that the Cd is more
stable on clean Au. Overall, more Cd is deposited at an
l
Epitaxial Compound Electrodeposition
underpotential on theTe-coated surface than on the clean
Au surface.
Two different LEED patterns were observed for
Au(lll) in ex situ studies of Cd deposition on Te atomic
layers [79,80], a (3 x3) and a (.j7 x .j7)RI9.l Structures
0.
were proposed, consistent with the observed LEED
patterns, coverages from Auger spectroscopy and
coulometry, and with some preliminary ex situ STM
images. The coverages of the two structures appeared
very similar, 4/9th ML of each element for the (3 x3)
structure and 317th ML of each for the (.j7 x .j7)RI9.l °
structure. The higher coverage (3 x3) structure was
observed when slightly higher coverages of Te and Cd
were deposited, as might be expected [79,80]. Figure 5 is
an in situ STM image of the CdTe monolayer. A hexag-
onal deposit is clearly visible, with a periodicity consist-
ent with a (3x3) unit cell. A structure proposed to
account for this image is shown in Fig. 6. The structure
is like a slice from the zincblende structure of bulk CdTe,
with twice the Te- Te distance in CdTe coincident with
three times the Au- Au distance ofthe substrate, account-
ing for the (3 x3) unit cell. The deposit thus does appear
epitaxial, but with the CdTe layer significantly com-
pressed, due to a 6% lattice mismatch. An equivalent
structure has recently been proposed by Hayden et al.
[63], and similar structures have been proposed by this
group to account for CdSe monolayers formed on Au(lll)
[77]. Related atomic-level studies of the electrochemical
formation of compound monolayers include studies of
CdTe on other Au low index planes [63,79,80,102], CdSe
[76,77], CdS [60,72,106], and GaAs [85,107].
10.0 0.5
I
0.2 _
7.5
0.0 _
5.0
2.5
o 2.5 5.0 7.5
Figure 5 Height mode in situ STM of the 4/9th coverage
Au(l1l)(3 x 3)-CdTe in 1 mM CdS04120 mM H 2S04 (pH 2.1)
at a potential of -0.6 V. Imaging parameters: Vbias = -14.7 mY,
Y, setpoint: 5.00 nA.
763
B. Thin-Film Formation via Electrochemical
ALE
Formation ofcompound thin films using electrochemical
ALE have been proceeding for several years [56,70,74].
Those studies have been tied to development of an
automated electrochemical flow deposition system, as
any manual method quickly becomes tedious. The system
presently used is computer controlled and repeatedly
runs a program consisting of the steps needed to form a
monolayer of the compound, one cycle. Figure 7 is a
schematic diagram of the apparatus presently being used
to deposit thin films by electrochemical ALE. The com-
puter is interfaced to a series ofsolenoid valves, peristaltic
pumps, a potentiostat, and an electrochemical cell. A
number of cell designs have been used and several have
advantages. Presently, a thin-layer flow cell is being used
and a diagram is shown in Fig. 8. The flow volume under
the substrate is a thin rectangular channel, with a trans-
parent indium-tin oxide (ITO) auxiliary electrode as the
opposite wall of the channel. This configuration avoids
problems with uncompensated resistance yet allows vis-
ual monitoring of deposit growth and trapped bubbles
n_
Figure 6 Proposed structure of Au(111)(3 x 3)-CdTe. Open
circles represent Au substrate atoms, gray circles are the Te
atoms, and the black circles are the Cd atoms. Both Cd and Te
are present at 4/9th coverage.
764 Wade et aI.

plexiglass BAS reference

substrate ,-------~ ...--i

back

~
N,

-=-~l
-, II I go"""
'III inlet-+ -outlet
1 11\

-4I
I
I Computer I
side

gasket_~~'i~l°rt
inlet..... R~ [~ i
6f
~
))==:::=.~ .... outlet

~
I I

Figure 7 Schematic diagram of automated flow cell depo-

sition system.
L
r
ITO counter

and illumination during deposition, if desired. The cavity

is defined using a gasket material, the thickness of which top
determines the cavity thickness. Gaskets ofTeflon, Viton,
and silicon rubber have all been used. Figure 8 Diagram ofelectrochemical thin-layer flow cell.
The substrates presently used are Si(lOO) wafers onto
which Au has been vapor deposited. Before Au
deposition, a thin layer of Ti is deposited to aid in (a)
adhesion. Optically, these substrates appear as Au Te solution fill at Cd solution fill at
mirrors. The substrates are large, easy to use, and rela- open circuit open circuit
tively inexpensive. Scanning probe studies of the films, -0'7V-~!,;--~ i--~ i--~ ~--I
however, reveal them to be a series of small 50-nm Au -O.6V-- \_ I rl I ,_ I II I \
'"'I ~ I ...... \ I l..
\~ I ~l I
bumps on the surface, making questions of epitaxy hard
to answer. (b) Cd deposition
current at -0.7 V
~ 'j
I
";
I

~
Most studies performed using the instrument shown
in Fig. 7 concerned the growth of CdTe [56,70,74], Te deposition ; I

although some deposits of CdSe, CdS [56], and ZnS [108] current at -0.7 V ~l ~
have been formed. At present, most deposits are formed ~I : ;1 ; ;1\
using 200 cycles, and the cycle program for CdTe is shown : : 1~ : :~
I ," I I'
in Fig. 9. The cycle in Fig. 9 is relatively simple compared I I \. I I '.
, I I I I
~
with cycles previously used, involving only two solutions: 100JJA- I I I
I 1
I
Pl
I •
_
I

one for the Cd and one for the Te. The solutions are OJJA-
I I
- ... •
I I
• - I
I I
__ I
I

pumped into the cell at open circuit, at times sufficient 120 s I

to exchange the previous solution, and then held at the
deposition potentials for 20 s without pumping. The
substrate is then allowed to go open circuit again, whereas
the solutions are exchanged and then the potential is held
for 20 s at the second deposition potential, without
pumping, to complete one cycle. Ideally, the currents
Figure 9 (a) Diagram ofpotential vs. time and (b) current vs.
time. In a, the deposition potentials were both -0.7. The poten-
tial drifted positively at open circuit, during rinsing. The first
cycle is shown with solid lines, and two more cycles are shown
with dashed lines.

l
 Epitaxial Compound Electrodeposition
should die out as the atomic layers are completed;
however, the deposition represented in Fig. 9 was
1 performed in the light, which appeared to catalyze
hydrogen evolution.
A typical CdTe deposit appears white or gold under
visual inspection. Figure 10 displays a glancing angle
-j x-ray diffraction (XRD) pattern for the deposit. A peak
\
consistent with the 111 plane of zincblende CdTe is
evident. Ellipsometric measurements on these deposits
indicate them to be 77-nm thick, which is consistent with
the 78 nm expected for formation of 200 monolayers of
CdTe, normal to the III plane.
CdTe growth as a function of the number ofcycles has
the linear dependence expected. That is, the deposit
thickness is controlled by the number ofcycles rather than
the potential, time, fiuxetc. InanALE process, controlled
by surface limited reactions, doubling the number of
cycles doubles the thickness of the deposit. Studies of
deposits formed with as many as 1000 cycles have been
performed and show this linear dependence [56]. Figure
11 is a diagram ofthe coverages of Cd and Te as a function
of the potential used to deposit the Cd atomic layers and
also shows behavior expected for deposits controlled by
surface limited reactions. That is, generally, if an
electrodeposit is formed at currents well below the mass
transfer limit, an exponential dependence would be
expected, for an activation controlled process.The depen-
dence on potential in Fig. II is clearly not exponential.
No deposit is formed at potentials positive of -0.5 V, as
the potential is too high for Cd to deposit, even at
underpotential on theTe. Since there is no Cd deposition,
noTe will deposit, and no CdTewill form. At more negative
1
18,000
16,000
14,000
.l!l12,000
c 10,000
g 8000
o 6000
4000
2000
o 0'---t----+---+---+---t----t----+----1e---J
20 30 40 50 60 70
28
Figure 10 X-ray diffraction pattern for CdTe films formed
with 200 cycles. A glancing incidence source at 2° was used with
I-s count times, per step, at O.OSO per step. The peak at 24 corre-
0
sponds to the III plane of zincblende CdTe. The peaks at 40
and 47° are a mixture of Au and CdTe planes, whereas the peak
at 66° is a Au peak.
1
765
potentials, between -0.55 and -0.65 V, a short plateau is
evident where the coverage is constant. Between -0.65
and -0.75 V, the coverage increases by half, but the
deposits still appear stoichiometric. Below -0.75 V, the
coverages start to increase rapidly, with the stoichiometry
becoming Cd rich, as some bulk Cd deposition begins.
Based on surface morphology and stoichiometry, the best
deposits were those formed in the short plateau region
(-0.55 to -0.65 V) [70]. Each step in the deposition cycle
can be used as a separate variable. The dependence of
deposit structure on these variables was the subject of a
previous study [70]. Note that a potential of -0.7 V was
chosen for the new cycle (Fig. 9), as the deposition pro-
gram differed fundamentally from that used in the pre-
vious studies just described.
In addition to studies of cycle variables, such as dis-
cussed above, there are a number ofother problems being
investigated in an effort to improve reproducibility,
deposit quality, and to address questions of epitaxy.
Presently, the most urgent issues are decreasing oxygen
levels in the cell, optimizing the cell design, and
improving substrate structure.
Reproducibility is a necessity for studies ofthis type. A
correlation has been shown between efforts to exclude
oxygen and reproducibility in deposit thickness and
morphology. All solutions are extensively degassed
before deposition; however, when the solutions leave the
bottle, they travel through tubing, a peristaltic pump,
and several valves.Voltammetric studies of oxygen levels
Q) 15
C)
~
~
010
()
~ ---- Cd - - Te
~
Q) 5
c:::
-0.85 -0.8 -0.75 -0.7 -0.65 -0.6 -0.55 -0.5
Cd Deposition Potential (V)
Figure 11 Graph showing the electron probe microanalysis
(EPMA) signals for Cd and Te from a sequence ofdeposits, each
made with 200 cycles ofelectrochemical ALE, as a function of
the Cd UPD potential. The EPMA signals have not been con-
verted to absolute coverages, but they are proportional to
coverage. The best deposits where observed for potentials
between -0.55 and -0.65 V.
766
in the cell clearly indicated that significant amounts can
be picked up. The oxygen appears responsible, under the
conditions used, for the systematic loss of atomic layers
and irreproducibility in deposit thickness. It is not clear
what factors make the problem intermittent, possibly
how worn the hose in the peristaltic pump is, or the vari-
able presence of small leaks at the fittings. One solution
was to enclose the pumps, valves, and cell inside a small
purged box and to use double tubing. That is, reagent
tubes were run through a second larger diameter tube that
connected the reagent bottle to the purged box. In that
way, gas was used to degas the solutions, then bathed the
reagent tubes as they ran into box, and then served to
purge the box as well. The resulting oxygen concen-
trations in the box were measured at 10 ppm or below.
Under those conditions, very good reproducibility was
achieved.
The electrochemical cells used in these studies have
gone through a number ofmajor modifications, and there
is still a lot ofroom for improvement. In principle, the sol-
utions should flow in a laminar sheet over the deposit
(Fig. 8). Each solution should be rinsed from the cell in
an efficient manner, replaced by the next reactant
solution. Nonlaminar flow has been shown to greatly
reduce deposited amounts, such as at the entrance to the
cell where the solution turns a corner. In addition, there
are edge effects where solution exchange is greatly
impeded, and bubbles get trapped in the cell and disrupt
flow patterns. The bubbles appear to come from the sol-
utions or small leaks at the fittings. Overall, however,
when there are no bubbles, the flow is laminar, and far
from the gasket the deposits are very smooth and
uniform.
Substrate structure is ofprimary concern in studies of
epitaxial thin film formation. As described in the
Introduction, the lattice mismatch results in stress when
a film is deposited. This stress, in turn, determines the
type and number ofdefects that will form and the quality
of epitaxy. Au electrodes have been used extensively in
these studies because of their robustness, although there
has been some work on ITO [108] and on Ag single
crystals by other workers [106]. The electrochemistry of
Au is reasonably well understood, and there are a number
ofcleaning procedures in the literature that do not require
DHV system. However, it is not well lattice matched with
CdTe [a 6% mismatch on Au(lll)] or other compounds.
Further, as discussed above, the Au on Si(IOO) substrates
presently used are quite rough on the nm scale.
The net result of using substrates with nm scale
roughness is a commensurate roughness in the deposited
films. Differentiating between defects due to substrate fea-
tures (steps and kink sites), lattice mismatch, or the depo-
Wade et al.
sition process is nearly impossible. Ideally, an atomically
flat Au surface would be used, and the evolution ofdefects
could be imaged and interpreted. There are a number of
ways to obtain good-quality atomically flat Au surfaces,
forexample, Au on mica [109-112], on glass, and on quartz
[113]. An added complexity of the studies described here,
however, is that the substrates are placed in a flow cell with
a gasket and subjected to hundreds of rinses. So where
Au on mica may hold up well for in situ STM studies, it is
hard pressed to survive 200 cycles of electrochemical
ALE. However, those substrates are presently under study.
An Au substrate of particular interest is referred to as
template-stripped Au [114]. Template-stripped Au makes
use ofthe Au atoms in contact with the mica ofa piece of
Au on mica. That is, the exposed Au face is glued to a flat
substrate, like a piece of glass, and the mica is then
removed, revealing the surface that was in contact with
the mica. Recently, good results have been had with
flaming Au that has been vapor deposited on glass
substrates. In general, our experience has been that as
the substrates get smoother, as the grain size ofthe Au gets
larger, the deposit morphology improves com-
mensurately. In addition, as the number of cycles
increases, no noticeable increase in surface roughness
occurs, as expected for a layer by layer growth mode.
III. CONCLUSIONS
In conclusion, compound semiconductors can be
electrodeposited and they can be electrodeposited
epitaxially. This has been shown by a number of workers
and recently by high-quality transmission electron
micrographs, obtained by Villegas [] 15] on CdTe deposits
formed by electrochemical ALE. Luminescence has
recently been measured for as deposited CdTe, formed
by electrochemical ALE, as well. Questions remaining
concern the rules and conditions under which epitaxy
can be achieved in a compound electrodeposition
process. Codeposition has been used to form epitaxial
deposits under some conditions, and significant
improvements are continuing. At present, codeposition
is used in a commercial process to form high-quality
CdTe photovoltaic cells. Electrochemical ALE is being
developed, in a number of different laboratories, as it
offers increased control over the deposition process, by
breaking compound deposition down into a series of
individually controllable steps. In addition, breaking up
the deposition process allows examination of the
mechanisms of compound electrodeposition in general.
Recent results include the electrodeposition of the III-V
compound InAI' from aqueous solutions for the first time,
using electrochemical ALE [116]. The issues facing this
'·t
Epitaxial Compound Electrodeposition
process are much the same as those that face development
of a VPE process. Good-quality deposits have been
L formed using electrochemical ALE, consistent with the
qualityofthe substrates used. Layer-by-Iayer growth con-
trolled by surface limited reaction has been shown, as
expected for an ALE process.
-t
\
ACKNOWLEDGMENTS
Supported by the National Science Foundation, under
Grant No. DMR-9017431 and in part by the Navy, Office
of the Chief of Naval Research, under Grant No.
NOOOI4-91-J-1919. Their assistance is gratefully
acknowledged.
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~ 43
Interfacial Electrochemistry of Conductive Oxides for
Electrocatalysis
Sergio Trasatti
University ofMilan, Milan, Italy
t
ABSTRACT
The electrochemical properties of conductive transition
metal oxides for electrocatalysis are illustrated and
discussed. After a description of the preparation proce-
dure and the resulting morphology, the structure of the
oxide-solution interface is discussed in terms of surface
acid-base properties and point of zero charge-structure
correlation. The use ofvoltammetry as an in situ electro-
chemical spectroscopy is illustrated with specific
examples. Electrode reactions such as oxygen, chlorine
and hydrogen evolution, oxygen reduction, and organic
oxidation are discussed in terms of mechanism and
electrocatalysis. A generalized gas evolution reaction
mechanism is put forward. Stability problems are finally
i scrutinized.
!
I. INTRODUCTION
! in chior-alkali cells to replace graphite anodes that were
Oxides are intuitively thought of as insulating or
semiconducting materials. This is not the general case.
Transition metal oxides, which can exist in various
valency states, exhibit metal-like conductivity if half-
filled d-bands are present [1]. In other cases, due to the
procedure of preparation, heavily nonstoichiometric
oxides are obtained whose conductivity is only margin-
ally lower than that ofmetals [2]. These oxides can be used
as electrodes even for practical applications, because
the eventual ohmic drop across thin films is negligible [3].
This is the principle of "activated"electrodes [4], in which
1 ,
a support made ofan inert inexpensive material is coated
with a thin layer (a few .umeters) of an active generally
769
more expensive compound that is not available anyway
in massive form.
Transition metal oxides, precisely for their ability to
switch between different valency states, possess appreci-
able catalytic (and electrocatalytic) activity, which makes
them versatile materials for chemical and electrochemi-
cal reactions. For the same reasons, these oxides exhibit
remarkable stability toward chemical and electrochemi-
cal attack in appropriate conditions. The term of
"insoluble oxide electrodes" is often used referring to
these properties. But the term most known for activ-
ated oxide electrodes is definitely that of DSA ®
(dimensionally stable anodes) related to the origins of
their introduction into the electrochemical field [5].
Although Pb02, Mn02, and Fe304 had been used in
electrochemistry earlier, conducting oxide electrodes
became popular in electrochemistry as they were used
subject to heavy wear [6,7]. The name DSA originated
precisely from the absence of wear, which resulted in a
technological breakthrough [8].
As they were introduced, there was no fundamental
background for their properties, and the first attempts
to interpret their behavior rested on a large amount of
speculation based on current concepts. Fundamental
research came later to support the observed perform-
ances and to develop on a more scientific basis a strategy
to identitY the parameters for their properties so as to
optimize their performances. The first paper in the open
literature appeared in 1971 [9] and showed that the
approach to the study of the electrochemical properties
770
of these oxides required an additional interdisciplinary
background of solid-state chemistry, surface chemistry,
catalysis, and materials science.
Fundamental research has developed exponentially
after the first paper, and an avalanche of papers is now
available in the literature. Nevertheless, the field is still
open to new developments and improvements because
the number of parameters behind the performances of
these materials is exceptionally high. The field has been
organized in three different steps by the present author.
A two-volume book was edited in 1980/81 that covered
the literature exhaustively for all classes ofoxide materials
[10,11]. Later, a chapter issued in 1994 in a multiauthor
book [12] reviewed the literature up to the end of 1991.
Finally, a review specifically devoted to the interfacial
properties covered the field up to 1995 included [l3].These
three monographs still constitute the most comprehen-
sive work in the field of oxide electrodes, and the reader
is referred to them for a wider background. The aim ofthis
chapter is therefore to give a synthetic but complete view
of the field in the light of the last developments, with
special mention ofthe most recent results.
A. Classes of Oxides
DSA-type electrodes consist of a mixture of transition
metal oxides, some of which are electrocatalytically
active, whereas others are additives aimed at improving
selectivity and stability by synergetic action. The former
are usually conducting, whereas the latter are mainly
insulating or semiconducting.
Many oxides have been investigated, but most of the
interest has focused on dioxides, spinels, perovskites,
and pyrochlores. Typical examples are RuOz and IrO z
(active), TiO z, SnOz, ZrOz, and CeOz of the first; C0304
and NiCoz04 ofthe second; doped LaNi0 3and LaCo03
of the third; and PbzRu(or Irh07-y of the fourth class.
But other compounds such as PdO x , NiO~, CrZ03'
Rh z0 3, TazOs, etc. should also be mentioned. Readers
are referred to the previous reviews for a more complete
picture.
II. PREPARATION OF OXIDES
Oxides can be prepared in various ways, but the most
applied procedure is by thermal decomposition ofappro-
priate precursors dissolved in suitable solvents and
spread on a metallic support [14]. Nonstoichiometric
structurally defective oxides are generally obtained that
have to be carefully characterized. Bulk and surface,
physical, and chemical analyses provide outstanding
pieces of information that are of essential help for the
Trasatti
interpretation of electrocatalysis and stability per-
formances. The most used characterization techniques
are summarized elsewhere [12].
The nature of the precursor and the temperature of
calcination appear to be the primary factors influencing
the properties of the resulting oxides. Common pre-
cursors that have been used for some popular oxides
are listed in Table 1. Particle size, nonstoichiometry, and
morphology of the layer are strongly influenced by the
nature of the precursor. For instance, chlorides as pre-
cursors leave residual chlorine in the oxide lattice [15],
which nitrates do notVariously distorted lattices can thus
result [16]. Moreover, the range of temperature where
decomposition takes place depends on the precursor
[17].
The temperature of decomposition affects both the
chemical composition and the crystallinity of the layer
[18]. Nonstoichiometry is usually higher at low temper-
atures. More ordered lattices are obtained at higher
temperatures. In general, poorly crystalline to amorph-
ous layers are obtained at low temperature, which imparts
higher activity but lower stability to the oxide.
Other procedures have also been applied, although the
outcome is not always satisfactory. Spray pyrolysis [19] is
also a thermal decomposition method, but the precursor
solution is sprayed onto the support heated at the
decomposition temperature. The deposition can be more
reproducible but the impact gives problems of adhesion.
Plasma-spray [20] and reactive sputtering [21] have been
suggested as alternatives. The latter, however, normally
produces smooth stoichiometric surfaces and is thus
more suited for the preparation of reference oxide
samples.
Table 1 Common Precursors for the Preparation of Some
Oxide Electrodes by Thermal Decompositiona
Oxides Precursors
RuOz RuCl} . xHzO, Ru(NO)(N0 3h
IrOz IrCh . xH 20, H zlrCl 6 . 6H zO
MnOz Mn(N0 3)z . 4H 20
C0304 Co(N0 3h . 6HzO, CoC0 3 . xHzO
NiO Ni(N0 3h . 6H zO
TiO z TiCI3, TiCI4, Ti(OR)4
SnOz SnCl z . 2H zO, SnCI 4
PdO z PdCb
PtO x H zPtC1 6 . xHzO
RhO x RhCl 3 . xHzO
ZrOz ZrCI 4, ZrOClz, ZrO( N03)z
aSee the specific literature for composite oxides such as perovskites and
pyrochlores.
l
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis
One ofthe aims ofelectrocatalysts is to possess a large
working surface area. Therefore, it has been proposed
[22,23] to apply the so-called sol-gel procedure [24] to pre-
pare oxides for electrocatalysis.The method is used to pre-
pare catalysts with small particle size, and it has been
believed that these features could be useful also for elect-
rodes. The procedure in the end consists in obtaining a
metallorganic precursor that decomposes atlow tempera-
tures, thus producing fine particles. However, the method
has not turned out particularly useful for electrodes [25].
A. Mixed Oxides
In the case ofmixed oxides, solid solutions or phase separ-
ation occur depending on the nature ofthe oxides and their
relative consistency. Combination of auger electron
spectroscopy, (AES), x-ray photoelectron spectroscopy
(XPS), and inductive coupling plasma emission spectro-
scopy (ICPES) has revealed interesting cases of surface
enrichment that are summarized in Table 2. However, it
should be taken into account that the extent of surface
enrichment is expected to depend on the many variables
of preparation: temperature of calcination, nature of the
precursor, and procedure of preparation. In this respect,
itis necessary to ascertainwhetheror notthenominal com-
position is maintained in the bulk because in some cases
oxide yields lower than 100% have been reported [26].
Ternary oxides have also been prepared to investigate
the effect of replacing one component with another one.
Examples of ternary oxides can be found later on in the
various tables.
B. Morphology of Oxide Layers
When examined by scanning electron microscopy, oxide
layers very often exhibit a characteristic "cracked-mud"
look caused mainly by thermal shocks in the materials
[28]. At the same time, the use of other techniques to
investigate structural features reveals that the layer has
the structure of a compressed powder [12]. The layer as a
whole can be envisaged as including pores. However, the
"compact" part is in fact composed by crystallites
Table 2 Surface Segregation in Mixed Oxides
Mixed oxides Surface enrichment References
RuOz +IrO z Ir 27,28
C0304+RuOz Ru 29
IrOz +SnOz Ir 30,31
RuOz +ZrOz Zr 32
IrOz + TazOs Ta 33
RuOz+TiO z Ti 34
RuOz +PtO x Pt 35
771
separated by grain boundaries. Therefore, it is possible
to distinguish a macro-surface and a micro-surface. The
latter is less accessible to the environment. The ratio
between the two gives what is called "porosity:' However,
the actual value ofthis property depends on the technique
to measure the surface area [36].
III. THE OXIDE-SOLUTION INTERFACE
In a vacuum, oxide surfaces expose two main sites: metal
and oxygen ions. Oxide surfaces are reactive toward water
in the gas phase [37,38], especially because of the strong
Lewis acidity of metal ions. This property can be partly
or totally quenced by high-temperature treatments,
which may make an oxide surface hydrophobic.
Hydrophobicity is expected to be weaker at milder tem-
peratures of calcination.
As oxides are brought in contact with an aqueous sol-
ution the surface will become covered by a "carpet" of
OH groups [39] whose concentration will depend on the
nature of the oxide and its specific crystal face. The first
layer of chemisorbed water molecules will induce some
extra structuring in the adjacent liquid phase through a
network of preferentially oriented hydrogen bonds. The
ordered structure will penetrate more or less deeply into
the liquid depending on the properties of the first water
layer [40,41].
The mechanism of surface hydration can be easily
proved by detecting hydrogen with a nuclear analytical
technique [42,43]. If just left in the ambient atmosphere,
a profile of hydrogen can be found inside an oxide layer,
with a gradient that depends on the time of exposure. If
placed in water, oxides become rapidly hydrated
throughout the whole thickness. In this respect, some
oxides are more "hydrous" than others. For instance,
C0304 absorbs water poorly, whereas IrOz and RuOz
behave similarly, although in the case ofIrO z the amount
ofwater absorbed is distinctly higher.
Dry and hydrous oxides can be placed at the extreme
ends of a series of compounds with the same MIO ratio
but with variable proton content. Proton penetration
takes place along preferential pathways such as grain
boundaries, pores, cracks, etc. Thus, the hydrous behavior
is more a consequence of the texture than of its chemical
structure. Hydrous oxides are ultimately permeable to
protons, whereas dry oxides are not.
A. Surfaces Acid-Base Properties: Point of
Zero Charge
The OH groups on the surface of oxides in aqueous sol-
ution behave as weak acids or weak bases [38,44]. Differ-
772 Trasatti

ent sites may be present on the same surface, depending OXIDE SOLUTION
on the coordination in the lattice. Ifamphoteric behavior
is assumed for simplicity, surface OH groups can give acid - - - -. oxygen

//~~&
dissociation:
-M-OH + OH- --+ -M-O- + H20 (1)

or basic behavior:

-M-OH + H+ --+ -M-OHi (2)

Equations (1) and (2) illustrate the main charging mech- ~®

anism of oxide surfaces. The difference with respect to (±) lP--
'8 \
hY'(fogen
metals is that no excess or deficiency of electrons are
apparently involved. Thus, even the physical separation " \
I
ofthe oxide phase from the liquid phase is hardly identifi-
able because OH species are part of both phases simul-
taneously (Fig. 1). Due to the presence of charged sites,
o / I

an electric potential difference develops that is mainly a
function of the solution pH. Oxide surfaces behave as
nonpolarizable interfaces whose electrical state is con-
trolled by the composition of the solution. The pH at
which the surface charge is zero is called the point of zero
charge (PZC). * At pH <PZC the surface is positively
charged, at pH> PZC it is negatively charged.
Because of the mechanism of surface charging, the
open-circuit potential of oxides is sensitive to pH. This
has prompted the study of pH sensors based on these
materials, particularly Ir02 [45] and Pd~x [46]. If
protons are constituents of both phases, the solid and
the aqueous solution, a Nernstian response is an obvious
consequence of the interfacial equilibrium involving H+
ions. However, in most oxides protons are not con-
stituents ofthe bulk oxide; moreover, ifthe oxide is poorly
conducting, an additional potential drop may arise as a
consequence of the onset ofa space charge [38].
In the case ofconducting oxides, due to their metallic
or quasi-metallic conductivity, space charge effects can
be neglected to a first approximation. Nernstian behavior
has thus been assumed for RU02 [47] Ir02 [48], C0304
[49], Mn02 [50], and Zr02 [51]. Deviations occur if the
surface is no longer completely insoluble. Nevertheless,
there is no general consensus on the Nernstian response
of precious metal dioxides. Super-Nernstian behavior
has been suggested [52] on the basis of voltammetric
measurements, which are, however, not representative
ofan open-circuit behavior.
* The acronym PZC is sometimes used in electrochemistry for
"potential of zero charge," quite a different quantity. However,
the IUPAC-recommended symbol for the latter is £a=O,
whereas PZC is customarily used in colloid and surface
chemistry.
CC(±)&
!
Ci Cd
Figure 1 Sketch of an oxide-aqueous solution interface
showing water molecules, metal ions, and protons. The solid
particles belong essentially to the solid phase, whereas the
empty particles are part of the liquid. The mechanism of
charging is highlighted. The equivalent electrical circuit is also
indicated.
B. Point of Zero Charge
The PZC is an intensive quantity, i.e., it does not depend
on the extension ofthe surface area ofoxides. At the same
time, it is extremely sensitive to the surface structure.
Thus, the measurement ofthe PZC can be a key approach
to separate electronic and geometric effects in electro-
catalysis, as suggested by the present author [53,54].
The PZC can be measured by potentiometric titration
that gives the pH of zero surface charge, or by electro-
phoretic measurements that provide the pH of zero
charge on the Outer Helmholtz Plane (OHP) of the
double layer (isoelectric point, IEP). In the absence of
specific adsorption, PZC == IEP. Otherwise, they differ
according to well-established patterns depending on cat-
ion or anion adsorption.
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis
There exists an extensive literature on the surface
acid-base properties of oxides in solution because this
area is at the border with colloid chemistry [55,56]. The
field has been exhaustively reviewed by the present
author with special emphasis on electrocatalytic oxides
[12,13,38]. Extensive tables of PZC values are available
elsewhere [13].
A typical family of charge-pH curves obtained by
potentiometric titration is shown in Fig. 2. The common
intersection point identifies the PZc. The tangent to any
point ofthe curves measures the capacitance ofthe inter-
face, provided the potential-pH response of the surface
is known. The resulting capacitance-pH curve resembles
that of a diffuse layer around the conditions of zero sur-
face charge [12]. Thus, it has been proposed [47] that
the Gouy-Chapman-Stern-Grahame (GCSG) double-
layer model [57] is applicable to oxide-solution inter-
faces. Thus, the experimental capacitance can be split
into two contributions:
I/Cexp = l/Cj + I/SCd (3)
where Cj and Cd are the capacitance ofthe inner layer and
the diffuse layer, respectively, and S is the actual surface
area (Cexp and q are referred to the geometric surface
or to unit mass in the case ofa suspended powder). A plot
of 1/ Cexp vs. 1/ Cd (calculated by the Gouy-Chapman
theory), known as the Parsons-Zobel plot [58], should
give a straight line whose slope provides S and whose
intercept gives Ci.
2 3
1 f
OJ
r ll-
o~----
() ---------
b ""
~
f
J L~_,_._.
6 7 B 9
pH
Figure 2 Typical family of potentiometric titration curves
for C0 3 0 4 suspensions in aqueous solutions at different
KN0 3 concentrations. I, 5 x 10- 3 ; 2, 5 x 10- 2; 3, 0.12 mol
dm- 3 . The intersection point identifies the PZC of the oxide
in water.
773
The first application of Eq. (3) to an oxide-solution
interface was due to this author [47,59] in the case ofRu02
prepared by thermal decomposition of RuC!). The plot
was found linear, but S resulted somewhat higher than
the Brunauer-Emmett-Teller (BET) surface area, a rather
systematic observation [60]. The discrepancy can be due
to a packing factor in BET measurements, to the hydrous
nature of oxides that involve a thin surface layer and not
the pure surface in proton exchange, and to the
nonapplicability ofEq. (3) to oxide interfaces.
Thelastpointhasbeen scmtinizedby thepresentauthor
[61] by simulating Parsons - Zobel (PZ) plots for spherical
and plane particles to disclose what kind ofdeviations can
be observed if an incorrect geometry of particles is
assumed. The analysis has shown that variably nonlinear
plots are obtained, but in any case a linear dependence is
obtained at c---+ 00 for the electrolyte. This indicates that
thenoncoincidenceof "electrochemical"and BET surface
area is a problem beyond the geometry ofthe double layer
that involves the physical meaning ofthe method used.
Figure 3 shows the PZ-plot in the case of a ternary
oxide mixture (Ru02 + Ti0 2 + Ce02). It is seen that
assuming a spherical double layer, deviations are
observed indicating that the choice of the geometry is
incorrect. The assumption ofa planar geometry produces
deviations at low electrolyte concentrations where the
Debye length of the diffuse layer becomes comparable
with the radius of curvature of the suspended particles.
These deviations indicate that at higher electrolyte con-
centration, the choice of a planar geometry is correct.
16
•I
3 •
I
2
u... I
I
Ol 12 •,
I
•
,
~ ,
~
,... B •, y
x
,
• ,,"
.. ,"
'0
'['~.
"
0
0
---.L..-.---~_~_._'
5 10 15
_ _ L . __ •
20
Figure 3 Parsons-Zobel plot at the PZC for a mixed oxide of
composition 30% RU02 + 30% Ti0 2 + 40 mol% Ce02 in
aqueous solution. I, Cd calculated for a planar double-layer
geometry; 2, Cd calculated for a spherical double-layer
geometry; 3, limiting linear dependence.
774 Trasatti

Nevertheless, the resulting "electrochemical" surface "acidity" of a surface OH group is promoted by the
area is systematically higher than the BETvalue. strength of interaction between the oxygen atom and
Extrapolation of Parsons-Zobel plots to 11 Cd --+0 the surface metal ion. Although more elaborate theories
gives q, the inner layer capacitance. Problems of have been developed, a straightforward correlation has
inaccurate extrapolations have lead to propose for Cj been proposed by Butler and Ginley [66] between the
values differing by an order of magnitude [61,62]. q PZC and the "electronegativity" of an oxide MxO y ,
appears to be higher than the value expected for model defined as
metals such as Hg: Average values are around
60-80 /IF cm- 2 [60]. Xox = (~x6)l/x+y (4)
Ion adsorption takes place on oxides with a different
mechanism from that on metals [12,13]. Because the sign
and magnitude of the surface charge is primarily where XM and Xo are "absolute" electronegativities
governed by the solution pH, ion adsorption turns out (Mulliken's scale), which predicts that the PZC increases
to change at constant potential with a change in pH, (becomes more alkaline) as the electronegativity
whereas it remains constant at constant pH with a change decreases. In this context, the data for the oxides used
in potential. Thus, as a simple rule, at pH < PZC anions in electrocatalysis can be grouped around a single line
are adsorbed, whereas at pH > PZC cations are (Fig. 4) whose equation is
adsorbed. Ion adsorption on electrocatalytic oxides has
been investigated by the Russian school. New data are PZC = 7 - [(x ox - 5.9)/0.12] (5)
presently very scanty; this area would need to be devel-
oped further.
The plot can also give an idea of the stability of oxides
Non-ionic adsorption too is influenced by the special
under anodic conditions. If one considers that the PZC
features ofoxide-solution interfaces [12,13,38]. Although
is also the pH of minimum solubility [67], it ensues that
on metals the squeezing out effect (related to the
strongly acidic oxides are particularly stable in acidic
hydrophobicity of most organic molecules) is generally
solutions (e.g., Ir02, Ta20s), whereas alkaline or neutral
the driving force for adsorption, adsorption of organic
oxides are more stable in alkaline solutions (e.g.,
species on oxides is usually weak because the organic
NiCo 20 4, C0304, Ce02, NiO).
species penetrate with difficulty the interfacial layer of
The relationship between PZC and surface chemical
solvent. Rather, molecules with hydrophilic groups are
structure is emphasized by the correlation disclosed
preferentially adsorbed via hydrogen bonds on the sur-
between PZC and chemical shift from XPS spectra [68].
face OH groups [63]. Adsorption turns out to be a func- Such a plot is of considerable interest for the prediction
tion of the PZC of oxides [64]. It is interesting that the
ofPZC values from spectroscopic data.
weak adsorption oforganic substances on oxides makes
these materials weakly sensitive to organic impurities in
solution, although part of this effect is probably related
to the extension ofthe actual surface area.
Adsorption oforganic species is of interest also for its 10
", '~~~ I
!
ro,o,
implications in electro-organic reactions [65]. Oxides
offer interesting alternatives for electro-organic synthesis 8 ceo,~ ", j Co,o,
in view of their specific interfacial structure that could '~I MnO,
drive organic reactions to different intermediates or ~ 6 liO, j f" , PbO,
Zr0 2 ' , Ru0 2
products. , Sn0 2
4 ,,
''I, la,O,
,,,,,,j
I
C. PZC-Structure Correlation 2
IrO,
Factors governing the formation of the oxide-solution
interface can be reasonably singled out by correlating 0' 7
5 6
experimental properties with some physicochemical par- oxide electronegativity, xox
ameters of the solid phase. A number ofapproaches have
been attempted in this direction [13,38]. Figure 4 PZC of oxides plotted vs. the "electronegativity" of
The dependence of the PZC on the nature of the the oxide surface calculated according to Eq. (4).
oxide is readily understood if one considers that the Butler-Ginley correlation [66], Eq. (5). (From Ref. 13.)
f
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis 775

IV. VOLTAMMETRIC SPECTRA tures has lead to the possibility of obtaining the surface
composition "by Cv," in fairly good agreement with
The response ofan oxide surface to cyclic voltammetry is XPS data, as shown in Fig. 7. The same approach has also
a characteristic "electrochemical spectrum,"a fingerprint been proved successful for RU02 + Ir02 [69],
of the state and composition of an oxide surface. If the Sn02 + h0 2 [30], and NiO x + RU02 [70].
metal ion can exist in different oxidation states, the result- The CV surface response is related to redox reactions
ing curve will exhibit characteristic peaks at the given at the surface active sites assisted by proton exchange with
redox potential. The width of the peak is an indication the solution. Thus, a generic reaction can be envisaged as
of the surface heterogeneity. Thus, C0 3 0 4 and NiC0 204,
as shown in Fig. 5, differ substantially in their CV curve
in alkaline solution. Figure 6 shows the difference
It is evident from Eq. (6) that the surface charge spent to
between the cyclic voltammetry (CV) curve for the 011
change the potential within the range of solvent stability
face of RU02 and that for the polycrystalline surface:
measures the number of protons exchanged with the
The latter exhibits a much less featured curve.
solution. Thus, the surface charge (customarily denoted
The features of CV curves have been used by the pre-
with q*), derived by integration of the voltammetric
sent author to analyze the surface composition in situ.
curves, can be taken as proportional to the number of
In a series of CV curves for C0 3 0 4 + RU02 mixed oxides
active sites, i.e., to the actual surface area of the oxide
at different RU02 content [29], the characteristic peak of
[12,18].
C0 3 0 4 progressively disappears as the RU02 content
I The soundness of the above approach can be illus-
increases. At the same time, the background current at
I less anodic potentials increases. A sound use ofthese fea-
trated by a few examples. q* is usually found to decrease
as the calcination temperature is increased [71], as a

I
consequence ofcrystallization and sintering. Sometimes,
the q*-T dependence goes through a maximum [30],
which marks a T of transition at which the whole
(a) (b) precursor is decomposed. In the case of mixed oxides,
i
the charge normally goes through a maximum at inter-
mediate compositions [32] (Fig. 8), which can be under-
I stood in terms of smaller particle size (something like an
effect of the entropy of mixing) due to a lower probability
ofcrystal growth for particles of mixed composition.
The value of the surface charge, at a given de-
composition temperature, is remarkably dependent on

Figure 5 Comparison of voltammetric "spectra" for (a) i'- 100

(5
C0 30 4 and (b) NiC0204 in 1 mol dm- 3 KOH. Potential range: E
oto 0.5 V (SCE). Current range: arbitrary units. c:
80 B B

0
.~ •
'EQ) 60 o •
(a) (b) u
c:
0 0
u 40 ~

:::J 0
II:
Q)
u 20
III
't:
:::J
en
0 -
0 5 10 15 20
Bulk Ru concentration / mol %
Figure 6 Comparison of voltammetric spectra for (a) poly-
crystalline RU02 and (b) the 110 face of a RU02 single crystal Figure 7 Dependence of the surface concentration of Ru on
in 0.5 mol dm- 3 H 2S0 4. Potential range: 0.4 to 1.4 V(RHE). the bulk concentration of Ru for RU02 + C0304 mixed oxides.
Current range: arbitrary units. (.) XPS; ([J) Cyclic voltammetry. (From Ref. 29.)
776 Trasatti

obtained. The ratio Sjl ST provides the "electrochemical"

200 'I, porosity. An example of this approach is provided in Fig.
; \

;
; \
\
9 [30] (dependence of l/q* on v l/Z for £rOz + SnOz) and
; ,
OJ
, in Fig. 10 [29] (variation of the "electrochemical" porosity
E 150 ;

<)
I
with composition for C0 30 4 + RuOz).
Voltammetric curves have also been used to determine
.•
OJ ;
E ;

() 100
;
• the surface area from capacitance [36]. The approach
E
;
•,
sutTers from the same shortcomings as that based on q* .
\
,,
.,
;

"0- ;
;
, In any case, it does not provide more information than
50 ;
;
• q* itself.
; -;.- --I Recent (after 1991) studies of oxide surface char-
;

--~ acterization are summarized in Table 3.

o L . - . - ......

o 20 40 60 80 100
mol % Au0 2
016
Figure 8 Dependence ofthe voltammetric charge on compo-
- - 80%
sition for Ru02 + Zr02 mixed oxides. (From Ref. 32.)

i ft
.... -Ii
1.5

0 12i '., ' ------ --=-=- 20% - -

the procedure of oxide preparation and particularly on ;-
_~1l-
~--_.. -- ~---
------
the nature of the precursor. Thus, higher charges are
0-
:::-0.08 '-.._.--_._--------- .-- -- ----~~-
obtained for RuOz from the nitrate than from RuCh [17], ~ - . . . - _ .. - - -r- - - ...- - - - -
3%
0.5
for C03 0 4 from the carbonate rather than from the nitrate ___ "Ii

[72], and for RuOz + ZrOz from the nitrates rather than
from the chlorides [32]. In this context, the sol-gel method f
0.04~-·~-
does not give higher charges [25], butthis is normally lim- o
o 5 10 15 20 25
ited to a factor of 1.5-2, which does not justifY the more scan rate, V /2 I ( mV I s )'12
'
complex procedure ofoxide preparation.
It should be stressed that q* cannot be referred quanti- Figure 9 Extrapolation of the reciprocal ofthe voltammetric
tatively to a given surface area because the "area per unit charge to potential scan rate v = 0 for mixed Ir0 2 + Sn02 oxides
charge" is normally not known. Accordingly, the same at different Ir02 content. (From Ref. 30.)
value of q* cannot be taken as equality in surface area
for two ditTerent oxides. Nevertheless, for the same oxide,
the value of q* has a relative quantitative value, and in
any case its qualitative diagnostic character is retained. -
_ -1
The value q* is found [73] to depend on the potential
scan rate; more precisely, q* decreases with increasing
"0-
0
0.8 -,•
scan rate. Accordingly, in potential step experiments, q*
increases linearly with [liZ, as expected as a diffusion pro-
cess is involved. It has been found that the slow process
-..
~

"
0-
0.6 I
-- -...
;

f•. : • - - -t :
;
is the diffusion of protons (or protonated species) along "0- 0.4
0
r--
preferential pathways into the oxide layer. Thus, as a 11

potential step is applied, only the external surface

responds. Successively, the internal (less accessible) sur- 0.2l
face is involved. Thus, the variation of q* with time can I
Ol ___ ~---------.L.-

be used to separate outer and inner active surface area. 0 5 10 15 20

The procedure suggested by this author [74,75] is to
x I mol% Au
plot l/q* vs. v 1/Z (v is the potential scan rate) and q* vs.
v-liZ and to extrapolate to v = 0 and v = 00, respectively.
Figure 10 "Electrochemical porosity" of C0 3 0 4 + Ru02
The former gives the total surface, ST = So + Si, whereas mixed oxides as a function of the content of Ru02. (From Ref.
the latter gives So. The inner surface, Sj, can thus be 29.)
f!
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis 777

Table 3 Recent Work on the Surface Characterization ofOxides for Electrocatalysis'

Electrode material References

RU02 + Sn02 82,318

C/Mn02 83
Ru(steel) /Bi2Ru207 84
Ir02 + Ti0 2 85,94,119-122
RU02 + Ti0 2 22,34,90,93,94,95,116,117,118,119,121,320
RU02 + lr02 27,28,90,91,92
Ti0 2-b (also Ebonex@) 80,86,98,115
Ir02 + Zr0 2 76
RU02 + Ir02 + Ti0 2 87,121,123,319
Pb0 2 + Ta20S 88
RU02 43,79,89,101,103,106,107,114,304,306,307
Ir02 + Ta20S 33,94,321
RU02 + Sn02 + Ti0 2 94,117
RU02 + RhOx (powder) 96
Pb2Ru207 (pellet) 97
C0 3 0 4 19,23,43,99,100,102,104,305
NiC0 20 4 19,100,325
C0 30 4 + ZnO (powder) 81
Glass/CuCo20 4 77
LiMn204 (pellets) 317
RU02+VO, 78
Ir02 43,105,108
RU02 + Zr02 32
Ir02 + Sn02 30,31,125
Zr02/LnMn03 (Ln = rare earth) 110,308
Lnl-xSrxCo03 (Ln = rare earth) (pellets) 109,1ll
PdO x 112
C0 30 4 +NiO, 113
Ptl Fe304 124
RhOx 214
Mn x Co 3 _ x 0 4 303
LaNi0 3 309,325
Lal_xLnxCo03 310
Sn02 (doped) 311,312
Pb02 +C0 30 4 322

• Unless otherwise stated, the support is Ti.

V. SURFACE REACTIVITY: A. Chlorine Evolution

ELECTROCATALYSIS
Conducting oxide electrodes are electrochemically active
in many processes [12]. Their activity has been related to
their extended surface area but especially to their ability
to switch between different valence states ofthe metal cat-
ions [126]. The activity depends also on the strength of
interaction ofeventual intermediates with the oxides sur-
face [127-129]. However, specific oxides are requested
for specific conditions.
Oxide electrodes were introduced into the electrochemi-
cal technology to replace graphite electrodes in chlor-
alkali cells because of a lower overpotential and
especially ofa much higher dimensional stability (hence,
their name DSA) [7,8]. The low overpotential is, however,
mainly related to their extended surface area. In fact,
chlorine evolution is a "facile" reaction and proceeds at
a high rate on many electrode materials [130]. The advan-
tage of oxide electrodes is in their enhanced stability
778 Trasatti

under the most severe conditions. Recent studies
appeared in the literature (after 1991) are summarized in
Table 4.
Chlorine evolution proceeds on active oxides with a
10wTafei slope of about 40 mV [130]. This indicates that
the second electron transfer is rate determining.
However, in this case, a reaction order of 2 with respect
to Cl- should be observed, which is not the case. Thus, a
mechanism different from the classic examples has been
suggested to account for the observed kinetic features.
The mechanism, put forward by Erenburg et al. [140], is
characterized by the formation of Clad in a first step, with
further oxidation of Clad to Cl;d in a second step without
involvement of another Cl- from the solution, which
results in a unit reaction order.
The development of the mechanistic analysis for Ch
evolution on oxide electrodes has been discussed by the
present author elsewhere [130]. A distinctive feature of
Ch evolution kinetics on oxides is the pH dependence
of the reaction rate in a specific pH range (1-3). No pH
dependence is predicted either by Erenburg et al.'s mech-
anism or by the classic mechanisms. It has thus been pro-
posed [141] that the pH dependence is related to the
surface oxidation of the active sites, which results in an
activation of the surface for chlorine evolution:
-M-OH --+ -M-O + H+ + e
The proton released in Eq. (7) is responsible for the pH
dependence. In fact, a negative reaction order with
respect to H+ is observed experimentally [139]. In some
way, reaction (7) is a step common to all anodic reactions
on oxide surfaces.
With some electrode materials, notable Ru02-based
electrodes, a complex Tafel pattern is often observed with
a region ofdiscontinuity on the current axis. This behavior
has been related [142] to the exceptionally high activity
of these electrodes (also related to the extended surface
area) which results in a Ch diffusion-limited reaction rate.
This creates oversaturation of the reaction layer adjacent
to the electrode surface. Such behavior is possible
because oxide surfaces take the reversible potential of
the Cl2 reaction in the presence of Ch gas.
Increase in activity with increasing surface area meets
with a limitation in the case of the Ch reaction due to
the fact that the inner surface does not work because of
the difficult accessibility of Cl- [12,143]. After an initial
discharge, the inner surface is depletedofCI- ions so that
oxygen starts to be evolved "internally" with a local
decrease ofpH that further depresses Ch evolution [144].
Thus, high porosity is deleterious both for the purity of
the Ch gas produced and for the chemical stability of
the oxide layer if the oxide is sensitive to low pH.
B. Oxygen Evolution
Oxygen evolution is a"natural" reaction on oxide surfaces
because these already contain the intermediates of the
electrode reaction, and oxides are anyway formed
anodically on bare metal electrodes as precursors to O 2
gas formation. Oxygen evolution, differently from Ch
evolution, is a"demanding" reaction [145] and is therefore
(7) highly sensitive to the nature and the structure of
electrocatalysts [18,127-129]. Moreover, O 2 evolution
combines the demand for activity with the demand for
stability, because it takes place under the most severe elec-
trochemical conditions. Thus, although Ru02 and Ir02
are especially suited for acid solutions, spinels and
perovskites are specific for alkaline solutions. A sum-
mary of recent studies (after 1991) is given in Table 5.
As a general rule, oxides active for Ch evolution are
also active for O 2 evolution [196]. However, the spectrum

Table 4 Recent Studies ofCI2 Evolution on Oxide Electrodes a

Electrode Subject References

RU02 + Ti0 2 Effect temperature below 298 K 131

Ru02(lr02) + Ti0 2 Analysis gas by DEMS b 132
Critical parameters in chlorate synthesis 133
RU02 +PtO x Hypochlorite production 134
RU02 + Ir02 + Ti02 Chlorate production 135
RU02 + PtO x + Ti0 2 Effect PtiTi ratio 136
RU02 + Sn02 + Ti0 2 Effect composition 137
RU02 + Ce02 + Ti0 2 Effect Ce/Ti ratio 138
Various Mechanism on mixed oxides 130
Effect solution pH 139

a Unless otherwise stated, the support is Ti.

b DEMS =differential electrochemical mass spectrometry.
r
I
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis
of Tafel slopes is wider in the latter case, ranging from 30
to 120 mY A few oxides, such as Sn02, Pb0 2, and PtO x ,
are in fact so inactive in O 2 evolution as to be useful for
alternative reactions such as 0 3 formation [197] or com-
bustion of "hard" organic compounds [198]. The most
common Tafel slope is about 40 mY, with 60 mV in some
specific cases. Thus, the probable mechanism is EE or
EC, with low coverage ofintermediate species. A general-
ized mechanism, including four steps, which can explain
all observed Tafel slopes has been proposed by the present
author [145].
A typical feature ofO 2 evolution on oxide electrodes is
the fractional reaction order for E or EE mechanisms.
This has been interpreted as a typical response of oxide
surfaces to a change of the solution pH [199]. The linear
dependence generally observed between reaction rate
and voltammetric charge suggests that the inner surface
is not blocked. In fact, reacting species are the molecules
of the solvent, not limited by diffusional paths.
The demanding nature of O 2 evolution can be illus-
trated by a few examples. The Tafel slope changes from
about 60 mV to about 30 mVon RU02 electrodes as the
CV charge, q* , ofthe electrode surface increases [12,200],
corresponding to a decrease of the calcination temper-
ature. Thus the catalyst becomes more active (lower Tafel
slope) as the particle size decreases, as expected on the
basis of catalysis concepts. It is interesting that O 2 evol-
ution on the 011 surface ofa single crystal proceeds with
a Tafel slope of 60 mV [201], as at the low q* limit for
polycrystalline RU02.
The dependence of the Tafel slope on composition for
Ir0 2 + RU02 mixed oxides turns out to be a function
of different preparation procedures [12]. The Tafel slope
varies monotonically from 40 mVon RU02 to 60 mVon
Ir0 2. However, the way the transition takes place is
indicative of the degree of interaction between the
components, i.e., ofsynergetic effects.
The scale of activity of different oxides can be under-
stood on the basis of the concept of redox potential for
the surface active sites. This has first been forward by
Rasiyah and Tseung [126], who has demonstrated a linear
correlation between the potential of O 2 evolution on
oxides and the potential of redox transition for the
oxidation of the surface. Concepts along the same lines,
although differently formulated, have been advanced by
Krishtalik [127] and by Arikado et al. [128]. On the other
hand the present author [129] has noted correlations
between the catalytic activity and the metal-oxygen bond
strength on the surface of oxides. A plot of overpotential
vs. the enthalpy of transition of an oxide from a lower to
a higher valency state gives a typical "volcano"curve [12],
familiar in many areas ofcatalysis and electrocatalysis.
779
C. Hydrogen Evolution
Although electrocatalytic oxides are thermodynamically
predicted to be unstable in the potential range ofH 2 evol-
ution, they in fact evolve H 2 at low overpotential
exhibiting remarkable stability. Oxides do not take the
reversible potential of the H 2 reaction because H 2 is not
dissociatively adsorbed on oxide surfaces in solution.
After cathodic H 2 discharge, they may exhibit the
reversible potential for some time, but it is lost as soon
as hydrogen atoms in the lattice are desorbed as H2
molecules.
H 2 evolution modifies the voltammetric response of
oxides. In the case of RU02 and Ir0 2 the shape of the
voltammetric curve is retained, whereas the value of q*
as a rule increases [202]. This has been attributed to
wetting of less accessible surface regions promoted by
H+ discharge on oxide sites. Work on single crystals has
shown [203] that H 2evolution erodes the crystal face with
an increase of q* related to an increase in surface
roughness. Probably, both mechanisms are simultan-
eously operating.
H2 evolution proceeds on oxide electrodes with Tafel
slopes between 30 and 60 mY Recent works are listed in
Table 6. The most common value is 40 mY, which
indicates an EE mechanism at low surface coverage with
intermediates. The mechanism can change with aging,
as has been observed with Ir02 and RU02. Fresh RU02
electrodes exhibit a Tafel slope of 60 mV that becomes
40 mVafter some use [206]. The spinel C0 3 0 4 is also
active for H 2evolution, but its CV response is irreversibly
modified after the cathodic treatment, which indicates
penetration of protons into the lattice with reduction of
the oxide structure [71]. This is not the case of RU02 and
Ir02, which recover their CV features even after extensive
H 2 evolution [202,208].
The maintenance of the surface chemical structure is
confirmed by the observation of a fractional reaction
order on Ir0 2 and RU02 electrodes [215]. The difference
between these dioxides and, e.g., the spinels (C0 3 0 4 ), is
to be sought in the different nature of the electrical con-
ductivity. Due to their metallic conductivity, the electric
field does not penetrate into the bulk of RU02 and Ir0 2
so that proton penetration is not field assisted and cannot
proceed differently from the case of C0 3 0 4 . For this
reason C0 3 0 4 is reduced, whereas RU02 and Ir02 are not.
Therefore, the stability ofoxide cathodes is enhanced first
of all by increasing their metallic conductivity. Semi-
conducting oxides are unstable to hydrogen evolution.
Although the kinetics has not been studied, the surface
response of single-crystal RU02 and Ir0 2 to cathodic
sweeps has been investigated [216,217]. Hydrogen
780 Trasatti

Table 5 Recent Studies of 02 Evolution on Oxide Electrodes'

Electrode Subject b References

Various Bifunctional electrodes for water-electrolysis fuel-cells (SPE, a) 146

Ni/Lao.8Sro.2Co03 Effect of Ni, Fe, Cu, Cr substitutions for Co (b) 147
CoxNi1-xOy Effect ofcomposition (b) 148,149
Ptl Preparation by sol-gel (b) 150
Ni(CdO) ICU1.4Mnl.604 Effect substrate and catalyst loading (b) 151
Ir02/MnOx In seawater (b) 152
Fe-doped NiO x Effect doping (b) 153,154
NiCo2 0 4 Composites with Ni-PVC (b) 155
Preparation by sol-gel (b) 325
MxC03-x04 (M = Li, Ni, Cu) Comparative study effect dopant (b) 156
Ir02 + Ta20S (Ir02 + C0304) Use as anodes for metal electrowinning (a) 157
Ir02 + Ce02 + Ti0 2 Effect of Ce/Ti ratio (a) 158
Ni/Co 30 4 Effect ofpreparation procedure (b) 159
Preparation by sol-gel (b) 23
PdO x Effect ofpreparation procedure (a) 160
RU02 Effect ofPTFE modification (a) 161
RU02 + Ir02 Effect catalyst bonding to Nafion (a) 162
Effect composition on activity (a) 211
Ir02 + RU02 + Sn02 Statistical strategy effect composition (a) 163
RU02 +Sn02 +PdO x Compositional effect (a) 164
Ru-Adatoms catalyst Oxidation by Ce 1V (a) 165
Ir02 +C0 30 4 Influence ofcomposition and temperature ofpreparation (a) 166
Pt/lXand fJ-Pb0 2 Influence of structure on electrocatalysis and adsorption of intermediates (a) 167
PTFE-modified Pb0 2 Effect hydrophobicity (a) 168
Ni/LaNi0 3 Influence ofpreparation conditions (b) 169
Lal_xSrxCo03 Effect support and preparation (b) 170
Mn02+PdOx Effect ofPd doping (a) 171
Glass/Cul+xMn2-x04 Effect ofpreparation method on active site density (b) 172
C0 30 4 + CuO + ZnO Statistical approach effect ofcomposition (b) 173
Ni/NiCo 2_ x Rhx0 4 Effect ofcomposition (b) 174,190
Sn02 + CUC0 20 4 Kinetics and mechanism in 175
RU02 + Ti0 2 alkaline solution (b)
Ni/LaNi0 3 Preparation at low-T; effect of Fe doping (b) 176
CO/C0 30 4 Electrochemically generated oxide; effect ofSr (b) 177
RU02 + Sn02 + Ti0 2 Mixture design approach. Life tests (a) 178
Ni/NiCo2 0 4 Spray pyrolysis. Mechanism (b) 179
Pb/Pb02 Mechanism in H 2S04 (a) 180
Ti(SPE) I Influence ofanions (a) 189
Nil LaNi0 3 Sol-gel route. Effect high surface area (b) 181,325
Effect preparation (b) 185
PtiNi/CuCo 20 4 Effect loading, precursor solution concentration (b) 182
Ni/Co304 + Raney Ni Composite electrodes by vacuum plasma spray (b) 20
Ni/(Pb0 2 + C0 3 0 4) Composite electrodes 322
RU02 Anomalous effects at low-T 183
Ir02 Surface modification by ion implantation (a) 184
Effect aging (a) 192
C/Lao.6CaOACo03 For bifunctional air electrodes (b) 186
Ni/Lal_xMxC003 (M = Sr, Ca) Low-Tsynthesis. Mechanism and electrocatalysis (b) 187
NiO x Reactively sputtered on different substrate (b) 188
Ni/Mn x Fe3_x0 4 Low-Tsynthesis (b) 191
Ir02 + Ti0 2 + PtO x Impedance, SEM, EDX, CV (a) 193
RU02 + Ti0 2 + Ce02 Effect Ce/Ti ratio (a) 194
Ir02 + Ti0 2 Impedance, SEM, CV (a) 195
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis 781

Table 5 Continued.
Electrode Subject b References

Anode for Mn02 deposition (a) 313

Anode for Mn02 deposition (a) 313

a Unless otherwise stated, the support is Ti.

b (a), acid; (b), basic environment; solid polymer electrolyte (SPE); scanning electron microscopy (SEM); energy dispersion x-rays (EDX); cyclic vol-
tammetry (CV).

Table 6 Recent Studies ofH 2 Evolution on Oxide Electrodes

Electrode Subject References

Electrochemical surface characterization 204,208

Impedance 209
Kinetics and electrocatalysis in alkaline solution 205,215
RU02 + Ir02 Effect ofcomposition in acidic solution 206,208,211
Pt-doped Ti0 2 Hydrogen adsorption 207
C0 3 0 4 Mechanistic and electrocatalytic aspects in alkaline solution 71,215
RU02 single crystals Surface activation 203
RU02 Surface activation 208
Impedance 209
Cathode for chlorate 210
Effect intermediate layer 314
Alkaline solution 212
Mechanism 215
Ti n 0 2n - 1 Effect degree of reduction 213
C0304+Ru02 Effect ofcomposition 219
Ni/ (Ni + RU02) Electrodeposition composite layers 221,222,324

adsorption/desorption waves have been identified, which
confirms that the surface is "reduced" (otherwise H2 evol-
ution would not be observed at low overpotential), but
not beyond the first monolayer, and the oxide structure
is retained.
The 30- to 60-mV Tafel slope range is similar to that
observed for O 2 evolution. It is thus tempting to envisage
a general scheme of mechanism resembling that for the
anodic reaction based on four steps, ECEC. Hydrogen
evolution takes place on the whole active surface [218],
as in the case of O 2 evolution, and this can be understood
in the same terms: Reacting particles need not travel from
the bulk solution because H2 evolution originates from
water molecules whose supply is practically infinite
because already present in cracks, crevices, pores, grain
boundaries, etc.
Hydrogen evolution on mixed oxides can be enhanced
by synergetic effects if the mixtures is intimate at an
atomic level. Figure II shows that the Tafel slope depends
on RU02+Ir02 composition in an additive way, which
indicates that in this case the component of the mixture
behave as separate phases.
Mixed oxides of C0 3 0 4 + RU02 show an activity for
H 2 evolution increasing exponentially with the RU02
content [219]. This is related to the high activity of RU02
but also to the strong surface enrichment with RU02 [29].
The Tafel slope changes from 120 mVon pure C0 3 0 4 to
40 mV for pure RU02 going through 30 mV for inter-
mediate compositions (Fig. 12). Performances decay with
time, however, which is due to loss of RU02 particles
caused by the erosion of the C0 3 0 4 matrix.
Metal deposition on oxides does not proceed
by underpotential [220]. The absence of under-
potential deposition is indicative of weak metal-oxide
interaction in line with the mechanism of ionic
adsorption. Such a feature is beneficial for oxide
cathodes because they are less sensitive to metallic
impurities in solutions, i.e., to poisoning phenomena
generally occurring in technology.
Gas evolution reactions can produce erosion ofoxide
layers whose morphology is that ofa compressed powder.
For this reason, active oxides are often dispersed into a
mechanically more stable matrix.This is the case ofRu02
incorporated into an Ni matrix, which is obtained by
782 Trasatti

300
250 •
>
E
• • «
~ 200 •• • / E 200 ______ J- __ - r

c..> • •
« • "i 4'''' ...:-
• • ~
:; .. '

;~-'•
~15°L'=
,;

100
I

0 0.2 0.4 0.6 0.8 1

c..> 100 ~

o
L:/'
I

0 10 20
•

30
_ _ _ _ _ _ _ _ .L

40 50
~ _

60
Ru0 2 surface mole fraction amount of Ru0 2 , m / 9 dm- 3

Figure 11 Overpotential for H 2 evolution at) = 0.1 A cm-2 as Figure 13 Currentfor H 2evolution on an Ni surface modified
a function of the content of Ir02+Ru02 mixed oxides in acid by various amounts of Ru02 in the modifYing solution. (From
solutions. - - , Calculated for additive behavior. (From Ref. Ref. 222.)
206.)

-1

~~~ 15%

-1 .1 been searched for in many directions, including the field

~
ofoxide electrodes.
""'- ""-
-
>
Ql
1il -1.2
7.5
O 2 reduction involves the approach to and the adsorp-
tion on the electrode surface of molecules dissolved in
~

~\;
solution. This makes the process intrinsically difficult
LlJ
because of mass transfer and dissociative chemisorption
-1.3
~" problems. In fact, 02 molecules have to compete with

1~
. Nevertheless, the use of gas diffusion electrodes [224]
-1.4 L
0.01 0.1 1 10
j / mA cm- 2 bodies makes it possible to work with oxide electrode of
Figure 12 Current-potential polarization curves (Tafel plots)
for H 2 evolution from alkaline solutions on C0 3 0 4 + Ru02
mixed oxides at different Ru02 contents. (From Ref. 219.)
electrolytic deposition ofNi from a bath containing RU02
particles in suspension [221,222]. Figure l3 shows that
the activity of these electrodes increases by two orders of
magnitude as the RU02 content is increased. Although
an Ni electrode shows an overpotential increasing with
time, for an Ni electrode incorporating RU02 particles
the overpotential decreases with time by 0.2-0.3 V.
D. O 2 Reduction
02 reduction proceeds at best on Pt electrodes [223].
However, this is an expensive electrode material; in
addition, it is extremely sensitive to impurities in the 02
phase and/or in the solution. Alternative catalysts have
water molecules occupying surface active sites.
100 where the gas-liquid-solid contact develops in porous
excellent performances. Thus, active oxides are some per-
ovskites, cobaltites (spinels), and pyrochlores. Other
electrocatalytic oxides such as RU02 and Ir02 are poor
electrocatalysts for O 2 reduction, although the reaction
proceeds to H 20 2. A summary of recent works is given
in Table 7.
In general, O 2 reduction shows two Tafel slopes,
40-60 mVand 120 mVat high overpotentials. By chang-
ing the metal in the octahedral sites of cobaltites, it has
been proved [225] that the formerTafel slope is associated
with the M(I1) ions, whereas the latter is related to
Co(I1I) sites. Thus, C0 3 0 4 is poorly active, whereas
NiC0 2 0 4 is most active. This means that Ni-Co elec-
tronic interactions are responsible for the high activity of
the mixed oxide.
The mechanism of 02 reduction on oxides has been
discussed by Tarasevich and colleague [225,226] and
Tronov [227]. Fractional reaction orders have been
observed, which points to the importance of surface
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis 783

Table 7 Recent Studies of 02 Reduction at Oxide Electrodes

Electrode Subject References

Ru02 Mechanism in alkaline solution 228

Pd~, Mechanism in alkaline solution 229
Ir02 Kinetics in alkaline solution 230
Ni x C0 3 - x 0 4 Effect composition on mechanism 231
Bi2Ru207 Bifunctional electrode 232
Ru pyrochlores Zero-gap assemblage 233,241
Determination dissolved 02 240
Several Activity and stability in alkaline solution 234
CU1-xMn2-x04 Surface area and activity 235,236
Fe304 Well-defined composition 237,239
H 20 2 decomposition 243,244
Ti0 2- b Alkaline solution 238,247
LaO-x)SrxMn03 High-temperature cathode 242
Impedance 245
W 1S 0 49 , LaxW03 Role adsorbed species 246
Cr(l-x)Cu xMn20 4 Effect composition on mechanism 248
Cr02 Proton exchange membrane-bonded electrode 249
C0 3 0 4 Spray pyrolysis 250
NiC02 0 4 Spray pyrolysis 250

Table 8 Recent Studies of Organic Reactions at Oxide Electrodes

Electrode Subject References

C02 reduction. Effect adatoms 255

Electrochemical promotion for ethylene combustion 256
Oxidation oforganics (SPE) 257
Oxidation ofphenol 197
Effect ofNaCI in solution on phenol oxidation 258
Oxidation ofbisphenol-A 259
General treatment ofelectrocatalysis for conversion/combustion 254,316
Sensor for ethanol 260
Reduction p-NO2-aniline 261
Reduction 0/m-N0 2-aniline 262
Reduction N0 2-benzene 263
Reduction N02-toluenes 264
Reduction naphthols 265
Reduction maleic acid 266
Reduction aromatic N02 -compounds 267
Reduction N0 2-benzoic acids 268
Rh, Ir, Pt mixed Oxidation methanol oxides with Sn 269
Ru02 Theoretical model redox catalysis 270
Oxidation ethanol kinetics 271
Synthesis chioro-aromatic compounds 315
Oxidation benzyl alcohol 272
CI (hydrous) Oxidation of alcohols 276
NiiNiOxChydrous) Oxidation isobutanol 273
C/ Oxidation alcohols, sugars 277
C/ Oxidation methanol 278
C/several perovskites Oxidation methanol 274,275

SPE, solid polymer electrolyte.

784 Trasatti

hydration in all aspects ofthe electrochemical behavior of 0.1

oxides.

E. Electro-Organic Reactions

Although electrolytic oxides such as PbO z and Ni Ox have 0.07

long been used as electrodes in the field oforganic electro-
chemistry [251-253], the discovery ofDSA has awakened
the interest for oxide electrodes in the hope that the
different nature of the interactions of reactions or
intermediates with oxide surface might lead to different 0.04
reaction routes. The main difference with bare metal elec-
trodes is that strong chemisorption with bond break-
age is as a rule impeded, so that oxidation of organic
molecules to COz is basically much more difficult.
0.02
Nevertheless, oxide electrodes of high O 2 overpoten- 0.01
tial are recommended as electrodes for the anodic
~O
"combustion" oforganic pollutants in wastewaters [254].
Table 8 summarizes recent works in this area.
Organic reactions on oxides can proceed either
directly or indirectly. Cathodic reactions are not of great
I I I I I I I
interest in that the oxide electrode plays the role of elec-
tron injector as any other solid cathodes. More inter- -0.1 0.1 0.3 0.5
estingly, anodic oxidations can proceed by direct
transfer ofelectrons from the molecule to the oxide at high E vsSCE/V
overpotentials or indirectly by chemical reactions of the
organic compounds with species on the active sites, as a Figure 14 Oxidation ofethanol at different concentrations in
rule in correspondence of surface redox transitions. The solution (mol dm- 3) at the surface ofan NiCoz04 electrode.
latter mechanism is particularly interesting because the
selectivity is enhanced by the need oforiented molecules
for the reaction to proceed.
An illustrative example is provided in Fig. 14 where the
oxidation of ethanol is seen to take place on NiCo z0 4 at 0.6
potentials where the surface oxidation peak develops.
40mV
The situation is even more evident in Fig. 15 where
steady-state polarization curves are shown. Ethanol 0.5
~-
oxidation proceeds with a Tafel slope of 40 mY, which blank
>
. ......
stir
indicates that the second electron transfer and not the w ~ . .I
chemical interaction of the reactant with the oxide sur- ~0.4 - .: §
.----1--
face is rate determining. ~
.~..11 - -••
UJ
It is interesting that ethanol can be oxidized to acetic
0.3
c = 0.04 mol dm·3 .~ ot·:-- .
,.""
.-- /

acid quantitatively [65,279]. This emphasizes the import- ...- .... -t---.t-

ance of the orientation of the reactant toward the elec- ,,- c = 0.4 mol dm· 3
'.-
trode surface: Because the oxide surface is hydrophilic,
~---O.Q1-""::"~~-·-----:---~~
,.- -;
0.2
the molecule of ethanol approaches the electrode with 0.001 0.01 0.1 10 100
the hydrophilic end, i.e., the alcohol group that can thus j / rnA em· 2
be oxidized to acid selectively. This would not be the case
with hydrophobic surfaces. Oxidation ofethanol has been Figure 15 Quasi-stationary Tafel plots for ethanol oxidation
investigated on a series of mixed oxides of Ni and Co at an NiCo204 electrode surface. The blank solution (0 2 evol-
[280]. It has been found that C0 3 0 4 and NiO x are ution only) is shown for comparison. The effects of concen-
pratically inactive, whereas Ni activity is enhanced by tration and of stirring are also shown [280].
Interfacial Electrochemistry of Conductive Oxides for Electrocatalysis
Table 9 Generalized Mechanisms on Oxide Elec-
trodes
Reaction Mechanism
Oxygen evolution
S-OH ---+ S-O* + H+ + e
S-O* ---+ S-O
OH
S-O + OH- ---+ S( +e
o
OH
2S ( ---+ 2S-0H + O 2
o
Chlorine evolution
S-OH ---+ S-O*+H++e
S-O* ---+ S-~O
CI
S-O+ CI----+2S( +e
o
CI
S( +H++CI- ---+
o
Hydrogen evolution
S-OH+H++e ---+ S-OH 2
S-OH2 ---+ S-OH 2
S-OH2 + e ---+ S-H + OH-
S-H + H 2 0 ---+ S-OH + H 2
the presence ofCo in accordance with the observations in
the case of O 2 reduction.
F. Generalized Gas Evolution Reaction
Mechanism
O2, Ch, and H2 evolution at oxide electrodes occurs with
a Tafel slope commonly around 40 mY, which indicates
that the second electron transfer is rate determining. In
some cases, 60 mV is also observed (not for CI 2),
suggesting that a chemical step after the primary dis-
charge is rate determining. On the other hand, a 40-mV
slope would entail a reaction order of 2 with respect to
the discharging particles (H+, OH-, or CI-), which is
not observed experimentally.
With the aim to encompass the behavior ofmost oxides
in a single mechanism, a generalized scheme is proposed
in Table 9 in which the first step reflects the redox
transitions possible with transition metal ions. The
second step simulates a spill-over reaction that is reason-
able on heterogeneous oxide surfaces. If this is slow, the
Tafel slope is 60 mY; if it is fast, the second electron
785
Step
E
C
E
C
E
C
E
S-OH+CI 2 C
E
C
E
C
transfer is usually rate determining with a Tafel slope of
40 mY. Oxides with no redox transitions available as a
rule show high overpotentials.
VI. OXIDE STABILITY
Stability can be defined as the ability of an electrode to
maintain its potential constant in long-term per-
formances. Electrode stability is one of the most import-
ant parameters and is often the decisive parameter for
the choice of electrode materials. Table 10 summarizes
recent works in this area.
Stability is related to a number of factors and can be
distinguished between erosion, passivation, and wear.
These aspects have discussed at length elsewhere [12,145].
Here, it is to be recalled that erosion is a mechanical effect
[296], whereas passivation usually does not involve the
active component but the support [297].Wear can further
be distinguished into anodic dissolution [298] and chemi-
cal modification. The former is thermodynamically
predictable, e.g., if a soluble compound is formed at
786 Trasatti

Table 10 Recent Studies of Stability of Oxide Electrodes

Electrode Subject References

RuOz + IrOz + TiO z Stability in chlorate production 281

Corrosion under conditions of Cb evolution 288
Various Discussion ofdeterioration mechanism 282
RuOz Oxidation dissolution by periodate 283
Combination with 1r0z and TiO z
Role of stabilizing component and substrate 287
RuOz (or IrOz) Investigation ofthe behavior ofTi support 284
RuOz + TiO z (and others) Wear during hypochlorite production 285
Study by Rutherford backscattering 286
IrOz + TazOs Effect ofcoating thickness and surface treatment of support 289
Deactivation mechanism at high currents 290
Service life sulfuric acid for electroflotation 291
Improved service life in the presence of interlayers 292
Biz Ruz07 Surface stability upon oxidation or reduction 293
Oxidative stability in acid 294
SnOz (doped) Effect 1r0z interlayer on service life for anodic reactions 295
Corrosion studies by quartz microbalance, impedance, TEM, SEM 323
C0 3 0 4 Origin ofohmic losses on Ti support 3

TEM, transmission electron microscope; SEM, scanning electron microscopy.

anodic potentials (anodic dissolution) or cathodic
potentials (cathodic dissolution), Thus RU02 can dissolve
anodically ifthe potential ofRuO~- formation is reached
[299], Similarly, Mn02 is cathodically dissolved as
Mn 2+ and C0304 as Co2+.
Surface modification can take place anodically if a
defective oxide is turned into a stoichiometric oxide by
incorporation ofoxygen or cathodically ifan oxide is pro-
gressively reduced by proton penetration into the lattice.
Two effects can also combine. Thus, in RU02 + Ti0 2
mixed oxides passivation is observed if the dissolution
of RU02 results in surface enrichment with Ti0 2 [300].
Synergetic effects are often observed: Ir02 reduces the
dissolution of RU02 [30 I] but also vice versa [288]. Ti0 2,
Ta20s, and Zr02 are known to improve the chemical
stability of RU02 and Ir02 [302].
ACKNOWLEDGMENTS
Thanks are due to the National Research Council
(C.N.R.) and the Ministry for University and for
Scientific and Technological Research (M. U.R.ST.) for
financial support.
REFERENCES
I. JM Honig. In: S Trasatti, ed. Electrodes of Conductive
Metallic Oxides, Part A. Amsterdam: Elsevier, 1980, pp.
1-96.
2. ID Belova, VV Shalaginov, BSb Galyamov, YuE
Roginskaya, DM Shub. Zh Neorg Khim 23:286-290,
1978.
3. D Baronetto, 1M Kodintsev, S Trasatti. J Appl
Electrochem 24:189-194,1994.
4. S Trasatti. In: H Gerischer, CW Tobias, eds. Advances in
Electrochemical Sciences and Engineering, Vol. 2.
Weinheim: VCH, 1992, pp.I-85.
5. V De Nora, J-W Kuhn von Burgsdoff. Chern-lng-Tech
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44
Kinetic Modeling of Electrocatalytic Reactions: Methanol
Oxidation on Platinum Electrodes
S. Sriramulu, T. D. Jarvi, and E. M. Stuve
University of T#1shington. Seattle, Washington
ABSTRACT
Electro-oxidation of methanol to C02 on platinum elec-
trodes is plagued by accumulation of CO, which poisons
the reaction. The mechanism for C02 production has
not been resolved with claims of a serial path (involving
adsorbed CO) or a parallel path (non-CO pathway) being
advanced. In this chapter, we test the hypothesis that a
non-CO path (the parallel path) exists for methanol
electro-oxidation on a Pt(lll) electrode in perchloric acid
electrolyte. The experiments, which were performed in
an anaerobic dual-cell apparatus at room temperature,
consisted of chronoamperometry (for reaction times
between 0.03 and 300 s at 0.6 V) and linear sweep
voltammetry. The experimental results confirm the exist-
ence ofboth the serial and the parallel path mechanisms
at 0.6 Vand show that a simplified representation of the
surface chemistry is inadequate to explain all the results.
We developed a Langmuir-Hinshelwood kinetic model
incorporating both pathways and fitted the experimental
data over the entire range ofthe reaction time. The model,
which contains four kinetic and four mechanistic
parameters, reveals that the reactive intermediate in the
non-CO path has the stoichiometry H:C:O before
reacting to CO or C02. At steady state at 0.6 V, the parallel
path accounts for 75% of the CO2 produced, and the
CO coverage is 0.29 monolayers. Small changes in CO
coverage produce an amplified response of the overall
reaction rate by controlling the surface sites available for
reaction through the parallel path.
793
I. IN'rRODUC1'ION
An electrocatalytic reaction involves the transformation
ofreactant species to product species over a substrate that
serves as an electrode and as a catalyst. As electrode, the
substrate supplies the necessary electrons for reduction
or removes them for oxidation. As catalyst, the substrate
must initiate and complete the process in the same state
while selectively enhancing the rate of the desired
reaction. In examining an electrocatalytic reaction, one
typically assumes that the electrode current represents
the rate of the reaction itself. This assumption is accept-
able for sufficiently simple reactions where the reaction
of interest is the rate-limiting step in a series of other
events, like hydroxide adsorption or hydrogen desorp-
tion, that must also occur. For more complex processes,
however, the electrode current may not have a unique
relationship to the rate ofreaction. This occurs most com-
monly for the case of parallel surface reactions, in which
the electrode current alone cannot describe the
electrocatalytic process.
The information necessary for describing a complex
electrocatalytic system must come from additional
measurements providing qualitative and quantitative
information. These measurements, if not made on a
reacting electrode, must relate to the reacting electrode
in a straightforward manner. Examples of electrochemi-
cal measurements that provide quantitative information
include the ring current in a rotating ring disk electrode
configuration [1] and electro-oxidative assay of accumu-
lated surface species, as discussed in this chapter. A
794
nonelectrochemical example is differential electrochemi-
cal mass spectrometry (DEMS) [2,3], which can monitor
desorbing species during reaction with time constants
as fast as 0.2-0.5 s. In principle, in situ spectroscopic
techniques can provide qualitative information regarding
the nonfaradaic catalytic aspects of the mechanism and
identitY adsorbed species [4-6]. An improved under-
standing of electrocatalysis thus benefits from combi-
nation of complementary measurements.
We illustrate the procedure for obtaining mechanistic
and kinetic information for electrocatalysis of methanol
on a platinum electrode.This reaction has received a great
deal of attention because of its significance in direct
methanol fuel cells. In addition to the complete oxidation
product C02, a partial oxidation product CO is also
produced, and this CO leads to self-poisoning of the
overall reaction. There has been a long-standing contro-
versy over whether CO is produced in a series reaction
to C02 or as a side reaction, parallel to the overall
oxidation to CO 2. A complete review is beyond the scope
of this chapter, and the interested reader is referred to
the review literature [7,8]. In this chapter we describe an
experimental strategy that both verifies a hypothesis
and yields quantitative kinetic information. We develop
a kinetic model for methanol electrocatalysis based on a
Langmuir- Hinshelwood [9,10] description ofthe surface
chemistry. Such an approach aids in interpreting the
kinetic data and leads to an improved understanding of
methanol electrocatalysis.
II. EXPERIMENT DESIGN AND KINETIC
MODELING
The design of appropriate experiments depends on the
nature of the hypothesis. The kinetic analysis of the
experimental results, on the other hand, depends on the
level of detail that we choose to include in the model
description of the surface chemistry [11]. To begin, we
postulate the existence of a parallel path in the
electrocatalytic oxidation of methanol to C02, specific-
ally, a reaction path exists that does not involve Co. The
kinetic model for this hypothesis, when CO is the most
abundant reactive intermediate on the surface, is given by
CO
reo/! ,!s
(1)
CH30H/ r ""- C02
:>
p
where rca and r s stand for the rates of CO formation and
CO 2 production through the serial path and r p the rate
Sriramulu et al.
of CO 2 production through the parallel (non-CO) path.
Therefore, to veritY the hypothesis we must show that r p
has a finite value.
The number ofindependent pieces ofinformation that
we must have depends on the number of unknown quan-
tities in the reaction mechanism [11]. For example, we
must have at least two independent pieces of information
to monitor the two products CO and CO 2 for the model
in Eq. (1). On the other hand, we must have at least three
independent pieces of information to determine the rates
of the three reactions. Here, we obtain the three pieces
of information from the measurements of the charge
passed during potentiostatic methanol reaction qr, the
stripping charge qs required to oxidize the adsorbed
species after the reaction, and independent CO oxidation
kinetics.
Anticipating that the experimental results will veritY
the mechanism of Eq. (1), we attempt a more realistic
model of the surface chemistry. The two reactions by
which methanol makes CO and C02 comprise, of course,
far more than single steps. At the next level, we postulate
a reactive intermediate {RI} in the parallel branch,
r CO l'
c~ ~
CH30H r'co CO2 (2)
r '
R1
RI ~
in which we allow for the possibility that the reactive inter-
mediate may itself convert to Co. This model with
r~o = 0, represents the dual pathways mechanism first
postulated for formic acid oxidation [12,13].
Allowing for conversion of {RI} to CO helps
rationalize the many disparate claims made of this
mechanism. A study may find in favor of CO as the most
abundant reaction intermediate under conditions for
which either
rRI « rca (3)
or
rp « I
rca (4)
or alternatively, find in favor of a non-CO reactive inter-
mediate under conditions for which
rca, r~o « rRJ, r s (5)
The rates of each individual step depend on the rate con-
stant, surface concentrations of reactants, and avail-
ability of sufficient sites. Therefore, the possibility exists
Kinetic Modeling of Electrocatalytic Reactions
that differences in experimental variables-such as
potential, surface cleanliness and crystallographic
orientation, solution concentration, temperature, and
previous catalyst history~-among different experimental
studies could readily account for the different findings.
The model in Eg. (2) is not complete, as we must allow
for a source ofoxygen and for the electrode current. Either
an activated form of water [14,15] or adsorbed hydroxyl
from water dissociation [16,17] represents a likely source
ofoxygen
(6)
and desorption ofhydrogen accounts for the current flow
(7)
where it is assumed that H 20, H, and OH are adsorbed
species and that H+ is in solution. Hydrogen desorption
is generally considered a fast step and no doubt occurs
rapidly under the conditions of most electro-oxidation
reactions. Separating it from the overall catalytic scheme
in Eq. (2) gives a more accurate description of the real
process, iffor no other reason than the electrode current
alone cannot probe the kinetics of both pathways in the
parallel mechanism.
Comparing Eqs. (1) and (2), we see that an increase in
the level of detail is accompanied by an increase in the
quantity of information necessary to describe the
reaction. We must have at least eight independent pieces
of information to determine the individual reaction rates
for the model represented by Eqs. (2), (6), and (7). Clearly,
such a large number of independent measurements is
impractical; this necessitates some simplification and
parameter estimation from the results of a fewer number
of measurements. Acquiring data over a range of
experimental parameters (reaction time, potential, meth-
anol concentration, or temperature) can provide the
necessary information. In a later section we estimate the
rates of the individual reactions by comparing model
predictions with experimental data.
III. EXPERIMENTAL PROCEDURE
A. Dual Electrochemical Cell Apparatus
The three pieces ofinformation identified in the previous
section were obtained with a dual electrochemical cell
apparatus. Figure 1 shows the laboratory configuration
of the apparatus. The experimental system was com-
prised of two subsystems, the deaeration chamber (1)
795
and the electrochemical chamber (2). The deaeration
chamber, with dimensions 47 x 48 x 33 cm (H x W x D)
and made from clear polyvinyl chloride, housed the three
125-ml Teflon separatory funnels (al-a3) that served as
electrolyte reservoirs. Funnels (al) and (a2) contained
blank perchloric acid electrolyte, and funnel (a3) con-
tained methanol-bearing perchloric acid electrolyte.
Electrolyte deaeration was accomplished by continu-
ously sparging prepurified argon gas through the three
separatory funnels. The sparge gas exited the last
separatory funnel through a stripping flask (b) con-
taining ultrapure water and then into the deaeration
chamber. The argon gas exited from the deaeration
chamber into the laboratory atmosphere through a vent
at the rear of the deaeration chamber. A water trap
minimized back diffusion of oxygen through the vent
and a Swagelok pop-offvalve on the vent ensured against
accidental over pressurization of the deaeration
chamber. Teflon valves (c), secured to the front of the
chamber by stainless steel screws and viton o-rings, con-
trolled electrolyte flow to and from the electrochemical
cells. The drained electrolyte was collected in a reservoir
(d) for later disposal. The deaeration chamber had a
removable top for access to the components inside the
box. The top was sealed to the chamber box by a custom
viton gasket coated with Fomblin grease and compressed
by 16 wing nuts. The deaeration chamber was isolated
from the electrochemical chamber by a Teflon gasket (i)
through which the solution lines were routed. This iso-
lation permits pressurization of the electrochemical
chamber to facilitate draining of the electrochemical
cells.
The KF-50 cross (Duniway) (2) housed the two ident-
ical electrochemical cells (e). A detailed description of
the cells may be found elsewhere [18,19]. Briefly, each cell
consisted of a Teflon electrolyte cup (0.25 ml in volume),
a counter electrode of platinum foil (0.4 cm 2 surface
area), and a palladium a-hydride reference electrode.
Electrical connection to the cells was made through an
eight-pin electrical feedthrough (f). An inert atmosphere
was maintained over the cells by continuously flowing
prepurified argon gas. The purge gas and the solution
delivery/drain lines entered at the bottom ofthe cross (g).
A plexiglass transfer stage (h), shown magnified in the
inset in Fig. 1, enabled electrode transfer between the
cells. The single-crystal electrode (j) was mounted in a
glass sleeve (k) and attached offaxis to the transfer stage
through a Teflon bulkhead (1). The transfer stage was
sealed to a KF-50 blank flange by a viton gasket com-
pressed by four wing nuts (m).
Platinum single-crystal electrodes were made by
melting the end of a 0.5 mm platinum wire in a
796 Sriramulu et at.

Argon
Scm
-------u- I

(k)-
m_~~mple
a.2m

/
(1 )

Electrolyte Storage and Preparation Electrochemistry

Figure 1 Schematic of the experimental system divided into the deaeration chamber (1) and the electrochemical chamber (2). (a),
electrolyte reservoirs; (b), stripping vessel; (c) valves; (d), waste electrolyte reservoir; (e), electrochemical cells; (0, electrical
feedthrough; (g), inlet for solutions and purge gas; (h), transfer stage; (i), bulkhead connector; (j), single-crystal electrode; (k), glass
sleeve for the electrode; (I), Teflon bulkhead; (m), wing nuts; (n), vent valve.

hydrogen-oxygen flame to form a spherical bead about
2 mm in diameter [20]. A single-crystal bead was
formed only when great care was taken to remove the
molten bead from the flame slowly and to cool it
undisturbed in the ambient air. Etching this bead in
warm (55°C) aqua regia for 25 min revealed square etch
patterns characteristic of (100) facets and unetched flat
regions corresponding to atomically flat (Ill) domains.
The bead was mounted in a goniometer and precisely
(better than 6' ) oriented along its III axis by laser reflec-
tion off the (111) facets [21]. Once oriented, the bead
was polished with diamond paste to 0.5 ,um smoothness
to expose the (111) surface. The single-crystal bead was
spot welded to a connecting wire that was sealed to the
glass sleeve [(k) in Fig. 1]. The polished bead was flame
annealed in a hydrogen-air flame for 30 min to restore
surface order. Before each electrochemical measure-
ment, the electrode was cleaned in a hydrogen-air flame
for a few seconds and immediately immersed in argon
saturated ultrapure water. In the subsequent transfer to
the electrochemical chamber, a droplet of ultrapure
water protected the electrode surface from airborne
contaminants [21].
In operation, the cell was filled with electrolyte to form
a meniscus above the top of the cell. The working elec-
trode contacted the electrolyte at this meniscus. To
transfer the electrode between cells, the electrode was
raised slightly, the wing nuts (m) loosened, and the
transfer stage (h) rotated 180° to place the electrode over
the other cell. A drop of solution was allowed to reside
on the electrode during transfer to protect against
contamination. After electrochemical contact was
re-established with the meniscus in that cell, the wing nuts
were tightened.
The reference electrode in each cell was charged daily
at -150 ,uA to form the Pd- H phase. Current and poten-
tial measurements were performed with a Tektronix
TDS-520 high-speed digitizing oscilloscope and an
EG&G 263 potentiostat, both of which were interfaced
to a personal computer for data collection and analysis.
All measurements were performed at room temperature.
All potentials are reported with respect to a reversible
hydrogen electrode in 0.1 M HCI0 4 .
Performance ofthe dual-cell apparatus is illustrated in
Fig. 2, which shows a cyclic voltammogram of Pt(1ll) in
0.1 M HCl0 4 . The plateau in the hydrogen adsorption I
Kinetic Modeling of Electrocatalytic Reactions 797

B. Measurement and Data Analysis

150
The reaction charge was measured in cell A (Fig.l), which
contained methanol-bearing electrolyte, and the
stripping charge was measured in cell B, which contained
100 blank electrolyte. The procedure and examples of raw
C\I
I
data are depicted in the four panels of Fig. 3. The lower
E
u two panels show the potential waveforms applied to the
«::::t 50 working electrode, in this case Pt(lOO), in the respective
........ cells, and the upper two panels show the resulting
>. currents.
:t:::
en The measurements began with immersion ofthe clean
c
Q)
0 0 electrode into cell A at a potential of 0.055 V, where no
.....
c
reaction occurs. The potential was stepped to the desired
Q)
..... reaction potential E r and the resulting current transient
..... ir(t) recorded. The area under the reaction transient gives
~
() -50 the reaction charge qr passed during the reaction period
T. After the reaction period the reaction was quenched
by stepping the potential back to 0.055 V. The electrode
was rinsed under potential control with blank electrolyte
-100 to remove traces of methanol. A droplet of electrolyte
0.2 0.4 0.6 0.8 1.0
,
Potential / V RHE I>
l'l(a) CeliA (b) Cell B
Figure 2 Cyclic voltammogram (sweep rate, 50 mYls) of a
flame-annealed Pt(lll) crystal in 0.1 M HCl04. 0.5
~
E
(.)
desorption region is characteristic of a well-ordered sur-
face as is the sharp spike of the butterfly peak at 0.785 V.
« qr
E qs
.......
The height ratio of the butterfly spike to the hydrogen
plateau is 2.35; a ratio of 2 is generally accepted as evi- 0.0
~
...
dence of a clean well-ordered surface [22] and the best 1.0
obtained is 3.1 [23]. The absence of any other features in
the voltammogram is accepted as evidence of a clean
electrolyte. Trace amounts ofoxygen are a particular con- >
.......
cern, however, as oxygen reduction during methanol Er
co
:+J
oxidation will interfere with the measurement of the
reaction current.
Cleanliness of electrode transfer was verified by the
-C
Q)
0
c..
ability to obtain identical voltammograms in either cell
after electrode transfer from the other. This also showed 0.0
that the potential scales in each cell were equivalent and 16
that the reference electrodes in each functioned
identically. In addition, we have demonstrated the Time / s
absence ofoxygen in this system by several transfer exper-
Figure 3 Schematic representation of the multielectrolyte
iments with solution dosed saturated adlayers of CO on
experiment. The upper traces show the current measured on a
Pt(lll). These adlayers show complete stability, within Pt(IOO) electrode for the potential wave forms shown in the
0.0 I monolayers, when transferred between the cells, thus lower traces. The * denotes the electrode transfer from cell A to
showing that oxygen contamination, which would cell B. Respective concentrations (M) of HCl0 4 and CH30H
oxidize CO, was negligible [24]. were (a) 0.1, 0.1 and (b) 0.1, O.
798 Sriramulu et al.

covered the electrode surface as it was transferred 100 ~ I I I

(denoted by * in Fig. 3) to cell B. The potential in cell B • q,

was then ramped linearly (50 mV S-I) and the linear
o qs
sweep voltammogram recorded. The adsorbed residue 10
formed during methanol electro-oxidation in cell A was
oxidized in a single peak and the area under this N
'E
oxidation peak gives the stripping charge qs. u
Reaction charge and stripping charge measurements ()
E
can be performed at a constant reaction potential for
C1l
varying reaction periods or for a constant reaction period e> 0.1
and varying reaction potentials. Only the former set of Cll
..c:
()
measurements are discussed here because we wish to
focus on the mechanistic details of the reaction. A set of
0.01
time-dependent measurements at different potentials
would provide information on the potential dependence
of the kinetic rate constants but requires a mechanistic
0.001 I 11,,,,,1, ,10",,1 1'10'''.1 "10,,,,1 "10",,1
framework for interpretation.
0.01 0.1 1 10 100 1000
For comparison and later use in the modeling Time / s
exercise, the rate of residue oxidation at 0.6 V in blank
electrolyte was measured independently in a Figure 4 Reaction charge q, C.) and stripping charge qs CO)
double-step experiment. For this measurement the resi- measured on Pt(lll) for a reaction potential of 0.6 V The elec-
due was adsorbed after a lO-s reaction period of meth- trolyte was 0.1 M CH30H + 0.1 M HCl0 4 for the qr measure-
anol oxidation at 0.6 V in cell A. The residue-covered ment and 0.1 M HCl0 4 for the qs measurement. The solid lines
surface was transferred to cell B and residue oxidized in through the data points are the best-fit curves from the kinetic
blank electrolyte at a constant potential of 0.6 V, during model shown in Fig. 7 and the parameters listed inTable 1. Error
bars are shown at twice the relative standard deviation.
which time the oxidation current transient was
recorded.
to the oxidation of CO formed during methanol reaction.
IV. RESULTS With this assumption, the maximum CO coverage corre-
sponds to 0.29 monolayer (relative to the number of plati-
Figure 4 shows the results of the reaction charge and num surface atoms).
stripping charge measurements for methanol oxidation Figure 5 shows a semilogarithmic plot of the CO
on Pt(111) at 0.6 Vas a function of reaction period. Data oxidation rate measured in the double-step experiment
points were typically averaged over three measurements as a function of time at 0.6 V The linear relationship of
and only the significant error bars are shown at twice these data shows that CO oxidation has a simple
the standard deviation. These measurements cover four power-law dependence on time. Because CO coverage
others of magnitude of reaction period, from 0.03 to relates to the integral of these results, we can easily show
300 s. Even though the results are plotted logarithmically that the rate of oxidation has a simple power-law depen-
(to fit them all on a single graph), no simple relationship dence on CO coverage.
exists between the measured quantities and reaction With these three measurements (qr, qs, and CO
period. The reaction charge data appear to exhibit a lin- oxidation rate), we are in a position to verify the hypoth-
ear correlation, but as we discuss later, the deviations esis represented by Eq. (1). In Fig. 4, we observe that the
from linearity contain mechanistic significance. The stripping charge attains a steady value after lOs of reac-
reaction charge increases without limit, indicating that tion, which indicates that the surface reaction attains a
reaction continues indefinitely, i.e., the electrode main- steady state after this time. Note that this is also accom-
tains catalytic activity even for long times at the reaction panied by a distinct change in slope ofthe reaction charge;
potential of 0.6 V The stripping charge reaches a limiting the slope ofthe reaction charge after 10 s equals the steady
value of 0.14 mC cm -2 for reaction periods longer than value of the reaction current. The reaction current for
10 s. Several infrared studies have found CO as the most the mechanism in Eq. (1) is given by
abundant surface species at long times in concentrated
methanol solutions [4-6]. Therefore, it is reasonable to ir
attribute the limiting value ofthe stripping charge entirely
eM = 6r p + 4rco + 2rs (8)
Kinetic Modeling of Electrocatalytic Reactions 799

A. Yield Analysis: Evidence of Complex

Kinetics
We begin with a simple yield analysis to estimate the time
-, 0.01
dependence of the CO and CO 2 yield for the model in
(/)
Eq. (1). Because we wish to monitor two products, we
---c require two independent pieces of information: the
.2
CO reaction and stripping charge data shown in Fig. 4. The
"0
'x0 integral yield YP [7] ofpartial oxidation product describes
the net number of CO molecules formed per methanol
0

-
0
0
Q)
CO
molecule consumed during the reaction period r. For
the mechanism of Eq. (1) this is given by

S;[rco - rs]dt
a: yp(r) = f' (9)
0.001 0 0 Jo [rco + rp]dt
0
The fractional coverage of CO 8co (r) that builds up in
the reaction period r on an initially clean surface is given
0 20 40 60 by
Time /5

Figure 5 Rate of CO oxidation in 0.1 M HCI0 4 at 0.6 V

yp(r)
8co (r) = - -
M o
J' [rco + rp]dt (lOa)
measured in the double-step experiment. The CO was formed
on the electrode surface during 10 s of reaction in 0.1 M The stripping charge data independently monitor the CO
CH 30H + 0.1 M HCI0 4 at 0.6 V The solid line is a best-fit line coverage,
given by Eq. (32).
8co (r) = qs(r) (lOb)
2eM
where e denotes the charge of an electron and M the sur- where the factor of two arises from the two electrons
face atom density of Pt(lll) (1.5 x 10 15 atoms/cm 2); six, required to oxidize CO to CO 2 • The reaction charge
four, and two are the number of electrons transferred. relates to the individual reaction rates through the current
The rates in Eq. (8) represent the site time yield [10], transient i r [given by Eq. (8)]
which gives the number of molecules of product formed
per reaction site per second. Under steady-state con-
ditions, when the CO coverage equals 0.29, the rate of
qr = 1: irdt (II)

CO formation must equal the rate of its oxidation, i.e. Combination of Eqs. (8-11) gives the following
reo = r s . A previous DEMS study showed that the expression for yp :
presence of bulk methanol does not influence the
oxidation of adsorbed residue [25]. In view of this result 3qs
yp=-- (12)
we use the intercept of the data in Fig. 5 to estimate qr + qs
the rate of CO oxidation r s as 0.01 s-1 at a CO coverage
of 0.29 monolayers. Substituting this value into Eq. (8), where it is understood that all quantities in Eq. (12) are
we estimate r p as 0.035 S-I. Because r p has a finite value, functions of r. As CO and CO 2 are the only products con-
the parallel path does exist and thus verifies our sidered, the yield of complete oxidation product (C0 2)
hypothesis. Furthermore, the parallel path accounts for is given by
75% of the CO 2 produced under steady-state con- qr - 2qs
ditions. Yc = I -yp = - - - (13)
qr + qs
The mechanism represented by Eq. (I) is over-
simplified, of course, and describes the situation only at Figure 6 shows the yield of carbon dioxide (filled
long reaction times when CO is the most abundant sur- circles) determined from Eq. (13). At long times, the yield
face species. In the next section, with the aid of a yield asymptotically approaches a value ofunity. At short times,
analysis, we test the hypothesis that CO is the most abun- however, the calculated CO 2 yield is negative. Obviously,
dant adsorbate at all times. negative yields indicate a faulty assumption, in this case,
800 Sriramulu et at.

COa
keo/' "'-ks
0.8 ka kRl 7 ~
CH30Hs ~ CH30Ha ~ RIa k >- CO2, s
p
0.6
Figure 7 Proposed kinetic model for methanol electro-
oxidation.
0.4
"'C
Qi
'>, at short reaction times. This result shows that the simple
C\I 0.2
0
mechanism represented by Eq. (1) is inadequate to
<.) describe methanol electro-oxidation at all times. To
0 obtain a kinetic understanding of the reaction and
810

t
stripping charge data, we must invoke a more detailed
•
r:0

fi
m mechanism.
-02

-0.4 • r-

I
0.1 I I I I
0.1 10 1000 V. DEVELOPMENT OF THE KINETIC MODEL
Time! s

-0.6~
0.01 0.1 1 10 100
Time / s
Figure 6 Fractional yield of CO 2 Yc (.) [Eq. (13)] assuming
CO as the most abundant surface intermediate and (0) [Eq.
(14)] assuming H:C:O as the only adsorbed intermediate.
Details of the calculation are given in the text. Error bars for Yc
represent standard deviations. The solid line represents the yield
calculated from the kinetic model depicted in Fig. 7.
the assumption of CO as the only reactive intermediate. A
simple way to rectifY this problem is to choose a reactive
intermediate that requires three electrons for oxidation,
either HCO (formyl) or COHo Because we cannot dis-
tinguish between the two, we let H:C:O represent either
possibility. We can show the complete oxidation yield,
for H:C:O as the reactive intermediate [by a derivation
similar to that for Eqs. (9-13)], is given by [26]
qr - qs
Yc = qr + qs
The yield determined using Eq. (14) is also shown in Fig. 6
(open circles). With the H:C:O intermediate assumed,
the yield is always positive and varies from zero at short
time scales to unity at longer time scales. However pleas-
ing such a model might appear, the assumption ofH: C: 0
as the only intermediate contradicts the many infrared
findings in favor of Co. Note that at sufficiently long
times, the point is moot because both models [Eqs. (13)
and (14)] predict the same yield to within the scatter of
the data. Nonetheless, the results from the two models
do permit one deduction: CO is not exclusively formed
We use the results ofthe simple yield analysis to infer that
1000 methanol does not convert directly to CO in a sequence
of fast steps. The new mechanism, illustrated in Fig. 7, is
based on a Langmuir- Hinshelwood description of the
surface chemistry [9]. In particular, we assume that all
reactants are randomly adsorbed and that each reaction
step is an elementary process or an obvious combination
of elementary steps. The mechanism consists of irre-
versible adsorption of methanol followed by rapid
dehydrogenation to some, as yet unspecified, reactive
intermediate RI. The significance of RI is that branching
to the CO pathway occurs from this intermediate. We
use the stoichiometry of RI as a mechanistic parameter
in the model.
One obvious consequence of CO poisoning during
methanol oxidation is the availability of sufficient sites
for reaction. In an aqueous electrochemical environ-
ment, it is reasonable to suppose that water remains
adsorbed to the electrode surface. Indeed, in recent
infrared studies, water was found adsorbed on the Pt(111)
electrode surface at all potentials [27,28] and hence water
(14)
desorption should accompany methanol adsorption [29].
In the following equations, we write the site requirements
for the mechanism depicted in Fig. 7 in terms of the
water-covered reaction site W:
k,
CH30Hs +mW ~ CH30Ha +mHzOs (15)
k R1
CH 30Ha +xW ~ RIa +xHa +xHzOs (16)
keD
RIa + P W ~ COa + (4 - x) H a + P Hz Os (17)
1
Kinetic Modeling of Electrocatalytic Reactions 801

kp occurs only at potentials posItIve of 0.55 V [30,31].

RIa + W---+C0 2.s + (6-x) H a + (m + x-5) H20s
kd
2W ~ H a + OH a + H 20 s
L d
H a + H 20 s ~ H+ + e- + W
where the subscript a denotes adsorbed species and the
subscript s denotes solution species.
Table 1 lists the kinetic and mechanistic parameters
and the site requirements for each species in the model.
We divide the parameters into two groups: kinetic
parameters, which are continuously variable, and
mechanistic parameters, which can take on only discrete
values according to the number ofsites required by a given
species or reaction or the structure of the reactive
intermediate.
In the kinetic model described above, we assume that
RIa reacts with adsorbed water, whereas CO a reacts with
OH a. These assumptions require justification. In a
recent infrared study of methanol electro-oxidation on
Pt(lll), CO 2 was detected at a potential of 0.4 V [6].
Our previous potential-dependent CO 2 yield measure-
ments substantiated these results and suggested that
the parallel path was operative at low potentials on
Pt(lll) [30]. Because water dissociation is negligible for
potentials less than 0.55 Von Pt(lll), we attribute the
parallel path to the reaction of RIa with adsorbed water.
On the other hand, several investigations have found
that for subsaturation CO coverages, CO oxidation
Because this potential range also corresponds to water
(18) dissociation, we assume that CO oxidation takes place
by reaction with OH a [16,17].
We can reduce the 11 unknown parameters (listed in
(19) Table I) to a more manageable number through various
simplifYing assumptions. Of all possible adsorbed
species, we consider only three as important and specifY
these as the most abundant surface species [10]: RIa,
COa, and W We assume that the other species are
(21) present only in vanishingly small concentrations on the
surface. With these assumptions, we can write the
following site balance:
m(JRI + n(Jco + (Jw = I (22)
where (Ji represents the ratio of number of molecules of
species i to the number of surface metal atoms and m
and n represent the respective site requirements for RI
and Co.
Furthermore, we apply the "pseudo-steady-state
approximation" (PSSA) [10] to the minority species and
set the temporal derivatives of their coverages to zero.
For adsorbed methanol,
(23)
where (JM is the coverage of adsorbed methanol and eM
the bulk concentration of methanol. Here, the PSSA is
equivalent to the assumption that reaction of adsorbed
methanol is very fast compared with methanol

Table 1 Summary of Parameters in Methanol Electro-Oxidation Model

Description Parameter Value

Kinetic parameters (continuously variable)

Methanol adsorption kaCm 0.8 S-1
RI formation k R1 PSSA, CH 3 0H a
CO formation kcoC::; 5.6 s-1
RI oxidation to CO 2 (parallel path) kp 2.8 S-1
RI oxidation to CO (series path) ksC::; BOH 0.035 S-1
Equilibrium constant for water dissociation K w =kct/L ct PSSA,OH a
Proton desorption L H PSSA, H a
Mechanistic parameters (discretely variable)
Methanol adsorption sites m 3
CO adsorption sites n 2
Surface water required for series path p 3
Hydrogens removed to form RI x 3
802 Sriramulu et al.

adsorption. For adsorbed hydroxyl groups, the PSSA is where ir is given by Eq. (27) and the equation for qs as

d~H qs = eM [(6 - x)8Rl + 2()eo] (31)

------;It = kd()w2 n
- k-dCW()H()OH - ksCw()eO()OH =0
(24)
A. Solution Procedure
where Cw represents the water concentration in the bulk.
We anticipate that oxidation of CO will be much slower The three PSSA for CH 30H a , OH a , and H a eliminate
than water dissociation and association, so we may treat three kinetic parameters as indicated in Table 1. The
Eq. (19) as being in equilibrium, with the equilibrium remaining eight parameters must be determined from
constant fitting experimental results. Before proceeding with the
fitting exercise, we must ascertain that the experimental
K = ~ - ()H()OHCW (25)
data contains eight pieces of information to estimate the
w L d - ()2 eight parameters [11]. Note that of these eight parameters
W
only four, the kinetic parameters, are continuously
The PSSA for adsorbed hydrogen is variable. A cubic polynomial is the simplest curve that
can fit the qr data and a two-parameter curve the simplest
d()H = x k aCM()~ + (4 - X)keo()RI()Pw to fit the qs data. In addition, the CO oxidation data in Fig.
dt 5 require two fitting parameters. Thus, in the absence of
(26)
+ (6 - X)kp()Rl()W a model, we obtain eight pieces of information from
+ 2ks()eo()oH - LHCW()H = 0 curve fitting the experimental data. We can therefore use
the information contained in the experimental data to
Because the only charge transfer is Eq. (21), we use Eq. estimate the unknown parameters in our model.
(26) to calculate the reaction current directly, We can obtain an estimate for the rate constant for CO
oxidation from the kinetic data reported in Fig. 5. We
e~ =LHCw()H = XkaCM()~ + (4 - X)keo()RI()Pw can write the following rate equation for the CO
oxidation:
+ (6 - X)kp()RI()W + 2ks()eo()oH (27)
d()eo = k~()eo = (0.035 s-l )Beo (32)
Integrating Eq. (26) will result in a constant ()H, which in dt
turn will result in a constant current according to Eq. (27). where k~ is the apparent first-order rate constant for this
This is unrealistic. Instead, in this case, the PSSA implies process. The reaction rate for CO oxidation by Eq. (20) is
that the temporal derivative of ()H is negligible compared
with the temporal derivative ofeither ()eo or ()RI. Note that r s = ksC~()eo()oH (33)
although we set the time derivatives ofthe coverage to zero
in the PSSA, the physical reasons for the approximations and comparison ofEqs. (28) and (29) yields
are different for CH 30H a , OHa , and H a as discussed k~ = k s C~()OH (34)
above. See Ref. 10 for a further discussion of the PSSA in
surface reactions. The implication of the results of Fig. 5 and Eq. (30) is that
The two main kinetic equations are the temporal the surface concentration of hydroxyl groups remains
derivatives of RI and CO given by approximately constant throughout CO oxidation. This
is in keeping with the PSSA for OH and shows that water
d()RI m dissociation acts to keep the OH coverage approximately
dt = kaCM()w - kCO()Rlffw - kp()RI()W (28)
constant.
The kinetic differential Eqs. (31) and (32) were solved
and
numerically with a fourth-order Runge- Kutta method,
combined with Eqs. (22), (27), (30), (31), and (34) to
d()eo = keO()RI()Pw - ksC~()OH()CO (29) provide the best-fit parameters for the model. We found
dt
that in potentiostatic measurements, predominantly
We can now write the equation for qr as capacitive charging took place in the first 10 ms with neg-
ligible methanol reaction. As initial conditions, we set
qr = I irdt (30) both ()RI and ()eo to zero and ()w to unity at t = 10 ms.
The mechanistic parameters, m, n, p, and x were allowed

l
Kinetic Modeling of Electrocatalytic Reactions
to have only integral values over the entire reasonable
range for each parameter. The best-fit curves are shown
as the solid lines through the data in Fig. 4 and the corre-
sponding parameter values are listed in Table 1. The fits
to the data are excellent, with the curves passing through
every data point.
VI. DISCUSSION
The main benefit of the model at this time is its use in
explaining the poisoning process during methanol
oxidation. The kinetics of the individual reaction steps
are shown in Fig. 8 as a function of time. At short times
methanol adsorption is rapid, starting off at 0.8 S-I, but
the adsorption rate decreases with time due to the
accumulation of Co. The rates of CO formation and
direct oxidation of RI to CO 2 both go through a maxi-
mum with time before achieving their steady-state values.
This behavior follows from the response to poisoning.
On the unpoisoned surface (short time scales), methanol
adsorption is fast and the overall rate is limited by
reaction ofRI to CO 2 primarily but also by RI conversion
to co. The increasing CO coverage blocks sites for meth-
anol adsorption, thus transferring kinetic control to the
adsorption step. This decreases the supply of RI and the
rates ofRI reaction (to either CO or CO 2) fall accordingly.
Steady state is achieved when the rate of CO formation
.............. rs
0.1
";"
(fl
---2
ca 0.01
a:
0.001
0.Q1 0.1 1 10 100
Time / 5
Figure 8 Time dependence ofthe rates ofdifferent steps in the
kinetic model depicted in Fig. 7. ra represents the rate of meth-
anol adsorption, reo the rate of reactive intermediate (RI) con-
version to CO, rp the rate ofRI oxidation to C02, and rs rate of
CO oxidation to C02.
803
equals its rate of oxidation. At steady state the rate of
methanol adsorption equals the combined rates through
the parallel and the serial paths. An especially important
point, however, is that the predominant path for CO 2 for-
mation is the parallel path, whose rate is significantly
greater than that of the serial path at all times. Because
direct oxidation of CO is even slower at lower potentials,
this result indicates the need for further study of the
behavior of the parallel path at lower potentials.
The results shown in Fig. 8 shed light on the fine struc-
ture displayed by the reaction charge data of Fig. 4. In Fig.
8, we observe a change in the slowest step from CO 2 for-
mation (by the parallel path) to CO formation at 0.4 s.
Because charge transfer (through proton desorption)
accompanies both reactions, a change in the slowest step
should influence the measured current and hence the
reaction charge. This is indeed the case in Fig. 4 where
the reaction charge data exhibit a distinct change in slope
at 0.4 s. At short times CO oxidation does not contribute
significantly to the measured current. On the other hand,
once CO oxidation becomes significant it begins to con-
tribute to the reaction current as reflected in the change
in slope ofthe reaction charge at 10 s.
The above discussion illustrates the sensitivity of the
overall oxidation rate to CO poisoning. Because CO con-
trols methanol adsorption, a decrease in CO coverage
will cause an increase in the rate through the parallel
(non-CO) path. This could in part explain the observation
that the parallel path is more active on Pt(lll), which
poisons to a lesser degree, than on Pt(100), which is sus-
ceptible to a greater degree of poisoning [30]. Moreover,
if the CO coverage is greatly reduced, then the
rate-limiting step will transfer to the parallel path.
It is interesting to compare the more detailed model
(Fig. 7) with the two simpler ones described at the begin-
ning of the chapter. The complete oxidation yield
obtained from the complex model is shown by the solid
line in Fig. 5. Note that the curve makes a smooth
transition from the data for the H:C:O-only model (open
circles) to the CO-only model (filled circles) and is
remarkably close to our hypothetical yield curve [32] pre-
pared without knowledge of the model results. The inset
in the figure shows the relative abundance of RI, in this
case H:C:O (x = 3), to CO; the latter behaves as the domi-
nant species only after 5 s of reaction time. These results
1000 clearly resolve the dominant reaction path for methanol.
It is possible to get oxidation through either the parallel
or the serial path (or both), depending on reaction con-
ditions.
Throughout the entire modeling exercise, we have
assumed that partial oxidation products, most notably
formaldehyde, do not desorb from the surface. In a recent
804 Sriramulu et at.

study, Korzeniewski and Childers [33] found low yields of 3. B Bittens-Cattaneo, E Cattaneo, P Koenigshoven, W
formaldehyde at a reaction potential of 0.6 V Based on Vielstich. J Electroanal Chern, 17:181, 1990.
their study, they suggest that H 2CO could be a long-lived 4. S-C Chang,Y Ho, MJ Weaver. Surf Sci, 265:81, 1992.
intermediate in this reaction. In principle, a I : I ratio of 5. MI Lopes, I Fonesca, P Olivi, BBeden, F Hanh, JM Leger,
C Larny. J Electroanal Chern, 346:415, 1993.
H2CO and CO production would match the H:C:O-only
6. XH Xia, T Iwasita, F Ge, W Vielstich. Electrochirn Acta,
yield curve in Fig. 5. However, we were not able to obtain
41:711,1996.
a good fit for the model depicted in Fig. 7 with RI chosen 7. TD Jarvi, EM Stuve. In J Lipkowski, PN Ross eds.
as H2CO (x = 2). It is difficult to explain partial oxidation Electrocatalysis.Wiley-VCH, NewYork, 1998.
products like H 2CO on the basis of a long-lived H:C:O 8. R Parsons,T Vandernoot. J Electroanal Chern, 257: 9,1988.
intermediate, so one ofthe avenues offurther work in this 9. RI Masel. Principles ofAdsorption and Reaction on Solid
area is to propose a model that successfully accounts for Surfaces. New York: Wiley, 1996.
the desorption of partial oxidation products. 10. M Boudart, G Djega-Mariadassou. Kinetics of Hetero-
geneous Catalytic Reactions. Princeton, NJ: Princeton
University Press, 1984.
VII. CONCLUSIONS II. JA Durnesic, RF Rudd, LM Aparicio, JE Rekoske, AA
Trevino, The Microkinetics of Heterogeneous Catalysis.
Our experimental measurements verified the existence of ACS Professional Reference Book. American Chemical
a parallel path for methanol electro-oxidation on the Society,Washington, DC, 1993.
Pt(lll) electrode. Furthermore, the parallel path 12. A Capon, R Parsons. J Electroanal Chern, 45:205,1973.
accounted for the majority of CO produced under our 13. A Capon, R Parsons. J Electroanal Chern, 44:1,1973.
experimental conditions. A simple model did not 14. P Shiller, A Anderson. J Electroanal Chern, 339:201, 1992.
adequately account for all the experimental observa- 15. A Wieckowski, J Sobkowski. J Electroanal Chern, 63:365,
tions. As an alternative, we invoked a more detailed 1975.
Langmuir- Hinshelwood kinetic model with adjustable 16. E Herrero, K Franaszczuk, A Wieckowski. J Phys Chern
98:5074,1994.
parameters. This model provided an excellent fit to our
17. HA Gasteiger, N Markovic, PN Ross, EJ Cairns. J Phys
experimental data. Results from this modeling exercise
Chern, 97:12020, 1993.
show that adsorbed CO, in addition to poisoning meth- 18. RL Borup, DE Sauer, EM Stuve. Surf Sci, 293: 10, 1993.
anol adsorption, also influences the course ofthe surface 19. RLBorup, DE Sauer, EM Stuve. Surf Sci, 374:142, 1997.
reactions. With increasing CO coverage, kinetic control 20. J Clavilier. J Electroanal Chern, 107:205, 1980.
of the overall reaction transfers from oxidation of the 21. J Clavilier, D Armand, SG Sun, M Petit. J Electroanal
reactive intermediate to methanol adsorption and finally Chern, 205:267, 1986.
to CO oxidation. Further validation of the model must 22. DE Sauer, R Borup, EM Stuve. In G Jerkiewicz, MP
come from a microkinetic analysis based on comparisons Soriaga, K Usosaki, A Wieckowski, ed. Solid-Liquid
of model calculations with experimental results over a Electrochemical Interfaces. Washington, DC. 1997.
wider range ofexperimental conditions such as reaction 23. A Rodes, MA Zarnakhchari, K EI Achi, J Clavilier. J
Electroanal Chern, 305:115, 1991.
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24. TD Jarvi. Ph D Thesis. University of Washington, Seattle,
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25. J Wilsau, J Heitbaurn. Electrochirn Acta, 32:943, 1986.
26. TDJarvi, S Srirarnulu, EM Stuve. J Phys Chern B, 101:3649
ACKNOWLEDGMENTS
1997.
We gratefully acknowledge thoughtful discussions with 27. K Hirota, M-B Song, M Ito. Chern Phys Lett, 250:335,
Carol Korzeniewski and Charlie Campbell and financial 1996.
support from the Link Foundation (TnJ) and the 28. T Iwasita, XH Xia. J Electroanal Chern, 411:95, 1996.
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National Science Foundation (CTS-9502971).
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45
Properties of Bimetallic Electrodes: Spectroscopic
Characterization and Electrocatalysis
Christopher Stuhlmann* and Henning Hoffschulzt
University ofBonn, Bonn, Germany
Klaus Wandelt
Rheinische Friedrich-Wilhelms-University, Bonn, Germany
ABSTRACT
In this chapter the ultrahigh vacuum-based spectro-
scopies x-ray photoelectron spectroscopy (XPS), ultra-
violet photoelectron spectroscopy (UPS), Auger electron
spectroscopy (AES), and ion scattering spectroscopy
(ISS) are introduced. The relative merits of these tech-
niques, which can only be used in ex situ experiments, are
discussed. Three illustrative examples demonstrate the
broad applicability of XPS, UPS, and ISS and especially
of their combination: characterization of the emersion
process of Sn and Pt-Sn electrodes from sulfuric acid,
determination of the structure of Cd underpotential
deposition layers on Cu(lll), and the correlation of
spectroscopic surface composition data with the
electrocatalytic CO oxidation rate on Pt - Ru electrodes.
I. INTRODUCTION
Bimetallic and alloy catalysts often exhibit a much
enhanced catalytic activity or selectivity compared with
that of their pure components. The physical mixture and
the electronic interaction of the alloy constituents lead to
a modified interaction between the catalyst and the
reactants. Because the primary step in a heterogeneously
Current affiliations:
* Innosoft GmbH, Cologne, Germany.
t SAP AG, Walldorf, Germany.
805
catalyzed reaction is the adsorption of at least one of the
reactants from the gas phase or from solution, it is only
the surface of the catalyst that is involved in the process.
This restriction, however, makes an understanding of
the catalyst's influence not easier but rather more difficult.
Not only is the surface ofan alloy characterized by chemi-
cal (besides structural) heterogeneity, its surface compo-
sition may also deviate strongly from the known bulk
composition due to segregation effects. Surface/ interface
segregation is driven by a reduction in surface/interface
free energy and is mostly different for a free surface (in
ultrahigh vacuum [UHV]) and an adsorbate (or electro-
lyte) covered surface/interface. Thus, the most basic par-
ameter to be determined for an alloy surface is its true
composition, i.e., the relative number ofsurface atoms of
species A and B, respectively, per unit area (Fig. I). This
is feasible (though not easy) for alloy surfaces in ultrahigh
vacuum using a variety of electron- or ion-based surface
spectroscopies as, e.g., described in Sec. II. However, this
is much more difficult for an electrode surface immersed
in a solution, which excludes the application of such
spectroscopies. Instead, in situ electrochemical methods
make use of adsorption/desorption processes that (are
believed to) involve preferentially only one of the com-
ponents in the surface of the alloy electrode. These
"chemisorptive/ reactive titration" methods, however,
are based on an assumption about what a priori is
unknown, namely the adsorption behavior of the alloy
806 Stuhlmann et al.

(a) (b) (c)

Figure 1 Schematic representation of different distributions ofcomponents A and B at the surface ofa binary alloy AxB1- x at con-
stant x. Implications ofthe different distributions are discussed in the text.

surface as a function of surface composition, as empha- UPS (hv=40.8 eV)

sized above. For the time being, there is hardly any better CuPt,_,(111 )
Pt
way as to take an electrode out of the electrolyte and to
make it accessible to the surface spectroscopic methods, Pt(111)
::::l
that is to transfer it into an UHVapparatus. Given the most
careful and sophisticated transfer process, the mere .e~ Cu 015 PtO'5(111 )

change in environment, i.e., from the electrolyte into ~

CUO.25Pt075(111 )
·Cii
vacuum, must be suspected to cause changes in the chemi- c
Q) CUO.65Pt035(111 )
cal state ofthe surface, so that after all the result obtained ~
in UHV may not represent the surface composition in CU075Pt025(111 )
contact with the electrolyte before transfer. This dilemma
- CU(111)
remains to be solved, because a reliable determination of
the true surface composition in the electrolyte is offunda- o 246 8 10 12

mental importance. binding energy Eo" (eV)

Besides the average composition AxB1- x of a binary

alloy surface, it is equally important to know the distri-
bution ofthe atoms A and B. Figure I sketches three differ-
ent distributions at constant composition: an ordered
arrangement, island formation, and a statistical dis-
tribution. It is obvious that the availability of twofold
(bridge) and threefold (hollow) adsorption sites of given
composition, namely of "ensembles" like A 2, AB, B 2,
and A3, A 2B, AB2, B3, respectively, are quite different on
the three surfaces. Furthermore, a bridge bond to A2 will
differ from that to AB and, likewise, a triple bond to A 2B
will differ from that to AB2 and so on. This mere
"ensemble effect" introduces already a wide variety of dis-
similar adsorption sites at the surface ofa binary alloy.
In addition, interactions between the constituents of
the alloy will modifY their electronic structure and hence
their chemical properties. The valence electronic struc-
ture of an alloy is not a simple superposition of those of
Figure 2 He II (40.8 eV) excited angle-integrated photo-
emission valence band spectra ofCuxPtl-x(lll) alloy surfaces.
The CUOI5PtO.85 and CUO.65Pt035 surfaces are produced by
sputtering (followed by mild annealing) of the stoichiometric
CUO.25PtO.75 and CUO.75PtO.25 surfaces, taking advantage of pref-
erential sputtering of the lighter component Cu. Note the sys-
tematic change in electronic structure as a function of surface
composition.
the pure component metals. This is clearly demonstrated
in Fig. 2, which, as an example, displays angle-integrated
UV photoelectron spectra (see Sec. II.B.) of the valence
band region of Cu- Pt(lll) alloy surfaces of different
composition excited with He II radiation. The prominent
peak in the Cu(lll) spectrum corresponds to emission
from the Cu(3d) states, whereas the Pt(lll) spectrum is
characterized by the spin-orbit- and crystal-field-split
 Properties of Bimetallic Electrodes
Pt(5d) states. The high density of states near the Fermi
level (E~ = 0) explains the high catalytic activity ofPt for
many reactions in contrast to Cu. Alloy formation
between Pt and Cu causes a significant change in the elec-
tronic structure of both components. With decreasing Pt
content the splitting of the Pt(5d) states and the density
of states at the Fermi level decrease, whereas the Cu(3d)
states shift toward lower binding energies. The first obser-
vation may be conceived as a mere dilution effect, i.e.,
the average distance between the Pt atoms increases.
The shift of the Cu(3d) states suggests some charge
redistribution between the components or within the Cu
states. These electronic structure changes are commonly
termed "ligand effect" and lead to a further modification
of the adsorption properties of the alloy surfaces (as a
function ofcomposition) compared with the pure metals,
as was demonstrated for this specific alloy system in a
number of publications [1-3].
Moreover, the local electronic properties will also
depend on the above discussed geometrical distribution
of the components. Pt islands within a Cu surface (Fig.
lb, Pt black, Cu white) will probably behave more Pt-like
than the fully Cu surrounded Pt atoms in an ordered array
as sketched in Fig. la. Thus, the combination of surface
concentration, geometrical distribution, and resultant
electronic structure lead to a wide range ofadsorption site
properties on alloy surfaces.
Most catalytic reactions between two reactants seem
to proceed according to a Langmuir-Rinshelwood
\ mechanism, that is, both species are adsorbed on the sur-
face and are thereby "activated" before they react with
each other to give the product. One and the same pure
metal surface, e.g., pure Pt, may not be suited to "activate"
or even accommodate both reactants equally well. In
turn, each component of a suitably chosen binary alloy
may preferentially interact with just one of the two
reactants and thereby provide optimal "activation." This
"bifunctionality" of an alloy catalyst is demonstrated in
Sec. V. with the example of the electrocatalytic CO
oxidation using Pt-Ru electrodes. It is again obvious
from Fig. 1 that the distribution of adsorption sites, and
as a consequence the distribution of the adsorbed
reactants will have a tremendous influence on the
reaction kinetics. For instance, if a surface as shown in
Fig. lb leads to an islanding of the reactants, i.e., their
lateral segregation, the reaction will proceed only at the
island boundaries.
From these considerations it becomes obvious that not
only the surface composition but also the distribution of
the components, which at last may also depend on the
preparation conditions of a surface, playa crucial role
for an understanding of the catalytic activity of alloy
807
surfaces both in contact with a gas phase or with a
solution. To date there is no better way to determine the
surface composition by ex situ spectroscopies, that is, in
the absence of the electrolyte (or a gas phase). In this
chapter we first give a brief description of x-ray and UV
photoelectron spectroscopy (XPS, UPS), Auger electron
spectroscopy (AES), and ion scattering spectroscopy
(ISS) (Sec. II.). Although all three spectroscopies furnish
information about the surface composition and to some
extent about the surface distribution, the first two are also
best suited to study the electronic structure. The exact
determination of the distribution on an atomic level is
much more difficult. There are basically two possibilities,
either the distribution is given and known, as e.g., with
chemically ordered alloy surfaces, or the distribution
has to be determined atom by atom by scanning tunneling
microscopy/spectroscopy. The latter has been achieved
in URY, but to the best of our knowledge not yet in situ
at an alloy-electrolyte interface.
In the following three sections we apply XPS, UPS,
and ISS in combination with other surface sensitive tech-
niques to characterize the emersion process of Sn and
Pt-Sn electrodes from sulfuric acid (Sec. IILA.), to deter-
mine the structure of upd layers of Cd on Cu(111) in
hydrochloric acid (Sec. IV), and to correlate the
spectroscopic surface composition data with the
electrocatalytic CO oxidation rate on Pt-Ru electrodes
prepared by codeposition from electrolytes containing
varying concentrations of both metal ions (Sec.V).
II. EX SITU SPECTROSCOPIES
Once the sample has been brought to a URV environ-
ment in a transfer experiment, the whole plethora of
URV-based spectroscopies can be applied. Of particular
importance are spectroscopies involving low- and
medium-energy electrons emitted or scattered by the
surface. There are many different surface spectroscopies
exploiting electrons in an energy range between few eV
and about 2 keY with the common rationale of the
extremely small mean free path length ofelectrons in this
energy range in condensed matter. On the other hand, it
is this same reason, which makes electron spectroscopies
particularly fit for surface analysis, that also thwarts their
application to electrode surfaces in an in situ environ-
ment because it is impossible for free electrons to pen-
etrate the electrolyte. The same restrictions also apply to
ISS. Therefore, the techniques whose application to
bimetallic electrodes are discussed in this chapter,
namely photoelectron spectroscopy and ISS, can only
be used after transfer of the sample from the electro-
808
- I uf
__-------- Evac*----
- - - : - : : : - EF
valence
band
core
levels
/x ~ >'
spectrometer
(a)
Figure 3 (a) Energy diagram for the XPS process, showing both the sample and the spectrometer. Note that the quantity measured in
an experiment is E kin , the kinetic energy ofthe photoelectron in the spectrometer. (b) Energy diagram ofthe Auger process that may fol-
low the photoionization sketched in (a) as a secondary process.
chemical cell to UHV Problems associated with this
transfer are discussed in the next section.
A. X-Ray Photoelectron Spectroscopy
There is a number of good books on photoelectron
spectroscopy [4-8]. For a detailed discussion of all
aspects of XPS and UPS, the reader is referred to the
literature. We only give a short summary of those aspects
that are most relevant to electrochemical applications.
Photoelectron spectroscopy is based on the
photoelectric effect. An incoming photon is absorbed in
or near the surface of the solid and the energy of the
photon is transferred to an electron. If the energy of the
photon is sufficiently high, the electron may leave the
solid. A schematic diagram ofthis process is shown in Fig.
3. It is immediately obvious that the kinetic energy of the
electron after the excitation from the initial state X is
E kin = hv - Eb(X) - <1>" (1)
Stuhlmann et al.
-1-
>
J::.
uft
Evac
• EF
Z
I I
y
~
UJ'
,
x
~
UJ.!
Ix
sample sample
(b)
where hv is the energy of the incoming photon, Eb(X) is
the binding energy of an electron in state X, and <1>, is
the work function ofthe sample. The reason why <1>" enters
Eq. (1) is that in the solid state, binding energies are
usually given with respect to the Fermi energy E F rather
than with respect to the vacuum energy Evac. On the other
hand, E vac is the zero of the kinetic energy scale for elec-
trons in vacuum. Therefore, the difference between these
two reference points on the energy scale has to be taken
into account explicitly.
Because the Fermi energy E F equals, apart from a
small correction, the chemical potential of the electrons
in the solid, the Fermi levels of two conductors con-
nected by a wire have the same position on the energy
scale. This implies that the vacuum levels at the sample
surface and within the analyzer differ if the work function
of the sample <1>" and of the spectrometer <1>spect are
different, which is generally the case (Fig. 3a). The kinetic
energy of the electron has its zero at E vac , so the kinetic
energy within the analyzer E~in differs from that immedi-
 Properties of Bimetallic Electrodes
ately after the photoemission event Ekin. Therefore, the
quantity measured in an experiment is
(2)
where <l>spect is the work function ofthe spectrometer. With
the known photon energy hv and the spectrometer work
function <l>spect, the binding energy of the initial electron
state Eb(X) is now easily calculated.
A typical experimental setup consists of a laboratory
x-ray source and an electrostatic analyzer. The Al K a line
at 1486.6 eVand the Mg K a line at 1253.6 eVare widely
used for the excitation of photoelectrons. Often, x-ray
sources have a dual anode, enabling easy switching
between both excitation energies (see below). The achiev-
able energy resolution is usually limited by the natural
line width of the x-ray source, which is slightly less than
0.9 eV for Al K a and 0.7 eV for Mg K a • Qualitative analy-
sis of the chemical surface composition is usually
straightforward. The binding energies of core electrons
are quite characteristic of the individual chemical
elements, which can be identified by comparison with
tabulated values [9,10].
A detailed analysis of the binding energies of core
I'
I
levels reveals not only the chemical identity of a surface
species but also its oxidation state. As a rule of thumb,
binding energies shift to higher values with increasing
oxidation state of the source atom because of a reduced
screening of the positive charge of the nucleus by the
remaining valence electrons. Such "chemical shifts" of
up to several eV are not uncommon. Once again, refer-
ence data have to be used for a proper identification of
oxidation states.
XP spectra are usually complicated by the presence of
a secondary process, the emission of Auger electrons.
After emission of a photoelectron, the atom remains in
an excited state with a hole in a core level. One ofthe poss-
ible deexcitation processes is the Auger process (Fig. 3b).
The core hole in level X is filled by an electron from level
Y with the simultaneous emission of an electron from
level Z that picks up the energy released in the transition
from Y to X. The kinetic energy of the Auger electron is
(3)
Strictly speaking, Eb(Z) here is the binding energy of level
Z with a core hole present rather than that in a neutral
atom. Note that the energy of the exciting radiation does
not enter Eq. (3). Therefore, Auger electrons can easily
be discerned from photoelectrons if different photon
energies hv (from a dual anode, see above) are used for
the excitation. The kinetic energy of the Auger electrons
809
remains constant in this case whereas that of the
photoelectrons varies according to Eq. (2).
The kinetic energy of Auger electrons is element
specific and also subject to chemical shifts (AES), but
because three energy levels are involved [Eq. (3)], the
interpretation is usually not as simple as for photo-
electrons.
Quantitative analysis ofthe surface composition from
photoemission spectra makes use of the fact that the
intensity of each line in the spectrum is proportional to
the area density of emitting atoms n in the surface. A
calculation of absolute intensities from "first principles"
is, however, usually not possible because a lot of
parameters would have to be known that are difficult to
determine. This includes instrumental characteristics
like the x-ray flux, the transmission of the analyzer,
and physical parameters like the photoemission cross-
section. These parameters, though usually not well
known, remain constant as long as the experimental
setup is not modified. Therefore, calibration measure-
ments with samples of known composition are the safest
route to reliable quantitative data.
Of course, photoelectrons are emitted not only from
the topmost layer. Photoelectrons originating from
deeper layers are, however, subject to scattering at outer
layer atoms on their way to the surface, and their intensity
is damped accordingly. The total intensity is therefore
quite well described by
(4)
where n(z) is the area density ofatoms at a distance z below
the surface, A. is the mean free path length of the
photoelectrons in the respective material, and () is the
detection angle with respect to the surface normal. The
effective sampling depth of XPS can thus be adjusted
within certain limits by changing the direction angle ()
B. Ultraviolet Photoelectron Spectroscopy
Photoemission occurs not only from the core levels but
also from the valence band of a solid. The core levels
are relatively well-defined atomic levels even in a
close-packed solid, whereas the valence band arises as a
consequence ofthe significant overlap ofouter shell elec-
tron wave functions. The overall width of the valence band
is large (several eV), but there is a fine structure due to the
contributions of distinct atomic orbitals. If adsorbates
are present, photoemission from their molecular orbitals
is also found in the energy range of the valence band.
Because the valence electrons are responsible for chemi-
810 Stuhlmann et aI.

cal bonding, photoemission from the valence band reveals d bands

details of the nature of the adsorbate-substrate bond.
In an XPS experiment alone the fine structure of the I]
valence band is usually not accessible due to the limited
energy resolution of common x-ray sources. Therefore,
noble gas discharge lamps are to be preferred as excitation
sources for the investigation of the valence band. These
provide ultraviolet light with a line width in the meV
range, typical lines being He I (21.21 eV), He II (40.81 eV),
and Ne I (16.87 eV). * Once again, the reader is referred ::::l
to the literature for a more detailed discussion of the
experimental setup and possible applications [4,8,11,12]. ....
.0
~
As a typical example, an angle-resolved ultraviolet
z;.
photoelectron (UP) spectrum of Cu is shown in Fig. 4. "en
Note the improved resolution of this He I-excited c
spectrum compared with the angleintegrated signal in .....
Q)
c
Fig. 2. The spectrum is plotted in the usual way as an inten- Fermi
sity vs. Eb curve, where Eb has been calculated according level
to Eq. (2), which is valid for UPS and for XPS. The emi- \ -~

ssion sets in at the Fermi level E F, which is atthe same time
the zero of the Eb scale. The relatively weak emission just
below EF is from an s band, which is derived from the 4s
orbitals of the Cu atoms. At slightly higher binding
energies, three very intense and sharp lines are resolved,
which are due to the 3d bands of Cu, as mentioned in the
Introduction. At binding energies between 10 and 16 eVa
broad and structureless peak is seen. This peak is due to
secondary electrons that are generated by scattering of
photoelectrons from deeper layers ofthe sample. The pos-
ition on the Eb scale ofthe secondary electron hump does
not represent a true binding energy. It is a consequence
of the very low kinetic energy Ekin of the secondary
electrons. [Remember that according to Eqs. (1) and (2)
low values of Ekin correspond to high values of Eb.] The
cutoff at about 16 eV corresponds to the zero of the Ekin
scale, in other words to E vac . This allows the work function
to be determined from a UP spectrum: According to Eq.
(1) electrons with Eb = 0 (i.e., excited from the Fermi level)
have a kinetic energy of
Ekin(EF) = hv - <Ds (5)
At the cutoff Ekin (cutoff) = 0 so that
!1E = Ekin(EF) - Ekin(cutoff) = hv - <Ds (6)
Thus, the work function of the sample <Ds is easily calcul-
ated from the total width of the UP spectrum!1E and the
* With the advent of synchrotron radiation, the distinction
between UPS and XPS has become somewhat arbitrary.
However, we restrict our discussion to the use of laboratory
sources.
s band
llE
-5 o 5 10 15 20
~ (eV)
Figure 4 Angle-resolved ultraviolet photoelectron spectrum
of Cu(l11) excited by He I (21.6 eV) radiation.
known photon energy hv of the exciting radiation. It is
noteworthy that the absolute value of the work function is
determined in this manner, by contrast, e.g., with a Kelvin
probe that measures only relative changes of the work
function [13,14].
c. Low-Energy ISS
The surface sensitivity of XPS is characterized by the
mean free path length of photoelectrons A, which enters
Eq. (4). Because Ais on the order ofnanometers for typical
photoelectron energies, the XPS signal averages over up
to 10 atomic layers from the surface. In many cases it is
desirable to achieve a better sensitivity to the outermost
surface layers. In this respect XPS measurements are
ideally supplemented by low-energy ISS (LEISS). A beam
of low-energy ions (several 100 eV to several keY) is
pointed to the surface, and the energy of the elastically
scattered ions is analyzed. The surface sensitivity of this
method is extremely good due to the high neutralization
probability of ions penetrating into the bulk. The detected
signal comes almost exclusively from the topmost atomic
 Properties of Bimetallic Electrodes 811

layer only. A further advantage is that virtually no spectra. On the other hand, this sputter effect reveals infor-
additional equipment is needed because the same mation on the stacking order of surface components if a
energy analyzer can be used both for photoelectron time series ofspectra is recorded.
spectroscopy and for ISS, provided the polarity can be From Eq. (7) diagrams of the form shown in Fig. 5 are
changed. An ion gun is also mounted on most DHV easily calculated. For a given scattering geometry and
systems for sample cleaning. the known mass and initial energy Ei of the impinging
Qualitative analysis of the spectra is extremely simple. ions, peak positions can be assigned to target masses,
For elastic scattering of an impinging projectile from a using such diagrams. Thus, with a scattering angle of e
target, atom energy and momentum conservation yield 120° and incoming He ions of primary energy Ei = 1 keY,
Y, a peak at 820 eV (Er/ Ei =0.82) kinetic energy corre-

Er = (cos e+ J /12 - sin

2
e)
Ej 1+/1
where Ei and Er are the initial and final energy of the
projectile, /1 is the ratio ofthe target mass to the projectile
e
mass, and is the scattering angle. It should be noted that
by contrast with most other spectroscopies, the scattering
e
angle is not measured with respect to the surface normal
but rather with respect to the direction the projectile
would have travelled had it not been scattered by the tar-
get atom (Fig. 5, inset).
The derivation of Eq. (7) assumes that the target atom
can be treated as a free particle. This is a good approxi-
mation because typical binding energies are much smaller
than the ion energies in an LEIS experiment. The fact that
the target atom behaves like a free particle also means that
it will be bounced off the surface. Therefore, the surface
is gradually modified during the acquisition of LEIS
(a) He scattering
1.0 r-r-c~"""'~""""~"""~r-"rT,--.-.~..,....~,..,.,~--.-,~r-r-n
.... .:.. "-' ;.. ....:
......
0.9
I ,,
0.8 .
. I
I sensitivity of the method, increases with the projectile
0.7 . mass, but it decreases with the scattering angle. If the
2
(7)
sponds to a target mass of 63 atomic mass units (eu), as
gleaned from the solid curve in Fig. 5a.
A couple of considerations on how to optimize the
experiment can be derived from the diagrams in Fig. 5.
The smaller the slope ofthe curve, the worse the mass res-
olution because a small slope means that a large range
of target masses corresponds to only small variations in
Er/Ej. It is obvious that the mass resolution becomes
worse for larger masses, but the effect is less pronounced
for larger scattering angles and for heavier particles.
Therefore, large scattering angles and heavier ions are
to be preferred if good mass resolution for the heavier
elements is of primary importance. However, surface
damage by the sputtering effect tends to be worse for
heavier projectiles. It must also be noted that light
elements cannot scatter heavy projectiles through large
angles. Therefore, small target masses do not appear in
the spectrum. The limit for Ne is, e.g., near 20 amu, as
can be seen in Fig. 5b. t There are other trade-offs that
have to be considered. For heavier projectiles, a greater
kinematic broadening of the peaks occurs, which is a
(b) Ne scattering consequence of the finite acceptance angle of the ana-
lyzer, partly offsetting the improvement of mass res-
olution. The scattering cross-section, which governs the

""
I

0.6
w- 0.5 "'
i/ ~'~j)d""ro,
-J" sample "
analyzer is operated at fixed energy resolution, the mass
resolution can be improved by increasing Ei because the
ratio Er / E j does not change. This will, however, in general
uJ:, ... . I
0.4 ,I : I decrease the scattering cross-section. A more detailed
:' :' " I r - - - - - - - l J discussion can be found in the literature [15,16].
0.3 _ _ 8= 1200 :" --8= 120°
0.2 8 = 90° .I - - - - 8= 90°
: I

0.1 ··,·,,8= 60° : .... 8= 60°

III. POSSIBLE PROBLEMS IN A UHV
0.0 lL........';:::c:::::;:::;:;:::c:::::;:::;:;::~~-iL.JL':...............::::~c:::;:;:::;:;:L:::::::::J TRANSFER EXPERIMENT
o 50 100 150 200 50 100 150 200
target mass (amu) If an electrode surface and its interface with the electro-
lyte is to be studied in a DHV transfer experiment, the
Figure 5 E r/ E j as a function of the target mass in an
ion-scattering experiment (single scattering only). The curves
are shown for different scattering angles and for He ions (a) t Obviously, Eq. (7) does not have solutions for f.l < sin ebecause
and Ne ions (b). The inset in (a) shows the geometry of the of the square root. This defines the limit ofthe target mass for a
experiment. given e.
812 Stuhlmann et al.

question has to be addressed as to whether the transfer s,(eV)

itself induces changes at the surface. If such changes do
occur, it is of course very difficult, if not impossible, to 165 170 175 165 170 175
arrive at valid statements about the original electro- (c)
chemical interface from a transfer experiment. This ques- S(2p)
tion has been discussed since the early days of this

~
approach [17-22]. Several criteria have been given to
check for a successful transfer of the double layer, and
we refer the reader to an excellent review article by
Soriaga [23]. In the next section we present some of our
own results on the control of the success of an emersion
-:::J
.ri
.... (b) OH- (d)
and transfer process. ~
80 2
0(15)
i::'
'Ci5
C
0(15) A/"4 -

A. Spectroscopic Control of the Emersion
Process
In the course of an extensive study of the chemical and
electrocatalytic properties of Pt- Sn electrodes, as
prepared by electrochemical codeposition ofboth metals
from sulfuric acid solution [24], we also investigated the
influence of the transfer from the electrochemical cell
into URY The spectroscopic verification of a stable
double layer in the URV environment provides confi-
dence in all other electron spectroscopic data of these
electrodes, e.g., as regards the surface composition, as
being representative for the state of these surfaces before
emersion.
There is basically twofold evidence for the persistence
(or nonpersistence) of the electrolytic double layer after
emersion and transfer into URY First, for an intact
double layer the spectroscopic data should reveal directly
its atomic and molecular composition. Second, as dem-
onstrated by Katz and colleagues [19,25], there should
be a 1:1 correlation between the electron binding energies
of the double-layer constituents, e.g., sulfate ions, and
the electrochemical potential at which the electrode was
emersed. Namely, with increasing emersion potential
the S(2p) and O(1s) electron binding energies should
decrease as predicted by the PAX model [26,27]. Because
the double-layer particles reside outside the dipole layer
ofthe substrate surface, their electronic states "float" with
the surface or electrochemical potential [26,28].
In the present study the XPS spectra ofall Pt, Sn, and
Pt-Sn electrodes emersed and transferred into URV
without air contact showed a S(2p) peak near 169 eV (Fig.
6a), which corresponds to the oxidation state S6+. A con-
comitant strong O(1s) intensity near 532.5 eV (Fig. 6b) is
consistent with the existence of adsorbed sulfate ions
from the electrolyte. Additional O(1s) contributions at
~ 530 eV and ~ 533.5 eV point to an oxidic species and
adsorbed water, respectively. Mild sputtering of the thus
characterized electrodes leads to the changes shown in
Q)
.~ . . H2O
0 2-
I OH-
8042 -
/
525 530 535 525 530 535
~ (eV)
Figure 6 X-ray photoemission spectra of sulfur- and
oxygen-containing species adsorbed on Pt-Sn electrodes
emersed from sulfuric acid solution as emersed and transferred
into UHV (a and b) and after mild sputtering (c and d). (a and
c) (energy scale at the top). The S(2p) signal; (b and d) O(ls)
signal together with fit curves for oxygen-containing species.
Fig. 6c-d; the S6+(2p), the 0(1S)H2 0 , and the 0(1S)S02-
signals have disappeared. Only the oxidic peak at 530 eV
remains in Fig. 6d (a residual intensity near 532.5 eV is
also consistent with OR-). These spectral features for
sulfate and water observed immediately after transfer
and their changes due to sputtering point already to the
persistence of an intact double layer in URY Even more
direct support for this assumption, however, comes from
valence band photoemission spectra. As an example, Fig.
7 displays Re II-excited UPS spectra from a Pt-Sn elec-
trode prepared by electrochemical codeposition of Sn
and Pt from sulfuric acid solution at 100 mV vs. RRE.
Again spectra are taken before and after mild sputtering;
the difference spectrum with three peaks at 4.5, 7.0, and
10.6 eV is typical for emission from the orbitals Ib i , 3aJ,
and 1b2 of molecularly adsorbed water [29].
All these XPS core level and UPS valence band spectra
support the notion that an intact double layer persists in
URVon these emersed electrodes, which does not break
 Properties of Bimetallic Electrodes 813

14 169.8
532.4
169.7 (a) S(2p) (b) 0(15)
12 4.5 532.2
169.6
7.0 before ISS 532.0
-.
10 :> 169.5
~ 531.8
:::J uf 169.4 530.6
.0 8

~
~
169.3
530.4
~

-4
>.
·wc::
6
10.6
169.2
169.1
530.2

-2
Q)
c::
I
./\
\ I
I
,
"'\...
0 400 800 0
potential vs. RHE (mV)
400
530.0

I \ I

0 I
I "
J\
Figure 8 XPS-derived S(2p) and O(1s) electron binding ener-
~ ~
, ........... ., I
gies from emersed Pt-Sn electrodes as a function ofemersion
potential. (b) Measured O(1s) binding energies before and after
-2
-2 0 246 8 10 12 14 sputter removal of the electrochemical double layer (compare
Fig. 6).
~ (eV)

Figure 7 UPS (He II) spectrum ofaPt- Sn electrode as trans- (lower curve in Fig. 8b) is also basically independent of
ferred from the electrolyte (--) and after mild sputtering potential, and the 0 2 - ions are no longer outside the sur-
( ... ). The dashed trace represents the difference spectrum; its face dipole layer.
three-peak structure is indicative ofadsorbed water. Finally, one may ask the question about the thickness
of the transferred double layer. The answer to this ques-
tion rests on Eq. (4). Electrons being emitted from the
down due to spontaneous desorption of the water but
metal substrate are damped by the overlaying double
which is only removed by ion bombardment.
layer. The mean free path length A. of the electrons
As mentioned above, further proofof this conclusion
depends on their kinetic energy. Consequently, the
should arise from measurements of the photoemission-
intensities of two sufficiently different photoemission
derived electron binding energies as a function of the
lines are attenuated differently. Therefore, the thickness
emersion potential [19,25]. Figure 8 shows a plot of the
of the overlayer may be calculated from the ratios of the
S(2p) and O(1s) electron binding energies obtained after
intensities of such two Sn or Pt lines before and after
emersion at different electrode potentials. Both the S(2p)
sputter removal of the double layer. The present system
,. and the O(1s) binding energy decrease as the emersion
\ analysis of the XPS Sn(3d) and Sn(MNN) intensities
potential increases, in qualitative accord with the pre-
yields a double-layer thickness of ::::6 A, that is, one to
dictions by the PAX model mentioned above. A quanti-
two monolayers [24]. Even though this is only a rough esti-
tative correlation with the change in electrode potential
mate due to the approximations made in the calculations
is somewhat complicated by the low S(2p) intensity (Fig.
the result appears rather reasonable. '
6a) and the overlap of the O(ls) signals of several oxygen
Summarizing this section, both the electron
species (Fig. 6b). The average slope of both the S(2p)
spectroscopic data of molecular and ionic species, their
and the O(ls) potential shift corresponds to about
dependence on the emission potential, and the esti-
-0.8 eVil V In particular, the course of the S(2p) data,
mation of the overlayer thickness clearly demonstrate
however, seems to suggest two separate regimes of the
• binding energy shift. Between -100 and +400 mY, the
the persistence of a stable electrochemical double layer
on Sn and Pt-Sn electrodes after their transfer from the
S(2p) binding energy decreases by 550 mY, resulting, in
electrolyte into DRV
fact, in a 1:1 correlation between electron binding energy
and electrode potential. Above +400 mY, the S(2p) level
stays essentially constant. A similar two-stage behavior
was also observed by Borup et al. [30] for the system IV. UNDERPOTENTIAL DEPOSITION OF Cd
Pb/Pt(lll) and was interpreted in terms of a collapse of ON Cu(111) AS A MODEL SYSTEM
the double layer at the higher potentials. After sputtering, The system Cd on Cu(lll) even though not of electro-
the O(1s) binding energy of the remaining oxidic species catalytic relevance turned out to be an excellent model
814

to demonstrate the merits of the spectroscopies intro-

duced in Sec. II. Their combined application together
with low-energy electron diffraction (LEED) exper- 12000
Stuhlmann et al.

- - -0.9 V, cathodic I
I
- - - -0.7 V
iments has led to a rather complete characterization of
this bimetallic system [31]. '\
., I

Figure 9 displays the cyclic voltammogram of Cu(lll) III \

in 10 mM HCl containing 10- 3 M CdC}z. Two well- ,~

,I ~,
I X
10
-:- 10000
defined peaks due to the formation and dissolution of ::J
1
11
/
the Cd layer are clearly seen. If the potential scan is .0
.... '
I
I
I
stopped at certain potentials and the sample is trans- ~ I ,
1 I
ferred to the UHY, the deposited amount of Cd can be >- I
analyzed by XPS. Typical spectra obtained at two differ- .~ 8000 I "
-
I
ent emersion potentials are shown in Fig. 10. The Q)
c:
, I I
I
spectrum obtained after emersion at -0.9 V shows two I I

peaks at 404.5 and 411.2 eV By comparison with tab- "

ulated data [10], these can be assigned to photoemission 6000
from the 3d s/ 2 and the 3d 3/ 2 level of metallic cadmium,
respectively. Obviously, a Cd layer has formed on the
surface, as was to be expected from the voltammogram.
The situation is quite different after emersion at -0.7 V
4000 1 , II"' , , , , , , " , "1 I , , , I
At this potential, an underpotential deposition (UPD) 400 402 404 406 408 410 412 414
layer should not exist and, indeed, the Cd signal in the
XP spectrum is much smaller. Furthermore, the binding binding energy Eb (eV)
energies are shifted to significantly higher values,
405.8 eV for the 3d s/2 line and 412.7 eV for the 3d3/ 2 1ine. Figure 10 X-ray photoelectron spectra of Cu(lll) after
This peak shift indicates that the Cd is in the oxidation emersion from 10 mM HCl + 10- 3 M CdCh solution at differ-
ent potentials.
state +2. The Cd signal after emersion at -0.7 V is there-
fore due to Cd 2+ ions in the double layer rather than to a
Cd deposit on the surface. possible. Bulk Cd samples cannot be introduced into
The amount of Cd in the UPD layer could be deter- the UHV system because of the high vapor pressure of
mined if a calibration with bulk Cd were available, e.g., Cd (10- 10 mbar at room temperature). Contamination
with a thick Cd layer deposited at overpotential on the of the entire vacuum system with Cd vapor would be the
Cu substrate. In the case of Cd this is unfortunately not inevitable consequence. Therefore, a different approach
has to be made.
The Cd UPD layer forms an ordered superstructure
100 on the Cu(lll) substrate. The LEED pattern of this struc-
ture is shown schematically in Fig. 11. This LEED pattern
----- 5 mV/s
.::- can be constructed by a combination of adsorbate
E --10 mV/s
reflexes, substrate reflexes, and double diffraction if a
~ 50
2:
.~
Ul
C
Q)
'0
E
0
(-in 2/3 )
5/3
"
~
B -50 structure of the Cd layer is assumed.tWith one Cd atom

-1.0
L -0.9 -0.8 -0.7
per unit cell, this structure gives a Cd coverage of
0.474 ML with respect to the area density of Cu(lll).This
means that the Cd layer is relatively loosely packed with
potential vs. Hg/H92SO. (V)

Figure 9 Cyclic voltammogram of Cu(lll) in 10 mM t For those who prefer the Wood notation, this structure is the
HCl + 10- 3 M CdCh in the Cd UPD region. same as a (m x m)R23.4 structure. 0
 Properties of Bimetallic Electrodes 815

+ CI Cu
+
+ +
Cd
+
+

•
0
+
+

++
•
++
•
.0 0
0
0

• +
+
CI
o
+
+ • +
+ 0
o· ++ ++
+
+

o 0

+
+ • • -
>.
'00

+
+
• -
c
c
Q)
650 700 750

• •
Figure 11 Schematic representation of the LEED pattern of
the Cd UPD layer on Cu(lll).
200 400 600 800
I (s)

a Cd-Cd distance of 3.71 A compared with 2.98 A in

bulk Cd.
The situation becomes clear if the Cl signal is taken
into account. For Cl a calibration is possible because it
is known that the Cd free surface accommodates a Cl
coverage ofabout 1/3 ML [32]. Interestingly, the Cl signal
does not vanish upon formation of the Cd layer, but it
even increases to about 0.48 ML as determined by XPS,
suggesting that the Cd and Cl coverages are governed by
a 1: 1stoichiometry.
This is further supported by LEISS. A spectrum ofthe
surface immediately after emersion at a potential in the
UPO region is shown in the upper panel of Fig. 12. The
three peaks are easily assigned to Cu, Cd, and Cl, using
t-
the plot shown in Fig. Sa. Given the extreme surface
sensitivity of LEISS, the fact that the substrate is visible
indicates a rather open structure confirming the above
considerations. Exploiting the sputter effect of the ions,
the stacking ofthe three components in the direction per-
pendicular to the surface can now be derived. The spectra
in the center panel of Fig. 12 show that the Cl peak
decreases rapidly, whereas both the Cd and the Cu signal
increase. When most of the Cl has been removed, the Cd
signal also begins to drop, whereas the Cu peak continues
to grow (Fig. 12, bottom panel). These observations are
summarized in the inset of Fig. 12 where the time depen-
dence ofall three signals is plotted. It is obvious from these
curves that the Cd is adsorbed on top of the Cu (as was
600 700 800 900
~in (eV)
Figure 12 Time evolution of low-energy ion-scattering
spectra of the Cd UPD layer after emersion at -0.93 V vs.
Hg/Hg2S04. The initial energy of the incoming He ions was
1 keY. The inset shows the peak areas as a function oftime.
to be expected) and that the Cd layer in turn is covered
by a Cllayer.
Summing up the pieces of evidence, one arrives at a
structure of the Cd UPO layer, which is sketched in Fig.
13. A Cd-Cl bilayer is formed on the Cu(lll) substrate
with an arrangement of Cd and Cl species and a Cd- Cd
distance similar to those found in bulk CdCh.
v. ELECTROCHEMICALLY DEPOSITED PI-Ru
ALLOYS
Among the alloy materials with a potential for appli-
cation as CO-tolerant fuel cell anodes, Pt-Ru has been
investigated very thoroughly. The preparation of Pt- Ru
samples with a well-known composition is a prerequisite
for such studies.
A very simple method to produce alloy samples with
compositions adjustable in a wide range is by deposition
816
CI
• Cd
Cu
Figure 13 Ball model of the real-space structure of the
CI-stabilized Cd UPD layer on Cu(ll!) (see text).
from a solution of the respective metal salts. The draw-
back of this method is, however, that no assumptions
can be made about the composition of the alloy by
contrast, e.g., with the use of bulk alloy samples. The
deposited amount of each component depends on the
detailed kinetics ofthe deposition reaction, and generally
the relative concentrations in the deposit differ from those
in the electrolyte. Although this preparation method
and its variations are frequently used [e.g., 33-38], studies
including an analysis of the surface composition are sur-
prisingly rare. We demonstrate on the example of the
Pt- Ru system that a proper determination ofthe surface
concentrations of the alloy constituents is very important
[39].
The alloy samples were prepared by electrochemical
codeposition from solutions containing H2PtCl 6 and
RuCh. The supporting electrolyte was I N H2S04, and
the concentrations ofthe metal salts were adjusted in such
a way that the total metal content was always 10 mg/m!.
A polycrystalline gold foil was used as the substrate, and
the alloy films were grown at a potential of 50 mV vs.
RHE to a thickness of several pm. A signal from the Au
substrate was never detected in the subsequent
experiments, indicating that the alloy film forms a closed
film on the substrate.
In the following, samples are classified according to
the molar fraction of each metal in the deposition
solution. This value is generally not equal to the molar
fraction in the deposited films, as is seen later.
After deposition of the alloy film, the electrolyte was
exchanged for 1 N H2S04 and cyclic voltammograms
were recorded. Figure 14 shows the voltammograms for
Stuhlmann et al.
\
!~
I!
15
- - - - PtRu1 :9
10
- - PtRu5:5
5 -----
~ I
.§. I
0 ~
t,
"E
~
::::l
u -5
-~
-10
-15
0.0 0.2 0.4 0.6 0.8
potential vs. RHE (V)
Figure 14 Cyclic voltammograms oftwo Pt- Ru electrodes in
I N H 2 S0 4 deposited from two different deposition solutions,
the Pt : Ru concentration ratio of which was I : 9 and 5 : 5,
respectively. The potential sweep rate was 20 mY/so
Pt-Ru electrodes deposited from deposition solutions
of two different compositions. Although the differences
in the detailed shape ofthe curves are obvious, a determi-
nation of the surface composition from the volt-
ammograms is certainly impossible. Reliable results are
obtained if XPS is used for this purpose. Figure 15 shows
XP spectra of the most intense core level photoemission
line ofPt (4f) and ofRu(3d). In this case we are in the for-
tunate situation~by contrast to the Cd example in Sec.
IV~that bulk samples of both constituents can be used
for calibration. Such samples are simply produced by
having only one metal salt in the deposition solution.
The corresponding XP spectra are shown as the topmost
and the bottommost curves in Fig. 15. Because the
photoemission intensity is proportional to the area den-
sity of emitters (see above), the intensities of the cali-
bration spectra have to be divided by the densities of Pt
and Ru, respectively. This calibration procedure yields a
simple formula for the calculation ofthe Pt molar fraction
XPt from the XPS intensities I pt and hu of the Pt 4f and
the Ru 3d line [40]:
I pt
XPt = I +..!&L
Pt 1.26
Note, however, that the number value 1.26 is specific to
our experimental setup and may be different if another
apparatus is used. The molar fraction of Pt obtained by
this procedure is plotted in Fig. 16. The dashed line corre-
sponds to the hypothetical case that the surface compo-
sition exactly mirrors the composition of the deposition
solution. The values of XPt found in the experiment are
Properties of Bimetallic Electrodes 817

.• .
Q.)
(.)
Ru 3d ro
't: 1.0
:J /
..
en /

Q.) 0.8
.r=
.....
Pt Cii 0.6
0 ••
.~
....
...........
0.4 •
:J
PtRu8:2 a: 0.2
• XPS
+
.....
.D
....co
e:. 0.0 •
:;:::.
• LEIS

- 0- 0 20 40 60 80 100

->.
'ecn Pt in solution (at. %)

-Q)
c Figure 16 Relative Pt concentration at the surface of Pt- Ru
electrodes as a function of the composition of the deposition
solution. The surface concentrations were derived from XPS
spectra like those shown in Fig. 15 and from LEISS spectra like
those shown in Fig. 18 [39].

never seen in our experiments. More direct evidence of

70 75 280 285
binding energy (eV)
Figure 15 XPS spectra ofthe Pt 4fregion and the Ru 3d region
for Pt-Ru alloy electrodes of different compositions. The
spectra of the pure metals were used for a calibration of the
XPS sensitivity. The excitation was by Mg K o radiation and the
detection angle was 50 with respect to the surface normal. A
0 ency in the same direction.
linear background was subtracted from all spectra [39,40].
systematically above that line, indicating a significant Pt
enrichment in the alloy film.
Once the relative amounts of the constituents have
been determined, the question must be addressed,
whether the deposit constitutes a true alloy or has the
form of microcrystallites or nanocrystallites of the pure
metals. An electrochemical method has been proposed
by Gasteiger et al. [41], who found a splitting of the
oxidation peak in CO stripping voltammetry on bulk
Pt- Ru alloys after annealing in vacuo. Another criterion
is the appearance of two separate CO stretching
vibrations or only one stretching vibration of adsorbed
CO in the in situ infrared spectrum [42]. A splitting of
the CO oxidation peak in the voltammetric curves was
alloy formation is, however, provided by binding energy
shifts of the alloy constituents' core levels. Figure 17 dis-
plays the binding energy of the Ru 3d s/2 line and the Pt
4f7 / 2 line as a function of XPt at the surface. A systematic
and continuous variation of the binding energies with
the composition is observed. This indicates that the two
constituents are perfectly mixed throughout the entire
composition range and form a true alloy. It may appear
strange that the binding energy of Pt 4f7/ 2 goes down as
the Ptcontent increases, whereas that ofRu 3d s/2 remains
almost constant within the error bars with a slight tend-
In a naive picture one would expect that a re-
distribution of electrons between the alloy constituents
reduces the screening ofthe positive charge ofthe nucleus
on one of the constituents to the same extent as it
increases the screening on the other one. In such a
scenario an opposite shift of the binding energies would
be expected for the two constituents. The situation is,
however, more complicated in alloys. It has long been
known that core level binding energies of one alloy con-
stituent may shift, whereas those ofthe other constituent
remain constant [43] or even shift in the same direction
[44,45]. The explanation in this case is an intra-atomic
reorganization of the valence electrons where some elec-
trons undergo a transition from d orbitals into orbitals
with asymmetry. Thereby, the effective screening of the
core potential is altered without changing the formal
oxidation state of the alloy components.
818 Stuhlmann et al.

-t .. · .••+ .1
280.2
Pt
280.0
279.8 • 1--
~ 279.6 :::J Ru
~
.e
....
279.4 • Ru3d5/2 ~

~
Q)
279. • Pt4f 7/2
-I~c::
::J
•
• l/l

Q)
C> 71.8 .!)
....
....
c::
c::
:ac::
:0
71.6
71.4
-
~
ctS

"w 160 165 170

71.2 c:
Q)
71.0
...... binding energy (eV)
c:
70.8 1 1 1
0.0 0.2 0.4 0.6 0.8 1.0
PV(Pt+Ru) ratio at the surface

Figure 17 Binding energy of the Pt 4f7/ 2 and of the Ru 3d s/ 2

line as a function of the relative Pt concentration at the surface.
The values are taken from the peak positions in spectra like
those shown in Fig. IS [40J.
As already demonstrated in the case of UPD
Cd/Cu(lll), the comparison with LEISS data may yield
valuable additional information. Figure 18 shows two
LEIS spectra; one of them was recorded immediately
after transfer from the base electrolyte (1 N H 2 S0 4), the
other one after a long series of LEIS spectra. In the first
spectrum in addition to the Ru and Pt peak, a quite pro-
nounced S peak is seen. This signal is mostly due to
adsorbed sulfate transferred from the electrolyte. The
sulfate adlayer damps the two metal signals significantly.
In the second spectrum, most of the sulfur has been
sputtered away, and the metal signals have grown
accordingly. Notably, there is still a small Ssignal left.This
residual S signal cannot be removed by sputtering,
suggesting that a small amount of sulfur is incorporated
into the film bulk. An interesting detail is revealed by
the corresponding XP spectra of the S(2p) region, which
are shown in the inset of Fig. 18. The two peaks in
spectrum (a) are clearly assigned to two different
oxidation states of sulfur. The peak with the higher bind-
ing energy at 168.5 eV is due to S in the oxidation state
+6, i.e., to sulfate. The other peak at 162 eV is assigned
to sulfur in the oxidation state 0 or -2. Only this second
sulfur species is found in spectrum (b), indicating that
the residual sulfur is bound as a metal sulfide.
A quantitative interpretation of the LEIS spectra can
be performed in a similar way as that of the XP spectra
1000 1500 2000
E (eV)
f
Figure 18 He LEIS spectrum ofPtRu4 : 6 immediately after
emersion from the electrolyte (a) and after prolonged recording
of spectra (b). The primary energy of the He ions was 2 keY
and their scattering angle was 122 The inset shows correspond-
0
•
ing XP spectra ofthe sulfur species [39J.
using spectra ofthe pure metals as calibration standards.
The resulting values are shown as filled circles in Fig. 16.
They agree with the XPS data remarkably well. Given
the different probing depths of both methods, a constant
alloy composition within the probing depth of XPS (five
to six layers) is deduced.
The electrochemical characterization of the alloy
samples with respect to their CO oxidation capability
was carried out by two methods. CO was dosed onto the
surface to saturation coverage at 100 mV vs. RHE, and
stripping voltammograms with a fixed potential scan
rate of 20 mV/s were recorded. Although such volt-
ammograms at a single scan rate certainly do not allow
a detailed analysis of the CO oxidation kinetics, a quick
overview is easily gained. Figure 19 shows the position
of the CO oxidation peak for a number ofdifferent alloy
compositions. The curve has two remarkable features.
First, there is a very pronounced minimum at XPt ~ 0.55
in qualitative agreement with investigations of Pt-Ru
Properties of Bimetallic Electrodes
:> 750 ,--.,----,----,--~______r-~,-----,--___,_~______r______,
.s
~ 700
a:
en
> 650
ctj
+=
cQ)
'0 600
a.
c Pt (x1 0)
o
~ 550
"0
'x
o
o 500
()
0.0 0.2 0.4 0.6 0.8
Pt/(Ru+Pt) ratio at the surface
Figure 19 Peak potential of the CO oxidation peak in CO
strippingvoltammograms as a function ofsurface composition.
The surface was covered with the CO saturation coverage before
the potential scan, and the scan rate was 20 mV/s for all samples
[39].
bulk alloys [41]. Second, there is a very steep increase for
XPt < 0.55 and very little change between XPt = 0.4 and
pure Ru. The dramatic changes around the composition
optimum show that it is extremely important to have con-
trol of the exact surface composition, which can only be
gained by use of surface spectroscopies like XPS and
LEISS.
As a second method for the electrochemical
characterization of the alloy electrodes potential step
experiments were carried out. After saturation of the
electrodes with CO at 100 mV vs. RHE, the potential
was stepped to different values in the CO oxidation region
and the current transient recorded. Details ofthe reaction
mechanism and the reaction kinetics for different alloy
compositions can be learned from such experiments. A
detailed analysis of the results is under way [46]. An
interesting detail can, however, be gleaned from the
transients shown in Fig. 20 without any calculations. Dif-
ferent reaction mechanisms apply for CO oxidation on
pure Pt and pure Ru. On pure Pt the reaction mechanism
is of the Langmuir - Hinshelwood type, requiring
coadsorption of an oxygen-containing species for the
CO oxidation. Such a mechanism results in a peaked
shape of the transient. For the case of Pt(lll), this has
been discussed by Petukhov [47]. On pure Ru, by con-
819
30
25
20
<'
E
:::::- 15
P~.5RLt.5
10
1.0
P~.4fLt.55
5
Ru
a
a 2 3 4
t(5)
Figure 20 Current transients for a potential step from 100 to
750 mV with CO saturated Pt - Ru alloy electrodes of different
compositions. The true surface composition ofthe alloys is given
as derived from the curve shown in Fig. 16 and the known con-
centration of the deposition solution. The potential steps were
carried out in CO free I N H 2 S0 4 •
trast, a monotonously decaying transient is observed,
pointing to an Eley-Rideal reaction mechanism. The
transients for different alloy compositions (Fig. 20) indi-
cate that the transition between the two reaction
mechanisms occurs in a very narrow composition region
just below XPt = 0.5. This change of the reaction mechan-
ism is likely to be correlated with the sudden jump in the
position of the CO oxidation peak in the stripping
voltammograms (Fig. 19).
VI. SUMMARY
A full understanding ofthe electrochemical properties of
alloy electrodes requires at least a detailed knowledge of
their true surface composition. Pure electrochemical
methods are incapable to furnish this information
reliably. Even though synchrotron-based grazing inci-
dence X-ray fluorescence experiments are developed
820 Stuhlmann et a1.

today to acquire this information in situ, this approach is 15. H Niehus,W Heiland and E Taglauer. Surf Sci Rep 17:213,
not widely available. To date, ex situ DRV-based 1993.
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the surface composition of alloy electrodes. After a gen- 17. WN Hansen, DM Kolb. J Electroanal Chern 100:493, 1979.
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26. K Wandelt. in: Chemistry and Physics of Solid Surfaces
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Chemistry. Weinheim: VCH, 1985. Bunsenges Phys Chern 100:599,1996.
7. DJ O'Connor, BA Sexton, RStC Smart (eds.) Surface
38. W Chrzanowski, AWieckowski. Catal Lett 50:69, 1998.
Analysis Methods in Materials Science, Springer Series
39. F Richarz, B Wohlmann, U Vogel, H Hoffschulz, K
in Surface Sciences,Vol. 23, Ch. 7, Springer, Berlin, 1992.
Wandelt. Surf Sci 335:361, 1995.
8. S Hufner. Photoelectron Spectroscopy, Principles and
40. F Richarz, PhD thesis, University of Bonn, 1995, and
Applications, 2nd ed. Springer Series in Solid-State
Fortschr Berichte VDI, Reihe 6, Nr. 328. Dusseldorf:
Sciences,Vol. 82, Springer, Berlin, 1996.
VDI-Verlag,1995.
9. D Briggs, MP Seah. Ref. 5, Appendices 6 and 7.
10. J Chastain, ed. Handbook of X-ray Photoelectron 41. HA Gasteiger, N Markovic, PN Ross, EJ Cairns. J Phys
Spectroscopy. Eden Prairie, MI: Perkin-Elmer Corp., Chern 98:617, 1994.
1992. 42. S Zou, I Villegas, C Stuhlmann, MJ Weaver. Electrochim
II. G Ertl, J Kuppers. Ref. 6, ch. 4. Acta 43:2811, 1998.
12. DJ O'Connor, BA Sexton, RStC Smart. Ref. 7, ch. 14. 43. K Wandelt, G Ertl, J Phys F 6:1607, 1976.
13. J Holzl, FKSchutte.Work Function of Metals, in: Springer 44. JE Houston, RLPark. J Vac Sci TechnoI9:579, 1972.
Tracts of Modern Physics, Vol. 85, Springer, Berlin, 1979, 45. E Kiillne. J Phys F 4:167,1974.
p.l.. 46. F Richarz, A Beer, M Lennartz, C Stuhlmann. (in
14. M Schmidt, M Nohlen, G Bermes, M Bohmer, K Wandelt. preparation).
Rev Sci Instrum 68:3866,1997. 47. AV Petukhov. Chern Phys Lett 277:539, 1997.
46
Electrocatalysis at Well-Defined Surfaces: Kinetics of
Oxygen Reduction and Hydrogen Oxidation I Evolution on
Pt(hkl) Electrodes
Nenad M. Markovic and Philip N. Ross, Jr.
Lawrence Berkeley National Laboratory, Berkeley, California
ABSTRACT
Kinetics of the hydrogen evolution/oxidation reaction
(HE/OR) and the oxygen reduction reaction (ORR) on
well-defined Pt(hkl) surfaces in aqueous solutions are
reviewed. Surface x-ray scattering (SXS) was used to
determine the structure in situ at Pt(hkl)-solution inter-
faces as a function ofthe applied potential. SXS measure-
ments show that both Pt(lll) and Pt(lOO) prepared by
flame-annealing method are not reconstructed at any
potential. Depending on the particular flame-annealing
procedure, a reconstructed Pt(lIO)-(l x 2) phase or an
unreconstructed Pt(lIO)-(1 x I) surface can be created.
On all single- crystal surfaces, the lattice spacing between
the first and the second layer was expanded relative to
the bulk spacing, a phenomenon generally referred to as
relaxation. The relaxation was found to be a function of
both the crystallographic orientation and the electrode
potential and is related to the adsorption ofH upd and/or
anions. The rotating ring disk technique was used to
establish the kinetics of the HE/OR and the ORR on
Pt(hkl) single-crystal surfaces. An analyses of the struc-
ture sensitivity of the kinetics of the HE/OR and the
ORR is presented based on the premise that the differ-
ences in the activities of the three low index faces of Pt
arise mainly from the structure-sensitive adsorption of
H upd and/or anions, such as hydroxyl and (bi)sulfate.
Finally, reaction mechanisms (reaction pathways) are
proposed for the ORR and the HE/OR on Pt(hkl)
single-crystal surfaces.
821
I. INTRODUCTION
Interest in the role ofthe local symmetry ofplatinum sur-
face atoms in electrocatalysis has risen steadily over the
last three decades. As early as 1965, Will [I] recognized
that the adsorption of hydrogen on platinum single
crystals is a function of the crystallographic orientation
of surface atoms, even though the crystals he used were
by today's standards neither well characterized nor well
prepared. Ever since the pioneering work of Will, one of
the major themes in electrochemical research has been
the study ofthe relationship between the electrochemical
reactivity and surface structure, a functionality generally
termed "structural sensitivity." It is now well established
that a well-defined and clean Pt(hk1) single-crystal elec-
trodes can be prepared either by sputtering and annealing
in ultrahigh vacuum (DRV) [2] or by annealing the single
crystal in a hydrogen-air flame, followed by cooling in
water [3], hydrogen (hydrogen-argon mixture) [4], or
vapor phase of b [5]. In early work, determination of
the stability of the well-defined structures in electrolyte
derived from ex situ DRV analysis of emersed surfaces
[6], e.g., by low-energy electron diffraction (LEEO).
Although LEEO is a well-developed and powerful tool
for surface structure determination in DRY, the
emersion process itself may disrupt the structural integ-
rity of Pt(hk1)-e1ectrolyte interface and may also leave a
sal t deposit on the surface after evaporation of the water.
822
Therefore, establishing the relationship between the
structure of the interface in electrolyte and that observed
in UHV was always problematic and had to be carefully
examined on a case-by-case basis. However, the recent
advances in the in situ methods of scanning tunneling
microscopy (STM) and surface x-ray scattering (SXS)
has alleviated this "emersion gap" and has provided
definitive surface structure determination of Pt(hkl)
while in electrolyte under potential control [7-9]. These
methods have made it possible to establish the true
relationship between the surface structure and the
electrocatalytic activity of Pt(hkl) electrodes, which is
the subject of this chapter.
Much of our knowledge concerning the study of the
electrocatalytic properties of Pt(hkl) electrodes has
arisen from measurements of the kinetics of electro-
chemical reactions using a stationary electrode, e.g., in
the so-called hanging meniscus geometry [3-5]. A com-
mon shortcoming of this electrode configuration is that
the mass transport of reacting species (e.g., 02, H2, CO)
is not well controlled and that short-lived intermediates
cannot be identified in steady-state measurements. The
best method to overcome these limitations is by the use
of the rotating ring disk electrode (RRDE) technique.
Until recently, a major impediment to utilizing the
RRDE method to Pt single crystal was the difficulty of
assembling the single crystal into a true RRDE configur-
ation without contamination. Recently, however, in our
laboratory we developed a method to transfer flame-
annealed Pt(hkl) electrodes into the disk position of a
RRDE in a clean manner [11], enabling the kinetics of
many electrochemical reactions and electrode processes
to be examined on well-defined Pt(hkl) surfaces [11-16].
The present article reviews recent progress, primarily
from our laboratory, toward the understanding the struc-
tural sensitivity of the kinetics and the mechanism of the
hydrogen evolution/oxidation reaction (HE/OR) and
the oxygen reduction reaction (ORR) on Pt(hkl) surfaces
in aqueous electrolytes. By utilizing both powerful in situ
SXS technique for structural determination and elegant
RRDE method for kinetic analysis of the HE/OR and
the ORR, our results illustrate the remarkable insight into
the effects of the nature of Pt(hkl) solution interface on
the kinetics ofelectrochemical reactions.
II. SURFACE STRUCTURES AND THE CYCLIC
VOLTAMMETRY OF Pt(iii)-(i Xi),
PT(i00)-(i Xi), AND PT(ii0)-(i X2)
ELECTRODES
During the past two decades, a great deal ofwork has been
done on Pt(hkl) electrodes prepared by both UHVand
Markovic and Ross
flame-annealing method, attempting to attribute specific
features in the cyclic voltammetry to electrode processes
at specific sites on the surface, i.e., the structure sensitivity
of the adsorption pseudocapacitance. In this section,
the current status ofknowledge ofthe structure sensitivity
ofthe adsorption pseudocapacitance (hydrogen, oxygen-
containing species, and anions) is reviewed. The presen-
tation here is restricted to a relatively brief overview of
the science; further details, including experimental pro-
cedures, can be found in the references cited.
A. Reconstruction of Pt(hkl) at the
Electrode - Electrolyte Interface
Modern surface crystallographic studies have shown that
on the atomic scale, most metals tend to minimize their
surface energy either by relaxing the distance between
the individual layers in the near-surface region or the sur-
face atoms take on a new lateral periodicity different from
the bulk, a process known as surface reconstruction. Re-
construction of clean metallic surfaces in UHV was one
of the most studied phenomena in surface science in the
1970s and 1980s, and these structures have been compiled
by Watson et al. [17]. Studies of the nature of
Pt(lll)-solution interface date back to early 1970s when
it was reported that UHV prepared (Ill)-(1 xl) structure
remains intact after contact with a solution [2]. Shortly
thereafter, examinations of the stability of well-ordered
Pt(1I I) surface in solution has also been the subject of
intense ex situ study. After the report by Clavilier et al.
[3] ofanomalous voltammetry on a (Ill) surface prepared
by a flame-annealing procedure, Wagner and Ross [18]
were able to produce the same voltammetry with a
UHV prepared crystal and to confirm using ex situ LEED
crystallography the extreme structure sensitivity of the
anomalous features in the voltammetry. Since that time,
a consensus has emerged on the interpretation of the
anomalous voltammetry, attributing specific features to
specific adsorption processes. These interpretations, with
somewhat different perspectives, may be found in else-
where [19-22]. Most recently, the Pt(lll)-(\ x 1) structure
at solid-liquid interfaces has been confirmed by in situ
SXS studies [8]. A voltammetric behavior of the
Pt(lll)-(l x I) surface in two different solutions along
with a schematic representation of the (lll)-(l x 1) plane
are illustrated in Fig. I.
In the clean annealed state in UHY, the Pt(IOO) surface
is known to reconstruct and to form a hexagonal
close-packed top layer quite similar to that which forms
on the Au(IOO) surface. Unlike the Au(lOO), however,
the Pt(lOO) surface is very unstable in the presence of
many adsorbing species, and it has been problematic to
r
i
Electrocatalysis at Well-Defined Surfaces
Pt(111) (a) Pt(111)
0.05 M H2S04 0.1 M KOH
0.2 0.4
E [VI
0.6 0.8 0.2 0.4
EM
0.6
Figure 1 CyclicvoltammetryofthePt(lll)-(l x I) surface in an
electrochemical cell: (a) in H 2S0 4 and (c) in 0.1 M KOH. The
potential was scanned at 50 mYls. Changes in interlayer spacing
(~d12) measured from the potential of minimum expansion,
PME (e.g., the least coverage by any adsorbates), on scanning
the potential at 2 mYls: (b) H 2S04 and (d) in 0.1 M KOH. Inset:
Ideal model for the Pt(lIl)-(1 x I) surface. Electrode potential
E is given vs. the reversible hydrogen electrode (RHE).
even transfer a (100) crystal from UHV into a solution and
preserve the reconstructed surface. A review of the stab-
ility ofPt(hkl) surfaces at solid-liquid interfaces by Kolb
[23] is an excellent place to find references to a specific
Pt(hkl)-electrolyte system. For our purposes here, we
note that in situ SXS results indicated that Pt(100)
(prepared by flame-annealing, followed by cooling in
hydrogen and/or argon [24]) is unreconstructed at all
applied potentials in aqueous solutions [8]. It is important
to note, however, that SXS data clearly showed that the
Pt(100) crystal prepared by flame annealing method-
ology is not a defect-free surface, and furthermore the
defect concentration may vary from one flame annealing
treatment to another. Great care must be taken, therefore,
when comparing results from different surface prepar-
ation. A schematic representation of the (100)-(1 xl)
plane is illustrated in Fig. 2. Unlike the case ofthe Au(1 00)
surface [23-27], there is no evidence that the "hex" rec-
onstruction can form under an electrochemical driving
force. The electrocatalytic consequence of the instability
of the Pt(100) surface is that electrode processes on the
Pt(100) electrodes prepared using current experimental
methods should be considered to take place on a
Pt(100)-(1 x 1) surface.
Upon annealing in UHY, Pt(llO) undergoes rec-
onstruction that in the clean state produces a (1 x 2)
symmetry, which is most commonly interpreted as a
"missing-row" structure [28] (see the model in Fig. 3). In
the early ex situ LEED analyses of UHV prepared
823
(a) (c)
Pt(100)
0.1 M KOH
0.8
!;20 ., ~"'~'"
r:~l:
... 1"Jil~
/
.... - I 2.0 '...... .'
0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8
E [VI EM
Figure 2 Cyclic voltammetry of the Pt(lIO)-(l x I) surface in
an electrochemical cell: (a) in H 2S04 and (c) in 0.1 M KOH.
The potential was scanned at 50 mYls. Changes in interlayer
spacing (~d12) measured from the potential of minimum
expansion, PME (e.g., the least coverage by any adsorbates), on
scanning the potential at 2 mYls: (b) in H 2S04 and (d) in 0.1 M
KOH. Inset: Ideal model for the Pt(IOO)-(l x I) surface. E vs.
RHE.
Pt(llO)-(1 x 2) electrode, it was found that upon contact
with several solutions, the reconstructed (1 x 2) surface
remained stable if potential cycling was restricted to cer-
tain potential regions, with the window of stability
differing in different reports [29,30]. A recent STM study
of the Pt(1lO) surface, prepared by flame-annealing and
quenching in 12 vapor, indicated that after desorption of
iodine at negative potentials, the surface has a (1 xl)
structure [31]. Most recently, the stability and the struc-
tural information ofthe pte II0) surface in several electro-
lytes were examined in situ by the SXS technique [9,32].
It was found that depending on the particular flame-
annealing procedure, a reconstructed Pt(1I0)-(1 x 2)
phase or an unreconstructed Pt(llO)-(1 x 1) surface can
be created [32]. The experimental details of both the
methods of preparation and the electrocatalytic proper-
ties of these two surfaces have been discussed at length
in recent publications [9,32]. Because the electrocatalysis
of the ORR and the HE/OR have been studied on the
Pt(llO)-(1 x 2) surface, the ideal model for the (1 x 2) sur-
face along with the cyclic voltammetry of this surface in
alkaline and acid electrolytes are illustrated in Fig. 3.
The inset of Fig. 3 shows a rocking scan (approximately
along [h 0 0]) through the (0, 1.5, 0.1) reciprocal lattice
position. The solid line is a fitted Lorentzian lineshape
to the data that allows the correlation length ofthe (1 x 2)
unit cell to be derived. From these measurements and
824 Markovic and Ross

Pt(110) spacing, and therefore outermost layer of atoms is

f
§ 100
~
(a)
(0.05 M H2S04)

.- ,
~ 200 L

°100
~
(e) 0.1 M KOH
.. expanded away from the second layer. One can extend
these concepts to the Pt(hkl)-electrolyte interface, and
'Ld'
f" _ ,
- .J I'" Drs I~,
o\:>. . . . . indeed relaxation has also been observed at the
Pt(hkl)-electrolyte interface. Figures 1-3 show the
j
D-O-O Q H + HSO.
;ew f OOOQH
. . . OOH
results for cyclic voltammograms of Pt(hkl) along with
° the changes in the interlayer spacing (Ad12, is a percent

"
E
Q.

!!!
~
'i
10

".. . ./,.{'i.;J...;}:p, I

0.4 0.8
1.5

1.0 W ,

'~,o, 0\~2
"E
;

l5
i
(0,0,1.55)

0.8
of the bulk interlayer spacing from the potential of mini-
mum expansion, PME) of top Pt(hkl) layer in 0.Q5 M
H 2S0 4 and 0.1 KOH. The current-potential curve of
Pt(lll)-(1 x 1) gives a distinctive voltammogram with a
broad nearly flat hydrogen desorption/adsorption peaks
between ~ 0,05 < E < 0.375 V in both 0,05 M H 2S04
EIV] and 0.1 M KOH (Fig, 1) that is indicative of hydrogen
adsorption not accompanied with concomitant anion
Figure 3 Cyclic voltammetry of the Pt(llO)-(l x 2) surface in adsorption. At more positive potentials, the so-called
electrochemical cell: (a) in H 2 S04 and (c) in 0.1 M KOH. The "anomalous" peaks are observed at ~ 0.4-0.6 V in acid
potential was scanned at 50 mYls. Changes in interlayer spacing solution and ~0,6-0.85 V in alkaline solution. These
(~d12) measured from the potential for minimum expansion, peaks are now understood to be anion adsorption
PME (e,g" the least coverage by an adsorbates), on scanning pseudocapacitance: in 0.05 M H2S04 the adsorption/
the potential at 2 mYls: (b) in H 2 S0 4 and (d) in 0.1 M KOH, (e) desorption of bisulfate anions; in 0.1 M KOH reversible
The measured x-ray intensity at (0,1.5,0.1) along the [0 I OJ direc-
adsorption/desorption of hydroxyl species, hereafter
tion along with an ideal model for the (I x 2) structure: solid
denoted as OH rv • In the hydrogen adsorption potential
circles represent H upd and OH rv . E vs, RHE.
region, the top platinum layer expends ca. 1.5-2%
( ~ 0.03 A) in both H 2S04 and KOH solutions (see Fig.
longitudinal scans (along [0 kO], not shown), a correlation 2b and d). In contrast, no change in the interlayer spacing
length of ~ 350 A was derived along the [100] direction is observed upon the adsorption/desorption of either
and ~ 250 A along the [010] direction, where these corre- bisulfate or hydroxyl anions,
spond to the parallel and perpendicular directions to the The main characteristic of well-ordered Pt(100) vol-
rows in the missing-row model of the (1 x 2) rec- tammetry in sulfuric acid (Fig, 2a) is that two
onstruction [9]. The (1 x 2) surface reconstruction was well-delineated peaks at 0.4 and 0.245 V corresponds to
stable over a wide potential range, e.g., even at 1.2 V there the coupled processes of hydrogen adsorption with the
was still a strong (110)-(1 x 2) diffraction pattern. Upon bisulfate anion desorption on 100 terrace sites and
sweeping the potential negatively, however, the (1 x 2) n(100) x (lll) step sites, respectively. The relative
reconstruction is finally lifted as the surface atoms move amounts of charge under the two peaks is extremely
to accommodate the oxide reduction. It should also be sensitive to the quality of the Pt crystal being used,
noted, the Pt(1l0)-(1 x 2) structure was so stable in aque- reflecting the variations in step densities that can be
ous electrolytes that adsorption of CO on this surface experienced, The main characteristic of well-ordered
did not induce the (1 x 2)~(1 x 1) transition that is Pt(100) in alkaline solution (Fig, 2c) is that the hydrogen
observed in UHV upon adsorption of CO [32]. adsorption/desorption and hydroxyl anion adsorption/
desorption are still decoupled processes as on (111) in
alkaline solution, but now the desorption of hydrogen
B. Relaxation of Pt(hkl) at the
0.05 < E 0,25 V is immediately followed by the reversible
Electrode- Electrolyte Interface
adsorption of hydroxyl anions. In the potential range
The structural relaxation of surface atoms has been well between 0.75 < E < 0.95 V, however, the observed asym-
documented at the solid-gas interface. In UHV, on metry in a current-voltage curve traces between positive
unreconstructed low-index single-crystal surfaces, it is and negative sweep directions clearly represents an irre-
often found that the outermost layer ofatoms is contracted versible state of adsorption of OHad species, which we
toward the second layer, as is compared with the bulk shall call "oxide" hereafter. In the potential region where
structure, Adsorption on the clean surface in UHVoften the hydrogen adsorption occurs, e.g., 0,05 V < V 0.45 V,
reverses the difference in interlayer spacing relative to the top Pt layer expands up to ca. 2.5% ofa lattice spacing
the bulk lattice, generally toward larger interlayer (0.05 A) away from the second layer, an expansion larger
r
Electrocatalysis at Well-Defined Surfaces
than observed for Pt(IIl), indicative, perhaps, of
hydrogen adsorption sites in the fourfold and threefold
hollows of the respective surfaces.
Figure 3 contains representative cyclic voltammo-
grams for the Pt(110)-(1 x 2) surface recorded in both
alkaline and acid solution. In 0.05 M H2S04, the
voltammetric features are the coupled processes of
hydrogen adsorption/desorption with the anion
desorption/adsorption at 0.05-0.35 V, followed by a
double-layer charging potential region, and the hysteretic
peaks associated with oxide formation and reduction at
more positive potentials. As with the (100) surface, a dis-
tinguishing characteristic of Pt(110) in 0.1 M KOH is
uncoupling of the hydrogen adsorption/desorption and
anion desorption/adsorption processes, e.g., on the
positive-going sweep the desorption of hydrogen,
0.05 < E < 0.375 V is immediately followed first by the
reversible adsorption ofOH, and then by the irreversible
formation of oxide. Of all Pt(hkl) surfaces we have
studied, this surface has the most dramatic potential
dependence of the interatomic spacing, having a clearly
defined minimum at the potential of minimum
expansion, the PME. The PME is at the potential where
the surface has the least coverage by any adsorbate, right
at the transition from hydrogen desorption to OH
adsorption. At the PME, the top-most rows ofPt atoms
are expanded into the electrolyte by about 15 % ofthe bulk
interatomic spacing. An additional expansion to 25% (!)
is observed on the surface covered by a monolayer of both
Hupd and OH ad species. What makes these expansions in
KOH even more remarkable is the fact that for the clean
annealed surface in UHV, the first layer is slightly con-
tracted toward the second layer [9]. In H 2S0 4, the relax-
ation of the top layer at potentials more positive of 0.3 V,
where bisulfate ions are the predominant adsorbed
species, is rather small. This could be indicative of
adsorption ofbisulfate anions at different specific surface
sites than either Hupd or OH ad .
In what follows, we present an interpretation ofthe sur-
face relaxation results based on supposition that the dif-
ference in a relaxation observed on Pt(hkl) surfaces
arise from variations in the sites for adsorption and the
strength of the adsorbate-metal bonding, the two of
course being interrelated. * In particular, we propose that
the smallest expansion was observed on the Pt(111) sur-
face because this surface is the most densely packed,
and thus the H upd is adsorbed onto the Pt(111) surface.
This model is consistent with a recent thermodynamic
* Note, x-ray scattering measurements are not directly sensitive
to the location ofadsorbed species.
825
analysis [16b] which shows that the apparent standard free
energy of hydrogen adsorption has a linear decrease with
the coverage by H upd , i.e., from;;::; 29 kl/mol extrapolated
at () ~ 0 to ;;::;8 kl/mol at () = 0.66 «() = 1is 1Hupd per Pt).
The best-fit values of the Frumkin parameter f = r/RT,
which characterizes a lateral interaction in the hydrogen
adlayer, is very high (f;;::;14-11 from the temperature
range of 274-333 K), suggesting a strong lateral repulsion
between H upd species that are adsorbed on the Pt(111) sur-
face [16]. t Strong lateral repulsion would imply that the
H upd is adsorbed on surface sites that are unscreened by
Pt atoms. On the (100) surface, some of Hupd adatoms
might sit in deeper potential wells, e.g., the four fold
hollow sites, and thus be more in the surface than on the
surface. In the case ofPt(1lO)-(1 x 2), the relaxation poss-
ibly indicates that the sites for H upd are the threefold
coordinated sites below the top-most (110) rows of Pt
atoms [9,32], as indicated in Fig. 3.
Recent studies using vibrational spectroscopy provide
a mixed picture about the adsorption sites of the H upd
state. Based on IR reflectivity spectra, Nichols [33]
reported that hydrogen adsorption on Pt(111) is quite dif-
ferent from Pt(100). The author suggested that H upd
("strongly bonded") on Pt(lOO) is adsorbed in four-fold
hollow sites. Conventional infrared spectra by
Ogasawaro and Ito [34] found H-Pt bands indicative of
an on-top adsorption sites on Pt(lOO) and Pt(l10) surfaces
but only at potentials very close to the Nernst potential.
It is not clear that Ogasawaro and Ito studied the
(110)-(1 x 2) structure, vs. the (1 x 1) structure, which
can also result from the flame-annealing procedure.
These results were similar to an earlier report by Bewick
and Russell [35] for polycrystalline Pt. Using visible-
infrared sum frequency generation, Tadjaddine and
Peremans [36] reported that the frequencies of the bands
in the 0-0.4 Vregion corresponded to terminally bonded
hydrogen on all three low index Pt surfaces.
Detailed knowledge about the adsorption/formation
of hydroxyl layer on the platinum surface is in similarly a
mixed circumstance. We do not know for certain what
physical processes are associated with either the
reversible adsorption or irreversible adsorption of
oxygenated species. The simplest case to understand, in
principle, is the reversible adsorption of the OH- anion
in the alkaline solution, which presumably is just adsorp-
tion with charge transfer, like H upd or halide ion
adsorption, but this has not been proven. For example,
t In Ref. [16] the pre-exponential term in Frumkin isotherm was
neglected, and consequently values of both MTi: and f were
slightly different from one presented in this chapter.
826
the similarity to H upd adsorption is most apparent on the
(110)-(1 x 2) surface, where the relaxation of the Pt sur-
face is the same for both processes. This led us to postulate
that the adsorption sites for the reversible adsorption of
OHad and Hupd are the same, e.g., the threefold hollow
sites in the troughs, as shown in Fig. 3. It appears that
the transition from reversible to irreversible adsorption
of oxygenated species on this surface produces a surface
roughening, presumably by the place exchange
mechanism. It is important to note that a transition from
the reversible to irreversible adsorption occurs at a poten-
tial at which almost all threefold hollow sites are occupied
by OH rv , e.g., 80Hrv is ~ 1 ML at a transition potential.
Therefore, oxide starts to form on the Pt(1I0)-(1 x 2) sur-
face on the top sites of the Pt rows. By far the most under-
stood pseudo-capacitance is the anomalous feature on
the Pt(l1 1) surface in alkaline electrolytes, i.e., it is most
likely related to the adsorption of OH ad . Because the
anomalous feature occurs at the same potential with
respect to the RHE in HCI0 4 and KOH, the anomalous
feature in HCl0 4 is also most likely related to the adsorp-
tion of hydroxyl species but with H20 as the source of
OH ad [13]. Figure 1revealed that in the anomalous poten-
tial region the relaxation of platinum surface atoms is
almost negligible, suggesting that interaction of OH rv
with the Pt(111) is relatively weak, at least in comparison
with the adsorption of Hupd. The reversible state of
OH ad is also observed on Pt(100) in 0.1 M KOH and
0.1 M HCI0 4 as the reversible pseudo-capacitive feature
recorded in a potential range of0.175 < E < 0.375. At more
positive potentials, however, the observed asymmetry in
the cyclic voltammetry of the Pt(100) surface clearly rep-
resents the irreversible state of OH ad species, i.e., oxide
formation. Furthermore, Fig. 2 revealed that in the
OH ad potential region, the relaxation ofplatinum surface
atoms is smaller than in the H upd region. Based on this
fact, we postulate that interaction of OH rv with the
Pt(100) is weaker in comparison with the interaction of
Hupd; thus, OH rv is adsorbed on the (100) surface rather
than in or below the surface.
III. OXYGEN REDUCTION ON Pt(hkl)
In what follows, we review some of experimental results
obtained within the last 5 years for the ORR on Pt(hkl)
in the RRDE configuration. In particular, we show that
the elimination ofsurface heterogeneity and the enhance-
ment of the resolution in the voltammetry that results
from a single-crystal geometry can bring new insight into
our understanding of the reaction pathway of the ORR
on platinum electrodes in aqueous electrolytes. We
present an interpretation of the kinetics of the ORR on
Markovic and Ross
Pt(11l)-(1 x 1), Pt(100)-(1 x 1), and Pt(1IO)-(l x 2)
surfaces based on the supposition, which we shall sub-
stantiate below, that the differences in the activity of
three low index faces of Pt arise mainly from the
structure-sensitive adsorption of anions. There is some
structure sensitivity to 0-0 bond breaking and/or
O-H bond formation steps in nonadsorbing
electrolytes, but this imparts a much smaller effect on
the kinetics.
A. Structural Sensitivity of the ORR on
Pt(hkl)
Studies of the ORRon Pt(hkl) date back to the late 1970s,
when it was reported that essentially the same activities
for the ORR on all three Pt-low index single-crystal
surfaces [38]. In these experiments, however, Pt(hkl)
surfaces were partially disordered by oxide formation/
reduction cycling. Obviously, it turned out to be much
more difficult experimentally to use Pt(hkl) surfaces than
anticipated in 1979. It was even more difficult to use them
in a geometry like the RRDE, which is essential for study-
ing the kinetics and the reaction path of the ORR over a
practical potential range. Only in the last 10 years have
basic researchers been able to use single crystals in a
rotating geometry, first in an approximation to a RDE
called the rotating hanging meniscus electrode [39,40]
and more recently in the most desired geometry, the
RRDE [11,41]. Before we show complete set ofthe RRDE
data for the ORR on Pt(hkl) surfaces, obtained in our
laboratory, we present the methodologyofboth recording
and analyzing the polarization curves for the ORR on
Pt(hkl). The cyclic voltammogram of the Pt(111) in
oxygen-free 0.1 M HCl0 4 is characteristic of well-
orientated and clean surface, confirming that Pt(11l) (as
well as other single-crystal surfaces [11-13,41]) can be
transferred into the RRDE configuration without con-
tamination, (Fig. 4a). Figure 4 also summarizes a family
of polarization curves for the ORR on Pt(11l) in 0.1 M
HCl0 4 along with there kinetic analysis, presented in
the form of the Tafel plot of mass-transport corrected
currents for the ORR (inset b) and the Levich-Koutecky
plots (inset c). The values for the Tafel plots in acid and
alkaline electrolytes are tabulated in Table 1. Figure 4c
reveals that the Levich - Koutecky plots for various
potentials yield straight lines with intercepts correspond-
ing to the kinetic currents, h (see the rate constants in
Table 1), which gives the order of absolute kinetic activity
of this surface. In addition, the slope of the straight lines,
the so called B-factor, allows one to assess the number
of electrons involved in the oxygen reduction reaction
(Table 1). From a similar set of data as shown in Fig. 4
Electrocatalysis at Well-Defined Surfaces 827

Table 1 Some Kinetic Parameters for the ORR on Pt(hkl) in Aqueous Solutions at 298 K
0.1 MHCI0 4 0.05 MH2S04 0.1 MKOH

n aE/ alogi k x 102 n Ealogi k x 102 Ad Jli

n aEi alogi k x 102
(hkl) 0.3 > E/V > OJ (mY/dec) (ems-I) m 0.3> ElY > 0.3 (mV/dee) (ems-I) (kJ mol-I) 0.3 > ElY > 0.3 (mV/dee) (em S-I)

III 4 to 4 77 2.45 4to 4 120 0.10 42 4 to 4 75 3.8

(1 x I) 2 2 3

100 4 to 4 led 100 0.85 4 to 4 led 65 2.0 42 4 to 4 led 86 0.64

(1 x I) 2.5 hed 120 2.5 hedl20 3.2 hedl68

llO 4 4 led llO 2.5 4 4 led 80 2.5 42 4 4 led 89 0.76

(1 x 2) hed 82 hedl20 hed269

n. number of electrons; a£1 alog i. Tafel slope; led and hcd stand for high current density and low current density; m. reaction order; k, rate constant obtained from
Levich- Koutecky plots at £=0.8 V; !iF", apparent activation energy.

(a) we return to the structural sensitivity ofthe ORR on plati-

1600 rpm Pt(111)
0.1 M HCI0 4
num low-index single-crystal surfaces. Figures 5-7 show
50 mV/s a comparison of the ring-disk electrode for the oxygen
reduction kinetic data along with the voltammetry in
160 EM (b) @900rpm
oxygen-free solutions for each Pt(hkl) surface. Clearly,
120 0.7
/'
the kinetics of the ORR on Pt(hkl) surfaces vary with
:? 71mV/~/
80 400 EM 0.•
/
crystal face in a different manner depending on the
40
2,
-~ , -2 -, 0 1 2 solution. In perchloric acid solution (Fig. 5), the variation
00 RPM
IIDH(lD-ll]
2
in activity at 0.8-0.9 Vis relatively small between the three
low index faces, with the activity increasing in the order
g:_:~
400

'~~
,
2500 (100) < (110) ~ (111). A similar structural sensitivity is
:? 1.0 l'
.s ~',
, ~
0

2.0
0.0 0.2 0.4 0.6
EM
Figure 4 Disk (Jo) and ring (!R) currents during oxygen
reduction on Pt(lll) in 0.1 M HCl04 at a sweep rate of 50 mYls
(ring potential, 1.15 V): (--) positive-going sweeps; (- - -)
negative-going sweep at 900 rpm. (a) Cyclic voltammetry of
Pt(111) in the RRDE assembly in oxygen-free electrolyte with
and without rotation; (b) Tafel plot at 900 rpm; (c) Levich plot
at various electrode potentials. E vs. RHE.
but for the ORR on Pt(100) and Pt(110)-(1 x 2)+ in three
different electrolytes, values for the Tafel plots and the
kinetic parameters assessed from the Levich - Koutecky
plots are also summarized in Table 1.
Having reviewed the methodology of recording and
analyzing the polarization curves for the ORRon Pt(hkl),
t For brevity, the Pt(llO)-(1 x 2) surface will be denoted just as
Pt(llO) hereafter.
<:::>
/
' ..
/
observed in KOH (Fig. 6), with the activity increasing in
the order (100) < (110) < (111) but with larger differences.
0
o 0.01 0.03 0.05
In sulfuric acid solution (Fig. 7), the variations in activity
Of%[rpm%]
with crystal face are much larger, with the difference
0.8 1.0
between the most active and the least active surface being
about two orders of magnitude and increase in the
opposite order, i.e., (111)« (100) < (110). To understand
the structure sensitivity more clearly, it is useful to make
comparison of the kinetics ofthe ORR on the same plati-
num low-index single-crystal plane but in different
solutions. The best form of representation will be by
comparing the Tafel plots of mass-transport corrected
currents at Pt(hkl) surfaces, as summarized in Fig. 8.
The Pt(l1 1) surface shows the largest variation in activity
between the three electrodes, with the activity in sulfuric
acid being nearly three orders of magnitude lower than
in either of the other two solutions. This is consistent with
very strong adsorption ofbisulfate anions on this surface
[42a,43]. The 100 surface has the least variation (factor
of 2-3) in activity with electrolyte, whereas 110 is similar
to 100 with somewhat larger differences with HCl0 4 and
H 2 S04 solutions. It is important to note that on Pt(111) a
single linear Tafel slope was obtained in entire potential
range (Table 1). In contrast, the Tafel slopes on Pt(100)
828 Markovic and Ross

20 20 Pt(111)
Pt(111)
r~-
J'
~
II
Pt(110) Pt(110)
10 ~ 10 Pt(100)
_j\.\~'
\ / Pt(100)
,., ---,t _/"1
/1 /
<t o ___ I <t
.= ~J:
0.1 M HCI04 .= 0
0.1 M KOH
_0

-10
/
,/
/ -- \ I 50 mV/s
900 RPM
_0

-10
50 mV/s
1600 RPM

"l
',j \1
II
1
-20 -20
0.2
H02 -
0.0 __ H,O,

~'" 1
- -0.2
"-
\
40
I
0.0

-0.2
_0

<t 80 t
\

\
_0

-04 ~ ~_ _ _
\

<t ~
-0.4 ----..... ........
.= \
\ .= 20
-'" 40 \
~-', \
\
-0.6
0.0 0.2 04 0.6 0.8
EM
'" \ '0 -0.6 I I

0.0
I

0.2 0.4
I I

0.6
I

0.8 EM
)

OL -----------.,. 0 ~
,
I
0.5 I
I, o'l \
<t
oS
I
I
° '" \ ,0 1.0
/
I

1.0
---',\. \
\ ~

/'../-7
1.5
---~
. . "'::::.:::----=:-
. ~----/
/

0.0 0.2 OA 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
EM E [V]

Figure 5 Top: Cyclic voltammetry of Pt(hkl) in oxygen-free
OJ M HCl04 electrolyte in the RRDE assembly. Bottom: Disk
(Io) and ring (IR) currents during oxygen reduction on Pt(hkl)
(ring potential, 1.15 V). Inset: Reduction of 1.2 . 10- 3 M HzO z
on Pt(hkl) mounted in the RRDE assembly. Sweep rate,
50 mV/s. Rotation rate, 900 rpm. E vs. RHE.
Figure 6 Top: Cyclic voltammetry of Pt(hkl) in oxygen-free
OJ M KOH electrolyte in the RRDE assembly. Bottom: Disk
(Io) and ring (IR) currents during oxygen reduction on Pt(hkl)
(ring potential, +1.15 V). Inset: Reduction of 1.2 . 10- 3 M
HzO z on Pt(hkl) mounted in the RRDE assembly. Sweep rate,
50 mYls. Rotation rate, 900 rpm. E vs. RHE.

and Pt(llO) increased monotonically with the over- disk currents is followed quantitatively by an increase in
potential.Wehave attributed the variations in activity with ring currents, which is measuring the flux of peroxide
crystal face as arising primarily from the structure produced during the ORR. This conclusion is confirmed
sensitive adsorption of ions in the electrolyte, e.g., at low independently by examining the reduction of hydrogen
overpotentials, bisulfate in sulfuric acid and OHad in peroxide on the Pt(hkl) disk electrodes in oxygen-free
KOH and HCl0 4 , and at high overpotentials H upd in all electrolyte, as shown in insets of Figs. 5-7. As expected,
electrolytes [14]. We review below the analyses that H202 reduction currents in the hydrogen adsorption
support these conclusions in reverse order. region behave the same way as O 2 reduction currents,
e.g., the deactivation affected by the adsorbed hydrogen
1. Effect of Hupd on the ORR is the most pronounced on Pt(lll), less pronounced on
Although the analysis of the ORR in Hupd region is not Pt(WO), and almost negligible on Pt(lW). In fact, the
important from a practical standpoint, these studies are activity for peroxide reduction ofthe Pt(ll1) surface in
closely related to the central issue of this chapter, that of acid solutions was essentially nil, consistent with the
the structural sensitivity of an electrochemical reaction. quantitative 2e- reduction of 02 in this potential region
Figures 5-7 show that in the potential region where (Table 1). The most significant feature evident from these
H upd is adsorbed, the rate of the ORR becomes strongly analyses is that the deactivation by adsorbed hydrogen
structure sensitive, with activity decreasing in the order is entirely due to a loss of adsorption sites that break the
Pt(lW) > Pt(WO) > Pt(lll). In addition, the decrease in 0-0 bond, as was reported earlier by Markovic et al.
r Electrocatalysis at Well-Defined Surfaces 829

~,~""""""
- - Pt(110)
20 " 0.7
,,",,
- - - - - Pt (100)
,," , , ,, ················Pt(111)
1'1(1 1
10
,, ,
I
I
-.....,/...
,
.....\ \ 0.05M H2S04 0.8 "
50 mV/s "
..../ - ~"-..'" ,,' "
~
1600 RPM
0 ---------;~-""".,_.-.

/
-. Ji'''' - ...; ' " -

······,:-·······\jl
...
0.9
10 ' '-'~\"'"
,, '
, ,'
\
\1
-- \
/
J

20 'c
o
0.7
.
'

«
80
....
:>
........ 0.8
j "
w
40
-<l.2 0 0.2
EN
0.4 0.6
0.9
.......- ..... :;.;.:
« o
~
i ,
1.0
~ ...... 0.7 Pt(110)
0.2 0.4 0.6
EN
0.8
Figure 7 Top: Cyclic voltammetry of Pt(hkl) in oxygen-free
0.05 M H 2 S0 4 electrolyte in the RRDE assembly. Bottom: Disk
(ID) and ring (IR) currents during oxygen reduction on Pt(hkl)
(ring potential, 1.15 V). Inset: Reduction ofl.2 . 10- 3 M H 20 2
0.9
on Pt(hkl) mounted in the RRDE assembly. Sweep rate,
50 mYls. Rotation rate, 900 rpm. Note: E vs SeE (saturated
calomel electrode).
o 1
[ID . I/(ID - I)]
[39], and not due to an interaction ofO 2 with H upd , as was
proposed by Damjanovic et al. [44]. As we mentioned Figure 8 Tafel plots for Pt(hkl) electrodes corrected for
in the previous section, the nature of adsorbed hydrogen diffusional resistance. Tafel plots are derived from the
on platinum in electrolytic solutions is still speculative. polarization curves shown in Figs. 5~ 7.
Based on the models described above, we suggest that
on an ideal Pt(lll) surface, the ORR is strongly inhibited
in the hydrogen region because H upd is probably Pt(lOO)-liquid interface, the active centers for the
adsorbed onto this surface and blocks the pairs of sites 0-0 bond breaking are the defect sites, which are
required for the 0-0 bond breaking. In the case of created during the surface annealing (see Sect. II). For
Pt(lOO), we suggest that some of the H upd lies in the sur- Pt(lW), we have suggested that H upd is adsorbed in the
face and therefore does not affect all active sites, such as "troughs" of the surface, thus leaving the top sites avail-
a-top and bridge sites that may serve as the sites of the able for O 2 and H 20 2 adsorption and consequently
0-0 bond breaking. It is also possible that at cleaving of 0-0 band [14].
830
2. Effect of OH ad on the ORR
The Pt(hkl)/KOH system is the most direct probe of the
effects of OHad on the rate of the electrode reaction,
because no other anions are co-adsorbed with hydroxyl
species. We recall that two different types of OHad occur
on Pt(100) and Pt(1lO), a reversible and an irreversible
form. On the other hand, only the reversible state of OH
adlayer is formed on Pt(111) in the same potential region.
Figure 6 shows that in the potential range where O 2
reduction is under combined kinetic-diffusion control
(E > 0.75 V), the order of activity of Pt(hkl) in 0.1 M
KOH increase in the sequence (100) < (110) < (111); the
same order is observed for the reduction of HO l (insets
in Figs. 5-7). The shift in half-wave potential between
the least active and the most active surface was ca. 110 mY,
which is more than an order of magnitude difference in
the kinetic rate. These differences can be attributed to
the structure sensitivity of hydroxyl anion adsorption on
Pt(hkI) surfaces and its inhibiting (site blocking) effect
on both the oxygen and HO l kinetics. Although we do
not contend that the two effects can be distinguished
under all conditions on all three surfaces, the weight of
experimental evidence favors the conclusion that the
reversible and irreversible forms of OHad affect the
ORR in different ways: The reversible form has little or
no measurable effect on the reaction mechanism, whereas
the irreversible form (oxide) effects both the reaction rate
and the reaction pathway. In perchloric acid, the variation
in structural sensitivity is relatively small between the
three low-index faces, with activity that increase in the
order (100) < (lll) < (110) (Fig. 5). The structure-
sensitivity of the ORR in the potential region of OH
adsorption in HCI0 4 (the oxidation in acid proceeds
from H 20) has the same origin as that in KOH, namely
the structure sensitive adsorption of the hydroxyl species
in the supporting solution. In general terms, the reversible
form of OH has a stronger inhibiting effect on Pt(100)
and than on Pt(llO) and Pt(lll). This is possibly related
to the specific type of site for OHad on these surfaces and
the effect of OHad at these sites on the rate of O~O bond
breaking and/or O~H bond making.
3. Effects of HS0 4 on the ORR
A close inspection of Fig. 7 revealed that the order of
activity ofPt(hkl) for the ORR in H2S04 increase in the
sequence Pt(lll) < Pt(100) < Pt(110). The simplest and
the most logical explanation for the higher overpotential
for O 2 reduction on the Pt(lll) surface is that its activity
is reduced by the relatively strong adsorption of
tetrahedrally bonded (bi)sulfate anions on the (lll) sites
observed in Fourier transform infrared [42] and radio-
tracer experiments [43]. These differences of (bi)sulfate
Markovic and Ross
adsorption in terms of coverage and bonding between
Pt(111) and the other two low-index faces are also appar-
ent in the significant positive shift in the potential for the
adsorption of oxygen-containing species. In addition,
they are consistent with the significantly lower activity of
Pt(1ll) for oxygen reduction compared with either
Pt(100) or pte110) (Fig. 7).The most active surface for oxy-
gen reduction, however, is the Pt(1lO) plane, as was also
found for O 2 reduction in 0.1 M HCI0 4. The difference
in activity between Pt(1lO) and Pt(100) in sulfuric acid
electrolyte may derive from either subtle differences in
(bi)sulfate adsorption or from other structure sensitive
surface processes, such as 0--0 bond breaking and/or
O~H bond making. The fact that the activity ofall three
low-index platinum planes is significantly higher in
HCI0 4 does, however, suggest that the major differences
in H2S04 electrolyte stem from the structure sensitive
adsorption of (bi)sulfate anions. It should be noted that
although bisulfate adsorption onto Pt(hkl) surfaces
inhibits the reduction of molecular 02, probably by
blocking the initial adsorption of O 2, it does not affect
the pathway of the reaction, because no H202 is detected
on the ring electrode for any of the surfaces in the
kinetically controlled potential region.
B. Temperature Dependence of the ORR on
Pt(hkl): Activation Energy
A kinetic analysis is not complete without determination
of the temperature effects and activation energies. Figure
9 summarizes some of the polarization curves for the
ORR recorded at 333 and 298 K [for details see 41].
Clearly, results obtained at 333 K are qualitatively similar
to the curves recorded at room temperature, and the order
of activity remains the same as at room temperature, i.e.,
Pt(1ll) < Pt(100) < Pt(llO). As expected, currents for the
ORR are higher at elevated temperatures in both the
mixed diffusion-kinetic potential region and in the
hydrogen-adsorption potential region. These higher
currents reflect the temperature dependence of the
chemical rate constant, which is approximately
proportional to e-IJ.Ho# /RT, where !!Jf# is the apparent
enthalpy of activation at the reversible potential (here-
after simply termed the activation energy) and T is the
absolute temperature. All kinetic analysis, including
extraction of the activation energies on Pt(hkl), is given
below and summarized in Table 1. It is also important to
note that the analysis of the polarization curves recorded
for the ORR at elevated temperatures revealed that the
Tafel slopes were directly proportional to the temper-
ature, with the transfer coefficient, IX, for the oxygen
r Electrocatalysis at Well-Defined Surfaces 831

(b) 0.9 )(
0
Pt(lll)

(a) 100
0.8
;;;-
298 K IlK
50 ---
~ 0.7
0 298
0 313
0.0 ---------.;-=..",...,.---1 0
: I "'.7' ~ V 333
0.6
/.
'I
I : :
.
.-

0.5 /
.~.

-~
0.5
I
J
/
::
::
<t::::l. -1 0 1 2
« idi / id-i) / mAcm'2)
" " .' .
log
~ 1.0 .......... ~.._--~.... . ' ~
"S
- 1. 5 /--.----,--r---r-.--.,--r--....---.--r---l
"E 100 u

~
~
0.0
: 333 K .5
-, 50 ~
... ....
is
~
0.0
• 0 •• ' . _~ _ _ • . _ ..... _

,.
" : .-
0
/

--Pt(111) :/ ...
0.5 ~ :
- - - - 'Pt(100) - /. .
J : :
'\ ..... "'Pt(llO) ;' ..;'
1.0
.,....---- --'" ~--'

1.5
0.0 0.2 0.4 0.6 0.8 1.0

E/V
3.0 3.1 3.2 3.3 3.4

Figure 9 (a) Disk (lD) and ring (lR) currents during oxygen reduction on Pt(hkl) in 0.05 M H 2S0 4 at 298, and 333 K. Rotation rate,
900 rpm. Sweep rate, 20 mY/so (b) Tafel plots for the ORR on Pt(lII) in 0.05 M H 2 S0 4 at 298, 313, and 333 K. (c) Arrhenius plots of
the exchange current densities at the equilibrium potential for oxygen reduction on Pt(hkl) electrodes. E YS. RHE.

reaction being independentoftemperature (inset b, Fig. 9). Our results for the ORR on Pt(hkl) surfaces 0.05 M
The data on the temperature dependence of the Tafel H 2 S04 are consistent with the previous reports for a poly-
slope for the ORR at the Pt electrode from different crystalline Pt in dilute acid solution by Damjanovic and
groups are not in good agreement; e.g., both the Sepa [48], i.e., a Tafel slope that is directly proportional
temperature-dependent [45,46] and temperature- to the temperature with the transfer coefficient ex a
independent [47,48] Tafel slopes have been reported. temperature-independent factor.
According to various authors, several different phenom- The well-defined linear Tafel regions for the ORR on
ena are invoked to explain a temperature dependent ex, Pt(hkl) can be used to extrapolate the current to the theor-
some of fundamental importance such as the tempera- etical equilibrium potential to obtain the exchange cur-
ture effect in proton transfer and/or electron tunneling, rent densities for the ORR on oxide-free Pt. At the same
a shift in the rate-determining step with temperature, or temperature, the exchange current density increases in
changes in the symmetry of the potential energy barrier the order iO(lll) < iO(IOO) < iO(lIO), which gives the order of
with temperature. Artifacts such as impurity effects can absolute kinetic activities ofthree surfaces.The activation
also contribute to the temperature dependence of ex [47]. energies for the ORR on each Pt(hkl) face were obtained
832
from the exchange current density at different tempera-
tures using the Arrhenious plots
dlog io liH o#
(1)
d(ljT) 2.3R
Inset c in Fig. 9 shows that the same slope, ::::::42 kllmol, is
obtained for all three single-crystal surfaces. Thus,
although the catalytic activity varies strongly with crystal
face, essentially the same activation energies are
obtained, implying that the structure sensitivity arises
primarily from geometric factors in the pre-exponential
term. As mentioned above, the extrapolation of the Tafel
slopes in KOH was more uncertain than in H2S04, i.e.,
depending on the fitting method the extrapolated io may
vary by ca. an order of magnitude. Consequently, the
energy of activation for the ORR in alkaline solution fall
in the range of ::::::45-55 kllmol for all three surfaces, i.e.,
there is the possibility of a variation in activation energy
with crystal face within this range ofvalues.
c. Reaction Pathway for the ORR on Pt(hkl)
In this section, the reaction pathway for the ORR on
Pt(hkl) rather than the reaction mechanism is dis-
cussed, because the RRDpt(hkl)E technique alone is not
capable to detect all possible reaction intermediates in
a reaction as complex as the ORR. From the many sev-
eral reaction pathways that have been proposed in the
past, we discuss our results in the context of the series
pathway, via an (02H)ad intermediate, using the general
reaction scheme for O 2 reduction proposed by
Wroblowa et a!. [49]. We will not attempt to resolve all
of the uncertainties that still persist over the reaction
mechanism of the ORR on Pt nor do we claim that our
analysis here is definitive. Rather, we attempt to improve
the understanding of the reaction pathway by comp-
aring the kinetics of the ORR onto Pt(hkl) surfaces with
the rate of the peroxide reduction under the same
experimental conditions and then to relate the kinetic
parameters, such as Tafel slope, exchange current
densities, and activation energies for the ORR on Pt(hkl)
with the activities and the RDS of the ORR on different
single-crystal faces.
For the ORR on polycrystalline platinum electrode
there are two views regarding the first reaction step in acid
solution. Damjanovic et a!. [50] proposed that the first
step is electron transfer to the 02 molecule; this step is rate
determining and is either accompanied by or followed
by a fast proton transfer. On the other hand,Yeager et a!.
[51] proposed that the first step most likely involves dis-
sociative chemisorption of the 02 molecule that occurs
simultaneous with the charge transfer. It appears that
Markovic and Ross
our results for the ORR on Pt(hkl) support the former,
primarily due to the resolution of component electrode
processes that is uniquely possible with single-crystal
electrodes. This resolution can be seen from two sets of
results for the ORR in H 2S04. The first is that the Tafel
slopes, together with the OH ad coverages that can be
inferred from the voltammetry curves in Fig. 7, are con-
sistent with the first electron transfer to the O 2 molecule
as the RDS:
RDS
02+e- ~ O2 (2)
This is most easily seen for the Pt(ll1) on which a single
Tafel slope of -2 x 2.3(RTIF) observed in the entire
potential region;k a value of -2 x 2.3(RTIF) is character-
istic for the first charge transfer as the RDS under
Langmuirian conditions of adsorption of O 2 [4l]. A
second new set of results are the polarization curves for
the peroxide reduction on Pt(hkl). A comparison of the
kinetics for the ORR and peroxide reduction shows that
the peroxide reduction takes place at lower over-
potentials than the ORR (Fig. 5). This implies that the
peroxide, which could be formed during the ORR, can
easily be further reduced between 0.6 and 0.05 V. In
addition, a close inspection of Fig. 5 shows that in the
hydrogen adsorption potential region, the H upd state has
the same effect on the ORR and the peroxide reduction,
remarkably so on the 111. Recently, the effects of H upd on
the kinetics of H 202 on Pt(hkl) have been discussed,
and these analyses are not repeated [for review see 11,14].
For our purposes here, we note only that the model pro-
posed for the strong inhibition of oxygen and peroxide
reduction induced by the H upd state is consistent with
the series reaction pathway with the first electron transfer
being the rate-determining step.
Finally, we summarize the data and analyses that
support the assignment of structure sensitivity in the
ORR primarily to structure-sensitive anion adsorption
in 0.05 M H 2S04. The analysis of the Arrhenious plots
clearly showed that the same activation energy for the
ORR, close to 42 kllmol, has been found for all three
Pt(hkl) surfaces. We presented an argument showing that
the same reaction pathway is operative on all three
single-crystal faces. How then does on account for the
very strong differences in the kinetic rate, io, on the differ-
ent Pt(hkl) surfaces? The key observation that guides us
to the answer is that this structural sensitivity is most
pronounced in electrolytes in which there is strong
adsorption of anions, especially in sulfuric acid. We had
proposed a simple form ofPt site elimination by adsorbed
anions [11,14], and if the standard free energy of adsorp-
tion of molecular O 2 is independent of coverage
Electrocatalysis at Well-Defined Surfaces
(Langmuirian conditions), then the rate of O 2 reduction
may be expressed as
(3)
where n is the number of the electrons, k is the rate con-
stant, CO2 is the concentration of O 2 in the solution, Bad
is the partial coverage by H upd and anion species (e.g.,
HS0 4ad , OH"d, and oxide), i is the observed current, '1 is
the applied overpotential, and CI. is the transfer coefficient.
It appears that in this rate equation for the ORR, all the
variables are independent of surface crystallography,
except the surface coverage by Hupd, anions, and
oxygen-containing species. Therefore, the structure
sensitivity in the kinetics of the ORR on Pt(hkl) is deter-
mined entirely by structure sensitivity in the pre-
-exponential term (l-B ad). In the case of sulfuric acid
solution, there is independent spectroscopic evidence
[42] for structure sensitive adsorption of bisulfate anion,
the coverage of HS04"d being much higher on the (111)
surface than on the (l00) surface.
IV. HER AND HOR ON Pt(hkl)
In this section we review some ofthe recent developments
in the understanding of the kinetics of both the HER
and the HOR on Pt(hkl) in alkaline and acid solution.
The results reviewed here emphasize the different role
play by two forms of Had' that produced in the
underpotential region (0-0.35 Vanodic of the reversible
potential), and that produced in the overpotential region
of the HE/OR. For convenience, we distinguish these
two forms of Had as the H upd state and the H opd state
(Conway's notation), respectively. Heretofore in this
chapter, we have discussed only the Hupd form of Had.
Less is known about the H opd state, even its existence is
a matter ofconjecture.
A. Structural Sensitivity of the HER and HOR
(HE/OR)
The hydrogen reaction on a platinum electrode is among
the most widely studied electrochemical reactions. Early
kinetic studies of the HE/OR were carried out either on
a polycrystalline platinum electrode [52] or on platinum
single crystals that had poorly defined surface structures
[53,54]. In 1970, Physnogreva et al. [53] and Schuldiner et
al. [54] reported that the kinetics of the HER on Pt(hkl)
are not sensitive to the surface crystallography. In these
experiments, however, the electrodes were "activated"
and cleaned by cycling the electrode potential deep into
the region of the oxide formation, a pretreatment that
we now know disorders the surface. Only recently have
833
the kinetics of the HE/OR been studied on well-ordered
platinum single-crystal electrodes. Based on measure-
ments on both stationary electrodes and on RHME, it
was reported that even on well-ordered Pt(hkl) the
kinetics of the HER at room temperature is insensitive
to the crystallography ofthe surface [55]. The significance
of these results is, however, questionable because it is
not clear that true kinetic rates were actually measured
in any of these studies. As emphasized by Bagotzky and
Osetrova [56], and much earlier by Breiter and Clamroth
[57], the hydrogen reaction on "active" Pt in acidic sol-
utions is one of the fastest known electrochemical
reactions (with an io > 10- 3 A/cm 2), and it is experimen-
tally very difficult to measure anything but diffusion
polarization. It becomes obvious, therefore, that to eluci-
date the true structural sensitivity of the HE/OR on
Pt(hkl), the kinetics of this reaction should be reduced
by more than one order of magnitude from that in acid
solution at ambient temperature. Given that the rate of
the HE/ORon a polycrystalline electrode is much slower
in alkaline than in acid solution and that the kinetics of
electrochemical reaction is significantly hindered at
lower temperatures, the accurate measurement of kinetic
rates of the HE/OR on Pt(hkl) appears more tractable
in alkaline solution or at low temperature in acid
solutions, as we illustrate below.
1. HE/OR in Alkaline Solution
Polarization curves for the HE/OR on rotating Pt(hkl)
disk electrodes in 0.1 M KOH at 298 K are shown in Fig.
10. On the cathodic side, the order of activity for the
HER increased in the sequence (111) < (l00) < (110),
clearly indicating that the HER in alkaline solution is
structural sensitive reaction. The comparison made in
Fig. 11 also expresses some dramatic differences in the
kinetics of the HE/OR on Pt(hkl) in both the high and
low overpotential regions. In particular, at low positive
overpotentials (the Hupd region), the order of activity for
the HOR increases in the sequence (111) ~ (l00)« (110).
As we see in Sec. IVA., these differences in activity with
crystal face can be attributed to the different state of
H upd and to different effects ofthese states on the mechan-
ism of the hydrogen reaction. Figure 10 shows that at low
positive overpotentials the polarization curves for the
HOR on Pt(l1l) and (l00) have no rotation dependence.
This implies entirely kinetic resistance of the HOR to
about 0.2 V Sweeping the potential more positive, the
currents are under mixed control up to ~ 0.45 Vof over-
potential. On the Pt(llO) surface, the kinetics of the
HOR is faster than on both the Pt(l1l) surface and Pt(100)
surface, and consequently the currents are under mixed
control "only" up to ~ 0.2 V of overpotential. The fact

Figure 10 Polarization curves for the HER and the HOR on
Pt(hkl) in 0.1 M KOH at sweep rate of20 mY/so E vS. RHE.
that the kinetics of the HOR on Pt(hkl) in alkaline
solutions is very slow provides a relatively wide window
of the overpotential where the kinetic analysis can be
performed by using the Levich-Kouteckey equation;
the kinetic parameters for the HOR on Pt(hkl) surfaces
in 0.1 M KOH are summarized in Table 2. Further
inspection of Figs. 10 and 11 indicates that at high positive
overpotentials the kinetics of the HOR decreases in
the same sequence as we found for the ORR,
e.g., (100)« (110) < (111). Furthermore, and in harmony
with the ORR on Pt(hkl), the effects of surface
crystallography on the HOR in this potential region can
Markovic and Ross
be attributed to the structure sensitive adsorption of
OH ad species on Pt(hkl) and the effects the OH ad state
may have on the kinetics of the HOR. For example, the
reversible state of OHad on the Pt(lll) surface has no
effects on the kinetics of the HOR, and consequently a
pure diffusion limiting currents for the HOR are observed
within the "anomalous" potential range. This implies that
the reversible state of OH ad on Pt(111) does not block
active sites for dissociative adsorption of H 2 molecules.
In contrast to the HOR on the Pt(l1l) surface, the
diffusion limiting currents for the HOR on the Pt(lOO)
surface are observed only in a very narrow potential
region, e.g., in Fig. 10 between 0.55 and 0.6 V At higher
overpotentials, decrease in the kinetics of the HOR is
almost a mirror image of the curves recorded on the
Pt(100) surface in the H upd region. The "bell-shape" of
the polarization curves for Pt(100) implies that the
adsorption of OHad species suppresses activity in nearly
the same way as H upd does (Fig. 11). To complete this
excursion into the effects of OHad on the kinetics of the
HOR, we briefly mention that on the Pt(110) surface a fun-
damentally important difference in the role of OHad
species in the kinetics of the HOR is observed in Fig. 11.
In another words, although the OH rv state has a minor
effects on the kinetics of the HOR, the irreversible state
has a site blocking role in the HOR, as it does in the case
for the ORRon the Pt(110) surface. A comparison of the
polarization curve for the HOR with the base vol-
tammetry of the Pt(llO) surface in Fig. 11 revealed that
the onset of the deactivation of the HOR begins at ca.
0.6 V A particular behavior is again encountered with
the reversiblelirreversible transition of the OHad state
on the Pt(llO) surface (refer to the voltammetry in
hydrogen-free electrolyte in Fig. 11). It appears, therefore,
that OH rv and Hupd states have a similar role in the
kinetics of the HOR. Namely, both species do not playa
site-blocking role in the HOR, and the diffusion limiting
currents are observed on the Pt(110) surface, which is
almost fully covered with these species. In contrast, the
irreversible state of OHad can block the active platinum
centers for both the dissociative adsorption of molecular
hydrogen and adsorption of molecular oxygen. This dif-
ference in the role of the irreversible form of OH ad and
the Hupd state on the kinetics of the HOR and the ORR
on the Pt(1I0)-(1 x 2) surface is consistent with the model
of the specific adsorption sites, i.e., the reversible state
ofOH ad and the Hupd state being "in" the threefold hollow
sites in the troughs and oxide (the irreversible form of
OH ad ) being "on" the top-sites of the Pt rows. Following
this observation further, this would imply that the sites
for either H 2 dissociation or O2 dissociation on the
Pt(1I0)-(1 x 2) surface are the top sites of the Pt rows.
Electrocatalysis at Well-Defined Surfaces 835

Table 2 Kinetic Parameters for the HER and the HOR on Pt(hkl) in 0.05 M H 2 S0 4 at Different Temperatures and in 0.1 M KOH at
298 K
0.05 MH 2 S0 4 0.1 MKOH

Exchange current density aE/ aJogi

(rnA cm-2) Activation (mV/dec)
aE/ alogi energy Mechanism io Mechanism
Pt(hkl) (mV/dec) 274 K 303 K 333 K (kJ mol-I) (RDS) led hcd (rnA cm- 2) (RDS)

Pt(llO) Tafel- 55 140 0.70 Tafel-

I x2 2.3 R TI2F 0.65 0.98 1.35 9.5 Volmer Volmer

Pt(100) led: 2.3RT/3F 0.36 0.60 0.76 Heyrovsky- 65 140 0.05 Tafel-
IxI hcd: 2 x 2.3RT/F 12 Volmer Volmer

Pt(lll ) Heyrovsky or 75 120 0.07 Tafel-

1 xl o:::;2.3RT/F 0.21 0.45 0.83 18 Tafel- Volmer Volmer

Obtained from a linear polarization method.

2. HE/OR in Acid Solution: Effects of Temperature

To circumvent the problem of the fast kinetics of the
HE/OR in acid solutions at room temperature, the
kinetics of these processes can be measured at the lowest
+ temperatures possible with dilute acid solutions. In Fig.
5 12 typical examples are provided by the series of
«
.=!,
0 i
polarization curves for the HER and the HOR at 1 atm
E I
~ H 2 in 0.05 M H2S04 at 274°K. The comparison of the
::i I
(J I polarization curves in Fig. 12, in particular the exchange
\ I current densities (io) inferred from analysis of the
\ I
\. "micropolarization" potential region (inset of Fig. 12),
0.1 M KOH plainly revealed that both the HER and the HOR are
- - - Pt(100) 'f indeed structure-sensitive processes in acid solution, the
E 10
o
- Pt(111) activity increasing in the order (111) < (100) < (110).
«
--- Pt(110) £1 Although the structure sensitivity is very pronounced at
900 rpm ~-1 low temperatures (274-293 K), in the temperature range
'--L........:::'-:---'---~--'-----="-.,....-.L......J
-0.1 o 0.1 :::::: 303-333 K, the variation in the kinetics of the hyd-
IE] rogen reaction between crystal faces is less pronounced,

if ',
-'-'-;;-;;;':'...---:::::--::::----
..................
'-
especially between the (111) and (100) surfaces [for details
see 16]. This reconciles, at least in part, the absence of
E
() " ..... ..... structure sensitivity in all previously published results
«
oS 0~5 ""'- for the HER on Pt(hkl) at room temperature [16J. For
C 0 1 completeness, we should also mention that each crystal
~ face has an unique temperature-dependent Tafel slope
::J
() for the HOR (Table 2), e.g., the transfer coefficient, rJ., for
the hydrogen reaction being independent of temperature.
o 0.2 0.4 0.6 0.8 Inset of Fig. 12 shows representative Tafel plots of
E[V] mass-transport corrected currents for the HOR on
Pt(hkl) at 274 K. In this case, the Tafel slopes are deter-
Figure 11 Top: Cyclic voltammetry of Pt(hkl) in oxygen-free mined at low overpotentials, where measured current
0.1 KOH electrolyte in the RRDE assembly. Bottom: densities are essentially due to a mixed diffusion-kinetic
Polarization curves for the HER and the HOR on Pt(hkl) in resistance for the HOR. Note that at low overpotentials,
0.1 M KOH at sweep rate of 20 mYls. Inset: Tafel plots for the all three Pt(hkl) surfaces have symmetrical log i vs. E
HER and HOR extrapolated from bottom curves. E vs. RHE. relationships indicating that there is a single exchange
836 Markovic and Ross

i I(b) 0.15 1" """ """I lh

--Pt(lll)
274K
(a) ........ Pt(100)
_.-.-._. Pt(llO)
2 ~ 274 K 0.10
(.-.-::.:?'t. ........ _.........

,.;.'I
,..- 2 -->
Lt:l

if 0.05

<'i
au
o~ J 0

0.00 1.:ssI7:ih..:··.,r,;z;-·i"?t A" II ( , t , ,,!,.I I

~ ~":!Ii
0.1 I 10
__ ,I
·2 i.i I (i.-i) I rnA em"
-0.02 0.00 0.02
.£ -2 -'-'-'-' Pt(1lO)
~
(l) : ! ........ Pt(IOO)
"0 . I
--Pt(1II)
i:!
(l) 333 K __
8 2
/,
."
!/ 2
(c) ·2.8 [I 1 , 1

0 I 0
~ -3.2
·3.0

--~
-I
,•.P -3.4
-2
-2 ~ II -0.02 0.00 0.02 o Pt(llO)
~
, I , I -3.6
o
'iJ
Pt(IOO)
Pt(lll)
0.0 0.2 0.4 0.6
-3.8
E/V I I

3.0
' , I

3.2 3.4
!

3.6
). I

3.8

T·'/1O· 3 K'

Figure 12 (a) Polarization curves for the HER and the HOR on Pt(hkl) in 0.05 M H2S04 at 274 and 333 K. Sweep rate, 20 mV/s.
Rotation rate, 900 rpm. (b) Tafel plots of mass transfer corrected currents for the HOR on Pt(hkl) in 0.05 M H2S04 at 274 K. (c)
Arrhenius plots ofthe exchange current densities (io) for the HR on Pt(hkl) over the full range oftemperatures (274-333 K). E vs. RHE.

current density for the hydrogen electrode reaction appli-
cable to both anodic and cathodic processes. Using the
values of iO(hkl) assessed over the temperature range
274-333 Keither from micropolarization region or from
Tafel plots, the apparent activation energies for the
hydrogen reaction on Pt(hkl) in 0.05 M H 2 S04 can easily
be determined from the slopes of Arrhenius relation [see
Eq. (1) and Fig. 12c]. The apparent activation energy
increase in order 9.5 kllmol for Pt(1lO), 12 kllmol for
Pt(100), and 18 kllmol for Pt(lll). The fact that the most
active surface also has the lowest activation energy is a
"classic" result forelectrocatalytic reactions and indicates
that the energy ofadsorption of the reactive intermediate
plays the dominant role in the kinetics (vs. the pre-
-exponential terms, which contain the coverage factor).
These differences in activation energy with crystal face
are attributed to structure-sensitive heats of adsorption
of the active intermediate, Hapd, whose physical state is
unclear. In discussion that follows, from these exper-
imentally determined kinetic parameters, we examine
the possible relationship between this unknown state,
Hapd, postulated from kinetic models, with the
well-known adsorbed state of hydrogen, H upd , whose
adsorption energy is strongly structure sensitive.
r Electrocatalysis at Well-Defined Surfaces
B. Mechanism for the HE/OR on Pt(hkl)
The mechanism for the HOR on a polycrystalline plati-
num electrode in acid electrolytes [58] is usually assumed
to proceed by an initial adsorption of molecular
hydrogen, which involves either slow dissociation of H2
molecules into the atoms [Eq. (4)] or dissociation into
the ion and atom [Eq. (5)] followed by fast charge-transfer
step [Eq. (6)]:
(4)
(5)
(6)
i.e., historically referred to in some accounts as the
Tafel- Volmer (steps 4 and 6) and Heyrovsky- Volmer
(steps 5 and 6) sequences, respectively. The reaction
pathways of the HE/OR in alkaline solution are similar
to those in acid solution except that hydrogen is dis-
charged from H20 rather than from hydronium ions. If
we assume that close to the hydrogen reversible potential
the kinetic parameters (such as the Tafel slopes and the
activation energies) are the same for the HOR and HER,
then at low overpotentials the mechanism for the HER
would be the same as for the HOR. It is important to note
that the adsorbed hydrogen, designated as Hapd in Eqs.
(4-6), is the reactive intermediate in the HOR and the
HER, and therefore the kinetics ofthe hydrogen reaction
is completely determined by the interaction of Hapd with
the platinum surface atoms. Unfortunately, relatively
little is known about the nature ofHapd on Pt(hkl) in elec-
trolytic solutions at potentials close to the equilibrium
potential. For the purpose ofdistinguishing the different
possible states of adsorbed hydrogen, it is convenient to
use simply a thermodynamic notation, referring to a
(relatively) strongly adsorbed state as underpotentially
deposited hydrogen, Hupd, and to a weakly adsorbed state
as the reactive intermediate, Hapd [15,16]. The actual
physical state of either Hupd or Hapd on a platinum elec-
trode has been and continues to be the subject of intensive
study. Closely following the Protopoff and Marcus [55b]
proposition about the nature of Hupd and Hapd, we have
proposed [15,16] that the weakly adsorbed state Had on
Pt(hkl) is coupled to the strongly adsorbed state of Hupd
by an as yet uncertain mechanism, although the
coexistence of Hupd and Hapd on Pt(hkl) over the same
potential range has never been proven experimentally.
We also suggested that there is an indirect effect of Hupd
on the state of Hapd, thus on the kinetics of the HE/OR
837
on Pt(hkl). In the following, we propose two modes of
action of Hupd on the kinetics of the HE/OR on Pt(hkl)
in 0.05 M H2S04, Hupd adatoms may block the adsorp-
tion of H apd on active platinum sites, i.e., they compete
for the same site, and/or Hupd may alter the adsorption
energy of Hapd on the bare Pt sites neighbored by the
Hupd. For our purposes here, the effects of Hupd on the
state ofHapd are discussed only for the HE/ORon Pt(hkl)
in acid solution; details ofthe role ofHupd in the reaction
mechanism of the HE/OR on platinum single crystals in
alkaline electrolyte can be found elsewhere [15].
1. Mechanism of the HE/OR on Pt(110)
Assuming that the sites for the adsorption of Hupd on
Pt(llO) are the threefold coordinated sites below the
top-most rows ofPt atoms, H upd on Pt(1W) is mot prob-
ably a spectator during the hydrogen reaction. In the
absence of more definitive information about the state
of Hapd, the model that appears to rationalize the results
for the HOR at low anodic overpotentials on Pt(1lO) is
one that follows application of the Langmuir (ideal)
adsorption isotherm of Hapd and the ideal dual-site form
of the Tafel ~ Volmer sequence. The Tafel relationship
observed for Pt(llO) over two decades of current density
for the HOR at low overpotentials with a slope
~2.3RT!2F (Fig. 12 and Table 2) clearly indicates that
the atom -atom recombination step is indeed the RDS.
Considering that an activation energy of ~ 9.5 kl/mol is
reasonable for reaction like atom~atom recombination
step under Langmuirian conditions, we can propose that
the HOR on Pt(1W) proceeds by the Tafel-Volmer
sequence, the atom-atom recombination step being the
RDS. Assuming that on either side of the equilibrium
potential for the hydrogen reaction the (110) surface
always provides the same number of active centers (pair
of Pt top-sites), then the kinetics and the mechanism of
the HER and HOR should be the same, as confirmed by
the fact that the same values for the exchange current
densities are observed for the HER and the HOR. Thus,
in the HER on Pt(1lO) in sulfuric acid solution, a fast
charge transfer reaction is followed by rate-controlling
atom-atom recombination step (Volmer-Tafel sequ-
ence). On the bases ofsimilar analyses for the HE/OR in
alkaline solution, we have proposed the same reaction
mechanism to be operative in 0.1 M NaOH as well [for
more details see 15].
2. Mechanism of the HE/OR on Pt(100)
The HOR on Pt(100) occurs on the surface that is "fully"
covered by Hupd, as it was for the HOR on Pt(llO). Note
that, even when Pt(1W) is fully covered by Hupd, the top
rows ofplatinum atoms are still unoccupied and available
838
for the adsorption of Hapd, e.g., as terminally bonded
H-Pt. In contrast, on the geometrically homogeneous
Pt(lOO) surface, if there is only one type of site for
hydrogen adsorption, then a (100) surface covered by
1 ML of H upd should be completely inactive for the
HOR because the platinum sites are completely blocked
by Hupd. The implication is that unoccupied Pt sites,
required for the adsorption of the H apd state, can only be
created if some amount (unknown) of the H upd adatoms
sit in deeper potential wells on the surface, e.g., the
fourfold hollow sites, freeing top-sites, neighbored by
"subsurface" H upd , to serve as adsorption centers for
H apd . Although the number of on-top active sites near
o V is unknown, we propose that this number is relatively
small and that the Pt(lOO) surface is active for the HOR
at low overpotentials due to either a very high turnover
rate at these sites or surface defects, which can lead to
increase the number of "Pt(llO)-like" sites active for
adsorption of the Hapd state. Nevertheless, a small
number of active centers for the Hapd state adsorption
would greatly reduce the number of pair-sites required
for the chemical recombination step to occur. Con-
sequently, the preferred reaction pathway on Pt(lOO) at
low overpotential may be one that requires only one active
site in the RDS, like the ion-atom recombination
reaction. In fact, an activation energy of ~ 12 kl/mol for
the HER and the HOR found at the hydrogen reversible
potential and two separateTafel regions, 2.3RT/3Fat low
current densities and 2.3RT/Fat higher current densities,
found for the HOR may imply that the reaction mechan-
ism on Pt(lOO) is different from Pt(llO). Therefore, for
conditions of a small coverage by Hapd at low over-
potentials and a "maximum" surface coverage by Hapd
at high overpotentials, we propose that the mechanism
for the HOR on the Pt(lOO) surface proceeds through
the ideal Heyrovsky- Volmer sequence with the
ion-atom reaction as the RDS. As in the case ofPt(llO),
the anodic/cathodic symmetry for the polarization
curves for the (100) surface can be rationalized as arising
from a same mechanism in both overpotential regions,
i.e., the HER follows the Volmer-Heyrovsky sequence.
It is appropriate to mention, that on the basis of very
simple model relating the rate of the HOR to the ability
of "bare" platinum sites on Pt(WO) in alkaline solution,
we have suggested that the HOR follows the ideal
dual-site form of the Tafel- Volmer sequence [15]. Much
more work is needed, however, to resolve the true reaction
mechanism ofthe HE/ORon Pt(lOO) in alkaline solution.
3. Mechanism of the HE/OR on Pt(111)
The influence ofthe Hupd state on the kinetics ofthe HOR
is the most pronounced for the Pt(lll) surface. On Pt(lll),
Markovic and Ross
the onset of the HOR appears to be correlated with the
desorption of H upd , which suggests that the HOR
mechanism on Pt(lll) at low overpotentials follows a
dual-site pathway, the Tafel-Volmer sequence. The
relatively high activation energy for the hydrogen reaction
on Pt(lll), ~18 kl/mol, almost doubled vs. the same
reaction pathway on Pt(llO), may be due to the strong
repulsive interaction between the H apd state and the
Hupd state, as pointed out in Sec. II. It was hoped that the
reaction mechanism of the HOR would be resolved in a
definitive way by the analyzing the Tafel slopes, as we did
for Pt(llO) and Pt(lOO) surfaces. Unfortunately, this does
not appears to be possible atthis time, principally because
the Tafel slope of ~ 74 mV/dec at 243 K obtained for the
HOR at Pt(lll) cannot be interpreted unambiguously. A
Tafel slope of ~ 2.3RT/F, obtained over the entire tem-
perature range studied in this work, implies that the
adsorption of the reaction intermediates on Pt(lll),
H apd , does not follow Langmuirian conditions. Actually,
we noted recently that the equilibrium constant for the
underpotential deposition of hydrogen on Pt(lll) is an
exponential function of Hupd coverage and follows the
Frumkin isotherm. If Hapd simply follows the Frumkin
isotherm, then assuming that the rate-determining step
is either the atom -atom recombination step or atom - ion
recombination step yields the same slope of2.3 RT/F. Even
if the H upd state is not the active intermediate in the HOR
and the HER, H upd could still have a significant indirect
effect on the kinetics on the HER and the HOR on Pt(lll).
The Hupd state may alter both the number of Pt free sites
(active centers) and/or the interaction of H apd with the
surface, but the number of mathematical models for such
effects is arbitrarily large in the absence of other
knowledge. In alkaline solution, we have suggested that
the HORon Pt(lll) follows the ideal dual-site form ofthe
Tafel- Volmer sequence [for details see 15].
v. SUMMARY
Recent results, primarily from our laboratory, for the
HE/OR and the ORR on well-defined Pt(hkl) surfaces
in aqueous (both alkaline and acid) solutions are
reviewed. In situ SXS was used to determine the structure
ofPt(hkl)-solution interface as a function of the applied
potential. The absence of any in-plane superstructure
peaks indicates that Pt(lll) and Pt(lOO) prepared by
flame-annealing method are not reconstructed at any
potential. In the case of the Pt(llO) surface, depending
on the particular flame-annealing procedure, a recon-
structed Pt(llO)-(l x 2) phase or an unreconstructed
Pt(llO)-(l x 1) surface can be created. Both surfaces are
stable within the potential region of the thermodynamic
Electrocatalysis at Well-Defined Surfaces 839

stability of water, but the most interesting results were relaxation was observed on the Pt(lIO)-(l x 2) surface in
obtained on the (1 x 2) surface. On all three single-crystal alkaline solution. We proposed that the initial reversible
surfaces, the lattice spacing between the first and second formation of OHad adlayer (up to 1 ML) occurs on the
layer was expanded relative to the bulk spacing. The relax- threefold hollow sites in the troughs. Beyond the OHad
ation was found to be a function ofthe electrode potential. monolayer, the oxide formation proceeds by additional
We proposed a model of the surface relaxation from electrosorption of oxygen-containing species on the
which the sites for adsorption and the strength of the top-sites of the Pt rows. Reversible adsorption of both
adsorbate-metal bonding (the two being interrelated) HS0 4 and OHad on Pt(111), which produces an
could be derived. In the (under)potential region where "anomalous pseudocapacitance," has no effect on the
hydrogen adsorption occurs (Hupd), the relaxation surface relaxation, and thus OHad and HS0 4 are
increases in the order Pt(110)>> Pt(100) > Pt(111), indica- adsorbed on the Pt(111) surface. On Pt(100), the relax-
tive ofH upd adsorption sites in the threefold coordinated ation is smaller in the OHad potential region than in the
sites below the top-most (110) rows of Pt atoms, in/on H upd region, indicative of OH ad adsorption on the (100)
the fourfold hollows of the (100), and on the threefold surface rather than in or below the surface.
hollows ofthe (111) surfaces. In the potential region where Our group has used the RRDE technique with Pt(hkl)
the formation ofa hydroxyl adlayer takes place, the largest electrodes in the disk position to establish the structural

(a)

Pt(111) Pt(11 0)-(1 x2)

0.05 MH zS04
:'
,'

··
1"'"""""'1
, '

+ .;'·2',
'
'
........ S
~
, ''
"
•"
E 0) ,.
I
.. ".:~"
.,
, .. - - -: I
, : I ". '
.......
"
.. ,
.................. -_ .......
t;::::S 0
" . ...-
....... .. .. , _--- .

U ' .'
".. -.1
...... .,' ,
"
" I.·",
1"'"""""'1
I
........ .'
,'
, : :.' :,
~
, .·
, ,:
,
'

1. 02 + 4B+ + 4e' => 2B20

2, B 20 2 + 2B+ +2e' => 2B 20
3, B 2 <=> 2B+ + 2e-

0.0 0.4 0.8 0.0 0.4 0.8

E/Vvs, RHE
Figure 13 (a) Cyclic voltammograms for the Pt(111) in 0.05 M H 2 S04 ( . . .). Polarization curves for (1) ORR on the disk electrode, (2)
H 20 2 oxidation on the ring electrode, and (3) HER and HOR. (b) Cyclic voltammograms for the Pt(1lO) in 0.05 M H 2S0 4 ( ... ).
Polarization curves for (1) ORR on the disk electrode, (2) H 20 2 oxidation on the ring electrode, and (3) HER and HOR. E vs. RHE.
840
sensitivity of the HE/OR and the ORR. It is shown that
the elimination ofsurface heterogeneity and the enhance-
ment of the solution in the voltammetry that results from
single-crystal geometry brings new insight into the
understanding of the reaction mechanism (pathway) of
the HE/OR and ORR on platinum electrodes. An
interpretation of the structure sensitivity of the kinetics
of the HE/OR and the ORR on Pt(hkl) surfaces is pre-
sented based on the premise that the differences in the
activity of three low-index faces of Pt arise mainly from
the structure-sensitive adsorption of Hupd and anions,
such as OH ad and HSOi. We summarize some represen-
tative results for the HE/OR and the ORR on Pt(hkl)
surfaces in H 2S0 4 solution in Fig. 13. In the case of the
Pt(llO)(1 x 2) surface, the kinetics of both the HE/OR
and the ORR are relatively fast in the potential regions
ofadsorption ofeither H upd or OHad (or HSOi in H 2S04
solution). Because both the H upd state and anions are
adsorbed in the troughs of the surface, the top sites are
available for H 2, O 2, and H202 adsorption and bond
breaking. Thus, on this surface, Hupd and anion adsorp-
tion are not competitive with H2, O 2, and H 20 2 adsorp-
tion and bond breaking. In the potential region of the
oxide formation, however, the rate of the HOR and the
ORR is inhibited because the oxide starts to occupy the
active top sites on the Pt rows. The importance of this
adsorption site specificity in the electrocatalysis is even
better illustrated by comparing the electrocatalytic
activity ofthe Pt(1W) surface with that ofthe "flat" Pt(111)
surface. On the densely packed Pt(111) surface in Fig. 13,
H upd (below 0.2 V) and anions (above 0.6 V) are
adsorbed onto the surface, having a devastatingly nega-
tive effect on the reaction rate of the HE/OR and the
ORR, e.g., pair of platinum sites that are required for
the 0-0 and H-H bond breaking.
Finally, reaction mechanisms (reaction pathways)
for the ORR and the HE/OR are proposed. From the sev-
eral reaction pathways for the ORR that have been pro-
posed in the past, our results support the "series" pathway,
via the [H0 2]ad intermediate state. It is also proposed that
the HE/OR on Pt(1W) follows the Tafel-Volmer
mechanism, with theTafel step being the RDS. On Pt(100),
the HE/OR follows the Heyrovsky- Volmer sequence,
with the Heyrovsky reaction step being the RDS. The
reaction mechanism on Pt(111) could not, however, be
resolved by analyzing the kinetic parameters.
ACKNOWLEDGMENTS
We thank I. Tidswell and C. Lucas for their part in
performing and discussing the SXS measurements. We
are also indebted to H. Gasteiger and B. Grgur for their
Markovic and Ross
contribution in collecting and discussing the RRDE
results. This work was supported by the Office of
Basic Energy Sciences Division of Material Sciences
(OMS), and the U.S. Department of Energy under
Contract No. DE-AC03-76SF00098. Research was car-
ried out at the Stanford Synchrotron Radiation
Laboratory and the NSLS, Brookhaven National
Laboratory, which is supported by the OMS and Chemi-
cal Sciences Division of the U.S. DOE under contract
No.DE-AC02-76CH0006.
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47
Mechanism of Methanol Electro-Oxidation
Andrew Hamnett
University ofNewcastle, Newcastle upon 'IYne, England
ABSTRACT
The pathways for the electro-oxidation of methanol on
platinum and platinum-alloy electrodes are explored in
some detail, with evidence from a wide variety of physical
and electrochemical techniques summarized. Chemi-
sorption of methanol on platinum itself takes place very
rapidly on the bare electrode surface through a succession
of intermediates derived from methanol by successive
scission ofC-H bonds and formation ofPt-C bonds.
On low-index single-crystal surfaces in moderate to high
concentrations of methanol, the final adsorption prod-
ucts are linearly and bridge-bonded CO, with the adsorp-
tion of methanol inhibited by adsorbed HS0 4,
especially on Pt(lll). At potentials below 0.4 V vs. RHE,
little further oxidation of this final chemisorbate takes
place, and the electrode surface becomes essentially
poisoned. Above this potential, some oxidation of the
adsorbate can take place to an extent that increases
strongly with potential, especially on the Pt(IOO) surface.
It should be emphasised that the adsorbate layer formed
on chemisorption of methanol is not identical to that
formed on adsorption of CO in solution: Coverages are
lower in the first instance, and there is evidence for
coadsorption of anions and other carbon-containing
species. Under conditions of low methanol con-
centration, there is now quite strong evidence that one of
these species is the triply bonded Pt3C-OH. The mech-
anism of oxidation of methanol on promoted platinum
has also been extensively studied, particularly for PtiRu
alloys, which show a far higher activity for methanol
oxidation. There appear to be at least two effects
operating here: Ru promotes chemisorption of methanol
at lower potentials by providing a number of kinetically
more facile sites for chemisorption, though the final
843
coverage of methanol does decrease with increasing sur-
face Ru content at room temperature. A second and more
significant effect is that Ru can be oxidized at much lower
potentials than Pt itself, and the Ru--OH ads species that
form on the surface can promote oxidation of
chemisorbed fragments to C02. At relatively low Ru
coverage, it would appear that migration of CO ads to
Ru-OH ads sites is rate limiting, but at higher Ru
coverages, the oxidation of COads becomes limiting.
The optimal Ru:Pt ratio remains somewhat con-
troversial, particularly on well-defined surfaces at lower
temperatures. However, at higher temperatures and
methanol concentrations and for particulate catalysts, a
molar ratio approaching 1:1 Pt:Ru appears best.
I. INTRODUCTION
The direct methanol fuel cell (DMFC) is a highly
attractive alternative energy source, because it uses a
liquid fuel and runs at temperatures below 100°C. Recent
years have seen a steady increase in the performance of
DMFC's, which have, as anodic reaction
and as cathode reaction
However, the fuel cell remains limited by the performance
of both electrodes, with the anode reaction in particular
proving difficult to optimize. Until recently, a major prob-
lem with this electrode was our lack of understanding of
the mechanism of methanol electro-oxidation, but there
844
have been significant advances both in our understanding
of this reaction at the molecular level and in the develop-
ment of more active electrocatalysts for it. We are now at
the point where a relatively small increase in performance
of the anode would make DMFCs attractive com-
mercially.
An important simplifYing factor has been the obser-
vation that almost every electrocatalyst for methanol
oxidation is based on platinum, usually alloyed or simply
associated with one or more other metals or
metal-oxides that act as promoters. The key feature of
platinum is that it can dissociatively chemisorb methanol
quite rapidly, particularly at potentials above ca. 0.2 V
vs. SHE (the reference electrode used throughout this
review), forming chemisorbed species such as Pt 3C-OH
and Pt-Co. However, the conversion of these
adsorbates to form the final product, CO 2, requires attack
on the carbon by an oxygen-containing species, and this
process is both slow and strongly dependent on the nature
of that species. Most promoters for methanol oxidation
are believed to act primarily either by provision of
"active"oxygen adducts or by increasing the susceptibility
ofthe carbon-containing intermediates to oxygen-donor
attack. There are exceptions to this statement, but it does
provide a useful starting point for understanding the
detailed mechanism.
Inevitably, a review article of this type will reflect the
views of the author; indeed, in this area it is simply not
possible to write an article that attempts an unbiased
summary of the literature, because the literature itself is
highly contradictory. Part of the difficulty lies in the fact
that experiments are frequently carried out using differ-
ent protocols; the methanol reaction is sensitive to the
morphology of the surface (which is affected by its pre-
vious electrochemical history), the nature of the
coadsorbed anions (if any), the temperature, the concen-
tration of methanol itself (a critical factor), and the
presence ofadventitious impurities both on the Pt surface
and in the electrolyte. In addition, it has proved excep-
tionally difficult to measure the steady-state current for
methanol oxidation on platinum by conventional means,
especially at lower potentials, because the current is
observed to fall away to very small values indeed and
to decay indefinitely due to further poisoning of the
electrodes by adventitious organic impurities in the
methanol. Conventional mechanistic analysis has,
therefore, proved extremely diffi cult, though some results
have been reported, particularly for Pt particles.
Unfortunately, these results are themselves difficult to
relate to the behavior of macroelectrodes, whether poly-
crystalline or single crystal. There is now a general con-
sensus that the methanol oxidation reaction can, in
Hamnett
principle, take place through a variety of detailed routes
that probably differ but little in their free energies of
activation. The result is that the very title of this review,
insofar as it implies a single mechanism operating under
all conditions, is certainly misleading; it would be more
accurate to review the "mechanisms" of methanol
oxidation, recognizing that platinum particles, for
example, will certainly differ from single-crystal plati-
num in terms of the detailed course of the reaction.
There have been innumerable reviews of methanol
electro-oxidation in recent years. For the literature before
1988, readers are referred to the extensive review by
Parsons and Van der Noot [1]. More recent reviews have
been provided by several of the major contributors to this
field and are referred to below in the context of these con-
tributions. The structure of this review is to consider, in
order, the process of chemisorption, and the identifi-
cation of adsorbed intermediates, the kinetics of the
adsorption process itself, the processes following
adsorption, and in particular those processes leading to
C02 formation, and the action of morphological features
in enhancing these processes. We then turn to a consider-
ation of the mode of action of promoters for platinum
and consider in detail the role of ruthenium as the main
promoter for methanol; there is now a considerable con-
sensus as to the way in which ruthenium acts catalytically,
and this consensus points to further electrocatalyst devel-
opment in the next few years.
II. ADSORPTION OF METHANOL AND THE
NATURE OF THE ADSORBATE
A. Electrochemical Studies
Early studies on methanol adsorption exploited the fact
that the chemisorption process on clean platinum
surfaces, prepared by an appropriate potential/time
protocol (which usually involves stepping the potential
to a relatively high positive value for a fixed period and
then stepping to the potential at which the reaction is to
be studied), is far faster than the steady-state oxidation
rate for methanol. This allows us to separate the process
ofchemisorption ofmethanol from thatofthe subsequent
oxidation of the chemisorbed intermediates to C02. The
role of these intermediates is graphically illustrated in
Fig. 1 [2], which shows the very rapid decrease in current
for methanol oxidation on platinum after such a potential
step process. The origin of this decrease can only be the
accumulation of adsorbed intermediates on the surface
whose further oxidation to C02 is slow. The nature of this
intermediate can, in principle, be studied purely
electrochemically by measuring separately the charge,
1 Mechanism of Methanol Electro-Oxidation 845

Pt-CH2 -OH + Pt(s) ---* Pt2CHOH + H+ + e-

(2)

1.2
Pt2CHOH + Pt(s) ---* Pt3COH + H+ + e- (3)

'l'E
0 Pt3COH ---* Pt-CO + 2Pt(s) + H+ + e- (4)
«
E 0.8
--
'E Pt(s) + H20 ---* Pt-OH + H+ + e- (5)
~
'0"
Pt-OH + Pt-CO ---* Pt-COOH (6a)
0.4
or

Pt-CO + H 20 ---* Pt-COOH + H+ + e- (6b)

o
time/ ms
Pt-COOH ---* Pt(s) + C02 + H+ + e- (7)

Additional reactions described in the scheme above

Figure 1 Current-time transient for methanol oxidation on include
platinum foil at 60°C in I M HZS04 1l M CH30H, stepping
from 0.0 V, where the surface is free of carbon-containing Pt-CH 20H ---* Pt(s) + HCHO + H+ + e- (8)
residues, to 0.5 V. (From NA Hampson, MJ Willars, BD
McNicol. J Power Sources 4:191,1979.)
Pt2CHOH ---* Pt(s) + Pt-CHO + H+ + e- (9)

Pt-CHO + Pt-OH---* 2Pt(s) + HCOOH (lOa)

Qads, required to chemisorb methanol, the charge QH
required to cover the remaining the surface with or
adsorbed hydrogen (which can also be measured for the
intermediate-free surface, as Q~, and used to estimate Pt-CHO + H20 ---* Pt(s) + HCOOH + H+ + e-
the total surface area assuming a charge of 0.21 mC per (lOb)
true cm 2), and the charge Qox required completely to
oxidize the adsorbed fragments. Pt3C-OH + Pt-OH ---*
Given a limited number of possible intermediates, we (11)
3Pt(s) + Pt-COOH + H+ + e-
can draw up a scheme ofsquares of the form [3]
or
CH 30H ---* CH20H ---* CHOH ---* C-OH Pt3C-OH + H 20 ---*
x t xx t t (12)
xxx
2Pt(s) + Pt-COOH + 2H+ + 2e-
CH 20 ~ CHO ~ CO
The difficulties faced in analyzing a scheme of this
x tXt
complexity by purely electrochemical means are clearly
HCOOH---* COOH formidable, but at the least, potential step measurements
x t of the type described above should give unambiguous
CO 2 and reproducible results provided that the potential
protocol adopted to clean the surface before each
measurement does not alter the morphology of the
where x symbolizes a Pt-C bond and that summarizes surface; that the surface, once cleaned, will remain clean
the following reactions: indefinitely, save for such processes as we wish to study;
and the only contribution to the anodic charge observed
on stepping the potential from the positive limit usually
chosen (~1.2-1.6 V) is the chemisorption of methanol
846 Hamnett

to form adsorbed fragments (there will, of course, be a trons are required fully to oxidize each methanol
rapid cathodic transient due to oxide removal from the molecule, this implies that the intermediate must require
Pt surface). The first restriction has come under con- three electrons to form. In addition, we see that each elec-
siderable recent scrutiny. As Itaya et al. [4] have shown, tron passed involves one platinum atom, implying that
cycling of a Pt(lll) surface up to 1.5 V gives rise to sub- the intermediate must be coordinated to three Pt sites.
stantial roughening, in which all long-range coherence This led Bagotzky and Vassilyev to postulate that the
is lost. This roughening arises, in turn, from the methanol chemisorption process must involve reactions
place-exchange mechanism for surface-oxide (1-3) only above, with further oxidation ofthe Pt3 C-OH
formation: On reduction, randomly oriented islands being slow.
some 30-50 A in diameter and 1-2 atoms high are found Unfortunately, although the Russian group strongly
on the original Pt(lll) terraces and relaxation of the favored the Pt3C-OH species as being the dominant
resultant disordered surface is slow. The second intermediate, others have reported different results.
restriction requires very high degrees of purity of Biegler and coworkers [8,9] used a slightly different pro-
reagents and also requires the solutions to be changed tocol, with an anodic potential of 1.55 Vand Qox deter-
very frequently to prevent contamination by residual mined not by potential step in the methanol solution but
partially oxidized organic species building up in by replacement of the methanol solution with pure acid
solution. The third assumption is usually justified on followed by a slow sweep to anodic potentials. The results
the basis that the measured steady-state current, once obtained by Biegler, and reproduced for two methanol
chemisorption is complete, is far smaller than the concentrations in Table 2, show a more complex behavior.
currents observed immediately after the potential step, It is evident that no single type of intermediate can
but this is not unambiguous: Oxidation of methanol by account for Biegler's data; the results are consistent with
parallel routes, one leading to complete oxidation to a substantial fraction of the coverage at low potential
CO 2 and the other to the formation of relatively derived from a species such as Pt 3C-OH but at higher
unreactive intermediates, may be taking place, and there potentials/coverages, where Qads/ Qox --+ 2, the results
is strong evidence that this is indeed the case for formic are consistent with Pt-CO as the main intermediateThis
acid oxidation. Finally, an issue that has caused some observation was supported by Vielstich and coworkers
difficulty in the universal acceptance of the scheme of
squares above is the very different mechanism proposed
for methanol oxidation at the gas/solid phase. Methanol Table 1
is observed to adsorb molecularly from the gas phase
onto Pt(lll) [5] and Pt(llO) [6] below 170 K but Time of Cathodic pulses Anodic pulses
adsorption Qads QH - Q~ Qox
decomposes above this temperature to form COads and (mC cm- 2 )
(sec) (mC cm- 2) (mC cm- 2)
H ads . In the presence of chemisorbed 0, adsorption of
methanol below 140 K leads to CH 30 ads , but this again 0.7 0.027 0.023 0.03
decomposes to form COads and Hads at higher I 0.097 0.082 0.090
temperatures. This suggests that methoxy species, if IS 0.120 0.111 0.119
indeed they form at higher temperatures at the 120 0.15 0.149 0.154
liquid -solid interface, probably rapidly decompose to
form species containing Pt-C bonds.
These different caveats may explain the difficulty Table 2
experienced in the early literature in reconciling results Potential
from different groups. Measurements by Bagotzky and Solution Vvs. RHE Qads/Q~ Qox / Q~ Qox / Qads
Vassilyev [7] at 0.4 V, using an upper potential limit of
1.2 V for 20 s to clean the electrode and an electrolyte of 0.05 M methanol 0.28 0.88 0.64 1.37
0.1 M CH 30H in 0.5 M H 2 S0 4, are summarized inTable I MH 2 S0 4
I. The coverage ofmethanol on the surface can be calcul- 0.33 1.21 0.74 1.64
0.38 1.43 0.87 1.64
ated from the expression e= (QH - Q~)/ Q~ and the
0.43 1.96 0.95 2.06
number of electrons required per Pt site to oxidize the
adsorbed fragment from neps = Qox/(QH - Q~). The 0.5 M methanol 0.28 1.35 1.19 1.13
data of Bagotzky and Vassiliev would support the conten- I MH 2 S0 4
tion that the same charge is required to oxidize the 0.33 1.56 1.22 1.28
chemisorbed intermediate as to form it. Because six elec-
Mechanism of Methanol Electro-Oxidation 847

[10-12], who also showed that Qads/ Qox values varied

from unity at low coverages to close to 2 at high coverages:
these results that are reviewed in more detail below.
3 0
Biegler's results were confirmed by Lamy's group in
Poitier: their data for polycrystalline platinum [13,14] 2 • • eft . • •.... • •• .
",:-a-
showed that n eps was close to 2 for all adsorption times •
Tads in concentrated methanol solution (0.1 M), with the
coverage rising very roughly linearly with loge Tads) (Fig.
2). However, in more dilute methanol solution (0.001 M),
•
where coverages are far lower, neps was observed to rise
from values close to 1 at shorter times ( < 1 s) to values 0
close to 3 before decreasing slowly toward 2 at high
adsorption timesValues of n eps near 3 imply the formation
ofa formyl species, Pt-CHO on the surface at intermedi-
ate times, and low methanol concentrations, a result that
3
®
again strongly implies that the nature ofthe intermediate
changes according both to coverage and methanol con- 2
(J)
centration. The lower values of neps at low coverages and 0..
Q)
ethanol concentrations were also confirmed by Leiva z
and Giordano [15], who suggested that the species 1
responsible for the lower values of neps was probably
Pt3C-OH and that this species showed somewhat
higher activity toward further oxidation, at least on poly- 0
crystalline Pt, than did the Pt-CO, which appeared to
form at higher coverages and methanol concentrations.
Very interestingly, these authors also postulate the exist-
3 0
ence of two forms of linearly bonded adsorbed CO on
the surface on the basis ofa careful analysis of the results • • •
of potentiodynamic sweeps; they assign one type,
2
••
denoted CO:ds' to a metastable form of COads , perhaps
consisting of individual molecules of CO adsorbed on
more active sites, whereas the more stable form is
assigned to an "associated CO ads surface structure," a
remarkably prescient analysis as will be seen below. It is o
also interesting to note that this type of explanation has
also been proposed to account for the relative inactivity
of Pt3Sn to methanol oxidation as compared with CO
-1 o 1 2
oxidation, because the coverage of COads is smaller in Log (time/s)
the case of methanol oxidation and the CO:ds species
not accessed [16]. Figure 2 Number ofelectrons per site, neps vs. the logarithm of
adsorption time for (a) 0.1 M MeOH at polycrystalline Pt, (b)
In addition to the measurements of the kinetics of
0.001 M MeOH at polycrystalline Pt, (c) 0.1 M MeOH at a
chemisorption carried out by the French group, Bagotzky
Pt(lOO) single crystal. (From C Lamy and JM Leger. Bull
and Vassilyev [7] also reported some kinetic studies. Electrochem 7:493, 1991.)
Given that the current transient must be dominated below
ca. 0.5 V by formation of the chemisorbate, the current
coefficient, with a value usually close to 0.5, andfis the
. d8 ads
k' - inhomogeneity factor of the Pt surface, with a value of
l~ -
dt 10-11. Integrating this equation assuming that CMeOH
and E are constant, we obtain
If we assume that the adsorption isotherm for the
chemisorbate is of the Temkin form, then 1
8ads ~ const. + rtf In t
i ~ k" . CMeOH . exp(-rtf8ads ), where rt is the transfer
848 Hamnett

whence i '" const. It. A plotofln(i) vs.ln(t) should be linear, established by Clavilier and coworkers [20,22] showed
as indeed it is over the midrange ofcoverage as shown in that Pt(llO) had the highest initial activity, but this activity
Fig. 3, data more recently confirmed by Wilhelm et al. [12], decayed to low levels with time and potential cycling; the
and by Lamy and coworkers [13], who reported that Bads Pt(lOO) surface had a lower initial activity but was able
rose approximately linearly with In(tads) as described to sustain this activity with time, and the Pt(111) surface
above. The justification for assuming that the adsorption had a rather low absolute activity (Fig. 4). These authors
isotherm was Temkin in form comes from earlier work also reported that methanol (at 0.1 M concentration)
by the Russian group [17-19] in which the equation and CO both showed similar behavior toward oxidation
on the different Pt surfaces, adding plausibility to the
1 assignment of COads as an important intermediate
Bads '" const. +lIn CMeOH (because COads is known to form when Pt is exposed to
CO dissolved in the electrolyte). In addition, it was estab-
was established. As we shall see below, this has important lished that there was a considerable difference in activities
implications for the electrochemical kinetics. for the Pt(lll) surface in perchloric and sulphuric acids,
The complex picture emerging from these studies with the latter showing strong anion adsorption that
impelled several groups to re-examine the problem using severely inhibited methanol oxidation. They also estab-
single-crystal platinum surfaces, with the aim ofworking lished that the oxidation offormic acid undoubtedly went
with well-defined surfaces, which would be highly through different intermediates from those invoked for
sensitive to any perturbation. Several groups have been methanol oxidation, at least on the Pt(111) and Pt(lOO)
active in these studies, with the earliest papers [20-22] surfaces, though it does appear that on the Pt(ll0) surface
demonstrating clearly that with single crystals in which the oxidation offormic acid may have a mechanism simi-
long coherence lengths are maintained, the different 1ar to that of methanol. This does add weight to the
platinum surfaces have very different activities for meth- suggestion that formic acid oxidation proceeds through
anol oxidation, at least as measured by potentiodynamic a Pt-COOH intermediate on Pt(111) and Pt(lOO) but
\--.
sweeps. This is in contrast to the earlier reports of the that oxidation of methanol proceeds, at least under the
Russian school [23], and this discrepancy is now known conditions of these experiments (high methanol con-
to originate from the electrochemical activation of the centration), through adsorbed CO or some other more
Pt surfaces used by the Russian school, which destroys inactive intermediate. Finally, it is of interest to note that
the long-range surface structure [4]. The activity order for both formic acid and methanol oxidation, the
behaviorofa poly-faceted Pt-beadelectrode can, to afirst
approximation, be described as the weighted sum of the
2.0
activities ofthethree low-index platinum surfaces, a point
that we return to later.
The marked effect of sulphate anions on oxidation of
methanol on Pt( 111) and other low-index surfaces has also
1.5
been studied by Kita et al. [24], Markovic and Ross [25],
and Herrero et al. [26]. There is considerable evidence
\! 1
that HS0 4 is strongly adsorbed on Pt(ll!); the cyclic vol-
tammetry (CV) of this surface is quite different in
sulphuric and perchloric acids, with marked structure
near 0.5 Vin the former electrolyte being shifted to higher
0.5 potentials (near 0.8 V) and substantially modified in the
1.5
, 1 0.5
,
latter. The adsorption of HS0 4 on Pt(ll!) has been
I
log Vads ~cm2
0,2 0,3 0,4 0,5 0.6 0,7
6R
studied spectroscopically and by radiotracer and
-0.5
J
0
I
0.5
I
1.0
I
1.5
L09' ultrahigh vacuum (UHV) techniques [27-32]: The results
show that the onset of HS0 4 adsorption correlates well
Figure 3 Dependence of the logarithm of the non- with the appearance of "anomalous" structure in the
steady-state current at 0.4 V in 0.1 M MeOH/0.05 M H2 S04 Pt(111) CV in H 2 S04 electrolyte near 0.35 V According
solution upon the logarithm of time, the surface coverage with to Gamboa-Aldeco et al. [27], the coverage by bisulphate
carbon-containing residues and the logarithm ofthe rate offor- reaches a maximum near 0.75 V, estimated by Thomas
mation of adsorbed hydrogen. (From VS Bagotzky, Yu B et al. [32] to correspond to B:::::; 0.34 but by earlier studies
Vassilyev. Electrochim Acta 12:1323, 1967.) [27] to be only 0.16 (a difference ascribed to the more
 Mechanism of Methanol Electro-Oxidation 849

~-..,----~--- 1 - 1- N
~
E 'e 20

~
u '-!
420 «
~ E
I,
I. "
• I
:."J 15
15- ",~
,":1
I "I
I .:,

: :;.'
I ,\ I
I 1,\
10 10
I
1
,
:. ""\
: I:: ,.
I '0

~
,
\

: r~ i\:\
5
:
:
:~: \\
I ~ :
I :.;
5
: }:

o -----=-=-=~---.;;-....::-~,~-:
... ---
o ------:;~--~--"-
o 02 04 00 0.8
E!VIR H.E )
(a)
o 0.2 0.0 0.6
ElVIRH.EJ
(b)
'"E
I

u
<l:
~3

.
,
/\
0

: '....

o 0.2 0.4 0.6 0.8

E/"IR .H£J
(c)

Figure 4 (a) Voltammogram of a Pt(lOO) single-crystal electrode (50 mV S-l, room temperature, 0.1 M HCI0 4 ): - - , 0.1 M
HCOOH; - - - -, 0.1 M MeOH (x 10); "', CO-saturated solution (i.e., ~1O-3 M CO). (b) Same for a Pt(llO) electrode but with the
methanol oxidation curve to scale. (c) Same for Pt(lll) electrode, again with the methanol curve to scale. (From C Lamy, JM Leger, J
Clavilier, R Parsons. J Electroanal Chern 150:71,1983.)

defect surface in the latter case), but then decreases at Pt(lll) surface geometry [32-34]; this matching permits
higher potentials (Fig. 6), reaching a value of essentially the development of a well-ordered Pt(1ll)(.J3 x .J3)R30°
zero above I V. The figure shows that bisulphate bisulphate adlayer. By contrast, no long-range ordering
adsorption is considerably greater on the Pt(lll) surface develops on adsorption of bisulphate into the Pt(lOO)
than on Pt(lOO), a result that the authors ascribe to the surface, accounting for the fact that the reduction in
near perfect symmetry match between the triangular methanol oxidation current on Pt(lll) is much higher in
terminals of the bisulphate oxygens and the hexagonal the presence of HS0 4 than it is on Pt(lOO). The details

1
850 "amnett

ofthis model have been recently challenged by Funikov et

Pt(111) Pt(100)
al. [35] using in situ scanning tunelling microscopy
--O'.. . HCIO. - - o 1M HCIO.
(STM): These authors observe an ordered HS0 4 layer
--- __ O,U HCIO•• 5.,0-~ CI- ----- 0' ..... HCIO•• 5.,0-~Cl-
······.····005 MH 2 SO. 005 MH 250. only at potentials positive of the spike seen in the CVof
Pt(Hl) in sulphuric acid at 0.5 V For some 200 mVabove
this potential, the structure remains unaltered but then
disappears between 0.7 and 0.8 V; maximum coverage
in this work was ~0.2. The actual structure of the adlayer
also differs from the simple (,)3 x ,)3)R30° observed in
the LEED patterns, being best described as having
E close-packed rows of maxima in the STM current with a
~
:; separation of ,)3 times the substrate atomic separation
U and at an angle of 30° to the underlying close-packed Pt
T T
,OQILA ,rollA rows but with a separation of maxima in neighboring
l l
AI •.
. ",
''...
, I

I •
rows of ,)7 times the underlying Pt atomic spacing and
at an angle of 19.1 ° to the underlying Pt rows.
I
I
•
•
This the authors describe as a
I ,

,, ,
I ,

o --- ...
(f ;)
o 0.2 0.4 0.6 0.8 a 0.2 0.4 0.6 0.8 adlattice, and ascribe to a coadsorbate ofbisulphate and
EN EN water. However, none of these models explains the
desorption of HS0 4 at higher potentials, which Kita et
Figure 5 Cyclic voltammograms for oxidation of 25 mM al. [24] ascribe to the formation of a strongly bonded
methanol on flame-annealed platinum single crystals in 0.1 M water monolayer that they believe to be partially dis-
HCl0 4,0.1 M HCI0 4+ 5.10- 5 M HCI, and 0.05 M H 2S04 with charged and that leads to sequential cleavage ofthe Pt-O
sweep rates of 50 mY S-I. (From N Markovic, PN Ross. J bonds of the HS0 4 ion.
Electroanal Chern 330:499,1992.)
For Pt(lll), the hydrogen region is comparatively little
disturbed during methanol oxidation in sulphuric acid,
strongly suggesting that methanol chemisorbs compara-
tively little on Pt(Hl) in this electrolyte, at least on the time
3.0 Ir-------.------r-~---_,___---___,
scale of the dynamic experiments carried out, but the
methanol oxidation currents are significantly lower in
E sulphuric acid as compared with perchloric acid, with
o
III
2.0 factors oflO reported by Kita et al. [24] and rather lower
~

:i factors (3-5) reported by others [25,26]. Furthermore,

o
~ the hydrogen region between 0.0 and 0.4 Vis significantly
"0
E suppressed (by about 40%) in perchloric acid, and the
;--
, 1.0 "butterfly"at 0.8 Vis absent, suggesting that in perchloric
...
o
)(
acid there much more rapid chemisorption of methanol.
L.. Interestingly, Markovic and Ross [25] suggest that part
of this anomalous "butterfly" region, particularly the
0.0 spike at 0.8 V, may be associated with Cl- adsorption,
-0.4 0.0 0.4 0.8 1.2
the Cl- arising as an adventitious but universal impurity
E/V (Agi Agel)
in perchloric acid; this is not universally accepted, with
the formation ofOHads also being suggested as the butter-
Figure 6 Potential dependence of bisulphate adsorption on fly origin [29].
(0) Pt(lOO). (.) Pt(l1l), (+) Pt(polycrystalline). The data were Results for the Pt(lOO) face show first that the effect of
obtained in 0.1 M HCI0 4 + 10- 3 M H 2S04 solution. (From sulphate adsorption is much less; the coverage of HS0 4
ME Gamboa-Aldeco, E Herrero, PA Zelaney, AWieckowski. J is only about one third that found for Pt(lll) at its
Electroanal Chern 348:451, 1993.) maximum, with the currents for methanol oxidation
1
I

Mechanism of Methanol Electro-Oxidation 851

being reduced at the maximum by a factor of 2 ongoing Table 3

from perchloric acid electrolyte to sulphuric acid, in
High-index surface Equivalent decomposition
qualitative agreement with the adsorption isotherm for
bisulphate on Pt(lOO) presented above; second, the 511 3(l00)x(111)
hydrogen region is appreciably affected, with coverages 310 3(100) x(llO)
of chemisorbed fragments being ca. 0.4 in H 2 S04 and 610 6(100)x(1l0)
0.6 in HCl04. Finally, the CVs show a strong decrease 211 3(l11)x(100)
again in methanol oxidation activity above 0.8 V, well 331 2(l1l)x(110) or 3(1ll)x(1ll)
before oxidation ofthe Pt surface takes place. 332 5(1ll) x (110) or 6(1ll)x(1ll)
320 3(l1O)x(100)
Results for Pt(llO) show that bisulphate adsorption on
210 2(IIO)x(100) or 2(100) x (l1O)
this face is comparable in coverage at the maximum to
Pt(lll) [28] but begins at a significantly lower potential
(near 0 V), shows a broad maximum extending from 0.2
to 0.7 Vand a rapid decrease to almost zero coverage at Table 4
1.0 V, with, as expected, the cyclic voltammogram in
Qox
background acid electrolyte markedly suppressed in
Crystal surface e n eps (mC cm- z)
sulphuric acid in the region from 0.2 to 0.7 V [26]. The
radiochemical data show strong agreement with the data Pt(100) 0.745 2.00 0.325
from in situ FTIR [36], in which the Il05- to 1115-cm- 1 Pt(511) 0.68 1.31 0.178
peak is used as a measure of adsorbed HS0 4. Oxidation Pt(31O) 0.71 1.52 0.205
ofmethanol on Pt(ll0) by contrast does not show any sig- Pt(61O) 0.67 1.47 0.220
nificant dependence on perchlorate vs. bisulphate but Pt(lll) 0.56 1.57 0.177
Pt(211) 0.68 1.23 0.156
does show, in both cases, very high activity, particularly
Pt(331) 0.80 1.46 0.187
on the clean surface; however, this activity decreases
Pt(332) 0.765 1.47 0.214
rapidly with time as the surface becomes strongly covered Pt(llO) 0.75 1.51 0.229
with adsorbed intermediate, and it would appear that Pt(320) 0.825 1.51 0.249
the intrinsic activity of the Pt(IlO) surface to methanol Pt(21O) 0.755 1.63 0.257
chemisorption is sufficiently high that even adsorption Poly-oriented 0.74 1.57 0.187
of bisulphate is insufficient to inhibit this process. Kita
et al. [24] draw attention to the puzzling decrease in
activity to methanol chemisorption at higher potentials,
an inhibition particularly marked on Pt(110) [26]: Unlike The results for the measurement of neps , e, and Qox for
polycrystalline Pt surfaces, where such a decrease in the various surfaces after exposure to 0.1 M methanol in
activity correlates well with the formation of surface 0.5 M H 2S04 are given in Table 4. The authors [37] also
oxides, no such correlation exists for the single-crystal carried out studies in perchloric acid for comparison
surfaces, a result that the authors interpret in a similar and found somewhat lower coverages, particularly on
manner to the interpretation of bisulphate desorption surfaces with 100 terraces; indeed for both perchloric
given above.What is clear from their paper is the fact that and sulphuric acid electrolytes, the coverage of inter-
coadsorption of anions must play an important role in mediate on these surfaces is almost independent of the
the formation ofthe methanol chemisorbate and may well size of the 100 terrace. Moreover, although the values of
account for some of the rather subtle differences between neps are significantly lower than 2, save for the 100 surface
CO ads formed from methanol and from CO dissolved in itself in sulphuric acid, in perchloric acid, values of neps
the electrolyte (see below). close to 2 are found for all 100-derived surfaces,
The most thoroughgoing purely electrochemical study suggesting that adsorbed linearly bonded CO dominates
of adsorption onto single-crystal surfaces has been car- on these surfaces in the absence of any anion specific
ried out by Sun and Clavilier [37]. These authors used a adsorption. This sensitivity to specific adsorption of ani-
wide range of surfaces, including not only the low-index ons is also found for the III face, which has neps close to
surfaces discussed above but higher index surfaces, which 2 in perchloric acid (though with a very low coverage of
can be thought of as possessing terraces of a low-index 0.37) but only 1.57 in sulphuric acid. The general obser-
surface interspersed with steps. The crystal surfaces used vation of neps :::: 2 is, however, reinforced by this study,
and their composition in terms oflow-index surfaces are and this can be ascribed either to simultaneous adsorp-
given in Table 3. tion of both Pt3C-OH and Pt-CO or, as the authors
852 Hamnett

point out, to a mixture oflinearly and bridge-bonded CO,
the latter having the structure Pt 2 CO or even Pt3CO for
CO bridging two Pt atoms on the surface or adsorbed in
a three-fold site. As we shall see below, there is some evi-
dence for both suggestions. Studies of the variation of
neps with time of adsorption have also been carried out
for different crystal surfaces; for Pt(lOO), Papoutsis et al.
[13] and Lamy and Leger [14] showed that neps rises from
a value of about 0.9, a short adsorption time to a value
close to 2 at higher times, the latter figure being in agree-
ment with Sun and Clavilier. The very low value of neps
at short times was ascribed to the formation of
bridge-bonded Co.
These authors [38] have also provided a more recent
and very thorough study of the Pt(lOO) surface and have
shown that for this surface oxidation of the adsorbed
methanol fragments gives to at least three separately
identifiable current peaks in the anodic potentiodynamic
sweep after chemisorption. The results show a complex
interplay between the various forms of intermediate.
Unfortunately, the limitations of the technique used do
not allow the authors to establish a unique value of neps
for each intermediate identified; a probabilistic analysis
leads to the rather unexpected conclusion that the formyl
intermediate, Pt-CHO, dominates at high coverage
and adsorption time. This is at variance with the earlier
results, showing neps tending to a value of 2 at high
coverage, and may be an artefact ofthe analytical method
chosen; however, the central message that the nature of
the intermediate evolves with time and coverage is clear.
We have not, as yet, seriously questioned the assump-
tion above: that methanol chemisorbs at lower potentials
essentially solely to give the chemisorbed intermediate(s),
with only a negligible quantity ofcharge being associated
with either any parallel oxidation pathway or with further
conversion of the intermediate to CO 2 . This problem
was first tackled by Breiter [39-42], who suggested a
parallel mechanism rather than a serial one at lower
an initially clean surface in contact with 1 M
methanol/0.5 M H 2 S04 at 0.55 Y, in terms of the partial
currents iA associated with the formation of CO ads and
iB associated with rate r3 are shown in Fig. 7, which also
shows the measured coverage ofCOads from anodic pulse
measurements and the total current h. Matsui et al.
obtained iA by measuring the rate at which COads formed,
but the measurement of iB required them to assume that
the rate of oxidation of COads was the same whether or
not methanol was present. The rate of oxidation of
COads in nonmethanol-containing electrolyte at a given
potential can be measured straightforwardly as a function
ofcoverage and potential: for the slightly platinized plati-
num electrodes used in this experiment, Matsui found
for 8 1 > ca. 0.15, i~ = 8co exp (31.4E-24.9) correspond-
ing to aTafel slope of 73 mY,
for 8co < 0.15, a more complex behavior is found with a
Temkin term:
i~ = 8c o exp (l68co )exp (31.4E - 27.2)
where i~ is the rate of COads oxidation measured in the
absence of methanol. Assuming the rate of oxidation of
COads does not depend on the presence of methanol,
early iB should equal 3( It is evident that at short times
the ratio (iA + iB)/h is quite close to one at 0.55 Y, but this
ratio decreases quite strongly with time (Fig. 7), and this
discrepancy between iA + iB and h can only be accounted
for by assuming that a parallel reaction is taking place at
this potential. The deviations are even more marked at
higher potentials (between 0.6 and 0.8 V) [45], where it
l
is clear that the parallel pathway becomes dominant.
Matsui and coworkers suggest that the parallel pathway
N
0'" ~8:::::8 G"""..A-_':'_-':'--':' __ A 1 1.0
'E ~'-o A"

potentials, with the formation of a second "active" inter-

mediate in a scheme of the form:
~
6, "
~-..:.,,-
,e:-'"
0,
0, 0....... . CD

[3 Cl
"
A"'~ F-~
'. ~6 · ...........0
0.5
0-2 .1... '0
COads~
A'
CO2
is H
CH 3 0H ~ b_o-o-o-e-
0-- I
--0-0-0-0
I 0;"" I I

° I 2°
1 I
CO 2
log ( tis)
This scheme was further investigated by Matsui et al.
[43,44], who assumed initially a series reaction scheme Figure 7 Variation in iA, iB, iT, and 8 with the logarithm ofthe
(for which r2p was assumed small, but no assumptions time for 1 M MeOH/0.5 M H 2S0 4 at 0.55 V, where the partial
were made about the constancy of rate r3 in the scheme currents iA, iB, and iT are defined in the text. (From H Matsui,
above). The variation of the total current with time for T Hisano. Bull Chem Soc Jap 60:863,1987.)
\1 Mechanism of Methanol Electro-Oxidation
does not involve the formation of significant coverage of
an "active" adsorbate at all, but rather that this parallel
pathway takes place through stepwise formation of
HCHO and HCOOH at or very close to the electrode
and that these species are further oxidized to C02. This
process is particularly marked at higher methanol con-
centrations in this potential region, though at concen-
trations below 0.1 M, pathways not involving HCHO
were found to be dominant. If indeed HCHO formation
is important in this higher potential range, then almost
certainly the branching takes place with the formation
of Pt-CH20H, as indicated in the scheme of squares
above, and the relative rates of formation of further
dehydrogenated adsorbates and the oxidation to form
HCHO will be sensitive functions ofsurface morphology
and experimental conditions.
At lower potentials, the importance of the parallel
pathway is far less easy to establish. In a careful study of
the instantaneous current transients on low-index plati-
num surfaces, Herrero et al. [26] were able to establish
that the Tafel slopes for it=o were 120 mVon Pt(lll) and
Pt(llO) and (over a very short range) 60 mVon Pt(100).
These data are comparable with those reported by
Bagotzky for polycrystalline Pt, where a Tafel slope of
135 mV in the range 0.1-0.35 V was derived [7]. All the
surfaces showed kinetic isotope effects that were more
pronounced at lower potentials ("'0.4 V), consistent with
the rate-determining step being C-H bond scission on
the clean surfaces. In addition the rate ofCOads formation
deduced from an analysis that assumed a parallel
pathway was found to be strongly correlated with the sur-
face activity, as deduced from the magnitude of it=o. The
effects of different surfaces and different anions on it=o
are also both extremely significant, as can be seen from
the data of Table 5 (in which icv refers to the peak current
density during the anodic sweep in the 0.2 M methanol
electrolyte). In particular, there is a good inverse corre-
lation between adsorption ofthe anion and initial current
density. At higher potentials, the Tafel slopes at it=o for
Table 5
Pt(lll)
Current 0.1 M 0.1 M 0.1 M 0.1 M
(rnA crn- 2 ) HCI0 4 H 2SO 4 H 3 P0 4 HCI0 4
icy 1.80 0.74 0.30 32.4
i E =0.2v 2.80 0.57 0.24 156
1=0
'E=OAV 97 4.8 1.37
11=0
Tafel 123 119 122 121
slope (rnV)
1
853
all surfaces increase strongly, an effect ascribed by the
authors to the increasing adsorption enthalpy of the
anion giving rise to an increasingly unfavourable
transition-state geometry for the first C-H bond
splitting. In agreement with the results of Kita et al. [24],
the authors report that at high potentials, the values of
it=o actually decrease with E, though increased ordering
of the anion layer is suggested as the cause. The effects
of different anions are qualitatively very similar to those
reported earlier by Sobkowski et al. [46], who also showed
that H2P04" and CO~- strongly inhibited methanol
oxidation on polycrystalline Pt.
Although the data of Herrero et al. [26] were inter-
preted in terms ofa parallel reaction scheme model, such
a model is certainly not established by their treatment,
and Vielstich and Xia [47] have criticized such a model
on the basis of their DEMS data [48], which is discussed
in more detail below. At least below a potential of 420 mY,
the very sensitive DEMS technique detects no C02
evolved from a polycrystalline particulate Pt electrode
surface on chemisorption of methanol; indeed, the only
product detected other than adsorbed CO, in very small
yield (one or two orders of magnitude smaller), is methyl
formate from the intermediate oxidation product
HCOOH. This is graphically illustrated in Fig. 8 in which
the clean electrode is maintained at 50 mY, a 0.2 M
methanol/OJ M HCI0 4 electrolyte introduced, and the
electrode swept at 10 mV S-1 anodically. The peak at
0.25 V is not accompanied by any indication in the
DEMS data of C02 formation at or near this potential
and must arise purely from methanol chemisorption. In
response, Herrero et al. [49] calculate the integrated
charge passed on stepping the potential to various values
and measuring the complete current transient. Their
results are of considerable interest and are given in Table
6 in units of f.1C cm- 2.
The maximum charge that could be passed for com-
plete coverage of COads on the surface is 920 f.1C cm-2
for Pt(111), 600 f.1C cm-2 for Pt(llO) and 840 f.1C cm- 2
Pt(llO) Pt(IOO)
0.1 M 0.1 M 0.1 M 0.1 M 0.1 M
H 2SO 4 H 3 P04 HCI0 4 H 2SO 4 H 3 P04
24.5 12.1 12.1 4.2 2.0
6.5 3.0 72 5.2 1.62
17.0 ILl 1.44
7.6 6.1
123 123 65 63
854 Hamnett

0,3 Table 6
-
1
(a) II Charge
I (IlC cm- 2 )
0.2
Potential
Vvs. NHE Pt(111) Pt(1lO) Pt(lOO)
<t:
.s 0.1 0.32 225 310 660
c 0.42 350 420 805
~ 0.52 1640 450 1860
u 0.62 2580 2830 3400
0,0
:1

3.0
r- I

I (b)
out that the analysis by these authors assumes that the
only intermediate present on the surface is eO ads , in
m/e=44! agreement with the earlier study by Papoutsis et al. [13].
Summarizing this first section, the use ofcurrent tran-
2.5
sient techniques has been able to give considerable insight
~ into the nature of the chemisorbed species forming on
~ )(
2.0
....
platinum. Provided the surface can be prepared and
~
cleaned in a reproducible fashion, the electrochemical

'~-:-'_:.·_.··__.I
• <:;
1,_
1,0
00 0,1 0.2 0,3 04
potential (V liS. RHE)
Figure 8 First potential scan at a porous platinum electrode in
0.2 M MeOH/O.l M HCl0 4 starting at 50 mV with 10 mV S-I.
(a) Current as a function of potential; (b) simultaneously
recorded mass signal for CO 2 (m/e 44). The lower curves are
from a blank experiment without methanol in solution. (From
W Vielstich, XH Xia. J Phys Chern 99:10421, 1995.)
for Pt(lOO). In fact, the actual coverages will be lower than
this, as Sun and Clavilier [37] point out, the coverage
being itself a sensitive function of experimental con-
ditions. It follows from Table 6 that at least for Pt(lOO)
the parallel mechanism appears to be significant even at
as Iowa potential as 0.42 V, though the evidence from
the other two surfaces is less clearcut. Even so, a parallel
mechanism must be operating above 0.5 V for Pt(ll1)
and above 0.6 V for Pt(llO). The corresponding charge
passed for polycrystalline platinum at 0.42 V is
370 f.1C cm -2, this is quite close to the experimental value
for Pt(111) and again suggests that at and below this
potential the current on polycrystalline Pt is dominated
by CO ads formation, in agreement with Vielstich. Finally,
a recent report by Jarvi et al. [50] again confirms on the
basis of charge transient measurements that on Pt(lOO)
the parallel mechanism becomes significant above
0.45 Vand dominant above 0.6 V. It should be pointed
data suggest that there is probably an evolution in the
nature of the chemisorbate with time and coverage on
all surfaces but that linearly bonded CO would appear
to be the final product on almost every surface. However,
0.5 06 although a value of neps of 2 is difficult to reconcile with
any other intermediate than linearly adsorbed CO, the
same is not true of lower values of neps found in many
studies; A value of 1, for example, is consistent with both
triply bridged =C-OH and doubly bridged =C=O,
and other techniques must be sought to resolve this prob-
lem. The nature of the chemisorbate also changes with
the concentration of methanol in solution, with appar-
ently a Temkin isotherm describing the coverage at any
given potential. However, although electrochemical
studies point to linear CO as the most likely species,
definitive proofhas had to await the development of more
advanced spectroelectrochemical and nonelectrochem-
ical techniques, and we review the evidence from these
in the next section.
B. Spectroscopic and Nonelectrochemical
Studies
Although the electrochemical studies discussed above do
point clearly toward linearly or bridge-bonded COads as
significant and possibly dominant components of the
methanol chemisorbate on platinum, particularly at high
adsorption times and high methanol concentrations,
the first definitive proof that adsorbed eo was present
came from in situ infrared experiments carried out by
Beden et al. [51]. These authors used electrochemically
modulated IR spectroscopy (EMIRS) [48], in which a
r
Mechanism of Methanol Electro-Oxidation
(a) 2 on the basis of well-established gas-phase studies to
2051
t band at 1890 cm- I and a rather complex shaped band at
Figure 9 (a) EMIRS reflectance spectrum from a platinum
electrode immersed in 0.05 M MeOHIl.O M H 2 S04. Mod-
ulation was from 0.05 to 0.45 Vat 8.5 Hz and a wavelength scan
rate of 0.0127 /lm S-I. (b) The dependence of the spectrum in
(a) on the modulation amplitude: (I) 0.05-0.3 V; (2)
0.05-0.55 V; (3) 0.05-0.8 V; (4) 0.05-0.95 V. Scan rate
0.00318 /lm S-I. (From B Beden, A Bewick, K Kunimatsu, C
Lamy. J Electroanal Chern 121:343,1981.)
dispersive IR instrument is used with the detector signal
fed to a phase-sensitive detector whose reference signal
is the potential modulation on the electrode. The tech-
nique works in the case of adsorbed CO not by virtue of
changing the coverage of the CO during potential
modulation (because the modulation was chosen to
lie between 0.05 and 0.5 V, which, for an equilibrated sur-
face in methanol has a stable adsorbed CO coverage
determined by the highest potential point in the
modulation) but because the stretching frequency of the
adsorbed CO is a function of potential, in fact,
(avc"o/aE)e ~ 30cm- 1V- I ). The result is the bipolar
spectrum shown in Fig. 9, in which a bipolar peak
centered at 2068 cm -I is clearly seen and can be assigned
1
855
linearly adsorbed Co. A second peak can also be seen at
1850 cm- I ; the monopolar nature of this peak at least at
0.5 M methanol concentrations indicates that it derives
from a species that is present to a greater degree at lower
potentials, and its frequency would suggest, on analogy
with gas-phase spectra, that it derived from a bridged
CO species that was favored at lower potentials. Inter-
estingly, at lower methanol concentrations, this peak is
reported as bipolar in later papers (v.i.). The French group
have now extended their work to single-crystal platinum
surfaces [52-54] (Fig. 10) and have shown that different
low-index surfaces do show quite different behavior in
EMIRS. The Pt(WO) surface, for example, shows, in
addition to a bipolar peak at 2040 cm- I , a monopolar
1700 cm- I , which was particularly prominent at low
adsorption times. This latter is assigned to a formyl
species, Pt-CHO, and is also seen as a weak structure
on polycrystalline platinum. Formyl would give neps
values of three, which has been reported above for poly-
crystalline Pt and low concentrations of methanol, and
the authors tentatively assign this formyl species to an
"active" intermediate that would account for a parallel
pathway for methanol oxidation. On PtOlO), the EMIRS
spectra are much simpler and are dominated by a bipolar
band at 2077 cm- I ; there is a weak band at 1795 cm- I
(perhaps corresponding to multiply coordinated COads)
and some indeterminate structure near 1690 cm- I
whereas, on the Pt(lll) surface the weaker bipolar struc-
ture at 2075 cm- I is accompanied by a broad bipolar
band extending from 1805 to 1920 cm- I , which the
authors suggest may in fact be the sum oftwo bipolar fea-
tures at 1790 and 1870 cm- I . The authors were able to
show that the behavior of polycrystalline Pt could, to a
first approximation, be understood in terms ofa weighted
contribution from the three low-index Pt surfaces. The
very remarkable results from the French group thus
established that linearly and bridge-bonded CO were
present on the Pt surface, but two problems remained:
the technique needed to be quantified so that the coverage
of CO could be determined, and it could be argued (and
indeed was!) that the process of potential modulation
could lead to the formation of species such as COads that
did not form under the normal conditions of electrode
operation.
Both these concerns were addressed by the develop-
ment of modified IR techniques. In the technique
of subtractively normalized Fourier transform IR
spectroscopy (SNIFTlRS) or potential difference IR
[48], the increased stability and sensitivity of Fourier
transform IR (FTlR) is exploited, allowing usable
856 Hamnett

spectra to be obtained by simple substraction andratioing

of spectra obtained at two potentials without the need
for potential modulation or repeated stepping. A second
D
technique that does not call for potential modulation
r
)
05
but actually modulates the polarization direction of the
incoming IR beam is termed photoelastically modulated
~Ier o I
.., . infrared reflectance absorption spectroscopy (PM-
IRRAS); this was applied to the methanol chemisorption
S?
problem by Russell et al. [55], and Beden's assignments
-05
verified, including the potential-induced shift model for
COacts.
-1 The quantification of the detection of COacts was car-
L- 1600 1800 2000 2200
ried out by Kunimatsu and coworker [56-58]. The poten-
tial difference FTIR spectrum observed between 0.05
(a)

--l
and 0.45 Von a Pt electrode in 0.01 M methanollO.5 M
H 2S04 electrolyte is shown in Fig. II. The spectral range

05
(\ L

~v-
Pt/IOmM CH30H 2054

I
2
~I:r 0 0.05 V - 0.45 V
..,
S?
-0.5

- ,

(b)
1600 1800 2000 2200

~
Q:
.....
01 to ~
1832

1873
l
Q:
<l
05
B

~I~
.., . 0 ~ ~
-I

S!

-05

-2
-1

L--- 1600 1800 2000 2200

20e,
(c) V/ _,
/ em

Figure 10 (a) EMIRS spectrum of the adsorbed species 1500 2000 2500
resulting from the chemisorption of 0.1 M MeOH in 0.5 M Wovenumbers Icm- I
HCI04 at a Pt(100) single-crystal electrode. The modulation
amplitude is 0.4 Vat 13.6 Hz and the mean electrode potential Figure 11 SNIFTIRS spectrum observed between 0.05 and
0.35 V. (b) The same for a Pt(llO) single-crystal electrode. (c) 0.45 V on a polycrystalline platinum electrode between 0.05
The same for a Pt(lll) single-crystal electrode. (From B Beden, and 0.45 V in 0.01 M MeOH/0.5 M H2S04. (From K
S Juanto, JM Leger, C Lamy. J Electroanal Chern 238:323, 1987.) Kunimatsu. Ber Buns Phys Chern 94:1025,1990.)
,
Mechanism of Methanol Electro-Oxidation
was, in fact, from 1100 to 3000 cm-I, but the only spectral
features observed in this well-equilibrated surface were
those corresponding to linear and bridged CO; inter-
estingly, the latter is also apparently bipolar, suggesting
that on this surface interconversion of the two species
may be inhibited. Quantification of the spectra was car-
ried out by Kunimatsu [56-58] using PM-IRRAS and
the intensity of the signal compared at equal coverages
with that derived from the adsorption of CO itselffrom
the electrolyte. Interestingly, as the PM-IRRAS spectra
showed (Fig. 12) differences in the position of the
IR-adsorption peak depending on whether CO ads is
derived from CO(aq.) or methanol, the latter showing a
slightly lower absorption frequency. Moreover, as the
total coverage of organic chemisorbate rises, there is an
increasing discrepancy between the intensity of the
linearly bonded CO ads peak from methanol chemisorp-
tion and CO adsorption (Fig. 13). Some of this discrep-
ancy is certainly due to the presence of bridge-bonded
species, but some may be due to different packing
t
I
arrangements on the surface and/or to the presence of
additional organic adsorbates of a noncarbonyl form, a
l 4
1 co
t
z
-
o
.....
0..2
a:
8rata, :::::0.86,
0.4 V/RHE
oCJ)
CD
~
o~"-~=~----1:::::::::=;:~~~
2100 2000
WAVENUMBER / cm- t
Figure 12 Comparison of the polarization modulated
(PM-IRRAS) spectra oflinear COads derived from adsorption
of CO and of methanol from solution onto a Pt surface from,
!
respectively, CO(sat)/0.5 M H 2 S0 4 and I M MeOH/0.5 M
H 2 S0 4 at 0.4 V for 15 min. The polarization modulation was
conducted at 80 Hz by using a rotating polarizer, and spectra
are referred to 0.8 V. The total adsorbate coverage of 0.86 is
1 common to the two spectra. (From K Kunimatsu. Ber Buns
Phys Chern 94:1025, 1990.)
857
point that we return to below. Kunimatsu's work does,
however, very clearly indicate that on well-equilibrated
surfaces, linearly bonded CO is the major adsorbed
species. PM-IRRAS also allows us to follows the chemi-
sorption process in more detail; Fig. 14 shows the depen-
dence of the signal from the linear CO ads species as a
function of potential, starting with a near clean surface
at 0.05 V There is evidently a substantial shift in peak pos-
ition as the potential and coverage are both increased,
with (Bvc""o/BE) ~ 100 cm- 1 V-I. There is clear evidence
that the frequency of the CO ads shows marked sensitivity
to coverage, and this has attracted some considerable
attention recently (v.i.). Thus, intensities must be treated
with some care, but nevertheless, the increase in intensity
of the CO ads band with time for an electrode maintained
at 0.4 V in 0.01 M methanol/0.5 M H 2 S04 was found
accurately to obey the expression aads ~ const.+
1/ rxf In t derived by Bagotzky and Vassilyev [7].
Normal SNIFTIRS or FTIR potential step exper-
iments also show a steady increase in coverage of CO ads
with increasing potential and time (Fig. 15) [59-63].
Simple potential-step experiments on polycrystalline Pt
surfaces show clear peaks at 2050 and 1836 cm- 1, which
cab be assigned to linear and bridged CO, with a small
peak at 1976 cm- I whose identity is discussed further
below [63]. These experiments also provide some evi-
dence that bridged species are more prevalent at lower
potentials [64], a result in general agreement with the
15 co
~
.;;;
..
c
c:
1.0
8Total
Figure 13 Integrated infrared absorption intensities on a
polycrystalline Pt surface of the linear COads derived from CO
(saturated) and methanol (l M CH 3 0H) in 0.5 M H 2 S0 4
respectively, plotted as a function of total adsorbate coverage.
(From K Kunimatsu. Ber Buns Phys Chern 94:1025, 1990.)
 I
858

2
Pt 110- M CH30H 2056 !OR/R x1000
Hamnett
I
a

i
2%
Eads.
V/RHE

1
z
0.4

o 0.3
~
a..
a::
o
en 0.2
CD
<t

3
2016
2

---
0.05 1

-1
-2
01'\./\: 'l~iD", 1\
I
~
2150 2100 2050 2000 1950
1 -3
WAVENUM8ER/cm-
-4
Figure 14 Dependence ofthe PM-IRRAS spectrum oflinear -5
COacts derived from methanol adsorbed onto PI in 0.01 M -6
MeOH/0.5 M H 2 S0 4 on the initial adsorption potential. (From -7
K Kunimatsu. Ber Buns Phys Chern 94:1025,1990.)
-8
-9 II I , ! , ' , ! ! I .! I, I \/,

studies on CO adsorption on Pt surfaces reported below.
A significant advantage of SNIFTIRS is that the forma-
tion of products can be clearly monitored; Fig. 15 also
shows, for example, the development not only of CO 2
and adsorbed CO at lower potentials but the formation
of significant quantities of formic acid at higher current
densities. There are also methanol loss features at 2840
and 2950 cm- 1 in the v(C-H) region and at 1476, 1450,
and 1405 cm- 1 in the v(C-O) and J(COH) regions,
and a gain due to formic acid at 1435 cm- 1 (v.i.).
The potential step FTIR method has now become
the preferred approach for exploring the nature of
chemisorbates at the surface, and an intensive attack has
been carried out using this and related techniques on
3000 2800 2600 2400 2200 2000 1800 1500 1400
Wavenumbers
(8)
Figure 15 (A) SPAIRS spectra derived from oxidation of
2.0 MCH30HIl M H 2 S0 4 on Pt starting from a reference clean
Pt surface at 0.1 Vand recording spectra at 0.05 V steps from
(a) 0.1 V to (i) 0.55 V. (B) The same for steps from (a) 0.55 V to
(c) 0.65 V in 0.05-V steps. (From PA Christensen, A Hamnett,
GLTroughton. J Electroanal Chern 362:207, 1993.)
single-crystal Pt surfaces to better understand the pro-
cesses taking place. These studies have frequently
included comparative investigations of CO adsorption
and oxidation, because there are strong similarities and
 Mechanism of Methanol Electro-Oxidation 859

intriguing differences between these processes, and we,

therefore, turn to a discussion of adsorbed CO on plati-
num first. The adsorption of CO on platinum has both
2072
[ 2x1(r' a.u.
structural and electronic aspects: The structural aspects
were initially explored with the aid ofex situ LEED, using
samples that were emersed from 0.1 M HC104 [65,66].
1847
These authors found that instead of the expected
0.39 V
(J3 x J3)-R30° structure at lower coverages [67], two
1! rectangular patterns were observed following adsorption
of 0.4 V, corresponding to (J3 x3), with linear and

t bridged CO in the ratio 5:2, and c( J3 x5), with a slightly

higher ratio (13:8) oflinear to bridged forms, the former
being found near saturation coverage (8 ~ 0.7); and the
0.33
1841

latter prevalent in the range 0.09 < 8 < 0.6. This latter is 0.26
a very interesting result, because the (J3 x J3)-R30°
would be expected for lower coverages, and the authors
suggest that the adsorbed CO forms islands at lower 8 0.12
values that are presumably stabilized by adsorbed water
[68]. It should be pointed out, however, that more recent
I
,w
STM /IRRAS data [69] have thrown into question the
-0.01
1784
I
! extent to which the CO structure may be modified by
introduction to the UHV system.
The fact that the structural transitions seen by
Wieckowski and coworkers [65,66] are accompanied by
-0.15
changes in the relative ratios of bridge to terminal CO
implies changes in the IRRAS spectra as well, and these
1770
have been discussed extensively by Chang and Weaver
[70,71]. For Pt(lll) in 0.1 M HC10 4 /CO, the results at a -0.25
constant coverage of0.65 are shown in Fig. 16; it is evident
that below ~0.4 V, there is a very low frequency vibration
(~1770-l790 cm -I) assigned to triply bonded CO, and 2200 2000 1800
above 0.4 V, there is a jump to higher frequencies
V / cm- 1
(1840-1850 cm- I ) assigned to doubly bonded Co. At
lower coverages, perhaps surprisingly, this triply bonded Figure 16 Sequence of IR absorption spectra in the 1700 to
form is replaced throughout the potential range by the 2200 cm~l range for adsorbed CO (8=0.65) on Pt(lll) in
doubly bonded form. In general, as a function of CO CO-saturated 0.1 M HCI0 4, obtained during a positive-going
coverage on this surface, the proportion of terminal to potential sweep at I mV s-I from -0.25 V vs. SCE. Each
bridged CO increases monotonically with 8. spectrum involved acquiring 100 interferometer scans
Qualitatively similar results are found for Pt(lOO) [72]: (consuming ~l min) subtracted from which was a similar set
At higher coverages there is a strong preference for of scans acquired after complete CO electro-oxidation. (From
bridged CO at lower potentials and terminal CO at S-C Chang, MJ Weaver. Surf Sci 238:142, 1990.)
higher potentials (Fig. 17); curiously, however, for
8 ~ 0.25, the situation is reversed, with both forms found
at low potential and only the bridged form above ~0.3 V. water under UHV conditions, conversion takes place of
This general preference for bridged form at lower some terminal to bridged form [68]. It may also reflect a
potentials may reflect the effect of coadsorbed hydrogen real electronic effect: The enhanced d" - p" bonding
or water: Neither of the surfaces prepared electro- expected at lower potentials should preferentially
chemically is completely covered with CO, and particu- stabilize the bridged form [70], a result that can be
larly at lower coverages, there is substantial mimicked under UHV conditions by coadsorption of
coadsorption of H at the lower potentials. In addition, ions and dipolar species [73,74] and can also be explored
under UHV conditions, terminal CO dominates on over wider potential ranges in nonaqueous solvents [75].
Pt(111) even for 8 < 0.25, whereas on coadsorption of There is evidence, however, that whereas CO adsorption
860 Hamnett

,
'I 1801 I A 9-0.85 B 9-0.60 C 9-0.25
EN
EN
0.40
0.32
2044. ~
1837

~
e-.J\-..
~
~
0.05

~ 1824

~
~
~
- ~
- -
-0.25
, -- -, II , , I I~ I-='
...........,
1
2100 1800 2000 1800
(a) V I cm- 1 V I cm- 1 2100 1900 2100 1900 2000 1800
(b) V I cm- 1

Figure 17 (a) IR absorption spectra for adsorbed CO on ordered Pt(IOO) in 0.1 M HC10 4 at -0.25 V vs. SCE. Spectra in A were
acquired by progressive electro-oxidative stripping (using pulses ofl-2 s duration at 0.5 V vs. SCE), commencing from a saturated
(B = 0.85) surface, whereas those in B were acquired by dosing for variable times from a 10- 5 M solution ofCa. (b) Sequence of IR
absorption spectra for CO ads on Pt(lOO) obtained during positive-going potential sweeps at 2 mV S-1 (A, B) or I mV S-1 (C) starting
at -0.25 V vs. SCE at different initial coverages. (From SoC Chang, MJ Weaver. J Phys Chern 94:5095,1990.)

on Pt(lll), even in the presence ofcoadsorbed H, leads to
segregated islands, on Pt(100) there is more likelihood
that mixed two-dimensional phases form. Certainly the
energy difference between these two types of
coadsorption appears smaller in the case of Pt(100), a
result supported by the kinetic evidence discussed below.
There is a marked contrast, however, with the data for
Pt(llO) [76], which exhibits only terminal CO (Fig. 18).
At high coverages, a single peak is seen at
2070-2080 cm- l ; at lower coverages (0.4 < e < 0.6), two
peaks due to terminal CO are seen, separated by
"'" 15-20 cm- I , but for e < 0.4, only a single band is seen.
This behavior was tentatively ascribed by the authors to
the effects of island formation with resultant local lifting
of the normally reconstructed Pt(llO) surface. Finally,
regardless ofsurface, it has been found, in agreement with
PM-IRRAS and EMIRS studies, that both terminal and
bridge-bonded CO shift with potential: At higher
(constan~) coverages, (ovc%E)ef o ""'30-35 cm-~ V-I
for termlOal CO, 40-45 cm- I V- for doubly bndged
CO, and 50-60 cm- I V-I for triply bridged CO; these
slopes tend to be ""'10-20 cm- 1 V-I higher at low CO
coverages.
More recent combined STM/IRRAS studies [77] of
CO adsorption on Pt(ll1) from HCI0 4 solution have
shown that for saturation coverage, and for E < 0.25 V, a
(2x2)-3CO adlayer forms possessing both terminal and
triply bonded CO (in the ratio 1:2), and with an IRRAS
spectrum showing peaks at 2066 and 1850 cm- 1 (with
intensity 2:1). However, above 0.25 V, a surface phase
transition takes place to yield a (.j19x .j19)-R23.4° struc-
ture with 13 CO molecules per unit cell. Moreover,
although this structure has only one terminal and 12
doubly, triply, or intermediately bonded CO per unit cell,
the IRRAS data showed only two peaks, at 2073 and
1850 cm- 1, with an intensity ratio of 2:1. Although
Mechanism of Methanol Electro-Oxidation 861

A B C D E

e 2069
e e e 2034
2072 0.13 0.04 0.06 2026
0.09

0.16 0.17 0.10 0.11

2043
2069
0.34 0.18 0.11

2076 0.50
0.65 0.45 0.28

2071 2071
3 2038
13x10- au

0.40
1.0 0.72 0.60

2100 2000 2100 2000 2100 2000 2100 2000 2100 2000
V/ cm- 1
Figure 18 Series of coverage-dependent IR absorption spectra for COads on ordered Pt(1lO) in 0.1 M HCl04 at 0.05 V vs. SCE
obtained by electro-oxidative stripping (1-2 s pulses to 0.5 V vs. SCE) commencing from a series ofdifferent coverages ranging from
e= 1.0 (A) to e= 0.28 (E). The initial coverages were obtained from various dosing times using 10- 5 M CO solutions. Spectra in C,
D, and E are scaled by factors of2x, 2x, and 4x, respectively. (From S-CChang, MJ Weaver. Surf Sci 230:222,1990.)

qualitatively the adlayer phase transitions as revealed by
IR and STM are consistent, there are then clearly
disquieting features, particularly with regard to the
relative band intensities that need to be resolved. This
can only be done by recognizing that the individual CO
molecular vibrations must be strongly coupled through
dipole-dipole effects. This coupling gives rise to two
effects: a general upshift in the frequency ofall the bands
and, if two bands of differing frequency are present, a
transfer ofintensity from the lower frequency component
to the higher. Strong evidence for the importance of these
effects was obtained by the authors through isotope
dilution effects, in which 12COads is steadily replaced by
13COads to reduce the coupling. In this way, by extrapol-
ation to 8 12co ---+0, the value of the "singleton" frequency
for terminal 12 CO can be found: It is 2035 cm- 1 onPt(lll)
at 0.0 V. In the same way, the "singleton" frequency for
the triply bonded form is estimated to be 1745 cm- 1 at
the same potential. The infrared spectra for the various
structures can now be simulated following the method
of Persson and coworkers [78,79]; by choosing sensible
parameters for the vibrational and electronic polar-
izabilities of the two forms of COads and an estimate for
the adsorbate-image plane distance, the IRRAS spectra
at low potentials can be quantitatively linked to the pro-
posed (2 x 2)-3CO structure, the simulated spectra clearly
showing the effects both ofupshift and intensity transfer.
Clearly, the structure at higher potentials is more
862
complex, with a variety ofmultiply bonded CO forms pre-
sent and linearly bonded Co. Similar isotope dilution
experiments allow an estimate to be made of the relevant
"singleton" frequencies at 0.35 V; for the doubly and
triply bridged forms and the linear form, these estimates
are 1810, 1750, and 2040 cm- I , respectively, and by using
interpolation to estimate the "singleton" frequencies for
intermediate coordination, a good semiquantitative fit
to the observed spectrum can be obtained. It is of con-
siderable interest that the signal due to the doubly bonded
form is not only substantially up-shifted but has lost
almost all its intensity, and the triply bonded form has also
been shifted dramatically up, the spectrum as a whole
being strongly reminiscent also of the SNIFTIRS
spectrum obtained for methanol oxidation on poly-
crystalline Pt [64] (see above). The importance of this
analysis can hardly be overstated: Both the position and
the relative intensity ofthe vibrational bands in the v( CO)
region are unlikely quantitatively to reflect the population
of the differently coordinated adsorbed CO molecules
on that surface.
A good illustration of this can be seen for CO adsorp-
tion on the high-index Pt(533) surface [80-82]. As
explained below, such surfaces can serve as interesting
models for platinum particles, the 533 surface itself being
[4(1ll) x (100)] in character. It is well established that the
step edge sites are preferentially occupied by CO at low
coverage, with terrace bonding only taking place at
higher coverages. At low coverages in 0.1 M HCI0 4
(8 ca < 0.3), an IRRAS band is seen at 2006-2025 cm- I ,
being shifted up at constant coverage by "-'15 cm- I in
the range 0.05-0.35 V This is assigned to terminally
bonded CO at step edge sites. Surprisingly, there is very
little change in frequency for this band as the coverage
increases from 0.0 to 0.3, which the authors ascribe to
coadsorbed hydrogen disrupting the expected
dipole-dipole coupling effects. A bridge-bonded CO is
also seen, with a much more marked shift to higher fre-
quency with coverage (from 1799 to 1821 cm- 1 at 0.35 V
as 81 8max increases from 0.11 to 0.35 and from 1788 to
1805 cm- 1 for the same increase in 818 max at 0.05 V).
The position of this COB is unclear, but models derived
from electron energy loss spectroscopy (EELS) and
TPD data under UHV conditions place this CO on the
edge sites with the terminal CO in a structure in which
bridge and terminal sites alternate. For 818max > 0.35,
marked changes are seen in the IRRAS spectra: There is
a marked upshift in the v( CO) for terminally bonded
CO, with the appearance ofa shoulder to lower frequency
that finally disappears for 81 8max >0.6. There is no doubt
that CO molecules populate the terraces under these con-
ditions, with the higher terrace-bonded CO frequency
Hamnett
now borrowing intensity from the lower edge frequency,
though the suddenness of the upshift may also reflect the
very enhanced dynamic dipole-dipole interactions on
the terraces as measured by isotopic dilution experiments
[82]. Avery broad band is seen in the bridging CO region,
partially resolved into two peaks at "-'1790 and
1860 cm- I ; at the highest coverages this low-frequency
component is lost, presumably by intensity transfer.
A review article Chang et al. in 1991 [83] summarizes
earlier work from Weaver's group on the kinetics of CO
oxidation on low-index surfaces of Pt. It is well
established that due to dipole-dipole coupling effects,
increasing CO coverage through dosing gives rise to a
pronounced shift in v(CO) to higher frequencies, but
reoxidation ofthe CO ads layer, once formed, does not give
rise to any immediate bathochromic shift, at least if the
CO is adsorbed on Pt(lll) or Pt(lIO) at relatively positive
potentials [84], because it appears that the CO ads , once
formed, prefers to become aggregated into islands. This
is marked contrast to time-equilibrated data on
polycrystalline Pt [85], where oxidation of the adsorbed
CO led to a steady decrease in v(CO) as expected
(v.i.). Support for this suggestion of island formation
on single-crystal surfaces comes from isotope
measurements: If a l3CO monolayer is formed and then
partially oxidized and then l2CO adsorbed, the 12CO is
preferentially oxidized to 12C02, suggesting that the CO
islands, once formed, are not involved in subsequent
nucleation and growth. In addition, CO ads sub-
monolayers oxidize at lower potentials, confirming the
view that coadsorbed water facilitates the oxidation of
CO (v.i.).
The authors also report that rapid reoxidation of
COads , especially on Pt(lOO), does, however, give rise to
a time-dependent CO frequency, a result also found for
polycrystalline Pt, with a timescale of 10-15 min,
suggesting that islands on this surface can relax to a more
disordered state, presumably driven by entropy effects
[86]. Time-dependent effects may also be seen if CO is
adsorbed at low potentials [84]. The mobility of COads
on Pt surfaces has been little considered until recently
by the electrochemical community, though it is a
well-established concept in gas-phase work [87]; this
mobility is certainly a function of coverage, because it is
known that strongly repulsive interactions exist between
adsorbed CO on adjacent sites [88], with the desorption
energy, Ed, decreasing by a factor of 2 as the coverage
increases; the decrease is especially marked at very high
coverage, leading to adsorbed CO molecules that are
substantially less stable and more mobile. Finally, the
multiple oxidation peaks seen for CO ads on platinum
are not, in Weaver's view, due to bridged vs. terminal
r
,
Mechanism of Methanol Electro-Oxidation
CO, (in contrast to earlier studies [89] that had suggested
such an effect for Pt(11l) but not Pt(lOO)) but arise from
the presence of CO domains of differing structure. For
example, on Pt(llO), the two oxidation peaks appear to
be associated with terminal CO, (COads)t, in unrecon-
structed (l xl) and reconstructed (l x2) domains.
The nature of methanol oxidation on various
low-index surfaces as studied by FTIR has been reported
by Weaver and coworkers [90,91]; in contrast to formic
acid, or CO itself, methanol oxidation (0.05 M in 0.1 M
HCI0 4 ) was found to lead to only moderate (:s 0.2) CO
coverages, with the CO predominantly in the terminal
configuration, though a weak band at 1820-1860 cm- I
is found for methanol oxidation on Pt(11l). By measuring
the hydride coverage, 8H , electrochemically, the authors
were able to show that (8 H + 8eo ) was comparable with
the saturation hydride or CO coverage on Pt(lll) ( ~0.7),
butthis total on Pt(lOO) or Pt(ll0) (~0.6) was significantly
smaller than saturation chemisorption values on these
latter surfaces. These results are consistent with the
presence of appreciable additional adsorbed species not
detected in the carbonyl region of the IR spectrum. In
agreement with earlier work, the authors found substan-
tial CO ads coverage only at potentials positive of the
classical hydride region (~0.3 V) on Pt(11l), with a steady
increase in both current and 8eo at higher potentials. In
comparison with the Veo data for adsorption from CO
solutions, the frequency at comparable coverage and
potential for terminal CO was intermediate, suggesting
that small islands of CO ads were forming but not on the
scale found for high coverage of CO ads described above.
Interestingly, no bridged CO was found for methanol
oxidation on Pt(lll) at the concentrations used
(0.05-5 M). For Pt(lOO), the situation is rather different:
Both bridged and terminal CO are found, the former
being present even at quite low potentials (0 V), with ter-
minal CO being found above 0.2 V It is also noteworthy
that on Pt(lOO), only bridged species are found at these
low coverages for adsorption ofCO from solution; clearly
the coadsorption of other species is stabilizing the ter-
minal form ofthe CO on Pt(lOO) in methanol.
A thoroughgoing LEEO/IRRAS comparative study of
the oxidation ofCO and methanol on Pt(lll) in sulphuric
acid (as distinct from the perchloric acid used in the
studies described above) [92] showed that for CO
oxidation on Pt(lll) in sulphuric acid, adsorption of CO
at 0.05 V gave peaks at 2128 and 1338 cm- 1 correspond-
ing to terminally bonded CO and adsorbed HSOi, at
0.4 V, four peaks were seen, at 2131 (terminal CO ads ), 1865
(bridged CO ads ), 1339, and 1250 cm- I . The last of
these corresponds to an ordered HSOi overlayer
(.J3x.J3)R30°, though the LEEO pattern is rather dis-
863
torted, and the former assigned to reorientation ofHSOi
caused by interaction with CO ads , the evidence for this
being that at higher potentials, when CO ads is much
reduced in coverage, this peak disappears. Ifthe electrode
potential is now swept sufficiently positive for the CO ads
to disappear completely and then reversed, a clear
(.J3 x .J3)R30° LEEO pattern is observed. By contrast,
in HCI0 4 , there is little evidence of adsorbed anion
structure. For methanol oxidation in sulphuric acid on
Pt(11l), no structure is seen until E > 0.3 V, when LEEO
showed adisordered (.J7 x .J7)-RI9.1 °pattern, with bands
at 1249 and 1343 cm- I associated with HSOi, with some
similarity to the adlattice structure described earlier for
HSOi on Pt(lll) with STM [36]. At more positive
potentials (>0.5 V), the 1250-cm- 1 band disappears and
the 1343-cm- 1 band becomes very sharp, as does the.J7
structure. Above 0.9 V, however, the current begins to
decrease (v.s.) and the .J7 structure also begins to
deteriorate. There does appear to be some correlation
between this structure and activity to methanol oxidation
on Pt(11l); in addition, the ratio 8HSO ' /8 eo is always
higher for methanol oxidation than CO oxidation.
We may summarize this subsection by reiterating the
fact that the CO adlayers formed on oxidation of meth-
anol clearly closely resemble those formed by adsorption
of CO from aqueous solution, but they also show
differences. Not only are coverages usually lower, but
there is at least some indications that in addition to the ter-
minal and bridge-bonded CO ads species expected, there
are probably other carbon-containing species on the sur-
face that affect the way in which methanol is oxidized. In
addition, although there is some evidence for the forma-
tion of islands of adsorbed CO on chemisorption of
methanol, these islands appear to be smaller than those
that form on adsorption of CO itself and, particularly in
the case of sulphuric acid, appear to be strongly associ-
ated with adsorbed anions.
The realization that not all spectroscopic measure-
ments converged on linearly bonded CO has come not
only from FTIR studies but from measurements using
additional techniques, particularly those based on mass
spectrometry. The most compelling evidence has come
from OEMS data [93-95]. By calibrating electrodes by
adsorption of CO from solution, these authors were able
to establish that in the absence ofany adventitious oxygen
the main adsorbate on their porous Pt electrodes required
three electrons per molecule to generate one molecule of
CO 2• This showed that the adsorbate must be =:C-OH
or -CHO, at least under the conditions of the
experiment. Interestingly, in the presence of oxygen, the
number of electrons required to generate one molecule
of CO 2 fell to between 2 and 2.5. The OEMS data also
864
established, as indicated above, that no CO 2 formed
below 0.42 V, but there was a small signal due to methyl
formate, whose magnitude was at most 1% of the CO 2
signal. The authors also investigated the effects of
chemisorbing deuteromethanol from 020 and oxidizing
the resultant species in H 20 and doing the reverse (i.e.
chemisorbing methanol and then oxidizing it in 020);
the results were initially inconclusive [93], but by using
dilute acid electrolyte [96] it was established that the inter-
mediate at low coverage was apparently =C-OH and
not -CHO, in direct contradiction to the suggestions by
the Poitier group. Further strong evidence for the fact that
hydrogen is associated with the has been obtained using
electrochemical thermal desorption mass spectroscopy
(ECTOMS) [12,97]. In this experiment, the electrode is
transferred from electrochemical cell to UHV chamber
without exposure to air and the chemisorbed layer
thermally desorbed. After calibration, the ratio of
hydrogen detected to CO gives an indication of the rela-
tive amounts of =C-OH and CO adsorbed on the
surface; the results are shown in Fig. 19 and clearly con-
firm the contention from electrochemical data that at
higher coverages adsorbed CO dominates, but at lower
coverages, =C-OH plays a very significant role. The
ECTOMS results are, of course, also consistent with
-CHO as a low coverage intermediate, but the isotope
data do not support this latter species. Clearly, if
=C-OH is the intermediate formed at low coverage, it
must also be very stable on the surface, because it differs
little in energy from CO, a fact that would tend to rule it
out as the "active" intermediate in any low-potential
parallel pathway.
The existence of =C-OH as an adsorbate is clearly
signaled by these studies, but unambiguous identification
by spectroscopic methods has proved much more
difficult. Calculations [98] suggested that v(C-O) might
be found at 1380 cm- 1 for =C-OH and 1900 cm- I for
-CHO at the Pt-gas interface, but the observed fre-
quencies in aqueous electrolyte are likely to be lower by
at least 100 cm- I . The first report to claim to have
observed this species with FTIR was Vielstich et al. [99],
who reported a small signal near 1230 cm- I that devel-
oped at higher potentials. However, this signal could also
be assigned to methyl formate [100]. Signals at 1320 and
1425 cm- I in addition to a signal at 1215 cm- I were also
reported by Nichols and Bewick [101], but again these
were obtained only at higher potentials (----0.7 V).
Moreover, these signals, which were assigned by Nichols
and Bewick to v(C-O) and b(C-OH) of =C-OH
and v(C-O) of (-CHxOH), respectively, might also be
assigned to formic acid. However, by carefully
monitoring the adsorption of 1 M methanol in 0.1 M
"amnett
HCI0 4 as a function of time on a clean reference surface
at 0.05 V, Iwasita and Nart [102] were able to observe at
0.35 V two small peaks at 1200 and 1273 cm -I, in
addition to rather larger signals in the linear and bridged
carbonyl region. On adsorption of C0 3 0H, the signal
at 1200 cm~1 disappears, presumably being down-
shifted out of the range of the window/detector system
used, and the authors assign the peak at 1273 cm- 1 to
v(C-O) of =C-OH and the peak at 1200 cm- I
tentatively to b(C-OH) ofadsorbed =CHOH.
Finally, in addition to studies on polycrystalline and
low-index single-crystal electrodes, IR studies on meth-
anol oxidation have also been carried out on Pt particles
and on higher-index Pt surfaces. The first observations,
on platinum roughened by repeated cycling, were made
by Beden et al. [103], who observed that although linearly
bonded CO could clearly be seen as a bipolar band in
EMIRS in 1 M methanollO.5 M HCI04, the signal due
to this species disappeared on dilution to 0.1 M methanol
in the same potential range (E = 0.2 V, 11£ = 0.4 V),
suggesting that adsorption of CO was significantly
reduced on these higher surface area samples or, more
probably in the light of the above discussion, that
transformation to such species as =C-H has taken
place. These studies were extended in a second paper
[104], in which roughened platinum electrodes again pre-
pared by potential cycling followed by electroreduction
showed both little COads coverage, especially at low meth-
anol concentrations, and a band between 1640 and
1700 cm -1 that was particularly marked at lower adsorp-
tion times and was assigned to -CHO or -COOH.
Rather different data were reported by Christensen and
coworkers [105,106]; these authors used stepping-mode
FTIR with a reference surface at 0.05 V, but the spectra
they obtained (which are shown in Fig. 20) are unusual
in showing that even at 0.05 V some methanol has clearly
already adsorbed on the Pt particles, in stark contrast to
the situation on smooth polycrystalline samples; that
there is a marked broad gain between 1650 and
2000 cm- 1, which the authors were able to show was
due to absorption by H 30+; that although there is a
bipolar feature at 2050 cm- I , it is reversed from the nor-
mal direction, showing a gain at lower frequency as the
potential is increased; and there is a gain at 1820 cm- I .
The authors attribute the gain at 2030 cm- I and loss at
2060 cm- 1 to migration of COads from terraces to steps,
in agreement with the work of Kim et al. [80~82], with
conversion of some remaining COads on terraces to a
multiply bonded form as the nett COads coverage is
reduced, giving rise to the 1820-cm- 1 peak. This distinc-
tion between different forms of CO on platinum has also
been discussed by Iwasita and Vogel [107] on the basis
Mechanism of Methanol Electro-Oxidation 865

I h)

[0)

mle- foetor
m/p- factor ~
C 28 ,,1
~ 28
c
~
"1
.~

....
Cl
.;
...
>-
.a
'"
= ...
.
..Q
'" 2 • 1
Cl

-...
2 ,,1

------
c

------------
Q
c
~ a.
. l5 1.4 .2

-- -
Q.
44 •2 ...'"
0
~
...'"
-.. ...
--------
'C
17 .2 ~ 17 .2
Q -=-
.2 C
.
'"
--- blo .2
- - blo
,,2

.2

300 sao 7IlO 900 300 500 700 900

(A) TIt< T/K

0 0
1 [0 I 0 r bI 0
0 0
rP ~
c: 0
,..., 00

-
0 0
0 0 0
0
0 -... c: ,..,
u o 0 3 0 0

-
0 x 0 +:
'-

III
0.5
x
0

x
0

0.5 ..,
_........
I'l)
u
0

0·5 -
•• • .;• "-
3Q

0
e
-- "," "
x·x
c
-o' . . .
n "0
C1I

E
~

+ •
a
0.5
-
~

..,
c
n
::
0
• ~ :J:
0 i ... :::l ...
~
Q

U • I,.j I
I
~

• .+ oL
o~ a a

0 0.5 1 0 05
(B) (overage / 8 (overage /8

Figure 19 (A) ECTDMS of methanol adsorbate obtained by exposure of the electrode to [aj 0.005 M MeOH/0.5 M H 2S0 4 and [bj
0.5 M MeOH/0.5 M H 2S0 4. Desorption traces given for mle = 28 (CO), 44 (C02), 17 & I (H 20), and 64 (S02). (B) Mole fraction of
two methanol adsorbates, COads and =C~OH obtained from the type of curves shown in raj: (.) adsorption from 0.005 M MeOH;
(+) adsorption from 0.5 M MeOH. (From S Wilhelm, T Iwasita,W Vielstich. J Electroanal Chern 238:383,1987.)
866
s
?..-
~, ---
2
:~~
f,
n
q.-
-IllII I I I I L~_....L-._~-,-~ I I
Cf>1l8 ?!ill~ i'~ml ? ~llll (cHI' mil ?HIlII 1~1I0 1fIllll I )~0 1"l'~ 151J8 141111
(0 I lIJovpnlll"her~/em-1
Figure 20 FTIR difference spectra collected at (a) 0.3 Vand (b) 0.4 Vduring an experiment in which the potential ofthe Pt particle
electrode immersed in 1.0 M MeOH/1.0 M H 2 S0 4 was increased from 0.05-V in 50-mV steps. The reference spectrum was obtained
at 0.05 V. (From PA Christensen, A Hamnett, J Munk, GLTroughton. J Electroanal Chern 370:251, 1994.)
of isotone exchange and potentiodynamic sweep
measurements: By simultaneously measuring charge
passed and the mass signal of the resultant CO 2 evolved
from the electrode, these authors identified a small pre-
peak beginning at ~0.4 V that is clearly associated with
CO ads bonded more weakly. This CO could be exchanged
isotopically, though it primarily forms only in the
presence of CO in solution rather than methanol.
Some confirmation of these concepts has recently
been obtained from studies on high-index platinum
surfaces. It is well known that such surfaces can serve as
good models for platinum particles [108], with the 533 sur-
face [4(1ll) x (l00)] serving as a model for edge atoms in
a truncated octahedron and the stepped-kinked 432 sur-
face as a model for corner atoms in the same type of
particle. Comparative studies of methanol oxidation on
Pt(lll) and Pt(533) surfaces [109] by stepped potential
FTIR show that on the former, methanol chemisorption
to give CO ads only takes place above ca. 0.3 V, once the
normal adsorbed hydrogen atoms have been stripped off,
whereas for the latter, COads is seen even in the hydride
region, albeit rather weakly. Adsorption from 0.1 M
Hamnett
Il~ II! ,Willi
(1
"""Il~~,.\.t~
-1
., _.'11-.--1.- I • I I ...1-._-1-_...1- _-1- __ ...1- __1---1-.__
,I,on ("I'll ;'1(111 (.IHII ;'(011 ~1\111 (HIlIl l~nn 18111l 1J~1l 1'.1111·1r,~0 1~lIe
lIJovpnlJ",her~ /em- I
(bl
methanol/O.1 M HCl0 4 at 0.15 V gives rise to clearly dis-
tinguishable peaks due to CO ads on terrace and edge sites,
the former being seen at 2059 cm- 1 and the latter at
2009 em-I; in addition, a peakcan be seen at1860 em -I.
This peak is assigned to bridging CO at edge sites,
because it is near in frequency to bridged CO observed
on Pt(lOO) sites, which exist only at the edges ofthe Pt(533)
surface. Increasing the potential in the same electrolyte
caused the frequency of the signal from the edge-site
linearly bonded CO to increase rapidly and to lose relative
intensity, eventually being lost (Fig. 21), a process associ-
ated with increasingly strong coupling between terrace
and edge COads species as coverage increases. Decreasing
the methanol concentration to 0.05 M gives rise to much
weaker structure at 0.15 V, with only a COads peak at
2049 cm- I being seen. At higher potentials, a doublet is
again seen in the COads region and a weaker peak at
1846 cm- I also appears.
A number ofother techniques has been used to attempt
to characterize the chemisorbed methanol layer. A recent
study using second-harmonic generation [110] estab-
lished that strong SHG signals on Pt could be seen for
Mechanism of Methanol Electro-Oxidation
A B
2057
I et al. [1ll,1l2]; these authors showed that for
2100 1900 2100 1900
Wavenumber (cm- 1)
Figure 21 IR spectra of COads formed during oxidation of
methanol at (A) Pt(335) and (B) Pt(lll) electrodes. The elec-
trodes were in aqueous 0.1 M HCl04 electrolyte solution with
0.1 M MeOH. Spectra were obtained, whereas the electrodes
were stepped from an initial potential of -0.25 V vs. SCE, and
the reference spectra were obtained at that potential. (From J
Shin, C Korzeniewski. J Phys Chern 99:3419,1995.)
weakly bonded H (H w ) and for linear and bridged Co. In
agreement with the work of Kunimatsu [58], the satu-
ration coverage by chemisorbed methanol was found to
be only about 70% of the coverage of linearly adsorbed
CO from saturated CO solutions. When stepped from
+ 1.15 V to lower potentials in 0.05 M methanol, the
SHG signal was observed to increase from zero in the
oxidized region by double exponential, corresponding
to formation of linear CO (k j ) and bridged CO (k b ):
stepping to 0.35 V gave k j = 1.15 S-I and k b as 0.029 s-I,
whereas stepping to 0.15 V gave k l = 0.036 S-I and k b as
2.07 s-I.Ifthe Pt is stepped down to -0.03 V, the surface
instantly became covered with terminal and weakly
bonded H, which was then only slowly replaced by CO
(k~0.054 S-I). Finally, if the electrode is now held at
867
0.0 Vand methanol admitted, no change in the SHG is
seen; however, on scanning at 20 mV s-I, the SHG
initially follows that in the methanol-free electrolyte (with
loss of H w ) to 0.25 Vand then increases as CO build-up
takes place.
Ellipsometric studies have been carried out by Frelink
methanol/O.5 M H2S04 solutions, platinum oxide for-
mation is not correlated with the onset of methanol
oxidation nor is the potential at which the Pt-oxide layer
begins to form significantly affected by the presence of
methanol, though on the reverse scan in the Cv, the
reactivation onset does correlate with the point at which
the oxide layer begins to reduce. The main difference in
(,1, 'II) values in the region 0-0.7 V between the pure acid
and methanol/acid solutions is that the small increase in
,1 seen in the pure acid and ascribed to HS0 4 adsorption
is not seen on platinum surfaces covered with CO ads .
13C-NMR studies have been reported by Day et al.
[113], in which the spin-spin lattice relaxation time was
used to characterize CO ads diffusion (see below) and the
spin-lattice relaxation time and Knight shift were used
to establish that the CO ads was primarily present as an
adsorbate end-on at a single type ofsite.
We can conclude this second section by asserting the
following: Chemisorption of methanol gives rise to lin-
ear and bridge bonding CO, the relative proportions
depending on the crystallographic face exposed. The
surface is only covered, however, to a relatively low level
with these adsorbates unless high methanol concen-
trations are used and long equilibration times are
allowed. In general, under normal operating conditions,
at least one additional adsorbate is present, with the bulk
of current evidence favoring =C-OH, particularly at
lower methanol concentrations. There is some evidence
that more than one pathway exists for methanol
oxidation, in addition to oxidation of adsorbed CO, par-
ticularly on Pt(lOO) above 0.5 V. Such a "parallel"
pathway may go through solution or very weakly
adsorbed intermediates, such as HCHO and/or formic
acid, or more probably may go through an adsorbate
such as CO;ds adsorbed on metastable site; evidence
below suggests that one possibility may be a site at the
edge of a CO ads island, because the evidence for forma-
tion of such islands is very strong. It is also clear that
CO ads , at least at the edges of islands, is quite mobile
on the Pt surface, and a great deal of experimental data
can be understood by assuming that over periods of a
few minutes, migration of CO ads can take place on Pt
surfaces to randomize the islands formed on saturation
chemisorption, once partial oxidation of these islands
takes place.
868
III. KINETICS OF OXIDATION OF METHANOL
TO CO 2 ON PLATINUM
We have seen that the process of oxidation of methanol
involves the formation of chemisorbed fragments, pre-
dominantly COads and (probably) =C-OH. At lower
potentials (E < 0.5 V), chemisorption of methanol on a
clean platinum surface is faster than subsequent oxidation
ofthe chemisorbed fragments to CO 2, but all investigators
have reported that a steady state can be established, in
which a small residual current flows. It is less clear what
the rate-limiting step is for this residual current, and inten-
sive studies were first carried out by Bagotzky andVassiliev
[7] to attempt to distinguish the mechanism. For 1 M
methanol/0.05 M H 2S0 4 on smooth polycrystalline
platinum, these authors found a Tafel slope of 55-60 mV
for 0.42 < E < 0.55 V and a slope of 110 mV for
0.55 < E < 0.72 V; however, lower concentrations of
methanol only showed the higher Tafel slope. At higher
potentials, or in more dilute methanol solutions, there
are pronounced deviations fromTafel behavior. Given that
the rate of adsorption of methanol on clean platinum
surfaces shows only a relatively weak dependence on
potential in the double-layer region, whereas the rate of
oxidation of methanol rises strongly, it is found that for
E > ~ 0.65 V, the former will certainly become rate
limiting. Indeed, above 0.8 V methanol oxidation rates
decrease strongly: in fact, if 80 is the coverage of oxide
on platinum, it is possible to show that: i ~ k exp( -IX~),
where IX'! ~ 7.7-8.4. This is consistent with oxygen chemi-
sorption affecting the rate of chemisorption of methanol
rather than any subsequent electrochemical step. If
oxidation of the methanol chemisorbate is rate limiting,
then assuming a Temkin isotherm, we would expect to
see i ~ k exp(fJf8 R ) where 8R is the coverage of the
chemisorbed fragment. We have already seen that as a
consequence of Temkin's isotherm, we expect
8R ~ const. + 1/f Inc and i ~ k ' cfJ , where c is the concen-
tration of methanol. Experimentally, Bagotzky finds
fJ ~ 0.5. Experimentally, it is also found that for 8R con-
stant, i ~ k exp(fJ'FE/RT), giving a general rate equation
i ~ k exp(fJf8 R ) exp(fJ'FE/RT), with fJ' having the value 1
at lower potentials and 0.5 at higher potentials. Now,
oxidation of the chemisorbed fragment can either take
place through
Pt-COads + OH ads ---+ Pt-COOH ---+ products
(13)
or
Pt-CO ads + H 20 ---+
(14)
Pt-COOH + H+ + e- ---+ products
Hamnett
In the first case, the coverage of OH ads will be given
by a Nernstian expression of the form E OH = Eg H+
RT / FIn (aOH . aw /aH,o), giving rise to a value of fJ' ~l.
The second possible rate-limiting step will give rise to a
value of fJ' closer to 0.5. In principle, this could account
for the observed behavior, particularly if there is a limit
to 80H imposed by the structure/morphology of the sur-
face (i.e., if OH ads can only form at a limited number of
active sites at the surface). This basic mechanistic analysis
has been extended by a number of authors. Kauranen et
al. [114] used it to model the behavior of particulate elec-
trodes successfully. Similar kinetic results were also
reported by Inada et al. [115], with these authors reporting
TafelslopesoflOO mVinthe range 0.55 < E < 0.7 V Below
0.55 V, these authors reported substantial time depen-
dency in their results; nonetheless, they report that the
oxidation current actually decreased in the steady state
with coverage below 0.55 V, though it increases, as
expected, above this potential. Inada et al. therefore
accept that reaction between OH ads and Pt-CO ads is rate
limiting for E > 0.55 V but suggest that chemisorption of
methanol may be rate limiting below this potential.
Kinetic analyses were also reported by Christensen et
al. [62], who used the rate ofgeneration ofC02 rather than
the current as a measure of the steady-state reaction
kinetics. In agreement with Inada et al. [1l5], they report
Tafel slopes on smooth platinum of 95 mV at higher
concentrations of methanol with rather poorly defined
Tafel regions for concentrations below 0.25 M. These
authors also explored the consequences of deliberately
roughening the platinum, finding that for higher concen-
trations of methanol, no well-defined Tafel region was
generated. Instead, behavior of the type shown in Fig. 22
was obtained, inwhich the currentbecomes almost poten-
tial independent between 0.4 and 0.55 V For lower con-
centrations of methanol, well defined Tafel slopes were
obtained, even for these roughened surfaces, and the
authors also reported that if the platinum was roughened
in the absence of methanol, and methanol then intro-
duced and current/potential curves obtained, behavior
characteristic of the roughened or smooth surfaces was
found depending on the rapidity with which the exper-
iments were carried out as shown in Fig. 23. Evidently,
cycling the potential in the presence of methanol
stabilized the rough surface, which otherwise would relax
over a period of tens of minutes, and this rough surface
possesses a finite number of active sites. The authors
suggested that diffusion of COads or =C-H ads to these
sites was rate limiting and suggested that such sites could
be low-coordination Pt atoms, possibly with either
OH ads or activated adsorbed H20ads, a suggestion also
made by Burke and Casey [1l6]. Similar conclusions as
Mechanism of Methanol Electro-Oxidation 869

(A) (B)

05
o

:"-::~ -: ~;/!J
o
"1:- 05
.3
C' -I
o
...J

-'5f
-2 l

-,~/
- 3 5 ~------ -.---- _. - -- ----=----::---=-::c---::---=---=--=-=---=-.,,-----"
045 05 0.55 06 0.65 0.7 03 0.35 0.4 045 05 055 06 065 07
ElV(RHEI (a) . E/VIRHE)

- 3. 5~'-=-=----=---,------=~=--"...--;:~__::___=-=----::"'-::-~~~--~
035 0.4 0.45 0 5 0.55 0.6 0.65 0.7
(b) E/V(RHEI

Figure 22 (A) Tafel slopes from CO 2 intensities for a series ofexperiments in which Pt was cycled in MeOH-free solution to clean it,
held at 0.05 V during introduction of varying concentrations of MeOH in 1.0 M H 2 S0 4 , and then the potential stepped to higher
values. Concentrations of MeOH are (a) 2.0 M (+); 1.0 M (x); 0.5 M (D); (b) 0.25 M (+); 0.1 M (x) and 0.05 M ([]). (B) Tafel
slopes acquired for a second set of experiments in which the Pt was cycled in MeOH solution before measurements were taken. The
different methanol concentrations are as in (A). (From PA Christensen, A Hamnett, GLTroughton. J Electroanal Chern 362:207, 1993.)

to the importance of COads diffusion to sites of OHads
adsorption were also reached by Gasteiger et al. [117] in
their consideration of the catalytic activity of adsorbed
Ru on Pt. The diffusion of adsorbed CO on both Pt and
Ru in vacuo is actually quite facile: Diffusion coefficients
oforder 10-9 cm 2 s- 1 have been reported for both metals
[118], and although these will certainly be rather smaller
in electrolyte solution, there is a high probabilityofthe sur-
face mobility playing a substantial role in methanol
oxidation. This conclusion is also strongly supported by
recent 13C-NMR studies by Day et al. [113], who estab-
lished that the spin-spin relaxation time, T2 , for 13C could
be modelled with a simple diffusion model, with an acti-
vation energy of 33 ± 8 kJ mol-I, a result very similar to
earlier data reported for both Pt and Pt-Ru (see below).
The importance ofplatinum surface morphology has also
been emphasised by Pletcher and Solis [119], who showed
that much higher transient currents were observed on
chemisorption of methanol in the double-layer region if
the Pt surface is first rapidly cycled between 0.55 and 1.6 V.
There have been several studies of the activation
energy for methanol oxidation on platinum, though these
have been restricted to polycrystalline or particulate
electrodes. Some caution needs to be taken with regard
to the figures quoted, because the activation energy as
measured is a function of the overpotential, and figures
are only meaningful if compared at the same over-
potential. That said, there is a remarkable consistency,
withvalues of40-45 kJ mol- 1 being commonly reported
[see, for example, 62,120,121]. These activation energies
870
-4
-4.5
01
o extensive islands on Pt(lll) at this adsorption potential.
~
-6f
-6.5~
-7~
I
-75L-- J crystalline platinum [123]. Similar behavior for Pt(111)
0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7
E/V(RHEl
Figure 23 Comparison of Tafel slopes obtained from current
measurements in which the Pt was initially cycled in methanol
free solutions and held at 0.05 Vduring introduction of 2.0 M
MeOH as above with the current measurements being taken
(+) after no delay and (x) after a delay of 45 min between
cycling the electrode and the polarization measurements. (From
PA Christensen, A Hamnett, GL Troughton. J Electroanal
Chern 362:207, 1993.)
usually refer to potentials near 0.7 V, near the
voltammetric peak for methanol oxidation.
The rate of oxidation of chemisorbed intermediate to
C02 has also been studied by potential step measure-
ments and by potentiodynamic methods, both of which
have been discussed above. Kunimatsu [57,58] estab-
lished clearly that on polycrystalline Pt, for 1 M
methanol/0.5 M H 2S04, CO ads coverage on a surface
whose potential had been cycled in the methanol solution
was constant up to 0.5 V and then fell rapidly at more
positive potentials, reaching zero near 0.7 V, a fall
strongly correlated with the observed rise in the CO 2
signal. This was confirmed by Corrigan and Weaver [61]
and Hamnett and coworkers [59,62,99,122]. The obser-
vation of the inverse correlation between the intensities
of the CO ads and CO 2 peaks constitutes important evi-
dence that on polycrystalline platinum, any parallel
pathway contributes relatively little to the overall current
at lower potentials. Similar results were reported by Bae
[110] using SHG. The results for single-crystal surfaces
are less clearcut, being dependent on both coverage and
methanol chemisorption potential. For Pt(111), Furuya
et al. [84] reported that CO ads derived from methanol
chemisorption at 0.05 V behaved in a manner similar to
polycrystalline Pt, but CO ads derived from methanol
chemisorption at 0.6 V was only removed from the sur-
face at potentials in excess of 0.85 V There is a small but
Hamnett
definite increase in 8co on chemisorption at 0.6 Vas com-
pared with 0.05 V, an increase that may be crucial in elim-
inating adsorption sites for water or OHads, thereby
providing a significant kinetic barrier to oxidation. The
mechanism of oxidation of COads also alters: For chemi-
sorption of methanol at 0.6 V, there is no bathochromic
shift with stripping potential, implying that the CO forms
However, for adsorption ofCO at 0.05 V, behavior is more
complex, with the CO ads forming a mixture of islands of
different size, with loss of CO taking place initially from
smaller islands. This behavior was also reported for poly-
and Pt(100) was reported by Chang et al. [124], with
stripping of COads being incomplete even at 0.8 Vat high
(5 M) concentrations of methanol. Again these results
are consistent with kinetic limitations to COads oxidation
if the coverage is large. Some additional insight into this
behavior has also come from electrochemical pulse
measurements carried out by Hampson et al. [125]. These
authors reported that adsorption of 0.1 M methanol in
1 M H2S04 at 450 mV followed by potential stepping into
the potential region 0.65-0.8 V (i.e. just before Pt oxide
formation begins) gave rise to current transients that
could be interpreted as a combination ofa current associ-
ated with growth of hemispherical centers in a
hemispherical diffusion layer [126], for which ig ~ d,
together with a diffusion current id ~ t-( The total cur-
rent for the transient canI be written:
I
1/ iT = 1/ig + 1/id,
whence i/im = 2/(t/t m )', + (t/t m )-, where t m is the time
at which the current reaches a maximum and im is the cur-
rent at that maximum. The fact that Hampson et al.'s
transients fit a mixed nucleation and diffusion equation
is highly suggestive, reinforcing the idea that oxidation
of CO ads requires the creation of nuclei on the surface in
which initial oxidation provides areas of adsorbed water
and OH ads . Note that if the size of the potential steps is
extended into the oxide-formation region, nucleation of
a Pt-O surface within the adsorbate layer, with chemical
reaction taking place at the OHads/COads boundary,
becomes rate determining [127].
It remains to consider whether oxidation of the
adsorbed CO ads or =C-OHads is taking place through
H 20 or OH ads . This has proved a thorny issue, partly
because of the sensitivity of the process to surface
morphology and to the formation conditions of the
adsorbed monolayer itselfbut also because kinetic analy-
sis has given ambiguous answers. In principle, both Tafel
slope and pH dependence should differ for reactions (13)
and (14) above, but whereas Bagotzky and Vassiliev's data
[7] are most naturally interpreted in terms of reaction (14)
above, the current equation derived from the studies of
Mechanism of Methanol Electro-Oxidation
Inada et a!. [115], i ~ kclUe~:lHCH2·6 exp(0.6FE/RT) is more
consistent with a pre-equilibrium process of the type
Pt + H 20 *+ Pt-OH + H+ +e-, for which a Tafel slope
of 60 mVand an inverse dependence on CH+ is expected.
However, Inada et a!.'s results are also not conclusive.
If reactions such as (14) are important, then some
consideration must be given to the details of the reaction.
The original suggestion by Gilman [128] that attack was
by adsorbed water has been the subject of semiempirical
calculation by Shiller and Anderson [129], who found
that the Tafel slope for this reaction would actually have
the wrong sign, because as the potential increases,
H 20 ads becomes much more strongly bound to the
surface; given that in any reasonable transition state, the
water molecule must be prised off the surface by ~I A
to attack the carbon of the COads, the increasingly
unfavorable enthalpy associated with this process
essentially offsets the expected increase in reaction rate
at higher potentials. An alternative is the direct attack
on COads by H 20 in the outer Helmholtz layer [130].
The evidence for this is twofold: There is a weak isotope
effect that would not be expected for attack by OHads
and there is only a small entropy change for the reaction
on platinised platinum, the latter being inconsistent with
the expected large negative entropy associated with the
formation of solvated proton and Pt-OHads. Again,
however, calculation gives rather ambiguous results [129],
though more convincing than attack by adsorbed water.
Attempts to calculate the potential dependence of the
reaction COads + OHads ---+ products [131] led initially to
similar results as for H 20 ads, namely that the increasing
adsorption strength of OH ads at increasing potential
essentially negated the expected increase in rate derived
from increasing coverage. However, the authors were also
able to show that at higher COads coverages, attack by
OH ads became much more facile, a result also presumably
true for reaction (14), though the authors do not comment
on this. At sufficiently high coverage of COads the calcul-
ated activation energy does, in fact, become smaller than
that found experimentally, leading the authors to suppose
that at the highest coverages, the rate-limiting step is
probably the actual formation of OH ads , in agreement
with the ideas above. Further calculations ofPt-OH ads
have been reported recently [132], suggesting that this
species will form preferentially on adsorption at Pt(111)
onefold sites rather than at Pt(100) where the twofold sites
are less stable. The authors suggest that this might
account for some of the differences between oxidation
of COads on the two surfaces, but some caution is needed
here, because there are other kinetic effects operating.
Some help in the resolution of these difficulties has
been provided by isotope measurements. Studies of
871
methanol oxidation below 0.5 V show that neither J3CO
nor =o J3 C-OH formed on the surface from electro-
sorption of J3CH30H exchange on immersion in
12CH30H, even during oxidation of the 12CH30H to
l2C02 [133,134]. Not only does this strongly support the
suggestion above that methanol adsorption leads to
islands ofadsorbed CO [135] but it also suggests, in agree-
ment with Christensen et al. [62], that oxidation to CO2
takes place only at the edges ofthese islands.This may well
be the resolution of the enigma of the parallel reaction
and brings the original suggestion ofLeiva and Giordano
[IS] back into focus: The adsorption of CO undoubtedly
leads to the formation of islands that are stable to
potentials above 0.6 V, potentials well above the point at
which rapid oxidation of solution methanol to C02 is
taking place. This oxidation probably involves the rapid
chemisorption of methanol at higher potentials on the
partially free surface of Pt to give COads that migrates to
the edges of islands to maintain their extension but which
is subsequently oxidized to form CO 2. The COads at the
center ofthe islands thus remains unaffected, at least over
short periods, by the oxidation of methanol, but the
so-called "active intermediate" is a COads molecule at
the edge ofthe island. This argument would not be signifi-
cantly different even if the chemisorbed intermediate
did not become completely dehydrogenated, provided it
was sufficiently mobile to migrate to the edges of
adsorbed CO islands rapidly compared with further
oxidation to form CO2.
The situation with regard to the actual oxidant does,
however, remain unresolved: On smooth platinum it
would appear that either direct attack on COads by water
molecules, presumably at the edges of COads islands, or
attack by OH ads is possible; in the latter case, given that
the coverage ofOHads on Pt is very low at lower potentials,
we must consider two possibilities: Either there is a fast
pre-equilibrium or there are specific surface sites at
which OHads forms with higher probability than that
expected from the Nernst equation. In the latter case, we
must, as pointed out by Christensen and coworkers and
Gasteiger and coworkers, consider diffusion as a possible
rate-limiting process. For either type of reaction,
however, there will be a severe kinetic inhibition at very
high COads coverages, because nucleation of free or
Pt-OH surface must take place before either reaction
can commence.
IV. PLATINUM PROMOTION
From the discussion above, we can say that the mechan-
ism of methanol oxidation on platinum is now fairly well
understood, though it will be apparent that there still
872
remain some uncertainties whose resolution must await
further technique development. However, platinum itself
is not sufficiently active to be useful in commercial
DMFCs, and there has been an intensive search for more
active materials. This search has been illuminated by the
mechanistic analysis given above; in particular, the
realization that the catalyst must be both capable of
chemisorbing methanol and oxidizing the resultant
chemisorbed fragments (the concept of bifunctionality)
has led to the search for materials that might be able to
combine with platinum, with the latter acting to
chemisorb methanol and the promoter then providing
oxygen in some "active" form to facilitate oxidation of
the chemisorbed Co.
The simplest method for enhancing oxidative activity
is to generate more Pt-O species on the platinum surface
by incorporation of metals as alloys that then dissolve to
leave highly reticulated and active surfaces, which are
known to be more active for methanol oxidation [62].
Alloys such as Pt3Cr and Pt3Fe have been shown to be
more active than platinum by virtue of this process [136],
and the same may be true in part for Pt3Sn, though there
is controversy here. The drawback with this method of
promotion is the poor long-term stability ofthe particles.
In addition, improved methods for platinum particle
deposition are important in creating more optimal sur-
face area and surface morphology. The use of more
powerful reducing agents can also improve electrode per-
formance [137].
A second approach has been the use of surface
ad-atoms, deposited by underpotential deposition on
the platinum surface. These have been studied extensively
[138-140], with Au [141] being identified early on, but with
most recent attention being on Sn [142-145] and Bi [145].
Several modes ofoperation have been suggested for these
ad-atoms, including the blocking of hydrogen
adsorption, the ability to modifY the electronic properties
of the platinum, the ability to act as redox centers, the
blocking of poison adsorption sites, or the ability of the
ad-atom to induce Pt-O formation on neighboring sites,
creating additional active sites for oxidation of COacts.
The ability ofboth Sn and Bi ad-atoms to enhance the rate
of methanol oxidation has been queried in a recent paper
[145]; the authors found that under very carefully con-
trolled conditions, the adsorption ofthese metals actually
inhibited methanol oxidation, even though there is good
evidence that Bi adsorption also inhibited formation of
adsorbed CO [146].
A third type of promotion is the use of alloys of plati-
num with different metals, where the second metal forms
a surface oxide in the potential range for methanol
oxidation. This is the basis for studies ofPt-Sn, Pt-Ru,
Hamnett
Pt-Os, Pt-Ir, etc. Unlike the Sn-ad-atom data [145],
there seems little doubt that Pt3Sn as an alloy does show
catalytic behavior [136,143,147,148], though this may
simply derive from the same mechanism as Pt3Cr,
perhaps with the resulting fractal particle surface being
stabilised by tin adsorption. Studies of Pt alloyed with
the other noble metals has shown that Ru has by far the
largest effect, giving a substantial catalytic advantage
[143,149]; the possible mechanisms of this effect are dis-
cussed further below. Ir and Os were also found to act as
promoters in this study [149], with Au and Pd inhibiting
the reaction. Pd was also not found helpful in acid sol-
utions in earlier studies [150]. Among the non-noble
metals, electrodeposited Pt-Re alloys were reported to
show substantial enhancement by Cathro [151], a result
that seems not to have been followed up. Reports of very
strong enhancement for electrodeposited Mo on Pt have
also been reported [152,153], particularly at low currents,
where there seems to be a different oxidation mechanism
operating. Given the effectiveness of binary alloy
formation, particularly with Ru/Pt, attention has turned
recently to ternary alloys. The apparently different
promotion mechanisms for Pt/Sn and Pt/Ru led
Troughton and Hamnett [136] to explore the Pt/Ru/Sn
system, but it was found that alloying Pt/Ru with tin tends
to expel the Ru, leading to no advantage. Ofother ternary
alloys studied, only Pt/Ru/Ga [154] and Pt/Ru/Os [155]
have shown any unequivocal advantages.
The fourth type of promoter to be described in the
literature is a combination of Pt with a base-metal oxide.
Initially, these were reported by Hamnett et al. [156], with
Nb, Zr, and Ta being found most active for Pt promotion,
particularly at higher currents. However, although the
effect on Pt itself is clear, attempts to use Zr02 to pro-
mote Pt/Ru were unsuccessful [157], suggesting that the
original mechanism for promotion by these oxides is
similar to that for Ru itself [158] Hamnett et al. originally
identified W0 3 as an inhibitor, but more recently, Shen
and Tseung [159,160] have identified hydrous W03-x as
a substantial promoter for activity when Pt is
electrodeposited on its surface, and this was confirmed
separately by Shukla et al. [161], who reductively
codeposited Pt and W0 3- x onto a porus carbon
substrate. Related are catalysts formed by doping
tungsten bronzes, of the structure LnO.1W03, with Pt; in
these catalysts, as in the ones reported by Tseung, the W
seems to be providing a redox couple, cycling between
W(IV) or W(V) and W(VI). Interestingly, the enthalpy
of activation is much lower for these catalysts than for
Pt itself [162]. There have also been reports of Pt on
mixed In/Pb oxides on carbon, which showed activity
but poor stability [163].
Mechanism of Methanol Electro-Oxidation
In addition to the electrodeposition or reductive
deposition of Pt onto an oxide surface, it is possible to
incorporate the Pt directly into many oxide structures,
and these species have been examined recently.
Perovskite-based oxides, in particular, SrRuo.sPtO.S03,
were found to give good current densities when used as
electrodes in Nafion-based cells [164], and similar results
were reported for Dy XPt3 0 4 [165]. It is unclear how stable
these oxides are in the longer term in acidic
environments, and reductive decomposition through
methanol adsorption to give finely divided platinum
particles at the surface which act as the main catalytic
sites remains a plausible mechanism.
Although platinum is overwhelmingly the most active
catalyst for electro-oxidation of methanol, the high
loadings necessary for commercial performance have
fueled the search for other materials. There are other
noble-metal catalysts, such as Ir, that have been investi-
gated [166,167], buttheyare all less active than Pt and offer
little in the way ofeconomic advantage.
v. OXIDATION OF METHANOL ON
PLATINUM-RUTHENIUM ELECTRODES
There is now general consensus that the activity of plati-
num for oxidation of methanol can be substantially
enhanced by promotion with ruthenium. Early studies
[168-171] also identified other transition and B-metals
such as Sn, Ti, Re, and Os as promoters, but although
controversy has surrounded these elements, with differ-
ent results reported by different authors being ascribed
to differences in precursor salt concentration, surface
preparation, catalyst deposition protocol, etc. [172,173],
no study has failed to demonstrate the positive effects of
ruthenium. For optimized systems, the effects of Ru are
very marked, as shown in Fig. 24 [149], and OEMS data
show activity some 200 mV more cathodic for Pt:Ru than
for Pt alone [174].
The mechanism of action of Ru was first suggested by
Watanabe and Motoo [171], who postulated a bifunctional
mechanism in which the platinum served as a catalyst
for the chemisorption of methanol and the surface
ruthenium atoms or islands acted as preferential sites
for OH adsorption. As we see below, this mechanism
has some powerful experimental evidence in its support:
It is now well established that at room temperature, meth-
anol does not chemisorb directly onto ruthenium metal
[175], but provided that both Ru and Pt are present at the
surface, it does not seem to matter precisely how the cata-
lyst is formulated, at least some enhancement of activity
will be seen. Methods used include bulk alloys [176-178],
reductive codeposition or electrodeposition of both
873
D.)
UJ 0.2
11l
::[
::[ 0.1
: 0
'0
.:: -D.'
-0.4 D::------!;.,-------~1OO'=---...,.15:'-:D,.---200~---.l25D
Curren"mAmg'
Figure 24 Current (per mg of Pt) vs. potential curves for
methanol oxidation using promoted Pt catalysts dispersed on
carbon in 1 M MeOH/2.5 M H 2 S0 4 at 60°C; (x) Pt/Pd; (+)
PUAu; (.) PUr; (e) PUOs; (T) Pt/Ru; and (.A.) Pt without
promoter. (From A Hamnett and BJ Kennedy. Electrochim
Acta 33:1613, 1988.)
metals [149,168,171,179~184], deposition of Ru on plati-
num particles [171,185,186], thermal decomposition of
chlorides and chloroacids [187], coimpregnation of metal
salts on carbon paper [188], implantation of Ru into Pt
by ion bombardment [189], formation of Raney alloys of
Pt/Ru [169], or spray deposition from organic solvents
[190]. Deposition of the Pt-Ru catalyst by whatever
means is usually followed by an activation step, and these
steps are crucial in ensuring that both platinum and
ruthenium are indeed present at the surface. As shown
by McNicol and Short, for example [173], activating the
Pt/Ru in hydrogen at 300°C gave a poorly active catalyst,
because this treatment favors Pt on the surface, whereas
activation in oxygen gives an active catalyst because this
treatment favors segregation of some ofthe Ru to the sur-
face to form oxides. This result was confirmed by Miura
et al. [191]. The fact that both Ru and Pt are essential on
the surface led to the suggestion that the ideal surface
atomic ratio should be 1:1 Pt:Ru, and this is indeed found
to be the best surface composition for CO electro-
oxidation [192], but for methanol oxidation there is some
controversy as described below. A critical fact to bear in
mind is that it is not possible to extrapolate safely from
bulk to surface composition; indeed, electrochemical
activation itself, which is usually carried out by potential
cycling up to potentials of 1.3-1.5 V, may itself cause
further changes in the Pt: Ru surface ratio due to preferen-
tial dissolution of Ru at and near the anodic limit
[193,194], and attempts to measure the surface area by
the use of the charge passed in the hydrogen region, a
technique that works well for Pt, is much less reliable for
874 Hamnett

Pt-Ru alloys, partly because the CV itself is a strong
function of the surface Pt:Ru ratio. Moreover, although
the bulk phase diagram for Pt/Ru is well known (Fig. 25
[195]), little is yet known of any two-dimensional phase
effects in Pt/Ru alloys. In this regard, a recent study [180]
suggested that alloys prepared by electrodeposition and
analyzed by a variety ofsurface UHVand electrochemical
measurements showed a very asymmetric dependence
of activity for electro-oxidation of CO on mole fraction
of Pt or Ru atoms on the surface. Were the distribution
of Pt and Ru sites statistical, the simple bifunctional
theory would lead to a symmetric activity curve, but there
appears to be a correlation with the bulk phase diagram,
which shows a two-phase system for 0.2 < x(Pt) < 0.4; if
equilibrium between bulk and surface exists, we would
then expect lateral segregation ofPt and Ru at the surface,
giving poor activity; only for XPt > 0.4, when a mixed bulk
face-centered cubic (fcc) phase forms, is there a sudden
increase in activity, corresponding to a statistical distri-
bution of Pt and Ru at the surface.
Studies on well-characterized Pt-Ru alloys have
provided important mechanistic evidence for the role of
Ru in methanol oxidation. The early paper of Watanabe
and Motoo [171] established that forunderpotential depo-
sition ofRu on Pt, where the Ru atoms do appear to be dis-
tributed statistically, oxidation of 1 M methanol/0.5 M
H2S04 showed a current density at 0.5 V that did fit the
expected parabolic curve with a maximum close to
2500, i i i i i i
,2314·C
..
2250 ............... "
• • • p,,"" .. .o.o ~ ~
: •... e.
o • ".
IT 2000
8Ru = 0.5. The origin of the parabolic dependence was
explained by the authors in terms of simple
Bragg- Williams theory: The average number of AB
pairs, nAB, on a surface of NL lattice points and Z nearest
neighbors is nAB = N L Z(28 A 8B + 28~S2)/2, where Sis
an order parameter. For S small, this equation predicts a
parabolic dependence of ion 8 (since 8A = 1 - 8 B ). As
expected, in the presence of Ru on the surface, the cover-
age oforganic species decreased markedly, again in agree-
ment with the bifunctional theory, as shown in Fig. 26,
and the limiting current also showed a substantial and lin-
ear decrease for 8Ru > 0.5. The results of this study were
challenged by Gasteiger et al. [196-198], who prepared a
series of well-characterized surfaces in which alloys of
well-defined bulk composition were sputter cleaned in
UHY, with the sputtered and annealed surfaces character-
ized by auger electron spectroscopy and low-energy ion
scattering. Following this, they were transferred under
potential control to the electrolyte (0.5 M H 2S04 with
either 0.5 M or 0.005 M methanol) and the potential was
constrained to lie below 0.75 Vat all times. The relation-
ship between bulk and surface composition was linear
for the sputtered surfaces, but on annealing in UHY,
strong Pt enrichment took place. The authors carried out
cyclic voltammetric evaluation of their sputtered
unannealed electrodes and found that for these electrodes
the most active surface composition for methanol
oxidation had a surface atomic ratio ofPt:Ru of9:l, a fig-
urevery different from that found earlier. Ofcourse, cyclic
voltammetry will not yield any easily interpretable data
i i ' , about the long-term steady-state activity of the
electrocatalysts, and indeed the authors find a significant
increase of the relative activity of more ruthenium-rich
surfaces at higher methanol concentrations and longer
times, though the 9:1 surface is always more active in
absolute terms than either pure platinum or a 1:1 Pt:Ru

-
•
QJ
surface. The authors explain their data in terms ofa simple
statistical model, which assumes no surface aggregation
.aeu 1750 of Pt or Ru and which takes into account the important
fact that methanol actually needs at least three adjacent
8-E 1500 Pt sites to able chemisorb at all. It follows that surfaces
.!! hcp with relatively low Ru:Pt ratios will certainly favor
chemisorption: Each threefold site is surrounded on a
1250 hexagonally packed surface by nine sites, only one of
which should be Ru, because this will optimize the rate
of both chemisorption and oxidation ofthe resultant CO
1000 i I I I II I ! I ! i I
or =C~OH fragment. Using simple binomial prob-
o 20 40 60 80 100 abilities, the probability offorming a threefold Pt3 site is
at% platinum in the bulk clearly ~X~t, and the probability of such a site having one
Ru neighbor and eight Pt neighbors is ~ 9XRu4t. The
Figure 25 Phase diagram of Pt/Ru. (From JM Hutchinson. overall probability is then the product of these two
Plat Met Rev 16:88, 1972.) expressions: P tot ~ 9XRuxM ~ 9XRu(l - XRu)11 . Even if

l
Mechanism of Methanol Electro-Oxidation 875

0.5
50

-
<s:
E
0.1
~ ~
E
1.0
~~

0.5

_1
0 0.5 ID 0 0.5 1.0
(a)
(b)
9R1.! eRu

1.0/

0.5

oL-.-----JI-I-...J.----.......
o 0.5 1.0
(c) ~
.....HU

Figure 26 (a) Correlation between activity at 0.5 V and ORu (0) Ru deposited at 0.05 V; (.) Ru deposited atO.20 V (b) Dependence
oflimiting current on ORu: symbols as in (a). (c) Dependence ofcoverage oforganic chemisorbate on ORu at 0.5 V in I M MeOH/0.5 M
H 2S0 4 : symbols as in (a). (From M Watanabe, S Motoo. J Electroanal Chern 60:267, 1975.)

we calculate the total probability of a threefold platinum
site having at least one neighboring Ru, so that
P tot = X~t(l - 4t), the maximum value of Ptot would be
found for XRu ~ 0.15, corresponding to a optimal surface
Pt:Ru ratio of more than 5:1. Additional support for this
idea comes from the observations that for oxidation of
both formic acid and CO, where chemisorption requires
only a single Pt site, the optimal surface composition
for electro-oxidation is 1:1 Pt:Ru [197] as would be
expected.
Further insight into the optimal Pt:Ru surface atomic
ratio has been provided by some very recent data on Ru
electrodeposited onto the three low-index surfaces of Pt
[199]. Theses authors found that the optimal Pt:Ru ratio
varied between surfaces, being 5:1 on Pt(lll), 3:1 on
Pt(IOO), and 7:1 on Pt(llO), with the Pt(lll):Ru surface
876
showing by far the largest activity at low potentials. All
optimized surfaces showed Tafel slopes of60 mVat lower
potentials, but the Pt(lll) surface showed a transition to
200 mVabove OJ Vand a marked reduction in activation
energy. This is strongly reminiscent of the data reported
by Christensen et al. [62] and may again signal a
transition from rate limitation due to inactivity of
oxidation sites to one associated with diffusion of
adsorbed intermediate.
The puzzling discrepancy between these results and
earlier data was initially addressed by assuming that the
various pretreatments of the Pt-Ru catalysts in earlier
papers had actually led to severe Ru depletion at the sur-
face and that a nominally 1:1 composition would corre-
spond to a much lower surface fraction of Ru. However,
in a later paper [198], a substantial shift in the relative
activities of the various surfaces was observed with
increasing temperature, and at 60°C, the temperature at
which many literature measurements of catalyst activity
have been made, a surface composition of ~2:1 Pt:Ru
was found to be the most active. Not only does the activity
of the Pt/Ru alloys for methanol oxidation strongly
increase with temperature [see, for example 200], but
there is a marked cathodic shift in onset potential for
methanol oxidation, which correlates with the observed
cathodic shift in the onset of Ru-OHads formation at
higher temperatures [201]. Moreover, pure ruthenium
itself shows appreciable activity for methanol oxidation
at 60°C, whereas at room temperature its activity is
minimal, implying that the chemisorption of methanol
on Ru is highly activated. If chemisorption does take
place on Ru, then the need for threefold Pt sites is much
reduced, and the optimal surface coverage should
approach 1:1 Pt:Ru, an effect actually observed, at least
at higher methanol concentrations [198]. Interestingly,
the activation energy for the Pt:Ru 2:1 surface at 0.4 V
was measured to be 60 kJ mol-I, in contrast to the value
ofonly 30 kJ mol- 1 for the 7% Ru surface alloy. This very
low value is actually consistent with the activation energy
for CO ads diffusion on Pt and Ru substrates [202-204],
whereas the higher values reported for higher Ru surface
coverages are consistent with the activation energy for
Ru--OH ads formation.
The evidence that Ru does indeed form chemisorbed
oxide or OHads species at significantly lower potentials
than platinum is very strong. Electrochemical evidence
suggests that M-OHads species form at a potential at
least 0.3 Vmore cathodic for M = Ru than for M = Pt, as
is evident from the CV (which shows that the hydride and
oxide regions overlap, with no double-layer region
between them) [177,196,205], and Herrero eta!. [206] have
reported that a redox couple for Ru adsorbed on Pt(lIO),
Hamnett
which appears to correspond to transformations involv-
ing suboxides ofRu, does correlate with activity for meth-
anol oxidation. X-ray photoelectron spectroscopy (XPS)
evidence also strongly supports the formation of add-
itional oxy-species, with a spillover effect apparent at
higher potentials [149] for samples transferred in air from
the electrochemical cell to the XPE spectrometer.
Ellipsometric measurements [1ll,1l2,207] confirm that
oxidation ofRu on the surface ofa Pt:Ru electrode com-
mences at much lower potentials than oxidation of Pt;
interestingly, these data also suggest that in the presence
ofmethanol, the Ru-OH ads coverage is reduced at lower
potentials during the first anodic potentiodynamic sweep, r
which is consistent with the bifunctional mechanism.
Herrero et al. [206] suggest that the Ru oxide is not RU02
but a suboxide. However, this interpretation is not consist-
ent with EQCM data [208] nor is it consistent with 99Ru
Moessbauer and XPS data [209], all ofwhich point to the
existence of a Ru(IV) hydrous oxide phase as the main
catalytic promoter, at least for samples examined in air.
It is, of course, true that all these observations can be
rationalized by assuming that at the potentials at which
methanol is oxidized the stable oxide is indeed one with a
Ru oxidation state ofless than 4, and this would certainly
be highly plausible for a hydrous oxide, where reduction
could be easily accommodated by proton ingress in a
manner similar to that found in manganese battery
oxides. In support of these ideas is the fact that 99Ru
Moessbauer studies also showed that Pt:Ru electrodes
decayed with time, particularly if they were polarized to
high potential for long periods [210], a decay that was
traced to the formation of the anhydrous RU02 on the Pt
surface, this oxide being inactive in platinum promotion.
Spectroscopic studies of Pt--Ru have been fewer in
number than for Pt itself. Iwasita et al. [176] have reported
in situ FTIR studies on a polished 85:15 Pt:Ru (bulk
composition) alloy. Only one signal corresponding to
COads was seen, and this signal was considerably weaker
at all potentials. In addition, after correcting for coverage,
the signal was shifted to higher frequency on the alloy
surface, as shown in Fig. 27, suggesting that there was a
distinct electronic effect associated with Ru in the bulk
alloy. This result is not in accord with data obtained by
Ianiello et al. [211] for direct adsorption ofCO onto Pt:Ru
alloys, where a decrease in frequency of 15-30 cm- 1
was reported, but they have been confirmed by more
recent results on a Pt electrode on which Ru was
electrodeposited to a coverage of 0.10 [208]. These latter
authors suggest that the differences between these results
actually reflect different ways in which coverage has been
estimated; if coverage is estimated from area under the
CO IR peak, all the data are consistent with a general
Mechanism of Methanol Electro-Oxidation 877

increase in frequency of CO on the Pt:Ru surface. [212], who showed that for both pure Pt and a bulk
Moreover, the basic conclusions from Iwasita's measure- Pt:lO%Ru alloy that has been chemically cleaned, a
ments were confirmed and extended by Markovic et al. single potential sweep from 0.06 V, at which the electrode
is initially contacted with 0.1 M HCI0 4 /O.05 M MeOH,
shows a peak in current at 0.25 V for the former and
"7
~0.15 V for the latter electrode, corresponding, as above,
e to the oxidative chemisorption of methanol to form pre-
~ 2050

..
~
.Q
dominantly CO ads in both cases. The observation of a
cathodic shift in the position of the current maximum in
e::J
..
a
c:
>
the first potential sweep on addition of Ru has also been
made by Krausa and Vielstich [213] for coelectro-
~ 2000 deposited Pt:Ru electrodes, and Markovic et al. [212]
were also able to show that the coverage of COads was
25 SO 7.5 rather smaller on the IO%Ru alloy than on pure Pt, in
Band intensity. 10 4
agreement with earlier radiochemical studies [175]. The
peak in the COads coverage was at ~0.5 V for pure Pt
Figure 27 Wave number of absorption of linear COads at
and ~0.45 V for the 10% alloy, with a bell-shaped curve
0.4 Vas a function of band intensity for CO adsorbed on (0)
Pt and (e) 85:15 Pt:Ru alloy from 1 M MeOH/l M HCI0 4 . of eco vs. potential in both cases as shown in Fig. 28.
Adsorption potentials were varied between 0.2 and 0.6 V and The observed shift in the current maximum on addition
the reference spectrum was taken at 0.05 V. (From T Iwasita, of Ru is not easy to explain, as Krausa and Vielstich have
FC Nart,W Vielstich. Ber Buns Phys Chern 94:1030,1990.) pointed out: Ifthe role of the Ru were purely to provide

N
...... a) b)
a) Pt
eu N~

eu
~ j 0
c
'2cu 0
...t:
"0 'a
lU
0
"0 0 E/V 0.4
cu
t: --t:cu
a t: 150
0 EIV 0.4 }150 ='
u 1
0 --'-- o-
r- - r- -
• • 0.5 f- ~ -
0.5 • •
• 0 ,4
0 ~
u • • U '4
,
<I> • •
<!)
. .;.....
,
~

0 •
•
- • 0 ....
~ ........-.
(A) 0 0.5 (B) 0 0.5 0 0.5
E/V EN EN

Figure 28 (A) CVofsputtercleanedPtin 0.1 M HCI0 4 /O.05 M MeOH at 2 mV S-I ( ....) without methanol; (--) 1st sweep; (_._._)
2nd sweep and coverages of CO from SPAIRS measurements. The electrode was contacted with MeOH initially at 0.06 V, and the inset
provides a magnification of the hydride region. (B) Similar for sputter cleaned (a) 90:10 Pt:Ru; (b) 50:50 Pt:Ru. (From N Markovic,
HAGasteiger, PN Ross, X Jiang, I Villegas, MJ Weaver. Electrochim Acta 40:91,1995.)
878 Hamnett

nucleation sites for OH ads formation, the position of the
peak in the chemisorption process should, if anything,
shift in an anodic direction, at least at room temperature.
That it does not may have two possible explanations:
The lower coverage by eOads may reflect the fact that only
the more stable eOads sites only are occupied, thus
shifting the peak by removing part or all of the
high-potential structure, or it may reflect a true synergic
effect of Ru on Pt, with eO ads being stabilized on alloy
surfaces. The latter is more in accord with the
spectroscopic evidence and may well be an important
key to understanding the remarkable promotional power
of ruthenium.
Very different behavior was seen for a 1:1 alloy:
although a peak is still seen in the first sweep, near 0.2 V,
no eO ads is seen in the IR at or near this potential; there
is a small coverage of eO ads above OJ V, but the coverage
remains below 0.1 (Fig. 28). No e0 2 is seen in the IR
below 0.3 V, and the inescapable conclusion is that the
much lower coverage of chemisorbed intermediate on
the 1: 1Pt: Ru alloy has led to the predominant formation
of multiply bonded species, such as =e-OH. This adds
considerable support to the idea that at higher Ru
coverages and near room temperature, adsorption of
methanol on alloy surfaces becomes strongly inhibited.
Further confirmation of the basic observation that
adsorbed intermediates are present in much smaller
coverages on Pt:Ru has also been given by Ley et al. [155]
for chemically reduced and deposited high-surface-area
electrodes. These authors obtained in situ spectra from a
working fuel cell and found that not only was the coverage
by linearly bonded eO ads smaller on 1:1 Pt:Ru, but that
no multiply bonded eo species were found on the latter.
However, they did report two separate peaks in the
eO ads region on Pt:Ru at 90o e, at 2078 and 2025 cm- I .
This result is similar to that reported by Friedrich et al.
[29] for in situ studies ofeo oxidation on Pt(lll) surfaces
with electrodeposited Ru (XRu,s ~ 0.5). Electrodeposition
0.05 V but that coverage is always much smaller than on
pure Pt particles of similar size. As indicated above, the
IR results for Pt particles suggest considerable mobility
for adsorbed eo, and the results for Pt:Ru particles show
similar behavior, with loss of eOads at 2044 cm- 1 and
gain of a very small peak at 2003 cm- 1 , both of which
values are lower than those found for pure Pt, but where
this decrease can be understood in terms of the much
lower coverages. The catalyst particles themselves in this
experiment were obtained from E-TEK Ltd., and char-
acterization [215,216] has shown that there are predomi-
nantly single nanocrystals, with diameters in the range
2.0-2.5 nm, and all are solid solutions ofPt:Ru with com-
positions showing little variation from the nominal. They
appear to have cubo-octahedral shape, exhibiting {200}
and {lll} facets, with {]]3} facets also being observed.
Munk et al. [214] suggest that the loss in eO ads at
2044 cm- I , which is seen to occur before there is signifi-
cant gain of e02 (Fig. 29), may be caused by migration
of eO ads from Pt terraces to step sites at which Ru atoms
have congregated; further oxidation at these sites then
leads to e02 formation.
liR/R x1000
01 1 \ I
-1 ~~~-vV''V'---'\r-IV'\.~""""",..roJV'"'W~~~~~~
-3
·4
I 400 mV
-5
-6
-7
-8

appears to give rise to islands of Ru on the Pt surface, as -9

evidenced by STM measurements, and two linear eOads -10

peaks are seen at 2065 and 2003 cm -I at 0.08 Vand 2076
·11
and 2021 cm- I at 0,48 V. In addition, these authors also
report a small signal at 1780 cm- I at 0.08 V and -12

1801 cm- 1 at 0,48 V, though this latter is much smaller ·13 H ! I I ! I I I

2600 2400 2200 20UU 18UU 1BUU 1400

than the multiply bonded eo seen on pure Pt. The
authors assign the peak at 2003/2021 cm- I to eo
adsorbed on Ru; given that Ley's work was carried out
at a high enough temperature for methanol to chemisorb
on Ru, this would seem to be consistent. IR measure-
ments have also been carried out on Pt:Ru particulate
electrodes [214]; these authors observe that methanol
can chemisorb on these electrodes at potentials as low as
Wavenumberslcm-'
Figure 29 FTIR spectra collected at 0.2, 0.3, and 0.4 Vduring
an experiment in which the potential of the e1ectrocatalyst
immersed in 1.0 M MeOH/1.0 M H2S04 was increased from
the reference potential of0.05 Yin 50-mV steps. (From J Munk,
PA Christensen, A Hamnett, E Skou. J E1ectroanal Chern
401:215,1996.)

...
Mechanism of Methanol Electro-Oxidation
VI. CONCLUSIONS
There does now seem to be consensus about the following
aspects of the methanol oxidation reaction on Pt and
Pt:Ru electrodes:
1. Methanol strongly dissociatively chemisorbs on plati-
num surfaces, but the extent of adsorption depends
critically on the surface morphology, the crystal face
exposed, and the presence ofother anions in solution
that themselves can competitively coadsorb.
2. Adsorption on a clean surface shows a strong kinetic
isotope effect, implying that the initial chemisorption
process involves C-H bond scission. Adsorption
appears to be facilitated by the presence of step-edge
sites, because adsorbed intermediates are seen at
low potentials on both polycrystalline Pt and on
high-index Pt(335) surfaces.
3. The final products ofchemisorption of methanol are
=C-OH and singly and multiply bonded CO ads ,
the relative proportions being dependent on the
methanol concentration, adsorption time, and the
nature ofthe anion. Long adsorption times, concen-
trated methanol solutions, and coadsorbed anions
favor linearly bonded COads , whereas short adsorp-
tion times and low methanol concentrations favor
multiply bonded species. The spatial distribution of
the CO ads can also change with time, with stable
islands forming over long times. Only the CO mol-
ecules adsorbed at the edges of these islands appear
to be electroactive at lower potentials. On surfaces
possessing step-edge sites, such as polycrystalline
Pt and Pt(335), CO ads species adsorb both on the
terraces and on the step sites can clearly be dis-
tinguished.
4. Below ~0.45 V the chemisorbed intermediates
formed on methanol adsorption are stable on any
smooth platinum surface, with the steady-state cur-
rent for methanol oxidation being extremely small.
Above this potential, oxidation of methanol takes
place at a rate that increases exponentially with
potential, with the product being primarily CO 2• In
addition, above potentials of approximately 0.6 V,
the surface is steadily stripped of adsorbed
carbon-containing species, with the loss of such
species being complete near 0.8 V It would seem
likely on most surfaces that it is oxidation of COads
or =C-OH in a sequential reaction pathway that
leads to CO2, but more active intermediates, such as
CO adsorbed at less stable sites, such as those at the
edges of the COads islands, are implicated as
intermediates at lower and intermediate potentials.
879
5. The CO ads islands are electroinactive save at the
periphery, where attack by water or OH ads is possible.
The size of these islands remains uncertain, and
clearly where they are small, as on platinum particles,
or less tightly packed, as on Pt(lOO), movement of
CO ads and relaxation ofthe surface structure can take
place even at high coverage.
6. Platinum itselfcan be made more active in a number
of ways, including surface roughening, but the most
successful electrodes for methanol oxidation are
those in which a second metal is added as a promoter.
On roughened platinum, migration of CO ads species
to active sites, such as low-coordination Pt* atoms
may become rate limiting.
7. The most active promoter is ruthenium, and this
appears to be effective in two ways. Ru promotes
adsorption ofmethanol at lower potentials by provid-
ing a number of more kinetically facile sites for
chemisorption, though the extent of chemisorption
of methanol decreases with increasing Ru coverage
at the surface: This is an electronic effect. Second,
Ru can be oxidized at far lower potentials than Pt
itself, and the Ru-OHads species that form can pro-
mote oxidation of chemisorbed fragments to CO 2 : a
bifunctional model. It would appear that both of
these effects are needed to explain the remarkable
activity of Ru as a promoter.
8. On surfaces of Pt:Ru alloy catalysts containing only
relatively low Ru coverages, migration of CO ads to
Ru-OH ads sites appears to be rate limiting, but at
higher Ru coverages, the oxidation of the COads
becomes limiting. The optimal Ru:Pt ratio remains
controversial, particularly at room temperature.
However, for high methanol concentration and
higher temperatures, approximately equal surface
coverages of Pt and Ru seem to be the most active.
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