Electroanalyttcal Chemtstry and Interfacial Electrochemistry, 54 (1974) 25-38 25

© Elsevier Sequoia S.A.,Lausanne - Printed m The Netherlands

UNDERPOTENTIAL DEPOSITION OF METALS AND WORK F U N C T I O N

DIFFERENCES

D. M KOLB, M. PRZASNYSKI and H. GERISCHER

Frttz-Haber Institut der Max-Planck-Gesellschaft, Berhn-Dahlem (G.F.R )
(Received3rd March 1974)

INTRODUCTION

The deposition of a monolayer amount of metal atoms onto a foreign metal

electrode at potentials positive with respect to the reversible Nernst potential has
been recognized long ago 1'2. Since then this effect, termed as underpotential
deposition, has been studied intensively by means of electrochemical 3-21, radioactive
tracer 2z-25 and optical 26-a° methods. Many experimental data have been collected,
concerning the deposition potentials of the bulk phase and the monolayer (see
refs. in Table 1), the total amount of charge of the adsorbed monolayer 5'13-15'31,
the partial ionic character of the adatoms 32-37, the adsorption isotherm 38, the
influence of coadsorption a9-41, and many more. Until now, however, no physical
model has been offered to explain this effect. In the present study, we have
investigated the underpotential deposition of 22 couples; many of them were
reported already in the literature, but the experiments were performed under more
complicated conditions, e.g., in solutions containing chloride ions. Then, all available
data were used to establish a correlation between the difference in deposition
potentials of the bulk phase and the monolayer and another physical quantity
pertinent to the system. An explanation of the underpotential deposition is given,
which stresses the fact, that this phenomenon is a general one, if the necessary
conditions are fulfilled; it is even found at the solid-vacuum interface. A letter
explaining the physical meaning of this phenomenon in general terms has been
published recently42.

EXPERIMENTAL

Experiments were performed to establish cyclic current-potential curves.

The experimental arrangement included standard equipment like a solid-state
potentiostat, sweep generator and XY recorder. The electrolytic cell had a fritted
side compartment for the Pt counter electrode and a side compartment for the
reference electrode, separated by a Teflon stop-cock. All potentials are measured
and cited with respect to the saturated calomel electrode (SCE). The working
electrodes were discs of Pt, Au, Ag and Cu, 8 mm in diameter and 0.5 mm thick
and embedded in a Teflon rod. Before the measurements these electrodes were
pohshed with diamond pastes of various grain sizes, the smallest of them being
0.7 pm, until the surfaces appeared bright and highly reflecting. The supporting
26 D M KOLB, M. PRZASNYSKI, H. GERISCHER

electrolytes, aqueous solutions of NaC104, N a 2 S O 4, H 2 5 0 4 and HC104, and

LiC10 4 m acetonitrile and propylene carbonate, and the stock solutions of the
metal ions, l0 -2 M AgNO3, Cu(NO3)2, Pb(NO3)2, CdSO4, TINO3 and Hg(NO3)2
were prepared from reagent grade chemicals without further purification. For
measurements in acetonitrile and propylene carbonate, spectroscopically pure
solvents were used. In the latter case, the solutions were pre-electrolysed for several
hours to get rid of spurious amounts of water. The solutions were deaerated by
bubbling with purified nitrogen, which also accomplished stirring.

RESULTS

In Figs. 1-5 the anodic sweeps of the cyclic current-potential curves are
shown for some of the studied systems. The metal-ion concentration was usually
2 x 10 -4 M, except for the case of lithium, which was deposited directly from
the 1 M LiCIO4 supporting electrolyte in acetonitrile or propylene carbonate.
The current densities given in the figures refer to the geometrical electrode area,
without taking any roughness factor into account. Capacity measurements indicate
a roughness factor of about 2 for all electrodes. The large stripping peak at more
negative potentials is due to oxidative desorption of the bulk deposit, the smaller
peak at positive potentials arises from the monolayer desorption.
Some curves show a minor third peak between the other two peaks (e.g.
see TI on Au around - 4 5 0 mV and Pb on Au at - 2 6 0 mV). The charge, however,

80--
I

aJ Cd onAg
' f
]

d)Cu onAu
I

I~_ i

8O

40

0
I / 0

!
80
1"4
~b) Pb on Ag
1
~,~oo.o ~- 8O
E E
.~4o ~.o
..~
i
0

80 20
l clTI on Ag f ) TI on Au

10

0
, I i I , f , I t
-I 0 -0 5 0 -0 5 0 ÷0
UScE/V
Fxg. 1 Anodlc stripping curves for various metal deposits on Ag and A u m 1 M Na2SO4 (pH 3)
(curves a and c) and 1 M NaC104 (pH 3) (curves b, d, e and f). [ M e + I = 2 x 10 -4 M Scan rate=20 mV
s-1 The arrows indicate the peak potentials for bulk and monolayer stripping.
METAL MONOLAYERS 27

c o n n e c t e d w i t h this third peak, is m u c h less than that of the m o r e a n o d i c m o n o l a y e r

p e a k a n d therefore we a s s u m e that o n l y a m i n o r c h a n g e in c o v e r a g e is c o n n e c t e d
w i t h the third peak.

250 ' I ' [ ' I

I ' I r I I ' I 2a

80

I Cd o n C u
--

_
T[ o n C u
--

_
~ 150
'~
Li on Au
-

50

_ 0

-10 -05 0 -10 -05 0 -30 -20 -10 0

U seE/V UscE/V

Fig. 2 Ano&c stripping curves of Cd and T1 deposits on Cu in I M NazSO 4 [ C d 2 + ] = 5 × 10-'* M

[ T l + ] = 1 × 10 -3 M. Scan r a t e = 2 0 mV s -1.

Fig 3 Anodic stripping curve for L1 on Au m acetomtnle (1 M L1C104) Scan r a t e = 1 0 0 mV s -1

300 I -- ' I

L, on Ag
~E200
<[

,oo
0--
r I , I J I
---3 ( -20 -10 0
UscE/V
Fig 4 Ano&c stripping curve for L1 on Ag m acetomtnle (1 M L1C10,) Scan r a t e = 1 0 0 mV s - l .

300 ~ l I ' I '

l LI o n C u
200

< 100

0
, 1 I J j
-30 -2 0 -10
UscE / V
Fig 5. Anodlc strlppmg curve for L1 on Cu in propylene carbonate (1 M LxCIO4) Scan rate = 100 mV s - 1.
28 D M. KOLB, M. PRZASNYSKI, H. GERISCHER

TABLE 1

DATA FOR UNDERPOTENTIAL SHIFT AUp AND HALF WIDTH 3 OF THE MONOLAYER
STRIPPING PEAK
x. results of this work.

Substrate/metal i o n s Supportm9electrolyte A Up/V 6/V References

Pt/Ag + 05 M H 2 S O 4 0.435 0 25 x (15)

Pt/Cu 2+ 05 M H 2 S O 4 041 0.31 x (16,18)
Pt/Hg 2+ 0.5 M H2SO 4 0.47 0 14 x (20)
Pt/Sn 2+ 0 1M H+ ~ 0 53 -- 34
Pt/B13+ 0.12 M HC104 0 49 -- 21

Au/Ag + 0.5 M H 2 S O 4 0.505 -- x (10)

A u / C u 2+ 05 M N a 2 S O 4 (pH 3) 0.215 0.11 x(12)
Au/Cd 2+ 05 M Na2SO * (pH 3) 0 505 0.17 x
Au/T1 + 0.5 M Na2SO4 (pH 3) 0.685 0 19 x
Au/Pb 2+ 1 M NaClO 4 (pH 3) 0.40 0 12 x (8,29,61)
Au/Hg 2+ 0 5 M H2SO 4 043 0.16 x
Au/B13 + 0 1 M HC104 025 -- 19

A g / C u 2+ 0 5 M H2SO 4 _ _ L X

Ag/Cd 2+ 1 M N a 2 S O 4 (pH 3) 0 16 0 16 x
Ag/TI + 1 M Na2SO, (pH 3) 0.27 s 0 08 x
Ag/Pb 2+ 1 M NaCIO4 (pH 3) 0.16 0.05 x
Ag/B13 + 05 M HCIO4 0.065 -- 5

C u / C d 2+ 1 M Na2SO4 0 225 0.14 x

Cu/T1 + 1 M Na2SO 4 0 335 0.08 x

B1/Sn2 + 05 M NH,C104+0 5 M HC10 4

BI/Cd 2+ 0.5 M NH4C104+0.5 M HC104 m

Sn/Cd 2 + 05 M NH4CIO4+0.5 M HCIO4

Sn/T1 + 05 M NH4C104+0 5 M HC10 4
Pb/Cd 2+ 0.5 M NH4C104+0.5 M HC104

Pt/Ag + 1M L1CTO4 (acetomtnle) 0.44s 0.86 x

Au/Ag + 1M L1C104 (acetonltrlle) 0.55 0 52 x
Au/L1 + 1M L1CIO4 (acetomtrde) 1 23 0.53 x
Ag/L1 + 1M L1C104 (acetonltrde) 0 96 -- X
Ag/Li + 1M L1C104 (propylene carbonate) 1 00 0 30 x
Cu/LI + 1M L1C104 (propylene carbonate) 1.05 "0.35 x

Pt/LI + 2 x 10-2 M LI + (propylene carbonate) 1 30 0.50 49

Pt/Na + 1 x 10 -2 M Na + (propylene carbonate) ~ 1.1 0.27 49
Pt/K + 2 x 10-2 M K ÷ (propylene carbonate) ~ 1.3 -- 49
Pt/Cs + 2 x 10 -3 M Cs ÷ (propylene carbonate) ~1.7 0 26 49

Since our aim was the quantitative description of the underpotential

d e p o s i t i o n , two characteristic p o t e n t i a l values h a d to be c h o s e n to r e p r e s e n t the
energetic differences between bulk and monolayer deposition or stripping. An obvious
choice seems the use of the p e a k p o t e n t i a l s for the stripping processes (as i n d i c a t e d
by arrows in Fig. 1), the difference of which is independent of the concentration
of the metal ion. The pronounced current maximum at a peak potential Up for the
METAL MONOLAYERS 29

monolayer stripping process indicates, that most of the adsorbed atoms are deposited
around this potential with the least variation in adsorption energy as a function
of coverage. This peak potential Up therefore seems most suitable for the characteri-
zation properties of the adatoms, while for the bulk deposit the stripping peak
potential is within some 10 mV the same as the reversible Nernst potential. The
underpotential shift AUp can be understood as representing the difference in the
bond energies between the metal adatom on a foreign substrate and on.the metal
itself. In Tables 1 and 2 all available data on the underpotential deposition concerning
the potential difference AUp between bulk and monolayer stripping peaks are.
collected with the appropriate references. Furthermore, as a characteristic quantity
for the monolayer adsorption isotherm, the half width 6 of the monolayer stripping
peak is also given in Table 1, whenever possible. The collected data are divided
into two parts, namely CI- free and C1- containing solutions; the influence of C1-
coadsorption will be discussed at the end.

TABLE2

D A T A F O R U N D E R P O T E N T I A L S H I F T AU~pl- IN C I - C O N T A I N I N G E L E C T R O L Y T E S A N D
D I F F E R E N C E tSU~pI B E T W E E N M O N O L A Y E R S T R I P P I N G P E A K P O T E N T I A L S I N C1-
C O N T A I N I N G A N D C1- F R E E S O L U T I O N S
x' results of this work

Substrate/metal i o n s Supportingelectrolyte A UCl-/V 6 UCt-/V References

Pt/Cu 2÷ 0 1 M HC1 0 24s -0.17 25

Pt/Pb 2÷ 0 5 M NaC1 0.65 -- 9

Pt/B13÷ 0.1 M HCI 0.56 +O.O7 60

Au/Ag + 0 5 M H 2 S O 4 + 10 -a M NaCI 0.59 + 0 09 10

Au/T1 + 0.5 M KC1 0.46 - 0 22 5
A u / P b 2÷ 1 M NaCIO4 (pH 3)+0.2 M KC1 0.33 -0.07 x (61)

Ag/Pb 2÷ 0.5 M KC1 0 12 -0.04 x(5,7)

Ag/T1 ÷ 0.5 M KC1 0.185 -0.09 5 (59)
Ag/Cd 2÷ 0.5 M NaC1 0.19 +0.03 11

Cu/T1 ÷ 0 5 M KCI 0.20 --0.13 5

C u / P b 2÷ 0.5 M KC1 0.13 -- 5

DISCUSSION

The basic information we have obtained from the experiment is, that the
chemical potential of the first monolayer*, Pad, is markedly different from that of
the bulk film metal, /~e~. The chemical potentials of bulk phase and monolayer
can be obtained from the equilibrium conditions for the reactions,
Memo+iv+ Zemet~l ~--- Memet~l (la)

* In the following we term the adsorbed layer as monolayer, as long as 0 < 1. D u e to the
logarithmic potential dependence of 0 in the monolayer isotherm 0 = 1 is not reached before the bulk
deposition potential
30 D M. KOLB, M. PRZASNYSKI, H G E R I S C H E R

with
~Me~lv -~- ~ern. . . . = ]Ameta1 (lb)
and
Meg+olv+ 2es;~trate ~-~ Mead (2a)
with

(~ -=-I~+ zeo q) = electrochemical potential).

A comparison at the same composition of the solution (equal/7~¢~21v) gives
the difference in the chemical potentials between the deposit, #meul, and /Ao at the
underpotential Up. This is simply the difference in electron energies at the
respective electrode potentials in order to establish eqttilibrium conditions for
reactions (1) and (2):
/2metal--fla d = zeoAUp (3)
with the chemical potential/~ in atomic units.
To establish a model, which quantitatlxrely explains why monolayer adsorption
of metal atoms on a foreign metal substrate is in many cases energetically
favoured compared to bulk deposition, we have tried to correlate the data in
Table i, that is AUp, with some other physical parameters of our system which
may account for the energy gain. Such a correlation should be the key to the
problem. Since several workers have found partially discharged adatoms (see e.g.
ref. 37), one might assume that electrostatic interaction will play an important
role. Other workers have correlated adsorption parameters with electro-
negativity 43-45. A generally accepted model for a metal-adatom bonding is that
the amount of charge transferred from the adatom to the metal, is proportional
to the difference in electronegativities of both. The chemical bond thus gains a
polarity in the electron distribution. The absolute electronegativity, as given by
Mulliken 46 can be applied to both, solid and atom. It is defined as
7~ = ½(In +EA)~-- ~ (4)
where IA and EA are the ionization potential and the electron affimty of the atom,
respectively, and which are both equal to the work function q~ in the metal.
Furthermore, it has been shown by Gordy and Thomas 4v and later by
Trasatti 4s, that there is a definite correlation between Pauling's electronegativity
Zv of an atom (which xs correlated linearly to Mulliken's value 7~) and the work
function 4~ of the solid. The empirically found connection is (for • in eV):
ZP = 0.5 ~ - c o n s t . (5)

We theretore have reed to correlate the underpotential shift AUp with the
difference in the work functions of substrate and adsorbate, since the work functions
have been determined much more accurately than the electronegativities. We expected
that the ionic character of the metal-adatom bonding should increase with
increasing differences in work function of both materials and we assume that the
ionic contribution to the chemical bond of the metal-adatom complex, arising from
the partial charge transfer, is responsible for the deposition of the first monolayer
at underpotentials.
METAL MONOLAYERS 31

~.4 1 -I - f - I

1.0-- L,',ga i*

> 0.8 ~ !
_-~ 0 TI"/Au

"~ 0 6 ,~.~,'L o" o:0..,,o ~.%

0 4 - - "~"~*°° pb.. ,v~Pt k-i~

0 2 -- Ocu.., oc¢.,co
pb**lAg
TI*IAg
BI+~IA0

Cd~lAg
T( ICu

o I J J
0 0.5 1.0 A~IeV t 5 2.0 2.5
1
Fig 6 Underpotentlal sMft AUp between bulk and monolayer stripping peak as a tunctlon of A#,
the &fferencem work functions of substrate and adsorbate material The data are taken from Table 1
(O) Aqueous soluUon,(0) acetonltnle, (A) propylene carbonate

In Fig. 6 the underpotential shift A Up is plotted against the difference in

the work functions A4 of the substrate (40) and the monolayer (41) materials.
The 4-values were taken from Trasatti (ref. 48, Table 1)*. A linear correlation
between both quantities is found over a very wide range in A4 for 21 couples:
AUp=cxA4 with a = 0 . 5 V e V -1 (6)
Three pairs deviate from this relation in direction of greater AUp values, namely
Hg, Ag and T1 monolayers on gold. This deviation might be due to specific
interactions.
As long as no specific interaction occurs between monolayer and substrate,
which is true for most of the studied systems, we are able to estimate the
underpotential shift AUp from eqn. (6) for any couple of electrodes and ions.
The points for Li on Cu, Ag and Au were obtained as a test of this relation,
after we had seen, that the other systems follow this simple linear correlation.
Measurements of Fried and Barak .9 show that even such extreme couples as Cs
on Pt ( A 4 = 3.5 eV !) fulfil eqn. (6) (see Table 1). No explanation, however, can be
given for some pairs, which are reported to show no underpotential effect (see
Table 1). However, in these cases the differences in work function are relatively small.
The difference in electronegativity causes a polarity of the surface bond,
that is, a dipole layer is formed between substrate and adsorbate. The potential
drop across the dipole layer is a major part of the contact potential Uc(O). The
contribution of the dipole layer formed by adsorbed species is directly proportional
to the dipole moment re(O) and the number N of dipoles per cm 2 (refs. 50, 51)
AU~ (0) = m(O)N/eeo = m(O)NoO/eeo (7)

* The ~-values for the alkah metals were taken from ref 62
32 D M. KOLB,M. PRZASNYSKI,H. GERISCHER

When we assume that the dipole moment re(O)is built up by a partial charge
( 1 - 70)e 0 of the adatom and an equivalent counter charge - ( 1 - 70) eo at the surface
atom of the substrate, separated by the bond length l, we can derive the following
expression from eqn. (7) for the change in the contact potential AUe(0) arising
from the dipole layer:
AVe(0) = (No/eeo)O(1-7o)eol (8)
The formulation of the partial charge as (1 - 70) has been chosen here to correspond
with the definition of the so-called electrosorption valency 7, given by SchmidP °
and Schultze and Vetter 37. 70 is dependent on the coverage and will normally
increase with 0. It has been shown s°-52 that the work function of a monolayer
is already that of the bulk material.
Equation (8) gives for 70 as a function of AUe(0) approximately
70 ~ 1-0.05 eAU~(O)/Ol (9)
where AU¢(0) is expressed in V, I in A, and where we have assumed No = 1.2 × 10 Is
cm-2. Since AU¢(0) is limited by the differences in work function between substrate
and bulk deposit, the 78 values of most of the couples studied in the range
of 0/>0.5 and with A ~ < 1 eV must lie between 0.8 and 1.0. 70 values for the
partial discharge below 0.8 for complete metal monolayers would cause an
unreasonably high change A~ in the work function and can therefore be excludeck
Let us consider as an example the Cu monolayer on Pt. The difference in work
functions yields a contact potential AU¢ of about 0.85 V for 0= 1, e is assumed
to be two and l= 1.5 A, approximately the radius of the adatom. This gives a
70= 1 value of about 0.94.
The question arises, to what degree can the electrostatic energy of such an
electric double layer explain the difference in binding energies between adatoms
and a foreign substrate and atoms in the bulk? However, a simple calculation
shows that the electrostatic energy is far too small to account solely for this effect,
since the electronic charge q = ( 1 - 70)eo of the adatom is rather small. The electro-
static energy per adatom is given by:
Eel.star = NoO[m(O)]2/2 eeol = NoOq2/2 C (10)
where C=eeo/1 is a formal capacity of the dipole layer. For the above mentioned
example of a Cu monolayer on Pt, Eel stat is only about 0.02 eV, while the under-
potential shift yields an energy eoAUp=0.4 eV. Besides, the contribution of the
electrostatic energy would cause a quadratic dependence of A Up on A~ which is not
found in the experiment (see Fig. 6).
In Pauling's theory of the chemical bond 53 the bond energy between two
atoms contains an additional term which increases with increasing difference in their
electronegativities. This is caused by the contribution of ionic states to the covalent
binding because resonance between ionic and covalent bond will lower the energy.
Although Pauling's theory has been derived for 2-atomic molecules, the general
conclusions should equally hold for polyatomic molecules, of course with less simple
formulations. This concept has already been used to describe adsorption processes
on metal surfaces, where the resulting metal-adatom complex had been treated
as a surface molecule 54'55. Our observation shows that the interaction of an atom
METAL MONOLAYERS 33

with a solid metal surface follows indeed a rather simple relation, quite similar
to the interaction of 2 different atoms. However, we have to assume that for all
deposits the covalent eontribution to the surface bond is approximately the same
as in the bulk metal.
We know that the chemical bond of the adsorbed metal atoms has a polar
character which increases with increasing work function difference (see eqn. 8) and
decreases with increasing coverage. This is indicated by the shift in work function
with varying coverage 5°-52 and the shift of the excess charge on an electrode
during the deposition of the first monolayer. If we assume that a partial electron
transfer from the adatom to the substrate occurs only m such cases where the
ionization energy of the adatom is lower than the work function of the substrate, no
polarized bond could be formed for all of the studied systems except the alt:ali
metals. The experimental results, however, show that in all systems with under-
potential deposition a polar bond exists with a positive charge on the adsorbed
atom 37. This cannot be explained quantitatively, even by comparing the absolute
electronegativities of atoms and substrates. Therefore we think that the electro-
negativity of a metal atom interacting with a metal surface is best characterized
by the electronegativity of this atom in a metal lattice, namely the work function.
As mentioned above the dipole moment of the surface bond depends on the
work function difference as well as on the coverage. It is largest for small coverages
and tends to a lower limit as 0 approaches unity. As a consequence the interaction
energy of the adatom is also a function of A~ and 0 and therefore different
isotherms 0 = 0(U) will result for different A¢ values.
Figure 7 shows the half width ~ of the monolayer stripping peak as a
function of A~. Since in many cases the stripping peak is rather broad and often

600
I I I I

~00~00 CiAg'Au
l L~"~J,u .

E300 oc~..,~ / o L,',Ag

Ag*lP0t /
J0

20 0 T,.,A.
Hg..IAuO
OCd.°/ACdo'
g IAuO
Cd'*lCuO OHg+*lpt
leo ~ O *1ACu. u "OPb'÷Au l
"~t"Ikg O~t'~Cu
o I [ I I
0 05 1.0 1.5 2.0 2.5
B~/eV
Fig. 7. Half width ~ of the monolayer stripping peak as a function of A¢
34 D M KOLB, M PRZASNYSKI, H GERISCHER

unsymmetrical, 6 will only give a rough idea about the width of the adsorption
isotherm. In addition, the form of the isotherm will partly depend on the specific
interaction of the solvent molecules with the electrode material and the metal ions.
Therefore, xt is not surprising that the points m Fig. 7 scatter rather strongly.
However, a correlation is seen insofar as the width 6 will increase with increasing
A4~. The lower limit in 6 when A4~ goes to zero is about 40 mV, a value which
is typical for the half wadth, 2.3 (kT/e0)log 4, of a Langmuir isotherm. The broadening
with increasing A4~ may be explained by an increasing difference in the adsorption
energy for the adsorption sites at 0 g 0 and 0 ~ 1 (Temkin-type isotherm).
As we have shown above in our model the work function of the electrode
surface will change from 4~o (value of the substrate material) to 4~1 (value of the
adatom material) as the coverage proceeds from 0 = 0 to 0= 1 in analogy to the
results in the gas phase 5°-s2. This means that the potential of zero charge (p.z.c.)
which is proportional to the work function 4548 (given m volts),
Up z c = ~ - const. (11)
is shifted by Aq~ V during the adsorption or deposition of the monolayer. There
have been extensive investigations by various authors to determine the total amount
of an adsorbed monolayer. This was usually done by integrating the current-
potential curve for the adsorption or desorption peak between 0 = 0 and O= 1.
Then the amount for double-layer charging determined in a metal-ion-free solution
over the same potential range was subtracted. Since the p.z.c, is shifted by Aq~ V
during the deposition or dissolution of the monolayer, whereas this is not the case
m the metal-ion-free solution, the determined charge for the adsorbed monolayer
will be too small by about
Aq = CDLAUp~c = CDLA~ (12)
if this effect is not taken into account. Consequently, the partial discharge
coefficient ? which is given by the ratio of the experimentally determined and the
theoretical charge of a monolayer is somewhat in error when the experimentally
determined charge is not corrected by Aq. Unfortunately, no exact measurement
of Up z ~ is possible at the conditions of underpotential deposition.
As listed in Table 2 many of the reported experiments were performed in
C1- containing solutions where C1- coadsorption is known to take place 39. The
absolute amount of adsorbed C1- m the potential range of interest is rather small
(0 is usually less than 20%). In these electrolytes the monolayer peak is in most
cases shifted to more negative potentials, thus decreasing the underpotential shift
AUp. Qualitatively this effect can be interpreted in accordance with the well-known
shift in the p.z.c, to more cathodic potentials arising from C1- adsorption. The
specific adsorption of anions is caused by a contribution of covalent bonding and
therefore represents a partial electron transfer between the anion and the respective
surface layer. This reduces the mean electronegativity of the metal surface. If the
anions are more strongly adsorbed on the substrate than on the deposit, the apparent
difference in electronegativity will decrease. This is the normal situation because
'the more electronegative metal will usually have the larger affinity for electrons
from the adsorbed species. In accordance with the diminished difference in effective
work function between substrate and specifically adsorbed anions and submonolayer
METAL MONOLAYERS 35

and specifically adsorbed anions, the AUp values decrease in most cases. However,
if the deposit has a greater affinity for electrons than the substrate due to specific
chemical interactions, the effective difference in A4~ can also be increased resulting
in an increase of AUp in such exceptional cases. In Fig. 8 the anodic stripping
curves are shown for a Tl-deposit on Ag in a C1- free and a C1- containing
electrolyte. The influence of the C1- is seen quite clearly. Besides a change in
the underpotentlal shift A Up a considerable reduction in the width of the mono-
layer adsorption isotherm is noted. This shows that specifically adsorbed ions like
C1- introduce certain complications into the system and therefore should be
considered with caution in the interpretation of the underpotential deposition itself.

100

7
,<
~, 50

I
-1 -0 5
UScE/V
Fig 8. Ano&c stripping curves for a T1 deposit on Ag m 0.5 M NaC104 (pH 3) ( ) [Cl-]=0,
( )[CI-]=3xl0-2M [ T l + ] = 2 x l 0 - ' M . Scan rate= 20 mV s -1.

CONCLUSION

The proposed model of a polar metal-adatom complex correlates the observed

underpotential shift and subsequently the difference in bond energy with the difference
in electronegativitles or work functions of the materials involved. The results seem
to be surprising in so far as the electronegativity of a monolayer of adatoms is
described in this interpretation by the work function of the bulk metal rather
than by the electronegativity of the atom. However, although the optical properties
of such a monolayer are usually far from those of the bulk 27'3°, it has been shown
that the work function of a monolayer may be much the same as that of the
bulk 5°-52. Another unexpected result is that the excess bond energies of the adsorbed
metal atoms do not depend on the difference in cohesion energies of substrate
and deposit as one should expect from an application of Pauling's interpretation
36 D. M KOLB, M PRZASNYSKI, H GERISCHER

(covalent contribution). This may be a specific feature of monolayer films.

Since the proposed model describes a general phenomenon, one should
expect the same behaviour at the solid-vacuum interface. This is true indeed: flash
desorption measurements in u.h.v, have shown 51 that the first monolayer of metal
atoms on a foreign metal substrate (e.9. Na on Ni) is more tightly bound than
the next layers. The reason for this behaviour should be the same as for the
underpotential deposition at the interface electrode-electrolyte. In the latter case,
however, we are able to study the system under thermodynamic equilibrium
conditions and therefore can get direct information on the bonding energies involved.
For this reason, these experiments should be well suited to answer some general
questions m surface physics 56. A more detailed model, implying specific interactions
between adatom and substrate, may be able to account for the deviations, not
explained in the present study.
The model proposed in this work implies that the metal adsorbates are
nearly completely discharged, only a small partial charge remains to establish the
dipole layer. Therefore, the expression "cation adsorption", frequently used in the
literature to describe the underpotential deposition, is rather misleading and should
be restricted to such cases where the contribution of polar bonding is large.
Finally, an important consequence of the underpotential deposition on the
metal film growth should be mentioned. Since with increasing work function
difference A~ the bond between adatom and substrate becomes stronger than the
binding of the atom in the respective bulk, a monolayer film is favoured rather
than three-dimensional nucleation. Thus, the further layer growth should be
promoted by this initial step and at least for the next few atomic layers a very
smooth and continuous film may result without island formation. The latter is
usually observed for metal films deposited onto glass or quartz. Optical 27"s7 and
photoemission ss measurements indeed confirm this assumption: thin metal layers
on metallic substrates do not exhibit island structures. Furthermore, these layers
reach bulk optical properties already at a thickness of about 4-5 monolayers. This,
however, is about an order of magnitude smaller than the corresponding thickness
of evaporated metal films on insulating substrates.
SUMMARY

The electrolytic deposition of metal atoms onto foreign metal substrates at

underpotentlals has been studied in aqueous and non-aqueous solutions. It is shown,
that the potential difference between monolayer and bulk deposition is closely related
to the difference in the work functions of substrate and deposit, causing a partial
charge of the adatoms. The ionic contribution to the chemical bond, arising from
this partial electron transfer, can account for the favourable deposition of the first
monolayer. A formula is given which allows the prediction of the amount of
underpotential shift from differences in work function. This is explained in analogy
to Pauling's treatment of the chemical bond between atoms of different
electronegativity.

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