J. M. Thomas, W. J.

Thomas

Principles and Practice of Heterogeneous Catalysis

VCH

Weinheim New York Basel Cambridge Tokyo

Contents

Preface 1 1.1 1.1.1 1.2 1.2.1 1.2.2 1.2.2.1 1.2.2.2 1.2.2.3 1.2.2.4 1.2.2.5 1.2.2.6 1.2.2.7 1.2.2.8 Setting the Scene

V 1 1 2 4 6 10 10 12 13 15 16 20 23 24 26 27 29 30 42 44 48 49 57 60 60

Introduction The Selectivity of Catalysts Perspectives in Catalysis: Past, Present, Future . . '. Applied Catalysis since the 1940s Current Trends in Applied Catalysis Auto-Exhaust Catalysts Catalysts in Electrochemistry and Photoelectrochemistry Asymmetric Sites on Heterogeneous Catalysts Immobilized Transition Metals Immobilized Enzymes and Cells: Present and Future Catalytic Antibodies Ribozymes Catalytic Oxidation of Methane: the Centrepiece of Future Power Sources 1.3 Definition of Catalytic Activity 1.3.1 Magnitude of Turnover Frequencies and Active Site Concentrations. 1.3.2 Volcano Plots 1.3.3 The Evolution of Important Concepts and Techniques in Heterogeneous Catalysis 1.3.3.1 Mechanistic Insights from Isotopic Labelling 1.3.3.2 Concepts from Organometallic Chemistry 1.3.3.3 Contributions from Theoretical and Computational Chemistry . . . . 1.4 Some Intellectual and Practical Challenges for Catalysis in the 21st Century 1.5 Problems 1.6 Further Reading 1.6.1 General Background 2 2.1 2.1.1 The Fundamentals of Adsorption: Structural and Dynamical Considerations, Isotherms, and Energetics Catalysis Must Always be Preceded by Adsorption Physical Adsorption, Chemisorption and Precursor States

65 65 65

X 2.2 2.3 2.4 2.4.1 2.4.2 2.4.3 2.5 2.5.1 2.5.2 2.5.3 2.5.4 2.5.5 2.5.6 2.5.7 2.6 2.6.1 2.6.2 2.6.2.1 2.6.2.2 2.6.2.3 2.6.2.4 2.6.2.5 2.6.2.6 2.6.2.7 2.7 2.7.1 2.7.2 2.7.3 2.7.4 2.8 2.9 2.9.1 2.9.2 2.10 2.10.1 2.10.2 2.10.3 2.10.4 2.10.5 2.11 2.12

Contents The Surfaces of Clean Solids are Sometimes Reconstructed 69 There are Many Weil-Defined Kinds of Ordered Adlayers 72 Adsorption Isotherms and Isobars 79 The Empirical Facts 81 Information that can be Gleaned from Isotherms 81 Adsorption is Almost Invariably Exothermic 82 Dynamical Considerations 85 Residence Times 85 Rates of Adsorption 87 Applying Statistical Mechanics to Adsorption 89 Adsorption Kinetics Can Often be Represented by the Elovich Equation 91 Rates of Desorption 94 Applying Statistical Mechanics to Desorption 96 The Influence of a Precursor State on the Kinetics of Desorption . . . 98 Deriving Adsorption Isotherms from Kinetic Principles 99 Using the Langmuir Isotherm to Estimate the Proportions of Non-dissociative and Associative Adsorption 101 Other Adsorption Isotherms 104 Henry's Adsorption Isotherm 104 The Freundlich Isotherm 104 The Temkin Isotherm 104 The Brunauer-Emmett-Teller Isotherm 105 Developments from Polanyi's Adsorption Theory 105 Kaganer's Isotherm and the DKR Equation 107 The Virial Equation of State 107 Energetics of Adsorption 108 Estimating the Binding Energies of Physically Adsorbed Species. . . . 108 The Binding Energies of Chemisorbed Species 112 Estimating Heats of Adsorption From Thermodynamic Data 116 Decline of the Heat of Adsorption with Increasing Coverage 117 Mobility at Surfaces 119 Kinetics of Surface Reactions 120 The Influences of Precursor States on the Kinetics and Energy Distribution of Catalysed Reactions 122 Comparing the Rates of Heterogeneous and Homogeneous Reactions 123 Autocatalytic, Oscillatory, and Complex Heterogeneous Reactions 124 An Outline of Autocatalysis 125 Background to Oscillating Reactions 125 Instabilities and Transient Phenomena in Heterogeneous Catalysis . . 127 Multiple Steady States 127 Transient Phenomena 130 Problems 135 Further Reading 142

Contents 3 3.1 3.2 3.3 3.3.1 3.3.2 3.3.3 3.3.3.1 3.3.3.2 3.4 3.4.1 3.4.2 3.4.3 3.5 3.5.1 3.5.2 3.5.3 Characterizing Catalysts and their Surfaces Model Systems and Real-Life Catalysts A Portfolio of M o d e r n Methods: Introducing the Acronyms Which Elements and Which Phases are Present? X - R a y Fluorescence ( X R F ) , X - R a y Emission ( X R E ) and ProtonInduced X - R a y Emission (PIXE) Developing Techniques: I C P M S X - R a y Diffraction ( X R D ) and Electron Diffraction (ED) M e a n Size, Surface Area a n d Particle-Size Distribution from SAXS In-Situ Studies by X - R a y Diffraction Detecting, Identifying, a n d Counting the A t o m s at Solid Surfaces: Sub-monolayer A m o u n t s can be Measured Ion-Scattering Spectroscopy (ISS): A Detection Limit of 10~ 4 Monolayers Nuclear Microanalysis ( N M I ) : A Sensitive M e a n s of Detecting Specific Elements, Including Hydrogen, at Surfaces Rutherford Back-Scattering (RBS) Identifying the A t o m s at a Surface and Probing their Immediate Environment: SIMS, I R , H R E E L S , A E S and X P S Secondary-Ion Mass Spectroscopy (SIMS): A Detection Limit of 10~ 5 Monolayers Infrared Spectroscopy (IR): A Non-destructive Technique Usable on Catalysts Exposed to High Pressure High-Resolution Electron-Energy-Loss Spectroscopy ( H R E E L S ) : The M o s t Sensitive Tool for Identifying Surface Vibrational Modes Electron Spectroscopy: T h e Ability t o Probe Composition a n d Bonding at Surfaces The Realization that Electron Spectroscopy is Sufficiently Sensitive to Detect Fractions of a Monolayer Auger Electron Spectroscopy (AES) and Scanning Auger Microscopy ( S A M ) X - R a y Photoelectron Spectroscopy (XPS) UV-Induced Photoelectron Spectroscopy (UPS) Inverse Photoemission: A M e a n s of Probing Unoccupied States . . . . The Structure and Crystallography of Surfaces: Measuring the Symmetries, Order and Disorder, and Deducing Bond Lengths and B o n d Angles in the Adsorbed State Two- and Three-Dimensional Surface Crystallography Notations for Describing Ordered Structures at Surfaces H o w d o Bond Distances at Surfaces C o m p a r e with Those of Bulk Solids? W h a t of Displacive Reconstructions? Atomic Scattering and Diffraction E X A F S , S E X A F S , X A N E S a n d N E X A F S : Probing Bond

XI 145 145 146 149 149 151 151 153 154 157 157 158 158 159 159 161

164 166 169 170 171 175 177

3.5.4 3.5.4.1 3.5.4.2 3.5.4.3 3.5.4.4 3.5.4.5 3.6

3.6.1 3.6.2 3.6.3 3.6.4 3.6.5

179 179 183 1"85 185

XII

Contents Distances and Site Environments even when There is no LongRange Order The Origin of EXAFS and How it is Used Applications of EXAFS to the Study of Catalysts SEXAFS XANES and Pre-edge Structure: Deducing Site Symmetry and Oxidation States NEXAFS Other Structural Techniques for Characterizing Bulk and Surfaces of Catalysts Electron Spin Resonance (ESR): Probing the Nature of Catalytically Active Sites and the Concentration of Paramagnetic Intermediates on Surfaces and in the Gas Phase Examples of the Use of ESR in Heterogeneous Catalysis Electron Spin-Echo Modulation Spectroscopy (ESEMS): Probing the Environment of Paramagnetic Species Nuclear Magnetic Resonance (NMR): A Technique Applicable, at High Resolution, to Solids and their Surfaces Basic Principles NMR Spectra of Solids Applications of NMR to the Study of Catalysts, Adsorbents and Adsorbates Future Prospects for the Study of Catalysts by Solid-State NMR . . . Mossbauer Spectroscopy: A Means of Determining Valence, Spin States, and Site Environments of Ions Specific Applications Conversion-Electron Mossbauer Spectroscopy (CEMS): A DoubleResonance Technique of an Unusual Kind Electron Microscopy Scanning Probe Microscopy: STM and AFM Optical Microscopy Ellipsometry: A Non-invasive Technique Neutron Scattering: A Technique of Growing Importance in the Study of Catalysts Determining the Atomic Structure and Texture of Microcrystalline Catalysts, the Nature of the Active Sites and the Disposition of Bound Reactants Determining the Structure of, and Identifying Functional Groups in, Chemisorbed Layers at Catalyst Surfaces A Miscellany of Other Procedures Determining the Strength of Surface Bonds: Thermal and Other Temperature-Programmed Methods Temperature-Programmed Desorption (TPD) or Flash Desorption Spectroscopy (FDS) Temperature-Programmed Reaction Spectroscopy (TPRS) Magnitude of the Heat and Entropy of Adsorption

3.6.5.1 3.6.5.2 3.6.5.3 3.6.5.4 3.6.5.5 3.7 3.7.1

185 187 191 193 194 196 198

3.7.1.1 3.7.2 3.7.3 3.7.3.1 3.7.3.2 3.7.3.3 3.7.3.4 3.7.4 3.7.4.1 3.7.4.2 3.7.5 3.7.5.1 3.7.5.2 3.7.5.3 3.7.6 3.7.6.1

198 199 200 201 201 204 205 208 210 210 212 213 215 218 219 219

221 222 224 226 226 229 229

3.7.6.2 3.8 3.9 3.9.1 3.9.2 3.9.3

Contents 3.10 3.10.1 3.10.2 3.10.3 3.10.4 3.11 3.12 4 4.1 4.2 4.2.1 4.2.2 4.2.3 4.3 4.3.1 4.3.2 4.4 4.4.1 4.4.1.1 4.4.1.2 4.4.1.3 4.4.1.4 4.4.1.5 4.4.1.6 4.4.2 4.4.3 4.4.4 4.4.4.1 4.4.4.2 4.4.4.3 4.5 4.5.1 4.5.1.1 4.5.1.2 4.5.1.3 4.5.1.4 4.6 4.6.1 In-Situ Methods of Studying Catalysts: The Current Scene and Future Prospects Isotopic Labelling and Transient Response Infrared, Raman, NMR, Mossbauer and X-Ray Absorption Spectroscopy for In-Situ Studies In-Situ X-Ray and Neutron Diffraction Studies Combined X-Ray Absorption and X-Ray Diffraction for In-Situ Studies of Catalysts Problems Further Reading The Significance of Pore Structure and Surface Area in Heterogeneous Catalysis The Importance of Pore Structure and Surface Area Experimental Methods of Estimating Surface Areas The Volumetric Method The Gravimetric Method The Dynamic Method Experimental Methods of Estimating Pore Volume and Diameter. . . Gas Adsorption Method of Estimating Pore Volume and Diameter Mercury Porosimeter Method of Estimating Pore Volume and Diameter Models of the Pore Structure of Catalyst Materials Hysteresis and the Shapes of Capillaries Type A Hysteresis Loops Type B Hysteresis Loops Type C Hysteresis Loops Type D Hysteresis Loops Type E Hysteresis Loops Other Adsorption-Desorption Characteristics Geometric Models of Pores Wheeler's Semi-empirical Pore Model Mathematical Models of Porous Structures The Dusty Gas Model The Random Pore Model Stochastic Pore Networks and Fractals Diffusion in Porous Catalysts The Effective Diffusivity Molecular (Maxwellian) Diffusion or Bulk Diffusion Knudsen Diffusion The Transition Region of Diffusion Forced Flow in Pores Chemical Reaction in Porous Catalyst Pellets Effect of Intraparticle Diffusion on Experimental Parameters

XIII

232 233 238 241 243 247 254

257 257 258 259 264 265 267 268 272 275 276 277 279 280 281 282 282 283 285 286 286 287 288 290 290 292 294 294 295 295 303

XIV 4.6.2 4.6.3 4.6.4 4.7 4.8 5 5.1 5.2 5.2.1 5.2.1.1 5.2.1.2 5.2.1.3 5.1.3 5.1.4 5.2.4 5.2.5 5.2.6 5.2.6.1 5.2.6.2 5.2.6.3 5.2.6.4 5.2.7 5.2.7.1 5.2.7.2 5.3 5.3.1 5.3.1.1 5.4 5.4.1 5.4.1.1 5.4.1.2 5.4.1.3 5.4.1.4 5.4.2 5.4.3 5.4.4

Contents Non-isothermal Reactions in Porous Catalyst Pellets Criteria for Diffusion Control Experimental Methods of Assessing the Effect of Diffusion on Reaction Problems Further Reading The Solid-State and Surface Chemistry of Catalysts Classification of Heterogeneous Catalysts Structures Metals and Alloys Miller Indices and Miller-Bravais Indices Transition-Metal Alloys and Bimetallic Clusters Highly-Dispersed Metals Interstitial Phases Simple Metallic Oxides and their Non-stoichiometric Variants Shear and Block Structures Based on ReO3 More Complicated Metallic Oxides Even More Complicated Oxides Perovskites and their Defective Variants Perovskites as the Prototypes of New Homologous Series Spinels, Scheelites and the Bismuth Molybdates Heteropolyions (Keggin Structures) as Catalytically Significant Entities Clays, Zeolites and Related Structures Pillared Clays are Effectively Two-Dimensional Zeolites A Synoptic Guide to the Structure of Zeolitic and Related Solid Catalysts Computational Approaches A Resume of Available Methodologies Selected Applications A Chemist's Guide to the Electronic Structure of Solids and Their Surfaces Energy Bands Bands in ID and 3D Crystals Energy Bands in Ionic Solids Energy Bands in Transition-Metal Oxides: Understanding the Electronic Structure of the Monoxides of Titanium, Vanadium, Manganese and Nickel Energy Bands in Structures Related to ReO3 Fermi Levels in Insulators and Semiconductors Surface Electronic States and the Occurrence of Energy Levels Within the Band Gap Band Bending and Metal-Semiconductor Junctions: Schottky Barriers 305 308 313 314 317 319 319 320 320 321 324 325 327 328 335 339 340 340 341 344 346 347 352 353 364 364 369 377 378 381 384 386 387 389 391 392

Contents 5.4.4.1 Depletive Chemisorption on Semiconductors 5.4.4.2 The Bending of Bands when Semiconductors are Immersed in Electrolytes 5.4.5 Quantum Chemical Approaches to the Electronic Properties of Solids 5.4.5.1 The Cluster and Thin-Slab Approach 5.4.6 Hiickel and Extended Hiickel Calculations 5.4.6.1 'Ab-Initio' Methods 5.4.7 A Brief Selection of Quantum Chemical Studies 5.4.7.1 Band Widths, DOS and Fermi Levels of the Transition Metals 5.4.7.2 Heats of Chemisorption from EHT Calculations 5.4.7.3 The Adsorption of CO on Nickel 5.4.7.4 Dissociative Chemisorption of CO 5.4.7.5 Insight from Ab-Initio Computations: Methanol Synthesis and Olefin Metathesis 5.5 Epilogue 5.6 Problems 5.7 Further Reading 6 6.1 6.1.1 6.1.1.1 6.1.1.2 6.1.1.3 6.1.2 6.2 6.2.1 6.2.2 6.2.2.1 6.2.2.2 6.2.3 6.3 6.3.1 6.3.2 6.3.2.1 Poisoning, Promotion, Deactivation and Selectivity of Catalysts . . . .

XV 394 395 397 398 398 400 402 403 404 406 407 408 410 411 414 417 417 418 418 423 425 427 429 430 432 432 437 440 440 440 445 448 449 450 453 455 455 455

Background Effect of Mass Transfer on Catalytic Selectivity Effect of Intraparticle Diffusion Non-isothermal Conditions Effect of Interparticle Mass and Heat Transfer Bifunctional Catalysts Catalyst Deactivation Deactivation Processes Deactivation Models Steady-State Model A Dynamic Model Operational Consequences of Poisoning Modern Theories of Poisoning and Promotion General Theoretical Considerations Theoretical Interpretation of Poisoning and Promotion The Electronegativity of a Poison Seems to be of Secondary Importance 6.3.2.2 Other Factors Responsible for Promotion and Poisoning 6.4 Problems 6.5 Further Reading 7 7.1 7.2 Catalytic Process Engineering Statement of the Problem Kinetics of Heterogeneous Catalytic Reactions

XVI 7.2.1 7.2.2 7.2.3 7.2.4 7.2.5 7.2.6 7.3 7.3.1 7.3.1.1 7.3.1.2 7.3.1.3 7.3.1.4 7.3.1.5 7.3.1.6 7.3.2 7.3.2.1 7.3.2.2 7.3.2.3 7.3.2.4 7.3.2.5 7.3.3 7.4 7.5 8 8.1 8.1.1 8.1.2 8.1.3 8.1.4 8.1.5 8.1.6 8.2 8.2.1 8.2.1.1 8.2.1.2 8.2.1.3 8.2.1.4 8.2.1.5 8.2.2 8.2.3 8.2.4

Contents The Overall Rate of Reaction The Rate of Chemical Reaction Fundamental Kinetic Models The Effect of Intraparticle Diffusion The Effect of Interparticle (Fluid-to-Solid) Transport The Effect of Catalyst Deactivation Catalytic Reactors Experimental Laboratory Reactors Batch Reactors Tubular Reactors Continuous Stirred-Ta'nk Reactor Recycle Reactor Flowing-Solids Reactors Slurry Reactors Industrial Chemical Reactors Batch Reactors Continuous Tubular Reactors Fluidised-Bed Reactor The Trickle-Bed Reactor Metal Gauze Reactors Thermal Characteristics of a Catalytic Reactor Problems Further Reading Heterogeneous Catalysis: Examples and Case Histories The Synthesis of Methanol Proof that CO is not Dissociated During Methanol Synthesis The Role of CO2: Evidence that it is the Main Source of CH3OH . . . The State of Copper in the Working Catalyst The Role of Oxide Supports: Is There Anything Special About ZnO? Views on the Mechanism of the Reaction Process Conditions, Reaction Configurations and Kinetics Fischer-Tropsch Catalysis Mechanistic Considerations Does Synthesis Proceed via Hydroxymethylene Intermediates? What of the CO Insertion Mechanism? Synthesis by the Fischer-Tropsch Process First Requires Dissociation of CO Schultz-Flory Statistics Other Possible Mechanisms Fine-Tuning the Fischer-Tropsch Process Practical Fischer-Tropsch Catalysts and Process Conditions Reductive Coupling of Two CO Ligands Forming Acetylene from Syn-Gas 455 460 460 465 466 468 472 472 473 474 477 480 481 483 486 487 489 499 502 503 504 509 513 515 515 516 517 517 519 519 521 524 526 527 528 528 531 532 533 536 538

Contents 8.2.5 8.2.5.1 8.2.5.2 8.2.5.3 8.3 8.3.1 8.3.2 8.3.3 8.3.3.1 8.3.3.2 8.3.3.3 8.3.3.4 8.3.4 8.3.4.1 8.4 8.5 8.5.1 8.5.2 8.5.3 8.6 8.6.1 8.6.2 8.6.3 8.6.4 8.6.5 8.6.6 8.6.7 8.7 8.7.1 8.7.2 8.7.3 8.7.4 8.7.5 8.7.5.1 8.7.5.2 8.7.5.3 Methanation, Steam Reforming and Water-Gas Shift Reactions Methanation Steam Reforming Water-Gas Shift Reaction The Synthesis of Ammonia Catalyst Promoters are of Two Kinds Kinetics of the Overall Reaction: The,Temkin-Pyzhev Description. . The Surface of Iron Catalysts for Ammonia Synthesis Contain Several Other Elements: But is the Iron Crystalline? Does Ammonia Synthesis Proceed via Atomically or Molecularly Adsorbed Nitrogen? How and Where are the Reactant Gases Adsorbed at the Catalyst Surface? A Potential-Energy Diagram Illustrating How the Overall Reaction Leading to Ammonia Synthesis can be Constructed How Potassium Serves as an Electronic Promoter The Technology of Ammonia Synthesis Reactor Configurations are Important Industrially Oxidation of Ammonia: Stepping Towards the Fertilizer Industry . . In-Situ Catalytic Reaction and Separation Catalytic Distillation Pressure Swing Reaction Catalytic Membrane Processes Automobile Exhaust Catalysts and the Catalytic Monolith The Three-Way Catalyst (TWC) Why is Rhodium in the Auto-Exhaust Catalyst? The Catalytic Monolith Catalytic Monoliths may be Used in Several Applications Rate Characteristics of Catalytic Combustion Processes Combustion Reactions in a Catalytic Monolith Differ from Those Occurring in a Homogeneously Operated Combustor Simulation of the Behaviour of a Catalytic Monolith is Important for Design Purposes Photocatalytic Breakdown of Water and the Harnessing of Solar Energy Oxygen Generation by Photo-induced Oxidation of Water Hydrogen Generation by Photo-induced Reduction of Water Simultaneous Generation of Hydrogen and Oxygen by Catalysed Photolysis of Water Other Photochemical Methods of Harnessing Solar Energy Catalysis and Photoelectrochemistry: Photocatalysis and Photoelectrosynthesis The Principles Practical Examples The Prospects

XVII

540 540 541 545 548 549 549 551 553 554 557 558 559 561 564 567 567 571 572 576 577 578 580 581 582 583 585 590 591 593 594 596 597 598 602 604

XVIII Contents 8.8 8.8.1 8.8.2 8.8.3 8.8.4 8.8.5 8.8.6 8.8.7 8.8.7.1 8.9 8.9.1 8.9.2 8.9.2.1 8.9.2.2 8.9.2.3 8.9.3 8.10 8.11 8.12
Index

Catalysis Using Microporous or Mesoporous Solids and Modified Clays: Its Growing Role in the Petroleum Industry and Clean Technology 608 Activity of Zeolitic Catalysts 612 Shape-Selective Zeolitic Catalysts 614 New Microporous Crystalline Catalysts 616 Some Case Studies of In-Situ Monitoring, of Catalysis with ZSM-5 . . 619 A Rationally Chosen Zeolitic Catalyst.' 621 New Mesoporous Catalysts 622 Clays and Other Solid Acid Catalysts 624 Clays and their Possible Role in Replication, Evolution and the Origin of Life 626 Catalytic Processes in the Petroleum Industry 627 Catalytic Reforming 627 Catalytic Cracking 631 Cracking Reactions 632 Cracking Catalysts 633 The Catalytic Cracking Reactor 634 Hydrotreating 636 The Role of Catalysis in Energy-Related Environmental Technology 641 Problems 643 Further Reading 650
659