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Modern Heterogeneous Catalysis: An Introduction

Modern Heterogeneous Catalysis: An Introduction

Rutger A. van Santen

ISBN: 978-3-527-81025-3

Mar 2017

510 pages

Description

Written by one of the world's leading experts on the topic, this advanced textbook is the perfect introduction for newcomers to this exciting field.
Concise and clear, the text focuses on such key aspects as kinetics, reaction mechanism and surface reactivity, concentrating on the essentials. The author also covers various catalytic systems, catalysis by design, and activation-deactivation. A website with supplementary material offers additional figures, original material and references.

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Preface xv

Acknowledgments xix

Arrangement of This Book xxi

Part I Physical Chemistry and Kinetics 1

1 Heterogeneous Catalysis 3

1.1 What is Heterogeneous Catalysis? 3

1.2 Early Developments 4

1.3 The Three Basic Laws of Catalysis 7

References 12

2 Heterogeneous Catalytic Processes 15

2.1 Introduction 15

2.2 Important Heterogeneous Catalytic Reactions and Processes 19

2.3 Summary 48

References 51

3 Physical Chemistry, Elementary Kinetics 59

3.1 Introduction 59

3.2 Catalyst Characterization 63

3.3 Elementary Kinetics 68

3.4 Transient Kinetics: The Determination of Site Concentration 104

3.5 Diffusion 106

References 114

4 The State of the Working Catalyst 117

4.1 Introduction 117

4.2 Surface Reconstruction 119

4.3 Compound Formation: Activation and Deactivation 123

4.4 Supported Small Metal Particles 124

4.5 Structure Sensitivity of Transition Metal Particle Catalysts 129

4.6 Alloys and Other Promotors 133

4.7 The Working Zeolite Catalysts 136

4.8 The State of the Mixed Oxide Surface 139

4.9 Summary 139

References 140

5 Advanced Kinetics: Breakdown of Mean Field Approximation 145

5.1 Introduction 145

5.2 The Kinetic Monte Carlo Method: RuO2 Catalyzed Oxidation 146

5.3 Single Molecule Spectroscopy 149

5.4 Catalytic Self-Organizing Systems 153

References 165

Part II Molecular Heterogeneous Catalysis 167

Introduction 167

References 171

6 Basic Quantum-Chemical Concepts, The Chemical Bond Revisited (Jointly Written with I. Tranca) 173

6.1 Introduction 173

6.2 The Definitions of Partial Density of States and Bond Order Overlap Population 174

6.3 Diatomic Molecules that Have σ Bonds 176

6.4 Diatomic Molecules with π Bonds 182

6.5 Comparison of the Electronic Structure of Molecules and Solids 186

6.6 Chemical Bonding in Transition Metals 190

Appendix 205

References 205

7 Chemical Bonding and Reactivity of Transition Metal Surfaces 209

7.1 Introduction 209

7.2 The Nature of the Surface Chemical Bond 210

7.3 The Transition States of Elementary Surface Reactions 264

7.4 Reactivity of Surfaces at High Coverage 274

References 286

8 Mechanisms of Transition Metal Catalyzed Reactions 293

8.1 Introduction 293

8.2 Hydrogenation Reactions 293

8.3 Oxidation Reactions 321

8.4 Uniqueness of a Metal for a Particular Selective Reaction 337

References 338

9 Solid Acid Catalysis, Theory and Reaction Mechanisms 345

9.1 Introduction 345

9.2 Elementary Theory of Surface Acidity and Basicity 345

9.3 Mechanism of Reactions Catalyzed by Zeolite Protons 371

9.4 Acid Catalysis and Hydride Transfer by Enzyme Catalysts 420

References 421

10 Zeolitic Non-Redox and Redox Catalysis, Lewis Acid Catalysis 429

10.1 Introduction 429

10.2 Non-Reducible Cations; The Electrostatic Field 429

10.3 Catalysis with Non-Framework Non-Reducible Cations 433

10.4 Catalysis by Non-Framework Redox Complexes 440

10.5 Related Homogeneous and Enzyme Oxidation Catalysts 446

10.7 Catalysis by Redox Cations located in the Zeolitic Framework: The Thomas Oxidation Catalysts 463

10.8 Summary of Zeolite Catalysis 468

References 469

11 Reducible Solid State Catalysts 475

11.1 Introduction 475

11.2 Chemical Bonding of Transition Metal Oxides and Their Surfaces 475

11.3 Mechanism of Oxidation Catalysis by Group V, VI Metal Oxides 494

11.4 Metathesis and Polymerization Catalysis: Surface Coordination Complexes 507

11.5 Sulfide Catalysts 515

11.6 Electrocatalysis: The Oxygen Evolution Reaction (OER) 520

11.7 Photocatalytic Water Splitting 538

References 545

Index 553