Modern Heterogeneous CatalysisAn Introduction
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.
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 ? Bonds 176 6.4 Diatomic Molecules with ? 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
Rutger Anthony van Santen is professor at the Institute of Molecular Complexity at Eindhoven Technical University (TU/e, The Netherlands). He received his doctorate as theoretical chemist from Leiden University in 1971. After his initial stay at Shell Research (Amsterdam, The Netherlands), he became professor in Catalysis at the Technical University Eindhoven (The Netherlands) in 1986. In 1993, van Santen was the founding director of the Netherlands Institute of Catalysis and from 2001 to 2005 he was Rector Magnificus of TU/e. He is a member of the Royal Netherlands Academy of Arts and Sciences and a Knight in the order of the Dutch Lion. His research interests are in the field of the molecular aspects of heterogeneous catalysis with the following three main themes: computational studies of surface-chemical reactivity, mechanism in heterogeneous catalysis and physical chemistry of catalyst synthesis.
Written by one of the world's leading experts on the topic, this textbook is the perfect introduction for newcomers to the exciting field of molecular heterogeneous catalysis. In addition to the introductory parts, the book provides complementary in-depth material presented such that it can be read independently and at an advanced level. 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 the chemistry of important catalytic processes and catalytic systems, that are of current use or are promising new developments.
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