Transition Metal Oxides (eBook)

Front Cover 1
Transition Metal Oxides: Surface Chemistry and Catalysis 4
Copyright Page 5
CONTENTS 10
PREFACE 8
Chapter 1. INTRODUCTION 14
References 18
Chapter 2. BULK AND SURFACE STRUCTURE OF TRANSITION METAL OXIDE 19
2.1 Bulk Structure 19
2.2 Shear Structure in Intermediate Oxides of Ti, V, and Mo 25
2.3 Structure, Stability and Reconstruction of Oxide Surfaces 28
2.4 Structure of Supported Oxides 33
References 38
Chapter 3. PHYSICAL AND ELECTRONIC PROPERTIES 40
3.1 Surface Composition 40
3.2 Ionicity of Oxides 41
3.3 Magnetic Properties of Small Oxide Particles 49
3.4 Quadrupole Splittings of Surface Ions 56
3.5 Surface Electronic Structure 59
3.6 Surface Vibration 61
References 63
Chapter 4. SURFACE COORDINATIVE UNSATURATION 66
4.1 Formation of Surface Coordinative Unsaturation 66
4.2 Chemical Properties of Surface Coordinatively Unsaturated Sites 70
4.3 Adsorption of Small Molecules 74
References 82
Chapter 5. SURFACE ACIDITY 85
5.1 Surface Acid Sites 85
5.2 Formation of Surface Acid Sites 87
5.3 Determination of Acidity 93
5.4 Role of Acid Sites in Catalytic Reactions 101
References 102
Chapter 6. REDUCTION OF OXIDES 104
6.1 Introduction 104
6.2 Thermodynamics of Reduction 105
6.3 Kinetic Models 106
6.4 Mechanism of Reduction 109
6.5 Effect of Support 111
6.6 Effect of Other Components 113
6.7 Reactivity of Reduced Surfaces 113
6.8 Influence of Reduced Oxides on the Properties of Transition Metals 115
References 120
Chapter 7. OXYGEN ON OXIDES 123
7.1 Nature of Adsorbed Oxygen 123
7.2 Detection of Adsorbed Oxygen 124
7.3 Reactivity of Adsorbed Oxygen 129
References 132
Chapter 8. PREPARATION OF OXIDES 134
8.1 General Considerations 134
8.2 Preparation of Unsupported Single Component Oxides 136
8.3 Preparation of Supported Oxides 142
8.4 Preparation of Multicomponent Oxides 144
References 147
Chapter 9. METATHESIS AND ISOMERIZATION 149
9.1 Metathesis 149
9.2 Isomenrization of Alkenes 153
References 157
Chapter 10. DECOMPOSITION, HYDROGENATION AND RELATED REACTIONS 159
10.1 Decomposition of Alcohols 159
10.2 Decomposition of Nitrous Oxide 166
10.3 Hydrogenation, H-D Exchange of Hydrocarbons, and H2-D2 Scrambling 168
10.4 Reduction of NO 175
References 179
Chapter 11. SELECTIVE OXIDATION REACTIONS 182
1 1.1 Introduction 182
11.2 Types of Selective Oxidation Reactions 183
11.3 Features of Catalytic Selective Oxidation 183
11.4 Chemical Factors Affecting Selectivity 188
1 1.5 Oxidation of Propene to Acrolein and Ammoxidation to Acrylonitrile 194
11.6 Effect of Water on Propene Oxidation 207
References 208
Chapter 12. SELECTIVE OXIDATION REACTIONS 213
12.1 Selective Oxidation of Butenes 213
12.2 Selective Oxidation of Butane 223
12.3 Selective Oxidation of Methane 225
12.4 Selective Oxidation of Methanol 230
References 236
Chapter 13. CATALTYIC REACTION BETWEEN HYDROGEN AND CARBON OXIDES 227 240
13.1 Introduction 240
13.2 Alcohol Synthesis on Copper-Zinc Oxide and Other Cu-based Catalysts 241
13.3 Group VIII Metal/metal Oxide Catalysts 249
13.4 Isosynthesis Reaction 253
13.5 Water-Gas Shift Reaction 257
References 261
Chapter 14. PHOTO-ASSISTED SURFACE PROCESSES 265
14.1 Introduction 265
14.2 Photo-Assisted Adsorption and Desorption 269
14.3 Photocatalysis: Gas Phase Reactions 271
14.4 Photocatalysis: Liquid Phase Reactions 279
14.5 Photocatalysis by Metal/metal Oxide and Oxide/Oxide Composites 284
References 286
INDEX 290
STUDIES IN SURFACE SCIENCE AND CATALYSIS 296