Sách Xúc tác nano

Contents
Abbreviations xvi
Some Relevant Units xvii
Chapter 1 Some Milestones in the Development of Surface Chemistry
and Catalysis
1.1 Introduction 1
1.2 1926: Catalysis Theory and Practice; Rideal and
Taylor 2
1.3 1932: Adsorption of Gases by Solids; Faraday
Discussion, Oxford 2
1.4 1940: Seventeenth Faraday Lecture; Langmuir 2
1.5 1950: Heterogeneous Catalysis; Faraday Discussion,
Liverpool 3
1.6 1954: Properties of Surfaces 4
1.7 1957: Advances in Catalysis; International Congress
on Catalysis, Philadelphia 5
1.8 1963: Conference on Clean Surfaces with Supplement:
Surface Phenomena in Semiconductors,
New York 6
1.9 1966: Faraday Discussion Meeting, Liverpool 6
1.10 1967: The Emergence of Photoelectron Spectroscopy 6
1.11 1968: Berkeley Meeting: Structure and Chemistry of
Solid Surfaces 7
1.12 1972: A Discussion on the Physics and Chemistry of
Surfaces, London 7
1.13 1987: Faraday Symposium, Bath 8
1.14 Summary 8
References 11
Further Reading 12
xi
Chapter 2 Experimental Methods in Surface Science Relevant to STM
2.1 Introduction 13
2.2 Kinetic Methods 13
2.3 Vibrational Spectroscopy 14
2.4 Work Function 15
2.5 Structural Studies 16
2.6 Photoelectron Spectroscopy 18
2.7 The Dynamics of Adsorption 21
2.8 Summary 26
References 27
Further Reading 30
Chapter 3 Scanning Tunnelling Microscopy: Theory and Experiment
3.1 The Development of Ultramicroscopy 31
3.2 The Theory of STM 35
3.3 The Interpretation of STM Images 37
3.4 Scanning Tunnelling Spectroscopy 38
3.5 The STM Experiment 40
3.6 The Scanner 42
3.6.1 Sample Approach 43
3.6.2 Adaptations of the Scanner for Specific
Experiments 43
3.7 Making STM Tips 44
3.7.1 Tip Materials 46
References 48
Chapter 4 Dynamics of Surface Reactions and Oxygen Chemisorption
4.1 Introduction 50
4.2 Surface Reconstruction and ‘‘Oxide’’ Formation 52
4.3 Oxygen States at Metal Surfaces 55
4.4 Control of Oxygen States by Coadsorbates 64
4.5 Adsorbate Interactions, Mobility and Residence Times 65
4.6 Atom-tracking STM 69
4.7 Hot Oxygen Adatoms: How are they Formed? 71
4.8 Summary 72
References 74
Further Reading 75
xii Contents
Chapter 5 Catalytic Oxidation at Metal Surfaces: Atom Resolved
Evidence
5.1 Introduction 77
5.2 Ammonia Oxidation 78
5.2.1 Cu(110) Pre-exposed to Oxygen 79
5.2.2 Coadsorption of Ammonia–Oxygen Mixtures
at Cu(110) 81
5.2.3 Coadsorption of Ammonia–Oxygen Mixtures
at Mg(0001) 83
5.2.4 Ni(110) Pre-exposed to Oxygen 83
5.2.5 Ag(110) Pre-exposed to Oxygen 84
5.3 Oxidation of Carbon Monoxide 85
5.4 Oxidation of Hydrogen 89
5.5 Oxidation of Hydrocarbons 91
5.6 Oxidation of Hydrogen Sulfide and Sulfur Dioxide 95
5.7 Theoretical Analysis of Activation by Oxygen 98
5.8 Summary 99
References 100
Further Reading 102
Chapter 6 Surface Modification by Alkali Metals
6.1 Introduction 103
6.2 Infrared Studies of CO at Cu(110)–Cs 105
6.3 Structural Studies of the Alkali Metal-modified
Cu(110) Surface 105
6.3.1 Low-energy Electron Diffraction 105
6.3.2 Scanning Tunnelling Microscopy 106
6.3.3 Cu(110)–Cs System 107
6.3.4 Oxygen Chemisorption at Cu(110)–Cs 108
6.4 Reactivity of Cu(110)–Cs to NH3 and CO2 111
6.5 Au(110)–K System 113
6.6 Cu(100)–Li System 115
6.7 Summary 117
References 119
Further Reading 120
Chapter 7 STM at High Pressure
7.1 Introduction 121
7.2 Catalysis and Chemisorption at Metals at High
Pressure 123
7.2.1 Carbon Monoxide and Nitric Oxide 124
7.2.2 Hydrogenation of Olefins 126
Contents xiii
7.3 Restructuring of the Pt(110)–(1
2) Surface by
Carbon Monoxide 129
7.4 Adsorption-induced Step Formation 131
7.5 Gold Particles at FeO(111) 131
7.6 Hydrogen–Deuterium Exchange and Surface
Poisoning 132
7.7 Summary 133
References 134
Further Reading 134
Chapter 8 Molecular and Dissociated States of Molecules: Biphasic
Systems
8.1 Introduction 135
8.2 Nitric Oxide 136
8.3 Nitrogen Adatoms: Surface Structure 142
8.4 Carbon Monoxide 143
8.5 Hydrogen 145
8.6 Dissociative Chemisorption of HCl at Cu(110) 147
8.7 Chlorobenzene 148
8.8 Hydrocarbon Dissociation: Carbide Formation 150
8.9 Dissociative Chemisorption of Phenyl Iodide 150
8.10 Chemisorption and Trimerisation of Acetylene at
Pd(111) 151
8.11 Summary 152
References 153
Further Reading 155
Chapter 9 Nanoparticles and Chemical Reactivity
9.1 Introduction 156
9.2 Controlling Cluster Size on Surfaces 157
9.3 Alloy Ensembles 159
9.4 Nanoclusters at Oxide Surfaces 160
9.5 Oxidation and Polymerisation at Pd Atoms
Deposited on MgO Surfaces 165
9.6 Clusters in Nanocatalysis 167
9.7 Molybdenum Sulfide Nanoclusters and Catalytic
Hydrodesulfurisation Reaction Pathways 169
9.8 Nanoparticle Geometry at Oxide-supported Metal
Catalysts 171
9.9 Summary 175
xiv Contents
References 176
Further Reading 178
Chapter 10 Studies of Sulfur and Thiols at Metal Surfaces
10.1 Introduction 179
10.2 Studies of Atomic Sulfur Adsorbed at Metal
Surfaces 180
10.2.1 Copper 181
10.2.2 Nickel 185
10.2.3 Gold and Silver 189
10.2.4 Platinum, Rhodium, Ruthenium and
Rhenium 190
10.2.5 Alloy Systems 193
10.3 Sulfur-containing Molecules 195
10.4 Summary 199
References 200
Further Reading 202
Chapter 11 Surface Engineering at the Nanoscale
11.1 Introduction 203
11.2 ‘‘Bottom-up’’ Surface Engineering 204
11.2.1 Van der Waals Forces 205
11.2.2 Hydrogen Bonding 207
11.2.3 Chiral Surfaces from Prochiral Adsorbates 208
11.2.4 Covalently Bonded Systems 209
11.3 Surface Engineering Using Diblock Copolymer
Templates 211
11.4 Summary 214
References 214
Further Reading 216
Epilogue 217
Subject Index