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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 Supple- ment: 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 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 Chapter 5 Catalytic Oxidation at Metal Surfaces: Atom Resolved Evidence 5.1 Introduction 77 5.2 Ammonia Oxidation 78 5.2.1 Cu(ll0) 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(ll0) Pre-exposed to Oxygen 83 5.2.5 Ag(ll10) 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( 10)-Cs 105 6.3 Structural Studies of the Alkali Metal-modified Cu(l10) Surface 105 6.3.1 Low-energy Electron Diffraction 105 6.3.2 Scanning Tunnelling Microscopy 106 6.3.3 Cu(l10)-Cs System 107 6.3.4 Oxygen Chemisorption at Cu(l10)-Cs 108 6.4 Reactivity of Cu(1 10)Cs to NH3 and CO2 111 6.5 Au(l10)-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 7.3 Restructuring of the Pt(1 10)-(1 x 2) Surface by Carbon Monoxide 129 7.4 Adsorption-induced Step Formation 131 7.5 Gold Particles at FeO(ll11) 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 HCI 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(l 11) 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 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