Atom Resolved Surface Reactions

by Davies, P. R.; Roberts, M. W.

• ISBN13: 9780854042692
• ISBN10: 0854042695
• Edition: 1st
• Format: Hardcover
• Copyright: 2007-12-21
• Publisher: Royal Society of Chemistry

Summary

This book offers a unique perspective of the impact of scanning probe microscopes on our understanding of the chemistry of the surface at the nanoscale. Research oriented, with the concepts gleaned from Scanning Tunnelling Microscopy being related to the more established and accepted views in surface chemistry and catalysis, the authors have addressed the question "How do the models based on classical spectroscopic and kinetic studies stand up to scrutiny at the atom-resolved level?". In taking this approach the reader, new to the field of surface chemistry, should be able to obtain a perspective on how the evidence from STM confirms or questions long standing tenets. An emphasis is given to "how did we get to where we are now" and a large number of figures from the literature are included along with suggestions for further reading. Topics discussed include: - the dynamics of oxygen chemisorption at metal surfaces - control of oxygen states and surface reconstruction - dissociative chemisorption of diatomic and hydrocarbon molecules - nanoparticles and chemical reactivity - STM at high pressures - structural studies of sulfur containing molecules and molecular templating This book will appeal to all those who wish to become familiar with the contribution Scanning Tunnelling Microscopy has made to the understanding of the field of surface chemistry and heterogeneous catalysis and also to those who are new to catalysis, a fascinating and important area of chemistry.

Table of Contents

Abbreviations	p. xvi
Some Relevant Units	p. xvii
Some Milestones in the Development of Surface Chemistry and Catalysis
Introduction	p. 1
1926: Catalysis Theory and Practice; Rideal and Taylor	p. 2
1932: Adsorption of Gases by Solids; Faraday Discussion, Oxford	p. 2
1940: Seventeenth Faraday Lecture; Langmuir	p. 2
1950: Heterogeneous Catalysis; Faraday Discussion, Liverpool	p. 3
1954: Properties of Surfaces	p. 4
1957: Advances in Catalysis; International Congress on Catalysis, Philadelphia	p. 5
1963: Conference on Clean Surfaces with Supplement: Surface Phenomena in Semiconductors, New York	p. 6
1966: Faraday Discussion Meeting, Liverpool	p. 6
1967: The Emergence of Photoelectron Spectroscopy	p. 6
1968: Berkeley Meeting: Structure and Chemistry of Solid Surfaces	p. 7
1972: A Discussion on the Physics and Chemistry of Surfaces, London	p. 7
1987: Faraday Symposium, Bath	p. 8
Summary	p. 8
References	p. 11
Further Reading	p. 12
Experimental Methods in Surface Science Relevant to STM
Introduction	p. 13
Kinetic Methods	p. 13
Vibrational Spectroscopy	p. 14
Work Function	p. 15
Structural Studies	p. 16
Photoelectron Spectroscopy	p. 18
The Dynamics of Adsorption	p. 21
Summary	p. 26
References	p. 27
Further Reading	p. 30
Scanning Tunnelling Microscopy: Theory and Experiment
The Development of Ultramicroscopy	p. 31
The Theory of STM	p. 35
The Interpretation of STM Images	p. 37
Scanning Tunnelling Spectroscopy	p. 38
The STM Experiment	p. 40
The Scanner	p. 42
Sample Approach	p. 43
Adaptations of the Scanner for Specific Experiments	p. 43
Making STM Tips	p. 44
Tip Materials	p. 46
References	p. 48
Dynamics of Surface Reactions and Oxygen Chemisorption
Introduction	p. 50
Surface Reconstruction and "Oxide" Formation	p. 52
Oxygen States at Metal Surfaces	p. 55
Control of Oxygen States by Coadsorbates	p. 64
Adsorbate Interactions, Mobility and Residence Times	p. 65
Atom-tracking STM	p. 69
Hot Oxygen Adatoms: How are they Formed?	p. 71
Summary	p. 72
References	p. 74
Further Reading	p. 75
Catalytic Oxidation at Metal Surfaces: Atom Resolved Evidence
Introduction	p. 77
Ammonia Oxidation	p. 78
Cu(110) Pre-exposed to Oxygen	p. 79
Coadsorption of Ammonia-Oxygen Mixtures at Cu(110)	p. 81
Coadsorption of Ammonia-Oxygen Mixtures at Mg(0001)	p. 83
Ni(110) Pre-exposed to Oxygen	p. 83
Ag(110) Pre-exposed to Oxygen	p. 84
Oxidation of Carbon Monoxide	p. 85
Oxidation of Hydrogen	p. 89
Oxidation of Hydrocarbons	p. 91
Oxidation of Hydrogen Sulfide and Sulfur Dioxide	p. 95
Theoretical Analysis of Activation by Oxygen	p. 98
Summary	p. 99
References	p. 100
Further Reading	p. 102
Surface Modification by Alkali Metals
Introduction	p. 103
Infrared Studies of CO at Cu(110)-Cs	p. 105
Structural Studies of the Alkali Metal-modified Cu(110) Surface	p. 105
Low-energy Electron Diffraction	p. 105
Scanning Tunnelling Microscopy	p. 106
Cu(110)-Cs System	p. 107
Oxygen Chemisorption at Cu(110)-Cs	p. 108
Reactivity of Cu(110)-Cs to NH[subscript 3] and CO[subscript 2]	p. 111
Au(110)-K System	p. 113
Cu(100)-Li System	p. 115
Summary	p. 117
References	p. 119
Further Reading	p. 120
STM at High Pressure
Introduction	p. 121
Catalysis and Chemisorption at Metals at High Pressure	p. 123
Carbon Monoxide and Nitric Oxide	p. 124
Hydrogenation of Olefins	p. 126
Restructuring of the Pt(110)-(1 x 2) Surface by Carbon Monoxide	p. 129
Adsorption-induced Step Formation	p. 131
Gold Particles at FeO(111)	p. 131
Hydrogen-Deuterium Exchange and Surface Poisoning	p. 132
Summary	p. 133
References	p. 134
Further Reading	p. 134
Molecular and Dissociated States of Molecules: Biphasic Systems
Introduction	p. 135
Nitric Oxide	p. 136
Nitrogen Adatoms: Surface Structure	p. 142
Carbon Monoxide	p. 143
Hydrogen	p. 145
Dissociative Chemisorption of HCl at Cu(110)	p. 147
Chlorobenzene	p. 148
Hydrocarbon Dissociation: Carbide Formation	p. 150
Dissociative Chemisorption of Phenyl Iodide	p. 150
Chemisorption and Trimerisation of Acetylene at Pd(111)	p. 151
Summary	p. 152
References	p. 153
Further Reading	p. 155
Nanoparticles and Chemical Reactivity
Introduction	p. 156
Controlling Cluster Size on Surfaces	p. 157
Alloy Ensembles	p. 159
Nanoclusters at Oxide Surfaces	p. 160
Oxidation and Polymerisation at Pd Atoms Deposited on MgO Surfaces	p. 165
Clusters in Nanocatalysis	p. 167
Molybdenum Sulfide Nanoclusters and Catalytic Hydrodesulfurisation Reaction Pathways	p. 169
Nanoparticle Geometry at Oxide-supported Metal Catalysts	p. 171
Summary	p. 175
References	p. 176
Further Reading	p. 178
Studies of Sulfur and Thiols at Metal Surfaces
Introduction	p. 179
Studies of Atomic Sulfur Adsorbed at Metal Surfaces	p. 180
Copper	p. 181
Nickel	p. 185
Gold and Silver	p. 189
Platinum, Rhodium, Ruthenium and Rhenium	p. 190
Alloy Systems	p. 193
Sulfur-containing Molecules	p. 195
Summary	p. 199
References	p. 200
Further Reading	p. 202
Surface Engineering at the Nanoscale
Introduction	p. 203
"Bottom-up" Surface Engineering	p. 204
Van der Waals Forces	p. 205
Hydrogen Bonding	p. 207
Chiral Surfaces from Prochiral Adsorbates	p. 208
Covalently Bonded Systems	p. 209
Surface Engineering Using Diblock Copolymer Templates	p. 211
Summary	p. 214
References	p. 214
Further Reading	p. 216
Epilogue	p. 217
Subject Index	p. 219
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