Surface Science: Foundations of Catalysis and Nanoscience, Second Edition

Surface Science:Foundations of Catalysis and Nanoscience Second Edition......Page 2
Contents......Page 8
Acknowledgements......Page 16
Introduction......Page 18
I.1 Heterogeneous Catalysis......Page 19
I.2 Why Surfaces?......Page 20
I.3.2 Fischer-Tropsch Chemistry......Page 21
I.4 Semiconductor Processing and Nanotechnology......Page 22
I.6 Structure of the Book......Page 23
References......Page 26
1 Bulk and Surface Structure......Page 28
1.1.1 Ideal Flat Surfaces......Page 29
1.1.2 High Index and Vicinal Planes......Page 34
1.1.4 Bimetallic Surfaces......Page 36
1.1.5 Porous Solids......Page 37
1.1.6 Oxide Surfaces......Page 40
1.2.2 Clean Surface Reconstructions......Page 44
1.2.3 Adsorbate Induced Reconstructions......Page 45
1.2.5 Chiral Surfaces......Page 49
1.3.2 Metals, Semiconductors and Insulators......Page 52
1.3.3 Energy Levels at Metal Interfaces......Page 57
1.3.4 Energy Levels at Metal-Semiconductor Interfaces......Page 58
1.3.5 Surface Electronic States......Page 60
1.3.6 Size Effects in Nanoscale Systems......Page 63
1.4.1 Bulk Systems......Page 65
1.5 Summary of Important Concepts......Page 67
1.7 Further Reading......Page 68
1.8 Exercises......Page 69
References......Page 71
2.1.1 The Need for UHV......Page 74
2.1.2 Attaining UHV......Page 75
2.2 Light and Electron Sources......Page 77
2.2.3 Synchrotrons......Page 78
2.2.4 Free Electron Laser (FEL)......Page 80
2.3.1 Knudsen Molecular Beams......Page 81
2.3.2 Free Jets......Page 83
2.2.3 Comparison of Knudsen and Supersonic Beams......Page 85
2.4.1 Scanning Tunnelling Microscopy (STM)......Page 88
2.4.2 Scanning Tunnelling Spectroscopy (STS)......Page 93
2.4.3 Atomic Force Microscopy (AFM)......Page 94
2.4.4 Near-field Scanning Optical Microscopy (NSOM)......Page 98
2.5 Low Energy Electron Diffraction (LEED)......Page 101
Advanced Topic: LEED Structure Determination......Page 103
2.6 Electron Spectroscopy......Page 108
2.6.1 X-ray Photoelectron Spectroscopy (XPS)......Page 109
2.6.2 Ultraviolet Photoelectron Spectroscopy (UPS)......Page 114
Advanced Topic: Multiphoton Photoemission (MPPE)......Page 119
2.6.3 Auger Electron Spectroscopy (AES)......Page 120
2.6.4 Photoelectron Microscopy......Page 124
2.7 Vibrational Spectroscopy......Page 126
2.7.1 IR Spectroscopy......Page 128
2.7.2 Electron Energy Loss Spectroscopy (EELS)......Page 133
2.9 Summary of Important Concepts......Page 135
2.11 Further Reading......Page 136
2.12 Exercises......Page 137
References......Page 140
3.1 Types of Interactions......Page 144
3.2 Binding Sites and Diffusion......Page 145
Advanced Topic: Theoretical Description of Physisorption......Page 150
3.4.1 Theoretical Treatment of Chemisorption......Page 151
3.4.2 The Blyholder Model of CO Chemisorption on a Metal......Page 155
3.4.3 Molecular Oxygen Chemisorption......Page 158
3.4.4 The Binding of Ethene......Page 159
3.5 Dissociative Chemisorption: H2 on a Simple Metal......Page 160
3.6 What Determines the Reactivity of Metals?......Page 162
3.7.1 Scattering Channels......Page 165
3.7.2 Nonactivated Adsorption......Page 168
3.7.3 Hard Cube Model......Page 170
3.7.4 Activated Adsorption......Page 173
3.7.5 Direct versus Precursor Mediated Adsorption......Page 174
3.8 Microscopic Reversibility in Ad/desorption Phenomena......Page 178
3.9 The Influence of Individual Degrees of Freedom on Adsorption and Desorption......Page 183
3.9.1 Energy Exchange......Page 184
3.9.2 PES Topography and the Relative Efficacy of Energetic Components......Page 185
3.10.1 Effects on Adsorption......Page 186
3.10.2 Connecting Adsorption and Desorption with Microscopic Reversibility......Page 189
3.10.3 Normal Energy Scaling......Page 191
3.11.1 Nonactivated Adsorption......Page 193
3.12 Vibrations and Adsorption......Page 195
3.13 Competitive Adsorption and Collision Induced Processes......Page 196
Advanced Topic: High-Energy Collisions......Page 198
3.14 Classification of Reaction Mechanisms......Page 199
3.14.1 Langmuir-Hinshelwood Mechanism......Page 200
3.14.2 Eley-Rideal Mechanism......Page 202
3.14.3 Hot Atom Mechanism......Page 203
3.15 Measurement of Sticking Coefficients......Page 204
3.16 Summary of Important Concepts......Page 208
3.18 Further Reading......Page 209
3.19 Exercises......Page 210
References......Page 218
4.1.1 Binding Energies and Activation Barriers......Page 224
4.1.2 Thermodynamic Quantities......Page 226
4.1.3 Some Definitions......Page 227
4.1.4 The Heat of Adsorption......Page 228
4.2 Adsorption Isotherms from Thermodynamics......Page 230
4.3 Lateral Interactions......Page 233
4.4 Rate of Desorption......Page 234
4.4.1 First-order Desorption......Page 235
4.4.2 Transition State Theory Treatment of First-order Desorption......Page 236
4.4.3 Thermodynamic Treatment of First-order Desorption......Page 240
4.4.4 Nonfirst-order Desorption......Page 242
4.5.1 CTST Approach to Adsorption Kinetics......Page 243
4.5.2 Langmuirian Adsorption: Nondissociative Adsorption......Page 244
4.5.3 Langmuirian Adsorption: Dissociative Adsorption......Page 247
4.5.4 Dissociative Langmuirian Adsorption with Lateral Interactions......Page 248
4.5.5 Precursor Mediated Adsorption......Page 249
4.6 Adsorption Isotherms from Kinetics......Page 251
4.6.1 Langmuir Isotherm......Page 252
4.6.2 Classification of Adsorption Isotherms......Page 253
4.7.1 The Basis of TPD......Page 255
4.7.2 Qualitative Analysis of TPD Spectra......Page 257
4.7.3 Quantitative Analysis of TPD Spectra......Page 260
4.8 Summary of Important Concepts......Page 263
4.10 Further Reading......Page 264
4.11 Exercises......Page 265
References......Page 269
5.1 Structure of the Liquid/Solid Interface......Page 272
5.1.1 The Structure of the Water/Solid Interface......Page 275
5.2 Surface Energy and Surface Tension......Page 277
5.2.1 Liquid Surfaces......Page 278
5.2.2 Curved Interfaces......Page 280
5.3.1 Liquid-on-solid Films......Page 282
5.4 Langmuir Films......Page 284
5.5.1 Capillary Condensation and Meniscus Formation......Page 286
5.5.2 Vertical Deposition......Page 289
5.5.3 Horizontal Lifting (Shaefer?s Method)......Page 290
5.6 Self-assembled Monolayers (SAMs)......Page 291
5.6.1 Thermodynamics of Self-assembly......Page 292
5.6.3 Mechanism of SAM Formation......Page 294
5.7.1 The Gibbs Model......Page 298
5.7.3 Interfacial Enthalpy and Internal, Helmholtz and Gibbs Surface Energies......Page 300
5.8.1 Surface Charge and Potential......Page 302
5.8.2 Relating Work Functions to the Electrochemical Series......Page 305
5.9 Summary of Important Concepts......Page 307
5.11 Further Reading......Page 308
5.12 Exercises......Page 309
References......Page 310
6.1 The Prominence of Heterogeneous Reactions......Page 312
6.2 Measurement of Surface Kinetics and Reaction Mechanisms......Page 313
6.3 Haber-Bosch Process......Page 319
6.4 From Microscopic Kinetics to Catalysis......Page 323
6.4.1 Reaction Kinetics......Page 324
6.4.2 Kinetic Analysis using De Donder Relations......Page 325
6.4.3 Definition of the Rate Determining Step (RDS)......Page 326
6.4.4 Microkinetic Analysis of Ammonia Synthesis......Page 327
6.5 Fischer-Tropsch Synthesis and Related Chemistry......Page 330
6.6 The Three-way Automotive Catalyst......Page 334
6.7 Promoters......Page 337
6.8 Poisons......Page 338
6.9 Bimetallic and Bifunctional Catalysts......Page 340
6.10 Rate Oscillations and Spatiotemporal Pattern Formation......Page 341
Advanced Topic: Cluster Assembled Catalysts......Page 343
6.11 Sabatier Analysis and Optimal Catalyst Selection......Page 344
6.12 Summary of Important Concepts......Page 346
6.14 Further Reading......Page 347
6.15 Exercises......Page 348
References......Page 350
7.1 Stress and Strain......Page 354
7.2.1 Strain Relief......Page 358
7.3 Surface Energy, Surface Tension and Strain Energy......Page 360
7.4.1 Solid-on-Solid Growth......Page 362
7.4.2 Strain in Solid-on-Solid Growth......Page 363
7.4.3 Ostwald Ripening......Page 365
7.4.4 Equilibrium Overlayer Structure and Growth Mode......Page 366
7.5 Nucleation Theory......Page 368
7.6.1 Thermodynamics versus Dynamics......Page 371
7.6.2 Nonequilibrium Growth Modes......Page 372
7.7.1 Molecular Beam Epitaxy (MBE)......Page 376
7.7.2 Chemical Vapour Deposition (CVD)......Page 379
7.8 Catalytic Growth of Nanotubes and Nanowires......Page 381
7.9.1 Classification of Etching......Page 386
7.9.2 Etch Morphologies......Page 391
7.9.3 Porous Solid Formation......Page 392
7.9.4 Silicon Etching in Aqueous Fluoride Solutions......Page 394
7.9.5 Coal Gasification and Graphite Etching......Page 397
7.9.6 Selective Area Growth and Etching......Page 398
7.10 Summary of Important Concepts......Page 401
7.12 Further Reading......Page 403
7.13 Exercises......Page 404
References......Page 406
8 Laser and Nonthermal Chemistry: Photon and Electron Stimulated Chemistry and Atom Manipulation......Page 412
8.1.1 Light Absorption by Condensed Matter......Page 413
8.1.2 Lattice Heating......Page 415
Advanced Topic: Temporal Evolution of Electronic Excitations......Page 419
8.1.3 Summary of Laser Excitations......Page 426
8.2.1 Direct versus Substrate Mediated Processes......Page 427
8.2.2 Gas-Phase Photochemistry......Page 429
8.2.4 MGR and Antoniewicz Models of DIET......Page 431
8.2.5 Desorption Induced by Ultrafast Excitation......Page 435
8.3.1 Thermal Desorption, Reaction and Diffusion......Page 436
8.3.2 Stimulated Desorption/reaction......Page 437
8.3.3 Ablation......Page 445
8.4 Charge Transfer and Electrochemistry......Page 448
Advanced Topic: Semiconductor Photoelectrodes and the Gra?tzel Photovoltaic Cell......Page 451
8.5 Tip Induced Process: Mechanisms of Atom Manipulation......Page 455
8.5.2 Tip Induced ESD......Page 456
8.5.3 Vibrational Ladder Climbing......Page 458
8.5.4 Pushing......Page 460
8.5.6 Atom Manipulation by Covalent Forces......Page 461
8.6 Summary of Important Concepts......Page 463
8.7 Frontiers and Challenges......Page 464
8.9 Exercises......Page 465
References......Page 468
Appendix I Fundamental Constants and Conversion Factors......Page 472
Appendix II Abbreviations......Page 476
Appendix III Symbols......Page 480
Appendix IV Useful Mathematical Expressions......Page 486
Index......Page 490