Spectroscopy in Catalysis: An Introduction

Spectroscopy in Catalysis......Page 4
Contents......Page 10
Preface......Page 16
List of Acronyms......Page 20
1.1 Heterogeneous Catalysis......Page 22
1.2 The Aim of Catalyst Characterization......Page 25
1.3 Spectroscopic Techniques......Page 26
1.4 Research Strategies......Page 28
References......Page 30
2.1 Introduction......Page 32
2.2.1 Thermodynamics of Reduction......Page 34
2.2.2 Reduction Mechanisms......Page 36
2.2.3 Applications......Page 39
2.3 Temperature-Programmed Sulfidation......Page 42
2.4 Temperature-Programmed Reaction Spectroscopy......Page 43
2.5 Temperature-Programmed Desorption......Page 44
2.5.1 TPD Analysis......Page 50
2.5.2 Desorption in the Transition State Theory......Page 52
2.6 Temperature-Programmed Reaction Spectroscopy in UHV......Page 56
References......Page 58
3.1 Introduction......Page 60
3.2 X-Ray Photoelectron Spectroscopy (XPS)......Page 62
3.2.1 XPS Intensities and Sample Composition......Page 65
3.2.2 XPS Binding Energies and Oxidation States......Page 67
3.2.3 Shake Up, Shake Off, Multiplet Splitting and Plasmon Excitations......Page 71
3.2.4 Experimental Aspects of XPS......Page 72
3.2.5 Charging and Sample Damage......Page 73
3.2.6 Dispersion of Supported Particles from XPS......Page 75
3.2.7 Angle-Dependent XPS......Page 80
3.2.8 In-Situ and Real Time XPS Studies......Page 84
3.3 Ultraviolet Photoelectron Spectroscopy (UPS)......Page 86
3.3.1 Photoemission of Adsorbed Xenon......Page 92
3.4 Auger Electron Spectroscopy......Page 95
3.4.1 Energy of Auger Peaks......Page 96
3.4.2 Intensity of Auger Peaks......Page 98
3.4.3 Application of AES in Catalytic Surface Science......Page 99
3.4.5 Depth-Sensitive Information from AES......Page 101
References......Page 102
4.1 Introduction......Page 106
4.2 Secondary Ion Mass Spectrometry (SIMS)......Page 107
4.2.1 Theory of SIMS......Page 109
4.2.2 Electron and Photon Emission under Ion Bombardment......Page 111
4.2.3 Energy Distribution of Secondary Ions......Page 112
4.2.4 The Ionization Probability......Page 113
4.2.6 Conditions for Static SIMS......Page 115
4.2.8 Applications on Catalysts......Page 116
4.2.9 Model Catalysts......Page 120
4.2.10 Single Crystal Studies......Page 122
4.3 Secondary Neutral Mass Spectrometry (SNMS)......Page 126
4.4 Ion Scattering: The Collision Process......Page 127
4.5 Rutherford Backscattering Spectrometry (RBS)......Page 129
4.6 Low-Energy Ion Scattering (LEIS)......Page 133
4.6.1 Neutralization......Page 134
4.6.2 Applications of LEIS in Catalysis......Page 135
References......Page 138
5.1 Introduction......Page 142
5.2 The Mössbauer Effect......Page 143
5.3 Mössbauer Spectroscopy......Page 147
5.3.1 Isomer Shift......Page 149
5.3.2 Electric Quadrupole Splitting......Page 150
5.3.3 Magnetic Hyperfine Splitting......Page 152
5.3.4 Intensity......Page 153
5.4 Mössbauer Spectroscopy in Catalyst Characterization......Page 155
5.4.1 In-Situ Mössbauer Spectroscopy at Cryogenic Temperatures......Page 158
5.4.2 Particle Size Determination......Page 160
5.4.3 Kinetics of Solid-State Reactions from Single Velocity Experiments......Page 161
5.4.4 In-Situ Mössbauer Spectroscopy Under Reaction Conditions......Page 162
5.4.5 Mössbauer Spectroscopy of Elements Other Than Iron......Page 164
References......Page 166
6.1 Introduction......Page 168
6.2 X-Ray Diffraction......Page 169
6.2.1 In-Situ XRD: Kinetics of Solid-State Reactions......Page 173
6.2.2 Concluding Remarks......Page 175
6.3 Low-Energy Electron Diffraction (LEED)......Page 176
6.4 X-Ray Absorption Fine Structure (XAFS)......Page 180
6.4.1 EXAFS......Page 181
6.4.2 Quick EXAFS for Time-Resolved Studies......Page 191
6.4.3 X-Ray Absorption Near Edge Spectroscopy......Page 193
References......Page 196
7.1 Introduction......Page 200
7.2 Electron Microscopy......Page 201
7.2.1 Transmission Electron Microscopy......Page 203
7.2.2 Scanning Electron Microscopy......Page 205
7.2.3 Scanning Transmission Electron Microscopy......Page 207
7.2.4 Element Analysis in the Electron Microscope......Page 211
7.3.1 Theory of FEM and FIM......Page 214
7.4 Scanning Probe Microscopy: AFM and STM......Page 218
7.4.1 AFM and SFM......Page 219
7.4.1.1 Contact Mode AFM......Page 220
7.4.2 AFM Equipment......Page 221
7.4.3 Scanning Tunneling Microscopy (STM)......Page 226
7.4.4 Applications of STM in Catalytic Surface Science......Page 229
7.5 Other Imaging Techniques......Page 232
7.5.1 Low-Energy Electron Microscopy and Photoemission Electron Microscopy......Page 233
References......Page 235
8.1 Introduction......Page 238
8.2 Theory of Molecular Vibrations......Page 239
8.3 Infrared Spectroscopy......Page 245
8.3.2 Applications of Infrared Spectroscopy......Page 247
8.3.3 Transmission Infrared Spectroscopy......Page 248
8.3.4 Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)......Page 251
8.3.5 Attenuated Total Reflection......Page 254
8.3.6 Reflection Absorption Infrared Spectroscopy (RAIRS)......Page 255
8.4 Sum-Frequency Generation......Page 256
8.5 Raman Spectroscopy......Page 259
8.5.1 Applications of Raman Spectroscopy......Page 261
8.6 Electron Energy Loss Spectroscopy (EELS)......Page 264
8.7 Concluding Remarks......Page 268
References......Page 269
9.2 Supported Rhodium Catalysts......Page 272
9.2.1 Preparation of Alumina-Supported Rhodium Model Catalysts......Page 273
9.2.2 Reduction of Supported Rhodium Catalysts......Page 275
9.2.3 Structure of Supported Rhodium Catalysts......Page 278
9.2.4 Disintegration of Rhodium Particles Under CO......Page 282
9.3 Alkali Promoters on Metal Surfaces......Page 285
9.4.1 Sulfidation of Oxidic Catalysts......Page 293
9.4.2 Structure of Sulfided Catalysts......Page 297
9.5 Chromium Polymerization Catalysts......Page 305
9.6 Concluding Remarks......Page 313
References......Page 314
A.2.1 Surface Crystallography......Page 318
A.2.2 Surface Free Energy......Page 322
A.2.3 Lattice Vibrations......Page 323
A.2.4 Electronic Structure of Metal Surfaces......Page 326
A.2.5 Work Function......Page 330
A.3 Chemisorption on Metals......Page 332
A.3.1 Adsorption of Molecules on Jellium......Page 336
A.3.2 Adsorption on Metals with d-Electrons......Page 338
References......Page 340
Index......Page 342