Reactions at Solid Surfaces

Preface ix 1. Basic principles 1 1.1. Introduction: The surface science approach 1 1.2. Energetics of chemisorption 4 1.3. Kinetics of chemisorption 11 1.4. Surface diffusion 13 References 17 2. Surface structure and reactivity 21 2.1. Influence of the surface structure on reactivity 21 2.2. Growth of two-dimensional phases 24 2.3. Electrochemical modification of surface structure 29 2.4. Surface reconstruction and transformation 33 2.5. Subsurface species and compound formation 42 2.6. Epitaxy 44 References 47 3. Dynamics of molecule/surface interactions 51 3.1. Introduction 51 3.2. Scattering at surfaces 52 3.3. Dissociative adsorption 54 3.4. Collision-induced surface reactions 59 3.5. ‘‘Hot’’ adparticles 60 3.6. Particles coming off the surface 64 3.7. Energy exchange between adsorbate and surface 69 References 75 4. Electronic excitations and surface chemistry 79 4.1. Introduction 79 4.2. Exoelectron emission 81 4.3. Internal electron excitation: ‘‘chemicurrents’’ 86 4.4. Electron-stimulated desorption 88 4.5. Surface photochemistry 94 References 98 5. Principles of heterogeneous catalysis 103 5.1. Introduction 103 5.2. Active sites 105 5.3. Langmuir–Hinshelwood versus Eley–Rideal mechanism 109 5.4. Coadsorption 111 5.5. Kinetics of catalytic reactions 113 5.6. Selectivity 117 References 120 6. Mechanisms of heterogeneous catalysis 123 6.1. Synthesis of ammonia on iron 123 6.2. Synthesis of ammonia on ruthenium 134 6.3. Oxidation of carbon monoxide 139 6.4. Oxidation of hydrogen on platinum 149 References 154 7. Oscillatory kinetics and nonlinear dynamics 159 7.1. Introduction 159 7.2. Oscillatory kinetics in the catalytic CO oxidation on Pt(110) 163 7.3. Forced oscillations in CO oxidation on Pt(110) 169 References 172 Contents vii 8. Spatiotemporal self-organization in surface reactions 175 8.1. Introduction 175 8.2. Turing patterns and electrochemical systems 178 8.3. Isothermal wave patterns 183 8.4. Modification and control of spatiotemporal patterns 189 8.5. Thermokinetic effects 195 8.6. Pattern formation on microscopic scale 198 References 200 Index 205