Fundamental Concepts in Heterogeneous Catalysis

JENS K. NØRSKOV, PHD, is the Leland T. Edwards Professor of Engineering at Stanford University, USA. He is the founding director of the SUNCAT Center for Interface Science and Catalysis at Stanford University and SLAC National Accelerator Laboratory, USA. He has pioneered the development of a set of concepts allowing a molecular level understanding of surface chemical processes and heterogeneous catalysis. FELIX STUDT, PHD, is a Staff Scientist at the SLAC National Accelerator Laboratory, USA. His SUNCAT research group focuses on understanding catalytic processes for efficient energy conversion and using this as a basis for design of new catalysts. FRANK ABILD-PEDERSEN, PHD, is a Staff Scientist at the SUNCAT Center at SLAC National Accelerator Laboratory, USA, where his group focuses on the development of theoretical models of molecule surface interactions and models describing ultrafast surface processes measured in X-ray free electron lasers. THOMAS BLIGAARD, PHD, is a Senior Staff Scientist at at SLAC National Accelerator Laboratory, USA and the deputy director for theory at the SUNCAT Center, USA. His research group focuses on the development of electronic structure methods, kinetics tools, and data mining in catalysis.

• Preface viii1 Heterogeneous Catalysis and a Sustainable Future 12 The Potential Energy Diagram 62.1 Adsorption, 72.2 Surface Reactions, 112.3 Diffusion, 132.4 Adsorbate–Adsorbate Interactions, 152.5 Structure Dependence, 172.6 Quantum and Thermal Corrections to the Ground-State Potential Energy, 203 Surface Equilibria 263.1 Chemical Equilibria in Gases, Solids, and Solutions, 263.2 The Adsorption Entropy, 313.3 Adsorption Equilibria: Adsorption Isotherms, 343.4 Free Energy Diagrams for Surface Chemical Reactions, 40Appendix 3.1 The Law of Mass Action and the Equilibrium Constant, 42Appendix 3.2 Counting the Number of Adsorbate Configurations, 44Appendix 3.3 Configurational Entropy of Adsorbates, 444 Rate Constants 474.1 The Timescale Problem in Simulating Rare Events, 484.2 Transition State Theory, 494.3 Recrossings and Variational Transition State Theory, 594.4 Harmonic Transition State Theory, 615 Kinetics 685.1 Microkinetic Modeling, 685.2 Microkinetics of Elementary Surface Processes, 695.3 The Microkinetics of Several Coupled Elementary Surface Processes, 745.4 Ammonia Synthesis, 796 Energy Trends in Catalysis 856.1 Energy Correlations for Physisorbed Systems, 856.2 Chemisorption Energy Scaling Relations, 876.3 Transition State Energy Scaling Relations in Heterogeneous Catalysis, 906.4 Universality of Transition State Scaling Relations, 937 Activity and Selectivity Maps 977.1 Dissociation Rate-Determined Model, 977.2 Variations in the Activity Maximum with Reaction Conditions, 1017.3 Sabatier Analysis, 1037.4 Examples of Activity Maps for Important Catalytic Reactions, 1057.4.1 Ammonia Synthesis, 1057.4.2 The Methanation Reaction, 1077.5 Selectivity Maps, 1128 The Electronic Factor in Heterogeneous Catalysis 1148.1 The d-Band Model of Chemical Bonding at Transition Metal Surfaces, 1148.2 Changing the d-Band Center: Ligand Effects, 1258.3 Ensemble Effects in Adsorption, 1308.4 Trends in Activation Energies, 1318.5 Ligand Effects for Transition Metal Oxides, 1349 Catalyst Structure: Nature of the Active Site 1389.1 Structure of Real Catalysts, 1389.2 Intrinsic Structure Dependence, 1399.3 The Active Site in High Surface Area Catalysts, 1439.4 Support and Structural Promoter Effects, 14610 Poisoning and Promotion of Catalysts 15011 Surface Electrocatalysis 15511.1 The Electrified Solid–Electrolyte Interface, 15611.2 Electron Transfer Processes at Surfaces, 15811.3 The Hydrogen Electrode, 16111.4 Adsorption Equilibria at the Electrified Surface–Electrolyte Interface, 16111.5 Activation Energies in Surface Electron Transfer Reactions, 16211.6 The Potential Dependence of the Rate, 16411.7 The Overpotential in Electrocatalytic Processes, 16711.8 Trends in Electrocatalytic Activity: The Limiting Potential Map, 16912 Relation of Activity to Surface Electronic Structure 17512.1 Electronic Structure of Solids, 17512.2 The Band Structure of Solids, 17912.3 The Newns–Anderson Model, 18412.4 Bond-Energy Trends, 18612.5 Binding Energies Using the Newns–Anderson Model, 193Index 195