This book is based on a graduate course and suitable as a primer
for any newcomer to the field, this book is a detailed introduction
to the experimental and computational methods that are used to
study how solid surfaces act as catalysts.
Features include:
* First comprehensive description of modern theory of
heterogeneous catalysis
* Basis for understanding and designing experiments in the field
* Allows reader to understand catalyst design principles
* Introduction to important elements of energy transformation
technology
* Test driven at Stanford University over several semesters
Autorentext
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.
Klappentext
The first comprehensive text on the modern theory of heterogeneous catalysis
Heterogeneous catalysis is the cornerstone of chemical industry and also holds the key to new processes for sustainable energy conversion and sustainable production of feedstocks for the chemical industry. Heterogeneous catalysis involves chemical transformations taking place at the surface of a solid, and is a very complex phenomenon. There is now a consistent set of concepts that allow an understanding of surface catalysis and they even form a basis for design principles for new catalysts.
Based on a graduate/senior-undergraduate course and suitable as a primer for anyone interested in understanding the field, Fundamental Concepts in Heterogeneous Catalysis presents the following:
- The fundamentals of surface reaction phenomena including potential energy diagrams, free energy diagrams, and kinetic models
- Tools to reduce the complexity of heterogeneous catalysis including scaling relations
- An understanding of trends in catalysis including activity and selectivity maps
- An introduction to electronic structure effects in catalysis and an understanding of structural effects
- Application to a series of heterogeneously catalyzed reactions including reactions of interest in energy conversion
- An integration of the conceptual frameworks of electro-catalysis and thermal heterogeneous catalysis
- An understanding of the effect of promoters and poisons in heterogeneous catalysis
Unlike most textbooks in the field, the aim of this monograph is not to give a complete overview of the types of catalysts or catalytic processes, but to provide interested students and researchers with the atomic-scale concepts for understanding catalytic phenomena.
Zusammenfassung
This book is based on a graduate course and suitable as a primer for any newcomer to the field, this book is a detailed introduction to the experimental and computational methods that are used to study how solid surfaces act as catalysts.
Features include:
- First comprehensive description of modern theory of heterogeneous catalysis
- Basis for understanding and designing experiments in the field
- Allows reader to understand catalyst design principles
- Introduction to important elements of energy transformation technology
- Test driven at Stanford University over several semesters
Inhalt
Preface viii
1 Heterogeneous Catalysis and a Sustainable Future 1
2 The Potential Energy Diagram 6
2.1 Adsorption, 7
2.2 Surface Reactions, 11
2.3 Diffusion, 13
2.4 AdsorbateAdsorbate Interactions, 15
2.5 Structure Dependence, 17
2.6 Quantum and Thermal Corrections to the Ground-State Potential Energy, 20
3 Surface Equilibria 26
3.1 Chemical Equilibria in Gases, Solids, and Solutions, 26
3.2 The Adsorption Entropy, 31
3.3 Adsorption Equilibria: Adsorption Isotherms, 34
3.4 Free Energy Diagrams for Surface Chemical Reactions, 40
Appendix 3.1 The Law of Mass Action and the Equilibrium Constant, 42
Appendix 3.2 Counting the Number of Adsorbate Configurations, 44
Appendix 3.3 Configurational Entropy of Adsorbates, 44
4 Rate Constants 47
4.1 The Timescale Problem in Simulating Rare Events, 48
4.2 Transition State Theory, 49
4.3 Recrossings and Variational Transition State Theory, 59
4.4 Harmonic Transition State Theory, 61
5 Kinetics 68
5.1 Microkinetic Modeling, 68
5.2 Microkinetics of Elementary Surface Processes, 69
5.3 The Microkinetics of Several Coupled Elementary Surface Processes, 74
5.4 Ammonia Synthesis, 79
6 Energy Trends in Catalysis 85
6.1 Energy Correlations for Physisorbed Systems, 85
6.2 Chemisorption Energy Scaling Relations, 87
6.3 Transition State Energy Scaling Relations in Heterogeneous Catalysis, 90
6.4 Universality of Transition State Scaling Relations, 93
7 Activity and Selectivity Maps 97
7.1 Dissociation Rate-Determined Model, 97
7.2 Variations in the Activity Maximum with Reaction Conditions, 101
7.3 Sabatier Analysis, 103
7.4 Examples of Activity Maps for Important Catalytic Reactions, 105
7.4.1 Ammonia Synthesis, 105
7.4.2 The Methanation Reaction, 107
7.5 Selectivity Maps, 112
8 The Electronic Factor in Heterogeneous Catalysis 114
8.1 The d-Band Model of Chemical Bonding at Transition Metal Surfaces, 114
8.2 Changing the d-Band Center: Ligand Effects, 125
8.3 Ensemble Effects in Adsorption, 130
8.4 Trends in Activation Energies, 131
8.5 Ligand Effects for Transition Metal Oxides, 134
9 Catalyst Structure: Nature of the Active Site 138
9.1 Structure of Real Catalysts, 138
9.2 Intrinsic Structure Dependence, 139
9.3 The Active Site in High Surface Area Catalysts, 143
9.4 Support and Structural Promoter Effects, 146
10 Poisoning and Promotion of Catalysts 150
11 Surface Electrocatalysis 155
11.1 The Electrified SolidElectrolyte Interface, 156
11.2 Electron Transfer Processes at Surfaces, 158
11.3 The Hydrogen Electrode, 161
11.4 Adsorption Equilibria at the Electrified SurfaceElectrolyte Interface, 161
11.5 Activation Energies in Surface Electron Transfer Reactions, 162
11.6 The Potential Dependence of the Rate, 164
11.7 The Overpotential in Electrocatalytic Processes, 167
11.8 Trends in Electrocatalytic Activity: The Limiting Potential Map, 169
12 Relation of Activity to Surface Electronic Structure 175
12.1 Electronic Structure of Solids…