Fundamental concepts in heterogeneous catalysis / Jens K. Norskov, Felix Studt, Frank Abild-Pedersen, Thomas Bligaard.

Format:

Book

Author/Creator:

Nørskov, Jens K.

Contributor:

Studt, Felix.

Abild-Pedersen, Frank.

Bligaard, Thomas.

Wiley InterScience (Online service)

Language:

English

Subjects (All):

Heterogeneous catalysis.

Physical Description:

1 online resource (ix, 196 pages) : illustrations (some color

Place of Publication:

Hoboken, New Jersey : Wiley, [2014]

System Details:

text file

Summary:

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 Catalysts 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. Book jacket.

Contents:

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 Adsorbate-Adsorbate 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 Slate Theory 49

4.3 Recrossings and Variational Transition State Theory 59

4.4 Harmonic Transition State Theory 61

5 Kinetics 68

5.1 Microkinelic 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 Stale Energy Scaling Relations in Heterogeneous Catalysis 90

6.4 Universality of Transition State Scaling Relations 93

7 Activity and Selectivity Mans 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 Methanaton 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 Catalysis 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 Solid-Electrolyte Interface 156

11.2 Electron Transfer Processes at Surfaces 158

11.3 The Hydrogen Electrode 161

11.4 Adsorption Equilibria at the Electrified Surface-Electrolyte 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 175

12.2 The Band Structure of Solids 179

12.3 The Newns-Anderson Model 184

12.4 Bond-Energy Trends 186

12.5 Binding Energies Using the Newns-Anderson Model 193.

Notes:

Includes bibliographical references and index.

Electronic reproduction. Hoboken, N.J. Available via World Wide Web.

Description based on print version record.

Other Format:

Online version: Nørskov, Jens K. Fundamental concepts in heterogeneous catalysis

ISBN:

9781118892114

1118892119

Publisher Number:

99969395881

40024257914

Access Restriction:

Restricted for use by site license.