Principles and Practice of Heterogeneous Catalysis

Professor Sir John Meurig Thomas, FRS, FREng, Former Head of Physical Chemistry , University of Cambridge, is one of the most renowned researcher in the field of heterogeneous catalysis and solid state chemistry. He has been awarded the Davy Medal, the Messel Gold Medal, the Willard Gibbs Gold Medal, U.S. Presidential Green Chemistry Challenge Award, the Linus Pauling Gold Medal and many others. He is the author of over a thousand research papers on the materials and surface chemistry of solids, and over 100 review articles on science, education and cultural issues and the co-author of 30 patents.W. John Thomas, FR Eng, is Professor Emeritus of Chemical Engineering at the University of Bath.

• Preface XIX1 Setting the Scene 11.1 Prologue: Advances since the Early 1990s 11.2 Introduction 131.3 Perspectives in Catalysis: Past, Present and Future 161.4 Definition of Catalytic Activity 321.5 Key Advances in Recent Theoretical Treatments: Universability in Heterogeneous Catalysis 521.6 Milestones Reached in Industrial Catalysis in the Twentieth Century, and Some Consequential Challenges 54Problems 61References 64Further Reading 662 The Fundamentals of Adsorption: Structural and Dynamical Considerations, Isotherms and Energetics 672.1 Catalysis Must Always Be Preceded by Adsorption 672.2 The Surfaces of Clean Solids are Sometimes Reconstructed 712.3 There Are Many Well-Defined Kinds of Ordered Adlayers 742.4 Adsorption Isotherms and Isobars 792.5 Dynamical Considerations 862.6 Relating the Activation Energy to the Energy of Chemisorption. Universality in Heterogeneous Catalysis and the Brønsted–Evans–Polanyi (BEP) Relation 1012.7 Deriving Adsorption Isotherms from Kinetic Principles 1052.8 Energetics of Adsorption 1132.9 Mobility at Surfaces 1262.10 Kinetics of Surface Reactions 1272.11 Autocatalytic, Oscillatory and Complex Heterogeneous Reactions 1322.12 Microkinetics: A Summary 147Problems 155References 161Further Reading 1623 The Characterization of Industrial and Model Solid Catalysts 163Part I: Characterization of Industrial Solid Catalysts 1633.1 Non-invasive Methods Suitable for Studies Involving Catalytic Reactors 164Part II: Laboratory Characterization of Solid Catalysts 1723.2 A Portfolio of Modern Methods: Introducing the Acronyms 1723.3 Which Elements and Which Phases Are Present? 1753.4 Probing Surfaces with IR, HREELS, AES and XPS 1843.5 Ultraviolet–Visible and Photoluminescence Spectroscopy 1913.6 Structure and Crystallography of Surfaces: Nature of Ordered and Reconstructed Surfaces 1933.7 Other Structural Techniques for Characterizing Bulk and Surfaces of Catalysts 2143.8 A Miscellany of Other Procedures 2583.9 Determining the Strength of Surface Bonds: Thermal and Other Temperature-Programmed Methods 2593.10 Reflections on the Current Scene Pertaining In situ Methods of Studying Catalysts 265Problems 281References 288Further Reading 291General 291Additional 291In situ Techniques 2914 Porous Catalysts: Their Nature and Importance 2934.1 Definitions and Introduction 2934.2 Determination of Surface Area 2964.3 Mercury Porosimetry 3064.4 Wheeler’s Semi-empirical Pore Model 3084.5 Diffusion in Porous Catalysts 3144.6 Chemical Reaction in Porous Catalyst Pellets 319Problems 337References 340Further Reading 341Specific Books 342General 3425 Solid State Chemical Aspects of Heterogeneous Catalysts 3435.1 Recent Advances in Our Knowledge of Some Metal Catalysts: In Their Extended, Cluster or Nanoparticle States 3455.2 Comments on the Catalytic Behaviour of Nanogold 3525.3 Recent Advances in the Elucidation of Certain Metal-Oxide Catalysts 3595.4 Atomic-Scale Edge Structures in Industrial-Style MoS2 Nanocatalysts 3635.5 Open-Structure Catalysts: from 2D to 3D 3645.6 Computational Approaches 3765.7 A Chemist’s Guide to the Electronic Structure of Solids and Their Surfaces 3895.8 Key Advances in Recent Theoretical Treatments of Heterogeneous Catalysis 4155.9 Selected Applications of DFT to Catalysis 4195.10 Concluding Remarks Concerning DFT Calculations inHeterogeneous Catalysis 429Problems 430References 433Key References Published Since the First Edition 436Seminal Books 436Monographs 437Book Chapters 437Further Reading 4376 Poisoning, Promotion, Deactivation and Selectivity of Catalysts 4396.1 Background 4396.2 Catalyst Deactivation 4526.3 Some Modern Theories of Poisoning and Promotion 463Problems 474References 477Further Reading 477General 477Studies of Model Surfaces 477Theory of Poisoning and Promotion 4787 Catalytic Process Engineering 479Part I: Recent Advances in Reactor Design 4797.1 Novel Operating Strategies 482Part II: Traditional Methods of Catalytic Process Engineering 4997.2 Traditional Catalytic Reactors 499Problems 534References 538General References for Part II 539General 539Kinetic Models 539Experimental Chemical Reactor Configurations 540Slurry Reactors 540Further Reading 5408 Heterogeneous Catalysis: Examples, Case Histories and Current Trends 5418.1 Synthesis of Methanol 5418.2 Fischer–Tropsch Catalysis 5468.3 Synthesis of Ammonia 5688.4 Oxidation of Ammonia: Stepping Toward the Fertilizer Industry 5888.5 In situ Catalytic Reaction and Separation 5928.6 Automobile Exhaust Catalysts and the Catalytic Monolith 6018.7 Photocatalytic Breakdown of Water and the Harnessing of Solar Energy 6148.8 Catalytic Processes in the Petroleum Industry 629Problems 645References 651Further Reading 6539 Powering the Planet in a Sustainable Manner: Some of Tomorrow’s Catalysts (Actual and Desired) and Key Catalytic Features Pertaining to Renewable Feedstocks, Green Chemistry and Clean Technology 6559.1 Introduction 655Part I: Prospects, Practices and Principles of Generating Solar Fuels 6589.2 Powering the Planet with Solar Fuel 6589.3 Some Significant Advances in Photo-Assisted Water Splitting and Allied Phenomena 6599.4 The Hydrogen Economy 6779.4.1 The Methanol Economy 682Part II: Current Practices in Powering the Planet and Producing Chemicals 6859.5 Some of Tomorrow’s Catalysts: Actual and Desired 6859.6 A Biorefinery Capable of Producing Transportation Fuels and Commodity Chemicals that Starts with Metabolic Engineering and Ends with Inorganic Solid Catalysts 7079.7 Non-enzymatic Catalytic Processing of Biomass-Derived Raw Materials to Selected Chemical Products 7119.8 Strategies for the Design of New Catalysts 719Part III: Thermochemical Cycles and High-Flux, Solar-Driven Conversions 7249.9 Solar-Driven, Catalysed Thermochemical Reactions as Alternatives to Fossil-Fuel-Based Energy and Chemical Economies 724Acknowledgements 726Problems 726References 729Further Reading 732Index 733