This long-awaited second edition of the successful introduction to the fundamentals of heterogeneous catalysis is now completely revised and updated. Written by internationally acclaimed experts, this textbook includes fundamentals of adsorption, characterizing catalysts and their surfaces, the significance of pore structure and surface area, solid-state and surface chemistry, poisoning, promotion, deactivation and selectivity of catalysts, as well as catalytic process engineering. A final section provides a number of examples and case histories. With its color and numerous graphics plus references to help readers to easily find further reading, this is a pivotal work for an understanding of the principles involved.
Intro Principles and Practice of Heterogeneous Catalysis Contents Preface Chapter 1 Setting the Scene 1.1 Prologue: Advances since the Early 1990s 1.2 Introduction 1.2.1 Selectivity of Catalysts 1.3 Perspectives in Catalysis: Past, Present and Future 1.3.1 Applied Catalysis since the 1940s 1.3.2 Some Current Trends in Applied Catalysis 188.8.131.52 Auto-Exhaust Catalysts 184.108.40.206 Catalysts in Electrochemistry and Photoelectrochemistry 220.127.116.11 Immobilized Metals 18.104.22.168 Immobilized Enzymes and Cells: Present and Future 22.214.171.124 Ribozymes 1.4 Definition of Catalytic Activity 1.4.1 Magnitude of Turnover Frequencies and Active Site Concentrations 1.4.2 Volcano Plots 1.4.3 Evolution of Important Concepts and Techniques in Heterogeneous Catalysis 126.96.36.199 Mechanistic Insights from Isotopic Labelling 188.8.131.52 Concepts from Organometallic Chemistry 1.5 Key Advances in Recent Theoretical Treatments: Universability in Heterogeneous Catalysis 1.5.1 Some Major Current Developments in Heterogeneous Catalysis 1.6 Milestones Reached in Industrial Catalysis in the Twentieth Century, and Some Consequential Challenges Problems References Further Reading Chapter 2 The Fundamentals of Adsorption: Structural and Dynamical Considerations, Isotherms and Energetics 2.1 Catalysis Must Always Be Preceded by Adsorption 2.1.1 Physical Adsorption, Chemisorption and Precursor States 2.2 The Surfaces of Clean Solids are Sometimes Reconstructed 2.3 There Are Many Well-Defined Kinds of Ordered Adlayers 2.4 Adsorption Isotherms and Isobars 2.4.1 The Empirical Facts 2.4.2 Information That Can Be Gleaned from Isotherms 2.4.3 Adsorption Is Almost Invariably Exothermic 2.5 Dynamical Considerations 2.5.1 Residence Times 2.5.2 Rates of Adsorption. 2.5.3 Applying Statistical Mechanics to Adsorption 2.5.4 Adsorption Kinetics Can Often Be Represented by the Elovich Equation 2.5.5 Rates of Desorption 2.5.6 Applying Statistical Mechanics to Desorption 2.5.7 Influence of a Precursor State on the Kinetics of Desorption 2.6 Relating the Activation Energy to the Energy of Chemisorption. Universality in Heterogeneous Catalysis and the Brønsted-Evans-Polanyi (BEP) Relation 2.6.1 Pareto-Optimal Catalysts 2.7 Deriving Adsorption Isotherms from Kinetic Principles 2.7.1 Using the Langmuir Isotherm to Estimate the Proportions of Non-dissociative and Associative Adsorption 2.7.2 Other Adsorption Isotherms 184.108.40.206 Henry's Adsorption Isotherm 220.127.116.11 Freundlich Isotherm 18.104.22.168 Temkin Isotherm 22.214.171.124 Brunauer-Emmett-Teller Isotherm 126.96.36.199 Developments from Polanyi's Adsorption Theory 188.8.131.52 Kaganer's Isotherm and the DKR Equation 184.108.40.206 Virial Equation of State 2.8 Energetics of Adsorption 2.8.1 Estimating the Binding Energies of Physically Adsorbed Species 2.8.2 Binding Energies of Chemisorbed Species 2.8.3 Estimating Heats of Adsorption from Thermodynamic Data 2.8.4 Decline of the Heat of Adsorption with Increasing Coverage 2.9 Mobility at Surfaces 2.10 Kinetics of Surface Reactions 2.10.1 The Influences of Precursor States on the Kinetics and Energy Distribution of Catalysed Reactions 2.10.2 Comparing the Rates of Heterogeneous and Homogeneous Reactions 2.11 Autocatalytic, Oscillatory and Complex Heterogeneous Reactions 2.11.1 An Outline of Autocatalysis 2.11.2 Background to Oscillating Reactions 2.11.3 Instabilities and Transient Phenomena in Heterogeneous Catalysis 2.11.4 Multiple Steady States 2.11.5 Transient Phenomena 2.11.6 Recent Thoughts on Spatio-Temporal Behaviour and Turbulence at Catalyst Surfaces. 2.12 Microkinetics: A Summary 2.12.1 Building Kinetic Models 2.12.2 Formulation of Kinetic Models in Terms of Transition States 2.12.3 Degree of Rate Control Problems References Further Reading Chapter 3 The Characterization of Industrial and Model Solid Catalysts Part I: Characterization of Industrial Solid Catalysts 3.1 Non-invasive Methods Suitable for Studies Involving Catalytic Reactors 3.1.1 Magnetic Resonance Imaging (MRI) 220.127.116.11 Visualizing the Spatial Variation of Esterification, Etherification and Hydrogenation within Fixed-Bed and Trickle-Bed Reactors with MRI 3.1.2 Positron Emission Methods 3.1.3 Use of Spatially-Resolved X-ray Absorption to Probe Supported Nobel Metal Catalysts during Operating Conditions Part II: Laboratory Characterization of Solid Catalysts 3.2 A Portfolio of Modern Methods: Introducing the Acronyms 3.3 Which Elements and Which Phases Are Present? 3.3.1 X-ray Fluorescence (XRF), X-ray Emission (XRE) and Proton-Induced X-ray Emission (PIXE) 3.3.2 Developing Techniques: ICPMS 3.3.3 X-ray Diffraction (XRD) and Small-Angle X-ray Scattering 18.104.22.168 Mean Size, Surface Area and Particle-Size Distribution from SAXS 22.214.171.124 In situ Studies by X-ray Diffraction 126.96.36.199 Experimental Aspects 3.4 Probing Surfaces with IR, HREELS, AES and XPS 3.4.1 Infrared Spectroscopy (IR): A Non-destructive Technique Usable on Catalysts Exposed to High Pressure 3.4.2 High-Resolution Electron-Energy Loss Spectroscopy (HREELS): the Most Sensitive Tool for Identifying Surface Vibrational Modes 3.4.3 Merits and Limitations of Electron Spectroscopy 3.5 Ultraviolet-Visible and Photoluminescence Spectroscopy 3.6 Structure and Crystallography of Surfaces: Nature of Ordered and Reconstructed Surfaces 3.6.1 Two- and Three-Dimensional Surface Crystallography. 3.6.2 Notations for Describing Ordered Structures at Surfaces 3.6.3 How Do Bond Distances at Surfaces Compare with Those of Bulk Solids? What of Displacive Reconstructions? 3.6.4 EXAFS, SEXAFS, XANES and NEXAFS: Probing Bond Distances and Site Environments Even When There is No Long-Range Order 188.8.131.52 Origin of EXAFS and How It Is Used 184.108.40.206 Applications of EXAFS to the Study of Catalysts 220.127.116.11 SEXAFS 18.104.22.168 XANES and Pre-edge Structure: Deducing Site Symmetry and Oxidation States 22.214.171.124 NEXAFS 3.7 Other Structural Techniques for Characterizing Bulk and Surfaces of Catalysts 3.7.1 Electron Spin Resonance (ESR): Probing the Nature of Catalytically Active Sites and the Concentration of Paramagnetic Intermediates on Surfaces and in the Gas Phase 126.96.36.199 Examples of the Use of ESR in Heterogeneous Catalysis 3.7.2 Nuclear Magnetic Resonance (NMR): A Technique Applicable, at High Resolution, to Solids and Their Surfaces 188.8.131.52 Basic Principles 184.108.40.206 NMR Spectra of Solids 220.127.116.11 Applications of NMR to the Study of Catalysts, Adsorbents and Adsorbates 18.104.22.168 Future Prospects for the Study of Catalysts by Solid-State NMR 3.7.3 Sum Frequency Generation (SFG) and Infrared Reflection Absorption Spectroscopy (IRAS or IRRAS) 22.214.171.124 Essential Background and Mode of Operation 3.7.4 Scanning Tunnelling Microscopy (STM) and Clues for the Design of New Catalysts 126.96.36.199 Scanning Tunnelling Spectroscopy (STS) 188.8.131.52 Atomic Force Microscopy (AFM) and Fluorescence Microscopy (FM) 3.7.5 Electron Microscopy 184.108.40.206 Electron Crystallography 220.127.116.11 Electron Tomography (ET) 18.104.22.168 A Few Illustrative Examples of Static EM Images 22.214.171.124 In situ (Environmental) TEM 126.96.36.199 4D Electron Microscopy 3.7.6 Optical Microscopy and Ellipsometry (Non-invasive Techniques). 3.7.7 Neutron Scattering: A Technique of Growing Importance in the Study of Catalysts 188.8.131.52 Determining the Atomic Structure and Texture of Microcrystalline Catalysts, the Nature of the Active Sites and the Disposition of Bound Reactants 184.108.40.206 Determining the Structure of, and Identifying Functional Groups in, Chemisorbed Layers at Catalyst Surfaces 3.8 A Miscellany of Other Procedures 3.9 Determining the Strength of Surface Bonds: Thermal and Other Temperature-Programmed Methods 3.9.1 Temperature-Programmed Desorption (TPD) or Flash Desorption Spectroscopy (FDS) 3.9.2 Temperature-Programmed Reaction Spectroscopy (TPRS) 3.9.3 Magnitude of the Heat and Entropy of Adsorption 3.10 Reflections on the Current Scene Pertaining In situ Methods of Studying Catalysts 3.10.1 Isotopic Labelling and Transient Response 3.10.2 From Temporal Analysis of Products (TAP) to Steady-State Isotopic Transient Kinetic Analysis (SSITKA) 3.10.3 Infrared, Raman, NMR, and X-ray Absorption Spectroscopy for In situ Studies 3.10.4 In situ X-ray, Electron and Neutron Diffraction Studies 3.10.5 Combined X-ray Absorption and X-ray Diffraction and Other Techniques for In situ Studies of Catalysts Problems References Further Reading General Additional In situ Techniques Chapter 4 Porous Catalysts: Their Nature and Importance 4.1 Definitions and Introduction 4.2 Determination of Surface Area 4.2.1 Assessment of Porosity 220.127.116.11 Capillary Condensation the Kelvin Equation and the Barrett-Joyner-Halenda Method 4.2.2 Evaluation of Both Micropore and Mesopore Size Using Density Functional Theory and Grand Canonical Monte Carlo Methods 18.104.22.168 An Explanatory Note about Density Functional Theory (DFT) in the Context of Adsorption 22.214.171.124 How Does One Tackle a 'Breathing' MOF Nanoporous Structure?. 4.2.3 The Fractal Approach.
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