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Principles and Practice of Heterogeneous Catalysis

2. Aufl.

von: John Meurig Thomas, W. John Thomas
90,99 €
Verlag:	Wiley-VCH
Format:	PDF
Veröffentl.:	11.12.2014
ISBN/EAN:	9783527683802
Sprache:	englisch
Anzahl Seiten:	768

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Titelbeschreibung

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.

Inhaltsverzeichnis

Preface XIX 1 Setting the Scene 1 1.1 Prologue: Advances since the Early 1990s 1 1.2 Introduction 13 1.2.1 Selectivity of Catalysts 14 1.3 Perspectives in Catalysis: Past, Present and Future 16 1.3.1 Applied Catalysis since the 1940s 19 1.3.2 Some Current Trends in Applied Catalysis 23 1.3.2.1 Auto-Exhaust Catalysts 23 1.3.2.2 Catalysts in Electrochemistry and Photoelectrochemistry 25 1.3.2.3 Immobilized Metals 26 1.3.2.4 Immobilized Enzymes and Cells: Present and Future 29 1.3.2.5 Ribozymes 31 1.4 Definition of Catalytic Activity 32 1.4.1 Magnitude of Turnover Frequencies and Active Site Concentrations 33 1.4.2 Volcano Plots 35 1.4.3 Evolution of Important Concepts and Techniques in Heterogeneous Catalysis 36 1.4.3.1 Mechanistic Insights from Isotopic Labelling 47 1.4.3.2 Concepts from Organometallic Chemistry 48 1.5 Key Advances in Recent Theoretical Treatments: Universability in Heterogeneous Catalysis 52 1.5.1 Some Major Current Developments in Heterogeneous Catalysis 53 1.6 Milestones Reached in Industrial Catalysis in the Twentieth Century, and Some Consequential Challenges 54 Problems 61 References 64 Further Reading 66 2 The Fundamentals of Adsorption: Structural and Dynamical Considerations, Isotherms and Energetics 67 2.1 Catalysis Must Always Be Preceded by Adsorption 67 2.1.1 Physical Adsorption, Chemisorption and Precursor States 67 2.2 The Surfaces of Clean Solids are Sometimes Reconstructed 71 2.3 There Are Many Well-Defined Kinds of Ordered Adlayers 74 2.4 Adsorption Isotherms and Isobars 79 2.4.1 The Empirical Facts 80 2.4.2 Information That Can Be Gleaned from Isotherms 80 2.4.3 Adsorption Is Almost Invariably Exothermic 85 2.5 Dynamical Considerations 86 2.5.1 Residence Times 87 2.5.2 Rates of Adsorption 88 2.5.3 Applying Statistical Mechanics to Adsorption 91 2.5.4 Adsorption Kinetics Can Often Be Represented by the Elovich Equation 93 2.5.5 Rates of Desorption 96 2.5.6 Applying Statistical Mechanics to Desorption 98 2.5.7 Influence of a Precursor State on the Kinetics of Desorption 99 2.6 Relating the Activation Energy to the Energy of Chemisorption. Universality in Heterogeneous Catalysis and the Brønsted–Evans–Polanyi (BEP) Relation 101 2.6.1 Pareto-Optimal Catalysts 104 2.7 Deriving Adsorption Isotherms from Kinetic Principles 105 2.7.1 Using the Langmuir Isotherm to Estimate the Proportions of Non-dissociative and Associative Adsorption 106 2.7.2 Other Adsorption Isotherms 109 2.7.2.1 Henry’s Adsorption Isotherm 109 2.7.2.2 Freundlich Isotherm 109 2.7.2.3 Temkin Isotherm 110 2.7.2.4 Brunauer–Emmett–Teller Isotherm 110 2.7.2.5 Developments from Polanyi’s Adsorption Theory 110 2.7.2.6 Kaganer’s Isotherm and the DKR Equation 112 2.7.2.7 Virial Equation of State 112 2.8 Energetics of Adsorption 113 2.8.1 Estimating the Binding Energies of Physically Adsorbed Species 114 2.8.2 Binding Energies of Chemisorbed Species 118 2.8.3 Estimating Heats of Adsorption from Thermodynamic Data 121 2.8.4 Decline of the Heat of Adsorption with Increasing Coverage 123 2.9 Mobility at Surfaces 126 2.10 Kinetics of Surface Reactions 127 2.10.1 The Influences of Precursor States on the Kinetics and Energy Distribution of Catalysed Reactions 130 2.10.2 Comparing the Rates of Heterogeneous and Homogeneous Reactions 131 2.11 Autocatalytic, Oscillatory and Complex Heterogeneous Reactions 132 2.11.1 An Outline of Autocatalysis 133 2.11.2 Background to Oscillating Reactions 134 2.11.3 Instabilities and Transient Phenomena in Heterogeneous Catalysis 136 2.11.4 Multiple Steady States 137 2.11.5 Transient Phenomena 139 2.11.6 Recent Thoughts on Spatio-Temporal Behaviour and Turbulence at Catalyst Surfaces 145 2.12 Microkinetics: A Summary 147 2.12.1 Building Kinetic Models 149 2.12.2 Formulation of Kinetic Models in Terms of Transition States 154 2.12.3 Degree of Rate Control 154 Problems 155 References 161 Further Reading 162 3 The Characterization of Industrial and Model Solid Catalysts 163 Part I: Characterization of Industrial Solid Catalysts 163 3.1 Non-invasive Methods Suitable for Studies Involving Catalytic Reactors 164 3.1.1 Magnetic Resonance Imaging (MRI) 165 3.1.1.1 Visualizing the Spatial Variation of Esterification, Etherification and Hydrogenation within Fixed-Bed and Trickle-Bed Reactors with MRI 166 3.1.2 Positron Emission Methods 170 3.1.3 Use of Spatially-Resolved X-ray Absorption to Probe Supported Nobel Metal Catalysts during Operating Conditions 170 Part II: Laboratory Characterization of Solid Catalysts 172 3.2 A Portfolio of Modern Methods: Introducing the Acronyms 172 3.3 Which Elements and Which Phases Are Present? 175 3.3.1 X-ray Fluorescence (XRF), X-ray Emission (XRE) and Proton-Induced X-ray Emission (PIXE) 175 3.3.2 Developing Techniques: ICPMS 177 3.3.3 X-ray Diffraction (XRD) and Small-Angle X-ray Scattering 177 3.3.3.1 Mean Size, Surface Area and Particle-Size Distribution from SAXS 180 3.3.3.2 In situ Studies by X-ray Diffraction 181 3.3.3.3 Experimental Aspects 183 3.4 Probing Surfaces with IR, HREELS, AES and XPS 184 3.4.1 Infrared Spectroscopy (IR): A Non-destructive Technique Usable on Catalysts Exposed to High Pressure 184 3.4.2 High-Resolution Electron-Energy Loss Spectroscopy (HREELS): the Most Sensitive Tool for Identifying Surface Vibrational Modes 189 3.4.3 Merits and Limitations of Electron Spectroscopy 190 3.5 Ultraviolet–Visible and Photoluminescence Spectroscopy 191 3.6 Structure and Crystallography of Surfaces: Nature of Ordered and Reconstructed Surfaces 193 3.6.1 Two- and Three-Dimensional Surface Crystallography 193 3.6.2 Notations for Describing Ordered Structures at Surfaces 198 3.6.3 How Do Bond Distances at Surfaces Compare with Those of Bulk Solids? What of Displacive Reconstructions? 199 3.6.4 EXAFS, SEXAFS, XANES and NEXAFS: Probing Bond Distances and Site Environments Even When There is No Long-Range Order 200 3.6.4.1 Origin of EXAFS and How It Is Used 200 3.6.4.2 Applications of EXAFS to the Study of Catalysts 206 3.6.4.3 SEXAFS 209 3.6.4.4 XANES and Pre-edge Structure: Deducing Site Symmetry and Oxidation States 210 3.6.4.5 NEXAFS 211 3.7 Other Structural Techniques for Characterizing Bulk and Surfaces of Catalysts 214 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 214 3.7.1.1 Examples of the Use of ESR in Heterogeneous Catalysis 215 3.7.2 Nuclear Magnetic Resonance (NMR): A Technique Applicable, at High Resolution, to Solids and Their Surfaces 216 3.7.2.1 Basic Principles 216 3.7.2.2 NMR Spectra of Solids 219 3.7.2.3 Applications of NMR to the Study of Catalysts, Adsorbents and Adsorbates 220 3.7.2.4 Future Prospects for the Study of Catalysts by Solid-State NMR 224 3.7.3 Sum Frequency Generation (SFG) and Infrared Reflection Absorption Spectroscopy (IRAS or IRRAS) 225 3.7.3.1 Essential Background and Mode of Operation 225 3.7.4 Scanning Tunnelling Microscopy (STM) and Clues for the Design of New Catalysts 229 3.7.4.1 Scanning Tunnelling Spectroscopy (STS) 238 3.7.4.2 Atomic Force Microscopy (AFM) and Fluorescence Microscopy (FM) 239 3.7.5 Electron Microscopy 240 3.7.5.1 Electron Crystallography 245 3.7.5.2 Electron Tomography (ET) 246 3.7.5.3 A Few Illustrative Examples of Static EM Images 247 3.7.5.4 In situ (Environmental) TEM 248 3.7.5.5 4D Electron Microscopy 248 3.7.6 Optical Microscopy and Ellipsometry (Non-invasive Techniques) 250 3.7.7 Neutron Scattering: A Technique of Growing Importance in the Study of Catalysts 252 3.7.7.1 Determining the Atomic Structure and Texture of Microcrystalline Catalysts, the Nature of the Active Sites and the Disposition of Bound Reactants 256 3.7.7.2 Determining the Structure of, and Identifying Functional Groups in, Chemisorbed Layers at Catalyst Surfaces 257 3.8 A Miscellany of Other Procedures 258 3.9 Determining the Strength of Surface Bonds: Thermal and Other Temperature-Programmed Methods 259 3.9.1 Temperature-Programmed Desorption (TPD) or Flash Desorption Spectroscopy (FDS) 260 3.9.2 Temperature-Programmed Reaction Spectroscopy (TPRS) 262 3.9.3 Magnitude of the Heat and Entropy of Adsorption 263 3.10 Reflections on the Current Scene Pertaining In situ Methods of Studying Catalysts 265 3.10.1 Isotopic Labelling and Transient Response 269 3.10.2 From Temporal Analysis of Products (TAP) to Steady-State Isotopic Transient Kinetic Analysis (SSITKA) 272 3.10.3 Infrared, Raman, NMR, and X-ray Absorption Spectroscopy for In situ Studies 273 3.10.4 In situ X-ray, Electron and Neutron Diffraction Studies 275 3.10.5 Combined X-ray Absorption and X-ray Diffraction and Other Techniques for In situ Studies of Catalysts 278 Problems 281 References 288 Further Reading 291 General 291 Additional 291 In situ Techniques 291 4 Porous Catalysts: Their Nature and Importance 293 4.1 Definitions and Introduction 293 4.2 Determination of Surface Area 296 4.2.1 Assessment of Porosity 298 4.2.1.1 Capillary Condensation; the Kelvin Equation and the Barrett– Joyner–Halenda Method 300 4.2.2 Evaluation of Both Micropore and Mesopore Size Using Density Functional Theory and Grand Canonical Monte Carlo Methods 300 4.2.2.1 An Explanatory Note about Density Functional Theory (DFT) in the Context of Adsorption 302 4.2.2.2 How Does One Tackle a ‘Breathing’ MOF Nanoporous Structure? 303 4.2.3 The Fractal Approach 304 4.2.4 Practical Considerations 305 4.3 Mercury Porosimetry 306 4.4 Wheeler’s Semi-empirical Pore Model 308 4.4.1 Mathematical Models of Porous Structures 310 4.4.1.1 The Dusty Gas Model 310 4.4.1.2 Random Pore Model 311 4.4.1.3 Stochastic Pore Networks and Fractals 311 4.5 Diffusion in Porous Catalysts 314 4.5.1 The Effective Diffusivity 314 4.5.1.1 Molecular (Maxwellian) Diffusion or Bulk Diffusion 316 4.5.1.2 Knudsen Diffusion 317 4.5.1.3 The Transition Region of Diffusion 318 4.5.1.4 Forced Flow in Pores 318 4.6 Chemical Reaction in Porous Catalyst Pellets 319 4.6.1 Effect of Intraparticle Diffusion on Experimental Parameters 326 4.6.2 Non-isothermal Reactions in Porous Catalyst Pellets 328 4.6.3 Criteria for Diffusion Control 331 4.6.4 Experimental Methods of Assessing the Effect of Diffusion on Reaction 334 Problems 337 References 340 Further Reading 341 Specific Books 342 General 342 5 Solid State Chemical Aspects of Heterogeneous Catalysts 343 5.1 Recent Advances in Our Knowledge of Some Metal Catalysts: In Their Extended, Cluster or Nanoparticle States 345 5.1.1 Surface and Sub-surface Chemistry of Ag Particles 345 5.1.2 Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Catalysts 347 5.1.3 Platinum as a Hydrogeneration Catalyst 349 5.1.4 An Early Report That Monoatomic Pt Functions as an Active Heterogeneous Catalyst 350 5.1.5 An Exceptionally Active, Atomically Dispersed Pt-Based Catalyst for Generating Hydrogen from Water 350 5.2 Comments on the Catalytic Behaviour of Nanogold 352 5.2.1 What a Single Atom of Palladium Can Do in the Appropriate Environment 358 5.3 Recent Advances in the Elucidation of Certain Metal-Oxide Catalysts 359 5.3.1 An Illustrative Investigation; Coupling STM, IR, Thermal Reaction Spectroscopy and DFT of Formaldehyde Formation on Vanadium Oxide Surfaces 362 5.4 Atomic-Scale Edge Structures in Industrial-Style MoS2 Nanocatalysts 363 5.5 Open-Structure Catalysts: from 2D to 3D 364 5.5.1 A Brief Guide to the Structure of Zeolitic and Closely-Related Solid Catalysts 365 5.5.1.1 Notion of Framework Density 369 5.5.2 New Families of Nanoporous Catalysts 370 5.5.2.1 The Principal Catalytic Significance of New Families of Nanoporous Solids 375 5.6 Computational Approaches 376 5.6.1 Résumé of Available Methodologies 376 5.6.1.1 Selected Applications 382 5.7 A Chemist’s Guide to the Electronic Structure of Solids and Their Surfaces 389 5.7.1 Energy Bands 390 5.7.1.1 Bands in ID and 3D Crystals 393 5.7.1.2 Energy Bands in Ionic Solids 395 5.7.1.3 Energy Bands in Transition-Metal Oxides: Understanding the Electronic Structure of the Monoxides of Ti, V, Mn and Ni 398 5.7.2 Fermi Levels in Insulators and Semiconductors 399 5.7.3 Surface Electronic States and the Occurrence of Energy Levels within the Band Gap 402 5.7.4 Band Bending and Metal–Semiconductor Junctions: Schottky Barriers 403 5.7.4.1 Depletive Chemisorption on Semiconductors 405 5.7.4.2 The Bending of Bands When Semiconductors Are Immersed in Electrolytes 406 5.7.5 Quantum Chemical Approaches to the Electronic Properties of Solids 407 5.7.6 A Brief Selection of Quantum Chemical Studies 408 5.7.6.1 Band Widths, DOS and Fermi Levels of the Transition Metals 408 5.7.6.2 Dissociative Chemisorption of CO 410 5.7.6.3 Insight from Ab initio Computations: Methanol Synthesis and Olefin Metathesis 411 5.7.7 Recent Advances in the Study of Metathesis 413 5.8 Key Advances in Recent Theoretical Treatments of Heterogeneous Catalysis 415 5.8.1 Further Comments on Density Functional Theory (DFT) 416 5.9 Selected Applications of DFT to Catalysis 419 5.9.1 CatApp: a Web Application for Surface Chemistry and Heterogeneous Catalysis 421 5.9.2 TiIV Centred Catalytic Epoxidation of c-Hexene 423 5.9.3 Mechanism of the Aerobic Terminal Oxidation of Linear Alkanes at Mn-Doped Aluminophosphate Catalysts 424 5.9.4 Rate Control and Reaction Engineering 425 5.10 Concluding Remarks Concerning DFT Calculations in Heterogeneous Catalysis 429 Problems 430 References 433 Key References Published Since the First Edition 436 Seminal Books 436 Monographs 437 Book Chapters 437 Further Reading 437 6 Poisoning, Promotion, Deactivation and Selectivity of Catalysts 439 6.1 Background 439 6.1.1 Effect of Mass Transfer on Catalytic Selectivity 440 6.1.1.1 Effect of Intraparticle Diffusion 440 6.1.1.2 Non-isothermal Conditions 445 6.1.1.3 Effect of Interparticle Mass and Heat Transfer 448 6.1.2 Bifunctional Catalysts (or Dual-Function Catalysts) 449 6.2 Catalyst Deactivation 452 6.2.1 Deactivation Processes 452 6.2.2 Deactivation Models 455 6.2.2.1 Steady-State Model 455 6.2.2.2 A Dynamic Model 459 6.2.3 Operational Consequences of Poisoning 462 6.3 Some Modern Theories of Poisoning and Promotion 463 6.3.1 General Theoretical Considerations 464 6.3.2 Theoretical Interpretation of Poisoning and Promotion 466 6.3.2.1 The Electronegativity of a Poison Seems to Be of Secondary Importance 469 6.3.2.2 Other Factors Responsible for Promotion and Poisoning 471 6.3.2.3 Influence of Surface Carbon and Sub-surface Hydrogen in Hydrogenations on Palladium 473 6.3.2.4 Concluding Remarks 473 Problems 474 References 477 Further Reading 477 General 477 Studies of Model Surfaces 477 Theory of Poisoning and Promotion 478 7 Catalytic Process Engineering 479 Part I: Recent Advances in Reactor Design 479 7.1 Novel Operating Strategies 482 7.1.1 Fixed-Bed Reactors 482 7.1.1.1 Periodic Operation 483 7.1.1.2 Concurrent Flow 485 7.1.2 Microchannel Reactors 485 7.1.3 Multifunctional Reactors 492 7.1.3.1 Integrating Exothermic and Endothermic Reactions 492 7.1.3.2 Integrating Heat Transfer and Reaction 494 7.1.3.3 Integrating Reaction and Separation 495 Part II: Traditional Methods of Catalytic Process Engineering 499 7.2 Traditional Catalytic Reactors 499 7.2.1 Experimental Laboratory Reactors 499 7.2.1.1 Batch Reactors 500 7.2.1.2 Tubular Reactors 501 7.2.1.3 Continuous Stirred-Tank Reactor 504 7.2.1.4 Recycle Reactor 506 7.2.1.5 Flowing-Solids Reactors 507 7.2.1.6 Slurry Reactors 507 7.2.2 Industrial Chemical Reactors 510 7.2.2.1 Batch Reactors 511 7.2.2.2 Continuous Tubular Reactors 513 7.2.2.3 Fluidized-Bed Reactor 522 7.2.2.4 Trickle-Bed Reactor 525 7.2.2.5 Metal Gauze Reactors 527 7.2.3 Thermal Characteristics of a Catalytic Reactor 528 Problems 534 References 538 General References for Part II 539 General 539 Kinetic Models 539 Experimental Chemical Reactor Configurations 540 Slurry Reactors 540 Further Reading 540 8 Heterogeneous Catalysis: Examples, Case Histories and Current Trends 541 8.1 Synthesis of Methanol 541 8.1.1 The Nature of the Catalyst 543 8.1.2 Insight into the Mechanism of Formation of CH3OH 544 8.1.3 Aspects of Methanol Synthesis Technology 545 8.2 Fischer–Tropsch Catalysis 546 8.2.1 Mechanistic Considerations 549 8.2.1.1 Does Synthesis Proceed via Hydroxymethylene Intermediates? 550 8.2.1.2 Schultz–Flory Statistics 554 8.2.2 Fine-Tuning the Fischer–Tropsch Process 555 8.2.3 Practical Fischer–Tropsch Catalysts and Process Conditions 556 8.2.4 Commercial Fischer–Tropsch Plants 559 8.2.5 Methanation, Steam Reforming and Water-Gas Shift Reactions 559 8.2.5.1 Methanation 559 8.2.5.2 Steam Reforming: the Most Extensively Used Means of Manufacturing Hydrogen 563 8.3 Synthesis of Ammonia 568 8.3.1 Catalyst Promoters are of Two Kinds 570 8.3.2 Kinetics of the Overall Reaction: the Temkin–Pyzhev Description 571 8.3.3 The Surface of Iron Catalysts for Ammonia Synthesis Contain Several Other Elements: but Is the Iron Crystalline? 573 8.3.3.1 Does Ammonia Synthesis Proceed via Atomically or Molecularly Adsorbed Nitrogen? 575 8.3.3.2 How and Where Are the Reactant Gases Adsorbed at the Catalyst Surface? 576 8.3.3.3 A Potential-Energy Diagram Illustrating How the Overall Reaction Leading to Ammonia Synthesis Can Be Constructed 580 8.3.3.4 How Potassium Serves as an Electronic Promoter 582 8.3.4 The Technology of Ammonia Synthesis 583 8.3.4.1 Reactor Configurations are Important Industrially 585 8.4 Oxidation of Ammonia: Stepping Toward the Fertilizer Industry 588 8.4.1 Ammonia Oxidation at Surfaces Containing Pre-adsorbed Oxygen: Hot Ad-Particles 592 8.5 In situ Catalytic Reaction and Separation 592 8.5.1 Catalytic Distillation 592 8.5.2 Catalytic Membrane Processes 596 8.6 Automobile Exhaust Catalysts and the Catalytic Monolith 601 8.6.1 The Architecture of the Three-Way Catalyst 603 8.6.2 The Catalytic Monolith 604 8.6.3 Catalytic Monoliths May Be Used in Several Applications 605 8.6.4 Rate Characteristics of Catalytic Combustion Processes 606 8.6.5 Combustion Reactions in a Catalytic Monolith Differ from Those Occurring in a Homogeneously Operated Combustor 607 8.6.6 Simulation of the Behaviour of a Catalytic Monolith is Important for Design Purposes 609 8.7 Photocatalytic Breakdown of Water and the Harnessing of Solar Energy 614 8.7.1 Prologue 614 8.7.2 Artificial Photosynthesis 615 8.7.3 The Fundamental Energies Involved 618 8.7.3.1 Oxygen Generation by Photo-Induced Oxidation of Water 619 8.7.3.2 Hydrogen Generation by Photo-Induced Reduction of Water 620 8.7.3.3 Simultaneous Generation of Hydrogen and Oxygen by Catalysed Photolysis of Water 621 8.7.4 Some Selected Practical Examples 624 8.7.4.1 The Grätzel Cell and Its Influence 626 8.7.4.2 Tandem Cells for Water Splitting by Visible Light 628 8.8 Catalytic Processes in the Petroleum Industry 629 8.8.1 Catalytic Reforming 631 8.8.2 Catalytic Cracking 633 8.8.2.1 Cracking Reactions 636 8.8.2.2 Cracking Catalysts 638 8.8.2.3 The Catalytic Cracking (FCC) Reactor 638 8.8.3 Hydrotreating 640 8.8.3.1 Total Conversion of Heavy Oils into Good Quality Distillates 644 Problems 645 References 651 Further Reading 653 9 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 655 9.1 Introduction 655 Part I: Prospects, Practices and Principles of Generating Solar Fuels 658 9.2 Powering the Planet with Solar Fuel 658 9.3 Some Significant Advances in Photo-Assisted Water Splitting and Allied Phenomena 659 9.3.1 Strategies for Solar Energy Conversion 660 9.3.2 The Artificial Leaf 661 9.3.3 Earth-Abundant H2-Evolution Photocatalysts 664 9.3.4 Earth-Abundant O2-Evolution Photocatalysts 665 9.3.5 Lessons from Enzymes 666 9.3.6 A Selective Survey and Future Challenges 666 9.3.7 An Interim Status Report on Water Oxidation Photocatalysis 669 9.3.8 Core-Shell Co-Catalysts in the Photocatalytic Conversion of CO2 with Water into Methane 669 9.3.9 Modifying the Nature of TiO2 so as to Improve Its Photocatalytic Performance 670 9.3.9.1 Band Structure Engineering of Semiconductors for Enhanced Photoelectrochemical Water Splitting, with Special Reference to TiO2 and Fe2O3 674 9.3.10 Metal-Organic Frameworks (MOFs) and Their Photocatalytic Possibilities 675 9.3.11 Photocatalytic Solids for the Destruction of Toxic Pollutants and Otherwise Unwanted Molecules 676 9.4 The Hydrogen Economy 677 9.4.1 The Methanol Economy 682 Part II: Current Practices in Powering the Planet and Producing Chemicals 685 9.5 Some of Tomorrow’s Catalysts: Actual and Desired 685 9.5.1 Some Existing Industrial Catalysts Likely to be Difficult to Replace in the Near Future 687 9.5.2 Ammoxidation: Acrolein and Acrylic Acid 687 9.5.3 Poly(ethylene terephthalate) (PET) 692 9.5.4 Fischer–Tropsch Syntheses (FTS) 696 9.5.4.1 FTS Using CO2 to Generate Hydrocarbon Fuels 696 9.5.5 Adipic Acid; Nylon 6,6; Nylon 6 and Terephthalic Acid 697 9.5.5.1 The Practical Importance of Cascade Catalytic Reactions 700 9.5.6 Catalytic Cracking and Refining: the Impact of Mesostructured Y Zeolite 701 9.5.6.1 Ecofining: The Road to Green Refineries 705 9.6 A Biorefinery Capable of Producing Transportation Fuels and Commodity Chemicals that Starts with Metabolic Engineering and Ends with Inorganic Solid Catalysts 707 9.6.1 Renewables to para-Xylene and Other Aromatics 709 9.6.2 Biorefinery for Integrated Methods of Preparing Renewable Chemicals 711 9.6.3 Three Advanced Biofuels from Switchgrass Using Engineered Escherichia coli 711 9.7 Non-enzymatic Catalytic Processing of Biomass-Derived Raw Materials to Selected Chemical Products 711 9.7.1 Sustainable Chemistry by Upgrading Pyrolysis Oil 714 9.7.2 Catalytic Conversion of Microalgae into Green Hydrocarbons and Ethanol 716 9.7.2.1 Microalgae to Diesel 717 9.7.2.2 Microalgae to Bioethanol Using CO2 and Sunlight 718 9.8 Strategies for the Design of New Catalysts 719 9.8.1 The Merits and Limitations of Single-Site Heterogeneous Catalysis 720 Part III: Thermochemical Cycles and High-Flux, Solar-Driven Conversions 724 9.9 Solar-Driven, Catalysed Thermochemical Reactions as Alternatives to Fossil-Fuel-Based Energy and Chemical Economies 724 Acknowledgements 726 Problems 726 References 729 Further Reading 732 Index 733

Autorenportrait

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.

Back cover copy

This long-awaited second edition of the successful introduction to the fundamentals of heterogeneous catalysis is now completely revised and updated. Written by two top international 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 and numerous practical examples. It takes full account of the major advances made since the first edition, and highlights environmentally responsible processes, the use of renewable feedstocks, and new methods of studying and designing solid catalysts. Gerhard Ertl, Fritz-Haber-Institute, Berlin, Nobel Laureate: Since many years ‚“Thomas & Thomas” has been a comprehensive and profound guide to the complex area of heterogeneous catalysis and hence the community was waiting eagerly for the second edition. This is in fact much more than just a thoroughly revised version but rather an elegantly written new book covering the subject from its fundamental principles to its technological aspects, whereby all the important new developments during the last twenty years as well as relations to neighboring disciplines (such as biochemistry, electrochemistry or photochemistry) were taken into account. This work should become a classic and of indispensable value for everybody working in the field. Jens K. Nørskov, Director, Center for Interface Science and Catalysis, Stanford University: The Thomas textbook on heterogeneous catalysis provides the reader with an authoritative and comprehensive treatment of the science and technology of the field. The new version is completely updated with the newest developments and the elegant and extremely insightful presentation will capture the reader. It is required reading for anyone in the field, from starting students to practitioners in industry. Yasuhiro Iwasawa, former President of the Chemical Society of Japan, Emeritus Professor, University of Tokyo: The “Thomas & Thomas” has been a bible of the large community of heterogeneous catalysis, providing the scientific and technological compass, comprehensive guidance and profound knowledge of catalysis field as well as related disciplines. The second edition of the “Thomas & Thomas” with 9 chapters is a thoroughly revised and newly written book, covering diverse but important subjects from both fundamentals and industrial applications, documenting significant developments and historical milestones during the last twenty years, and involving emerging areas. This work should be highly recommended for everybody to have one copy each. Michel Che, Université Pierre et Marie Curie, Paris, Past President of the International Association of Catalyst Societies: This beautifully written second edition is a pure joy to read and is recommended both to senior university students and the practising researcher and industrialist. It gives the most general view of contemporary heterogeneopus catalysis, at the confluence of the practical and the fundamental and with the incentive of moving faster toward green chemistry, clean technology and sustainability.