Catalysis Books

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Book SynopsisThis book provides a comprehensive overview of the field of plasma catalysis, regarded as a promising alternative to thermal processes for energy and environmental applications. It bridges the gap between the plasma and catalysis research communities, covering both the fundamentals of plasma catalysis and its application in environmental and energy research. The first section of the book offers a broad introduction to plasma catalysis, covering plasma-catalyst systems, interactions, and modeling. The core of the book then focuses on different applications, describing a wide range of plasma-catalytic processes in catalyst synthesis, environmental clean-up, greenhouse gas conversion and synthesis of materials for energy applications. Chapters cover topics ranging from removal of NOx and VOCs to conversion of methane, carbon dioxide and the reforming of ethanol and methanol.Written by a group of world-leading researchers active in the field, the book forms a valuable resource for scientists, engineers and students with different research backgrounds including plasma physics, plasma chemistry, catalysis, energy, environmental engineering, electrical engineering and material engineering.Table of Contents

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Book SynopsisCatalysis is at the heart of the chemical industry, which uses solid catalysts for the large-scale production of commodity chemicals. Catalysis at surfaces is also the basis for the ongoing transition to a sustainable energy supply, which requires molecules such as hydrogen, ammonia or methanol to store energy in chemical bonds, and environmental protection equally relies on heterogeneous catalysis. Catalysis at surfaces is a truly interdisciplinary field, which requires profound knowledge from chemistry, physics and engineering as provided by this textbook. All essential tools are described ranging from the synthesis and modification of porous solids over bulk- and surface-sensitive characterization techniques to currently applied theoretical methods. A close-up to the important aspects of surface catalysis is provided, which comprises the established knowledge about mechanisms and active sites, promotors and poisons in redox and acid-base catalysis. This advanced textbook is recommended for Master and PhD students, for whom it provides the fundamentals and all relevant aspects of catalyst synthesis, characterization and application in suitable reactors. It is not only thermal catalysis that is covered in depth, but also photo- and electrocatalysis as emerging fields in the Energiewende.

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Book SynopsisThis book provides the reader with a comprehensive introduction to the topic of organometallic chemistry. With an easy to follow structure covering both nontransition metals and transition metals as well as the applications of organometallic reagents in organic synthesis, this book is a must-have for the organometallic chemist.

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Book SynopsisThe increase of renewable electricity production and the resulting surplus lead us to ask: how to improve energy efficiency through the use of hydrogen? This 2nd Edition of Power-to-Gas covers the global energy issues (generation, distribution, consumption, markets), the production of hydrogen via electrolysis, its transportation and storage or conversion in another form. It takes account of the new energy challenges facing the world and the development of experimentations by adding new projects and realisations.

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Book SynopsisThis textbook is a concise introduction to heterogeneous catalysis, focusing on the fundamentals and industrial implementation. It is written in a clear manner using language that is easily accessible to undergraduate students in chemical engineering and industrial chemistry. The textbook includes exercise problems and practice software. New in this edition are sections on catalyst preparation and manufacture, kinetic parameter estimation, and catalytic transport-line reactors. Solutions to all the example problems are now provided.

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Book SynopsisThis volume covers recent advances in the chemistry of ylidic compounds with focus on their application in the design of ligands with unique donor properties, the development of novel organic transformations as well as the use of ylides in homogenous catalysis. Thereby, this volume particularly aims at the community of organic and organometallic chemists engaged in synthetic chemistry and catalysis as well as in the use of special ligands for the stabilization of unusual main group element species and the “transition-metal free” activation of element-element/hydrogen bonds. These fields of research are highly active and vivid research areas to which ylide chemistry has only recently started to contribute, but has already led to fascinating developments in most different directions. This volume highlights these recent developments, thus giving not only an overview over the past achievements, but also possibilities for future applications. To this end, the chapters selected in this volume combine different aspects of ylide chemistry, starting with theoretical aspects in ligand design followed by synthetic organic methods, catalytic transformations and complex chemistry. Table of ContentsStructure and Reactivity of Carbones and Ylide Stabilized Carbenes: Contributions from Theory.- Synthesis, Structure, and Reactivity of Carbodiphosphoranes,Carbodicarbenes,and Related Species.- Synthesis and Structure of Carbodicarbenes and Their Application in Catalysis.- Sulfur Ylides in Organic Synthesis and Transition Metal Catalysis.- Reactivity and Applications of α-Metalated Ylides.

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Book SynopsisThis 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.Table of ContentsPreface 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

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Book SynopsisWritten by an excellent, highly experienced and motivated team of lecturers, this textbook is based on one of the most successful courses in catalysis and as such is tried-and-tested by generations of graduate and PhD students, i.e. the Catalysis-An-Integrated-Approach (CAIA) course organized by NIOK, the Dutch Catalysis research school. It covers all essential aspects of this important topic, including homogeneous, heterogeneous and biocatalysis, but also kinetics, catalyst characterization and preparation, reactor design and engineering. The perfect source of information for graduate and PhD students in chemistry and chemical engineering, as well as for scientists wanting to refresh their knowledgeTable of ContentsPreface xiii 1 Introduction 1Leon Lefferts, Ulf Hanefeld, and Harry Bitter 1.1 A FewWords at the Beginning 1 1.2 Catalysis in a Nutshell 1 1.3 History of Catalysis 3 1.3.1 Industrial Catalysis 4 1.3.2 Environmental Catalysis 5 1.4 Integration Homo–Hetero-Biocatalysis 5 1.5 Research in Catalysis 10 1.5.1 S-Curve, Old Processes Improvement Is Knowledge Intensive 10 1.5.2 Interdependence with Other Fields 11 1.5.3 Recent and Future Issues 12 1.6 Catalysis and Integrated Approach or How to Use this Book 14 References 14 2 Heterogeneous Catalysis 15Leon Lefferts, Emiel Hensen, and Hans Niemantsverdriet 2.1 Introduction 15 2.1.1 Concept of Heterogeneous Catalysis 15 2.1.2 Applications of Heterogeneous Catalysis 16 2.1.3 Catalytic Cycle 23 2.2 Adsorption on Surfaces 23 2.2.1 Physisorption and Chemisorption 24 2.2.2 Adsorption Isotherms 26 2.2.3 Chemisorption and Chemical Bonding 28 2.2.4 Connecting Kinetic andThermodynamic Formulations 33 2.3 Surface Reactions 35 2.3.1 Reaction Mechanism and Kinetics 35 2.4 Types of Heterogeneous Catalysts 41 2.4.1 Supported Metals 41 2.4.2 Oxides and Sulfides 51 2.4.3 Solid Acid Catalysts 62 Question 1 69 Question 2 69 References 70 3 Homogeneous Catalysis 73Elisabeth Bouwman,Martin C. Feiters, and Robertus J. M. Klein Gebbink 3.1 Framework and Outline 73 3.1.1 Outline of this Chapter 73 3.1.2 Definitions and Terminology 74 3.2 Coordination and Organometallic Chemistry 75 3.2.1 Coordination Chemistry: d Orbitals, Geometries, Crystal Field Theory 75 3.2.2 σ and π donors and back-donation: CO, alkene, phosphane, H2 77 3.2.3 Organometallics: Hapticity, Metal–Alkyl/Allyl, Agostic Interaction, Carbenes 80 3.2.4 Electron Counting: Ionogenic or Donor-Pair versus Covalent or Neutral-Ligand 81 3.2.5 Effect of Binding on Ligands andMetal Ions, Stabilization of Oxidation States 83 3.3 Elementary Steps in Homogeneous Catalysis 84 3.3.1 Formation of the Active Catalyst Species 84 3.3.2 Oxidative Addition and Reductive Elimination 85 3.3.3 Migration and Elimination 87 3.3.4 Oxidative Coupling and Reductive Cleavage 90 3.3.5 Alkene or Alkyne Metathesis and σ-Bond Metathesis 90 3.3.6 Nucleophilic and Electrophilic Attack 92 3.4 Homogeneous Hydrogenation 95 3.4.1 Background and Scope 95 3.4.2 H2 DihydrideMechanism:Wilkinson’s Catalyst 96 3.4.3 H2 Monohydride Mechanism and Heterolytic Cleavage 97 3.4.4 Asymmetric Homogeneous Hydrogenation 98 3.4.5 Transfer Hydrogenation with 2-Propanol 100 3.4.6 Other Alkene Addition Reactions 102 3.5 Hydroformylation 104 3.5.1 Scope and Importance of the Reaction and Its Products 104 3.5.2 Cobalt-Catalyzed Hydroformylation 105 3.5.3 Rhodium-Catalyzed Hydroformylation 107 3.5.4 Asymmetric Hydroformylation 110 3.6 Oligomerization and Polymerization of Alkenes 112 3.6.1 Scope and Importance of Oligomerization and Polymerization 112 3.6.2 Oligomerization of Ethene (Ni, Cr) 113 3.6.3 Stereochemistry and Mechanism of Propene Polymerization 115 3.6.4 Metallocene Catalysis 117 3.6.5 Polymerization with Non-Metallocenes (Pd, Ni, Fe, Co) 118 3.7 Miscellaneous Homogeneously Catalyzed Reactions 118 3.7.1 Cross-Coupling Reactions: Pd-Catalyzed C–C Bond Formation 118 3.7.2 Metathesis Reactions 120 Question 1 (total 20 points) 122 Question 2 (total 20 points) 122 References 123 Further Reading 124 4 Biocatalysis 127Guzman Torrelo, Frank Hollmann, and Ulf Hanefeld 4.1 Introduction 127 4.2 Why Are Enzymes So Huge? 129 4.3 Classification of Enzymes 137 4.3.1 Oxidoreductases (EC 1) 139 4.3.2 Transferases (EC 2) 147 4.3.3 Hydrolases (EC 3) 147 4.3.4 Lyases (EC 4) 157 4.4 Concepts and Methods 157 4.4.1 Cofactor Regeneration Systems 158 4.4.2 Methods to Shift Unfavorable Equilibria 159 4.4.3 Two-Liquid-Phase Systems (and Related) 164 4.4.4 (Dynamic) Kinetic Resolutions and Desymmetrization 164 4.4.5 Enantiomeric Ratio E 168 4.5 Applications and Case Studies 169 4.5.1 Oxidoreductases (E.C. 1) 169 4.5.2 Transferases (EC 2) 177 4.5.3 Hydrolases (EC 3) 179 4.5.3.1 Lipases and Esterases (EC 3.1.1) 179 4.5.4 Lyases (EC 4) 181 Question 1 186 Question 2 186 Question 3 187 Question 4 188 Further Reading 188 5 Chemical Kinetics of Catalyzed Reactions 191Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis 5.1 Introduction 191 5.2 Rate Expressions – Quasi-Steady-State Approximation and Quasi-Equilibrium Assumption 193 5.3 Adsorption Isotherms 198 5.3.1 One-Component Adsorption 198 5.3.2 Multicomponent Adsorption 199 5.3.3 Dissociative Adsorption 200 5.4 Rate Expressions – Other Models and Generalizations 200 5.5 Limiting Cases – Reactant and Product Concentrations 202 5.6 Temperature and Pressure Dependence 206 5.6.1 Transition-StateTheory 207 5.6.2 Forward Reaction – Temperature and Pressure Dependence 208 5.6.3 Forward Reaction – Limiting Cases 209 5.7 Sabatier Principle – Volcano Plot 213 5.8 Concluding Remarks 214 Notation 216 Greek 217 Subscripts 217 Superscripts 217 Question 1 217 Question 2 218 Question 3 218 References 219 6 Catalytic Reaction Engineering 221Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis 6.1 Introduction 221 6.2 Chemical Reactors 222 6.2.1 Balance and Definitions 222 6.2.2 Batch Reactor 224 6.2.2.1 Multiple Reactions 226 6.2.3 Continuous Flow Stirred Tank Reactor (CSTR) 228 6.2.4 Plug-Flow Reactor (PFR) 231 6.2.5 Comparison between Plug-flow and CSTR reactor 233 6.3 Reaction and Mass Transport 236 6.3.1 External Mass Transfer 237 6.3.2 Internal Mass Transport 242 6.3.3 Gas–Liquid Mass Transfer 248 6.3.4 Heat Transfer 254 6.4 Criteria to Check for Transport Limitations 257 6.4.1 Numerical Checks 257 6.4.2 Experimental Checks 260 Notation 264 Greek symbols 265 Subscripts 265 Question 1 265 Question 2 266 Question 3 267 References 269 7 Characterization of Catalysts 271Guido Mul, Frank de Groot, Barbara Mojet-Mol, and Moniek Tromp 7.1 Introduction 271 7.1.1 Importance of Characterization of Catalysts 271 7.1.2 Overview of the Various Techniques 271 7.2 Techniques Based on Probe Molecules 273 7.2.1 Temperature-Programmed Techniques 273 7.2.2 Physisorption and Chemisorption 275 7.3 Electron Microscopy Techniques 280 7.4 Techniques from Ultraviolet up to Infrared Radiation 283 7.4.1 UV/Vis Spectroscopy 283 7.4.2 Infrared Spectroscopy 286 7.4.3 Raman Spectroscopy 289 7.5 Techniques Based on X-Rays 291 7.5.1 Introduction 291 7.5.2 Interaction of X-Rays with Matter 293 7.5.3 X-Ray Photoelectron Spectroscopy (XPS) 294 7.5.4 X-ray Absorption Spectroscopy (XAS) 295 7.5.5 X-Ray Scattering 299 7.5.6 X-Ray Microscopy 302 7.6 Ion Spectroscopies 303 7.7 Magnetic Resonance Spectroscopy Techniques 304 7.7.1 NMR 304 7.7.2 EPR 306 7.8 Summary 310 Question 1 310 Question 2 311 Question 3 312 References 313 8 Synthesis of Solid Supports and Catalysts 315Petra de Jongh and Krijn de Jong 8.1 Introduction 315 8.2 Support Materials 317 8.2.1 Mesoporous Metal Oxides 318 8.2.2 Ordered Microporous Materials 326 8.2.3 Carbon Materials 331 8.2.4 Shaping 333 8.3 Synthesis of Supported Catalysts 333 8.3.1 Colloidal Synthesis Routes 334 8.3.2 Chemical Vapor Deposition 335 8.3.3 Ion Adsorption 338 8.3.4 Deposition Precipitation 341 8.3.5 Co-Precipitation 345 8.3.6 Impregnation and Drying 349 Question 1 357 Question 2 357 Question 3 358 References 358 Index 361

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Book SynopsisDiscover the latest research in photocatalysis combined with foundational topics in basic physical and chemical photocatalytic processes In Heterogeneous Photocatalysis: From Fundamentals to Applications in Energy Conversion and Depollution, distinguished researcher and editor Jennifer Strunk delivers a rigorous discussion of the two main topics in her field—energy conversion and depollution reactions. The book covers topics like water splitting, CO2 reduction, NOx abatement and harmful organics degradation. In addition to the latest research on these topics, the reference provides readers with fundamental information about elementary physical and chemical processes in photocatalysis that are extremely practical in this interdisciplinary field. It offers an excellent overview of modern heterogeneous photocatalysis and combines concepts from different viewpoints to allow researchers with backgrounds as varied as electrochemistry, material science, and semiconductor physics to begin developing solutions with photocatalysis. In addition to subjects like metal-free photocatalysts and photocarrier loss pathways in metal oxide absorber materials for photocatalysis explored with time-resolved spectroscopy, readers will also benefit from the inclusion of: Thorough introductions to kinetic and thermodynamic considerations for photocatalyst design and the logic, concepts, and methods of the design of reliable studies on photocatalysis Detailed explorations of in-situ spectroscopy for mechanistic studies in semiconductor photocatalysis and the principles and limitations of photoelectrochemical fuel generation Discussions of photocatalysis, including the heterogeneous catalysis perspective and insights into photocatalysis from computational chemistry Treatments of selected aspects of photoreactor engineering and defects in photocatalysis Perfect for photochemists, physical and catalytic chemists, electrochemists, and materials scientists, Heterogeneous Photocatalysis will also earn a place in the libraries of surface physicists and environmental chemists seeking up-to-date information about energy conversion and depollution reactions.Table of ContentsKinetic and Thermodynamic Considerations for Photocatalyst Design Design of Reliable Studies on Photocatalysis: Logic, Concepts and Methods In-Situ Spectroscopy for Mechanistic Studies in Semiconductor Photocatalysis Principles and Limitations of Photoelectrochemical Fuel Generation Photocatalysis - The Heterogeneous Catalysis Perspective Insights into Photocatalysis from Computational Chemistry Selected Aspects of Photoreactor Engineering Defects in photocatalysis Photocarrier Loss Pathways in Metal Oxide Absorber Materials for Photocatalysis Explored with Time-Resolved Spectroscopy: The Case of BiVO4 Metal-Free Photocatalysts Photocatalytic water splitting: Fundamentals and current concepts Photocatalytic CO2 reduction and beyond Photocatalytic NOx Abatement Photoactive Nanomaterials: Applications in Wastewater Treatment and their Environmental Fate

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Book SynopsisThe book gives a unique overview of this rapidly developing research field, presenting structures and properties of flavin derivatives as well as their proven application as bioinspired catalysts in various organocatalytic, biocatalytic, and photocatalytic reactions.Table of ContentsStructure and properties of flavins Natural flavins: occurrence, role and non-canonical chemistry Spectral properties of flavins Modes of flavin-based catalysis Organocatalytic monooxygenations Flavin-based supramolecular and coupled catalytic systems Flavoprotein monooxygenases and halogenases Flavoprotein-dependent bioreduction Flavoprotein oxidases Benzylic photooxidation by flavins New applications of flavin photocatalysis Light-driven flavin-based biocatalysis

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Book SynopsisElectrocatalysis in Balancing the Natural Carbon Cycle Explore the potential of electrocatalysis to balance an off-kilter natural carbon cycle In Electrocatalysis in Balancing the Natural Carbon Cycle, accomplished researcher and author, Yaobing Wang, delivers a focused examination of why and how to solve the unbalance of the natural carbon cycle with electrocatalysis. The book introduces the natural carbon cycle and analyzes current bottlenecks being caused by human activities. It then examines fundamental topics, including CO2 reduction, water splitting, and small molecule (alcohols and acid) oxidation to prove the feasibility and advantages of using electrocatalysis to tune the unbalanced carbon cycle. You’ll realize modern aspects of electrocatalysis through the operando diagnostic and predictable mechanistic investigations. Further, you will be able to evaluate and manage the efficiency of the electrocatalytic reactions. The distinguished author presents a holistic view of solving an unbalanced natural carbon cycle with electrocatalysis. Readers will also benefit from the inclusion of: A thorough introduction to the natural carbon cycle and the anthropogenic carbon cycle, including inorganic carbon to organic carbon and vice versa An exploration of electrochemical catalysis processes, including water splitting and the electrochemistry CO2 reduction reaction (ECO2RR) A practical discussion of water and fuel basic redox parameters, including electrocatalytic materials and their performance evaluation in different electrocatalytic cells A perspective of the operando approaches and computational fundamentals and advances of different electrocatalytic redox reactions Perfect for electrochemists, catalytic chemists, environmental and physical chemists, and inorganic chemists, Electrocatalysis in Balancing the Natural Carbon Cycle will also earn a place in the libraries of solid state and theoretical chemists seeking a one-stop reference for all aspects of electrocatalysis in carbon cycle-related reactions.Table of ContentsPreface xv Acknowledgments xix Part I Introduction 1 1 Introduction 3 References 5 Part II Natural Carbon Cycle 7 2 Natural Carbon Cycle and Anthropogenic Carbon Cycle 9 2.1 Definition and General Process 9 2.2 From Inorganic Carbon to Organic Carbon 10 2.3 From Organic Carbon to Inorganic Carbon 11 2.4 Anthropogenic Carbon Cycle 11 2.4.1 Anthropogenic Carbon Emissions 12 2.4.2 Capture and Recycle of CO2 from the Atmosphere 13 2.4.3 Fixation and Conversion of CO2 14 2.4.3.1 Photochemical Reduction 14 2.4.3.2 Electrochemical Reduction 15 2.4.3.3 Chemical/Thermo Reforming 16 2.4.3.4 Physical Fixation 16 2.4.3.5 Anthropogenic Carbon Conversion and Emissions Via Electrochemistry 17 References 18 Part III Electrochemical Catalysis Process 21 3 Electrochemical Catalysis Processes 23 3.1 Water Splitting 23 3.1.1 Reaction Mechanism 23 3.1.1.1 Mechanism of OER 23 3.1.1.2 Mechanism of ORR 24 3.1.1.3 Mechanism of HER 26 3.1.2 General Parameters to Evaluate Water Splitting 27 3.1.2.1 Tafel Slope 27 3.1.2.2 TOF 27 3.1.2.3 Onset/Overpotential 28 3.1.2.4 Stability 28 3.1.2.5 Electrolyte 28 3.2 Electrochemistry CO2 Reduction Reaction (ECDRR) 29 3.2.1 Possible Reaction Pathways of ECDRR 29 3.2.1.1 Formation of HCOO− or HCOOH 29 3.2.1.2 Formation of CO 30 3.2.1.3 Formation of C1 Products 30 3.2.1.4 Formation of C2 Products 31 3.2.1.5 Formation of CH3COOH and CH3COO− 33 3.2.1.6 Formation of n-Propanol (C3 Product) 33 3.2.2 General Parameters to Evaluate ECDRR 34 3.2.2.1 Onset Potential 34 3.2.2.2 Faradaic Efficiency 34 3.2.2.3 Partial Current Density 34 3.2.2.4 Environmental Impact and Cost 35 3.2.2.5 Electrolytes 35 3.2.2.6 Electrochemical Cells 36 3.3 Small Organic Molecules Oxidation 36 3.3.1 The Mechanism of Electrochemistry HCOOH Oxidation 36 3.3.2 The Mechanism of Electro-oxidation of Alcohol 37 References 40 Part IV Water Splitting and Devices 43 4 Water Splitting Basic Parameter/Others 45 4.1 Composition and Exact Reactions in Different pH Solution 45 4.2 Evaluation of the Catalytic Activity 47 4.2.1 Overpotential 47 4.2.2 Tafel Slope 48 4.2.3 Stability 49 4.2.4 Faradaic Efficiency 49 4.2.5 Turnover Frequency 50 References 50 5 H2O Oxidation 53 5.1 Regular H2O Oxidation 53 5.1.1 Noble Metal Catalysts 53 5.1.2 Other Transition Metals 64 5.1.3 Other Catalysts 72 5.2 Photo-Assisted H2O Oxidation 76 5.2.1 Metal Compound-Based Catalysts 76 5.2.2 Metal–Metal Heterostructure Catalysts 80 5.2.3 Metal–Nonmetal Heterostructure Catalysts 86 References 88 6 H2O Reduction and Water Splitting Electrocatalytic Cell 91 6.1 Noble-Metal-Based HER Catalysts 91 6.2 Non-Noble Metal Catalysts 93 6.3 Water Splitting Electrocatalytic Cell 96 References 99 Part V H2 Oxidation/O2 Reduction and Device 101 7 Introduction 103 7.1 Electrocatalytic Reaction Parameters 104 7.1.1 Electrochemically Active Surface Area (ECSA) 104 7.1.1.1 Test Methods 104 7.1.2 Determination Based on the Surface Redox Reaction 104 7.1.3 Determination by Electric Double-Layer Capacitance Method 105 7.1.4 Kinetic and Exchange Current Density (jk and j0) 105 7.1.4.1 Definition 105 7.1.4.2 Calculation 106 7.1.5 Overpotential HUPD 106 7.1.6 Tafel Slope 108 7.1.7 Halfwave Potentials 108 References 108 8 Hydrogen Oxidation Reaction (HOR) 111 8.1 Mechanism for HOR 111 8.1.1 Hydrogen Bonding Energy (HBE) 111 8.1.2 Underpotential Deposition (UPD) of Hydrogen 112 8.2 Catalysts for HOR 112 8.2.1 Pt-based Materials 112 8.2.2 Pd-Based Materials 120 8.2.3 Ir-Based Materials 121 8.2.4 Rh-Based Materials 121 8.2.5 Ru-Based Materials 121 8.2.6 Non-noble Metal Materials 122 References 130 9 Oxygen Reduction Reaction (ORR) 133 9.1 Mechanism for ORR 133 9.1.1 Battery System and Damaged Electrodes 133 9.1.2 Intermediate Species 134 9.2 Catalysts in ORR 134 9.2.1 Noble Metal Materials 134 9.2.1.1 Platinum/Carbon Catalyst 138 9.2.1.2 Pd and Pt 145 9.2.2 Transition Metal Catalysts 145 9.2.3 Metal-Free Catalysts 149 9.3 Hydrogen Peroxide Synthesis 154 9.3.1 Catalysts Advances 154 9.3.1.1 Pure Metals 154 9.3.1.2 Metal Alloys 156 9.3.1.3 Carbon Materials 157 9.3.1.4 Electrodes and Reaction Cells 158 References 161 10 Fuel Cell and Metal-Air Battery 167 10.1 H2 Fuel Cell 167 10.2 Metal-Air Battery 170 10.2.1 Metal-Air Battery Structure 171 References 181 Part VI Small Organic Molecules Oxidation and Device 183 11 Introduction 185 11.1 Primary Measurement Methods and Parameters 186 11.1.1 Primary Measurement Methods 186 11.1.2 Primary Parameter 193 References 197 12 C1 Molecule Oxidation 199 12.1 Methane Oxidation 199 12.1.1 Reaction Mechanism 199 12.1.1.1 Solid–Liquid–Gas Reaction System 199 12.1.2 Acidic Media 199 12.1.3 Alkaline or Neutral Media 201 12.2 Methanol Oxidation 203 12.2.1 Reaction Thermodynamics and Mechanism 203 12.2.2 Catalyst Advances 204 12.2.2.1 Pd-Based Catalysts 204 12.2.2.2 Pt-Based Catalysts 208 12.2.2.3 Platinum-Based Nanowires 208 12.2.2.4 Platinum-Based Nanotubes 210 12.2.2.5 Platinum-Based Nanoflowers 212 12.2.2.6 Platinum-Based Nanorods 214 12.2.2.7 Platinum-Based Nanocubes 215 12.2.3 Pt–Ru System 217 12.2.4 Pt–Sn Catalysts 218 12.3 Formic Acid Oxidation 219 12.3.1 Reaction Mechanism 219 12.3.2 Catalyst Advances 220 12.3.2.1 Pd-Based Catalysts 220 12.3.2.2 Pt-Based Catalysts 223 References 226 13 C2+ Molecule Oxidation 235 13.1 Ethanol Oxidation 235 13.1.1 Reaction Mechanism 235 13.1.2 Catalyst Advances 235 13.1.2.1 Pd-Based Catalysts 235 13.1.2.2 Pt-Based Catalysts 239 13.1.2.3 Pt–Sn System 243 13.2 Glucose Oxidase 250 13.3 Ethylene Glycol Oxidation 251 13.4 Glycerol Oxidation 251 References 254 14 Fuel Cell Devices 257 14.1 Introduction 257 14.2 Types of Direct Liquid Fuel Cells 258 14.2.1 Acid and Alkaline Fuel Cells 258 14.2.2 Direct Methanol Fuel Cells (DMFCs) 260 14.2.3 Direct Ethanol Fuel Cells (DEFCs) 261 14.2.4 Direct Ethylene Glycol Fuel Cells (DEGFCs) 261 14.2.5 Direct Glycerol Fuel Cells (DGFCs) 262 14.2.6 Direct Formic Acid Fuel Cells (DFAFCs) 262 14.2.7 Direct Dimethyl Ether Fuel Cells (DDEFCs) 263 14.2.8 Other DLFCs 263 14.2.9 Challenges of DLFCs 264 14.2.10 Fuel Conversion and Cathode Flooding 264 14.2.11 Chemical Safety and By-product Production 265 14.2.12 Unproven Long-term Durability 265 References 267 Part VII CO2 Reduction and Device 271 15 Introduction 273 15.1 Basic Parameters of the CO2 Reduction Reaction 276 15.1.1 The Fundamental Parameters to Evaluate the Catalytic Activity 276 15.1.1.1 Overpotential (𝜂) 276 15.1.1.2 Faradaic Efficiency (FE) 276 15.1.1.3 Current Density ( j) 277 15.1.1.4 Energy Efficiency (EE) 277 15.1.1.5 Tafel Slope 278 15.1.2 Factors Affecting ECDRR 278 15.1.2.1 Solvent/Electrolyte 278 15.1.2.2 pH 280 15.1.2.3 Cations and Anions 281 15.1.2.4 Concentration 282 15.1.2.5 Temperature and Pressure Effect 282 15.1.3 Electrode 283 15.1.3.1 Loading Method 283 15.1.3.2 Preparation 284 15.1.3.3 Experimental Process and Analysis Methods 284 References 285 16 Electrocatalysts-1 289 16.1 Heterogeneous Electrochemical CO2 Reduction Reaction 289 16.2 Thermodynamic and Kinetic Parameters of Heterogeneous CO2 Reduction in Liquid Phase 289 16.2.1 Bulk Metals 293 16.2.2 Nanoscale Metal and Oxidant Metal Catalysts 294 16.2.2.1 Gold (Au) 295 16.2.2.2 Silver (Ag) 296 16.2.2.3 Palladium (Pd) 297 16.2.2.4 Zinc (Zn) 298 16.2.2.5 Copper (Cu) 299 16.2.3 Bimetallic/Alloy 301 References 306 17 Electrocatalysts-2 309 17.1 Single-Atom Metal-Doped Carbon Catalysts (SACs) 309 17.1.1 Nickel (Ni)-SACs 309 17.1.2 Cobalt (Co)-SACs 311 17.1.3 Iron (Fe)-SACs 311 17.1.4 Zinc (Zn)-SACs 314 17.1.5 Copper (Cu)-SACs 314 17.1.6 Other 316 17.2 Metal Nanoparticles-Doped Carbon Catalysts 317 17.3 Porous Organic Material 320 17.3.1 Metal Organic Frameworks (MOFs) 320 17.3.2 Covalent Organic Frameworks (COFs) 321 17.3.3 Metal-Free Catalyst 322 17.4 Metal-Free Carbon-Based Catalyst 322 17.4.1 Other Metal-Free Catalyst 324 17.5 Electrochemical CO Reduction Reaction 324 17.5.1 The Importance of CO Reduction Study 324 17.5.2 Advances in CO Reduction 326 References 327 18 Devices 331 18.1 H-Cell 331 18.2 Flow Cell 333 18.3 Requirements and Challenges for Next-Generation CO2 Reduction Cell 338 18.3.1 Wide Range of Electrocatalysts 338 18.3.2 Fundamental Factor Influencing the Catalytic Activity for ECDRR 339 18.3.3 Device Engineering 340 References 342 Part VIII Computations-Guided Electrocatalysis 345 19 Insights into the Catalytic Process 347 19.1 Electric Double Layer 347 19.2 Kinetics and Thermodynamics 349 19.3 Electrode Potential Effects 350 References 352 20 Computational Electrocatalysis 355 20.1 Computational Screening Toward Calculation Theories 356 20.2 Reactivity Descriptors 358 20.2.1 d-band Theory Motivates Electronic Descriptor 359 20.2.2 Coordination Numbers Motives Structure Descriptor 361 20.3 Scaling Relationships: Applications of Descriptors 361 20.4 The Activity Principles and the Volcano Curve 363 20.5 DFT Modeling 366 20.5.1 CHE Model 367 20.5.2 Solvation Models 368 20.5.3 Kinetic Modeling 371 References 374 21 Theory-Guided Rational Design 377 21.1 Descriptors-Guided Screening 377 21.2 Scaling Relationship-Guided Trends 380 21.2.1 Reactivity Trends of ECR 380 21.2.2 Reactivity Trends of O-included Reactions 382 21.2.3 Reactivity Trends of H-included Reactions 385 21.3 DOS-Guided Models and Active Sites 386 References 388 22 DFT Applications in Selected Electrocatalytic Systems 391 22.1 Unveiling the Electrocatalytic Mechanism 391 22.1.1 ECR Reaction 393 22.1.2 OER Reaction 394 22.1.3 ORR Reaction 396 22.1.4 HER Reaction 397 22.1.5 HOR Reaction 398 22.1.6 CO Oxidation Reaction 400 22.1.7 FAOR Reaction 402 22.1.8 MOR Reaction 402 22.1.9 EOR Reaction 404 22.2 Understanding the Electrocatalytic Environment 406 22.2.1 Solvation Effects 406 22.2.2 pH Effects 409 22.3 Analyzing the Electrochemical Kinetics 410 22.4 Perspectives, Challenges, and Future Direction of DFT Computation in Electrocatalysis 413 References 414 Part IX Potential of In Situ Characterizations for Electrocatalysis 421 References 422 23 In Situ Characterization Techniques 423 23.1 Optical Characterization Techniques 423 23.1.1 Infrared Spectroscopy 423 23.1.2 Raman Spectroscopy 424 23.1.3 UV–vis Spectroscopy 426 23.2 X-Ray Characterization Techniques 427 23.2.1 X-Ray Diffraction (XRD) 429 23.2.2 X-Ray Absorption Spectroscopy (XAS) 429 23.2.3 X-Ray Photoelectron Spectroscopy (XPS) 431 23.3 Mass Spectrometric Characterization Techniques 431 23.4 Electron-Based Characterization Techniques 432 23.4.1 Transmission Electron Microscopy (TEM) 434 23.4.2 Scanning Probe Microscopy (SPM) 434 References 436 24 In Situ Characterizations in Electrocatalytic Cycle 441 24.1 Investigating the Real Active Centers 441 24.1.1 Monitoring the Electronic Structure 442 24.1.2 Monitoring the Atomic Structure 444 24.1.3 Monitoring the Catalyst Phase Transformation 446 24.2 Investigating the Reaction Mechanism 449 24.2.1 Through Adsorption/Activation Understanding 450 24.2.2 Through Intermediates In Situ Probing 451 24.2.3 Through Catalytic Product In Situ Detections 454 24.3 Evaluating the Catalyst Stability/Decay 457 24.4 Revealing the Interfacial-Related Insights 460 24.5 Conclusion 462 References 462 Part X Electrochemical Catalytic Carbon Cycle 465 References 466 25 Electrochemical CO2 Reduction to Fuels 467 References 479 26 Electrochemical Fuel Oxidation 483 References 495 27 Evaluation and Management of ECC 499 27.1 Basic Performance Index 499 27.2 CO2 Capture and Fuel Transport 500 27.3 External Management 500 27.4 General Outlook 502 References 505 Index 507

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Book SynopsisCatalysis in Confined Frameworks Understanding the synthesis and applications of porous solid catalysts Heterogeneous catalysis is a catalytic process in which catalysts and reactants exist in different phases. Heterogeneous catalysis with solid catalysts proceeds through the absorption of substrates and reagents which are liquid or gas, and this is largely dependent on the accessible surface area of the solid which can generate active reaction sites. The synthesis of porous solids is an increasingly productive approach to generating solid catalysts with larger accessible surface area, allowing more efficient catalysis. Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications provides a comprehensive overview of synthesis and use of porous solids as heterogeneous catalysts. It provides detailed analysis of pore engineering, a thorough characterization of the advantages and disadvantages of porous solids as heterogeneous catalysts, and an extensive discussion of applications. The result is a foundational introduction to a cutting-edge field. Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications readers will also find: An editorial team comprised of international experts with extensive experience Detailed discussion of catalyst classes including zeolites, mesoporous aluminosilicates, and more A special focus on size selective catalysis Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications is an essential reference for catalytic chemists, organic chemists, materials scientists, physical chemists, and any researchers or industry professionals working with heterogeneous catalysis.Table of ContentsPreface xiii 1 Engineering of Metal Active Sites in MOFs 1 Carmen Fernández-Conde, María Romero-Ángel, Ana Rubio-Gaspar, and Carlos Martí-Gastaldo 1.1 Metal Node Engineering 2 1.1.1 Frameworks with Intrinsically Active Metal Nodes 3 1.1.1.1 Metal–Organic Frameworks with Only One Metal 3 1.1.1.2 Metal–Organic Frameworks with more than One Metal in its Cluster 6 1.1.2 Introducing Defectivity as a Powerful Tool to Tune Metal-node Catalytic Properties in MOFs 8 1.1.3 Incorporating Metals to Already-Synthetized Metal–Organic Frameworks: Isolating the Catalytic Site 12 1.1.4 Metal Exchange 14 1.1.5 Attaching Metallic Units to the MOF 14 1.1.6 Grafting of Organometallic Complexes into the MOF Nodes 18 1.2 Ligand Engineering 21 1.2.1 Ligands as Active Metal Sites 22 1.2.1.1 Creating Metal Sites in the Organic Linkers. Types of Ligands 22 1.2.1.2 Cooperation Between Single-Metal Sites and Metalloligands 28 1.2.1.3 Ligand Accelerated Catalysis (LAC) 28 1.2.2 Introduction of Metals by Direct Synthesis 31 1.2.2.1 In-situ Metalation 32 1.2.2.2 Premetalated Linker 32 1.2.2.3 Postgrafting Metal Complexes 33 1.2.3 Introduction of Metals by Post-synthetic Modifications 34 1.2.3.1 Post-synthetic Exchange or Solvent-Assisted Linker Exchange (sale) 34 1.2.3.2 Post-synthetic Metalation 36 1.3 Metal-Based Guest Pore Engineering 38 1.3.1 Encapsulation Methodologies in As-Made Metal–Organic Frameworks 39 1.3.1.1 Incipient Wetness Impregnation 39 1.3.1.2 Ship-in-a-Bottle 42 1.3.1.3 Metal–Organic Chemical Vapor Deposition (MOCVD) 42 1.3.1.4 Metal-Ion Exchange 46 1.3.2 In Situ Guest Metal–Organic Framework Encapsulations 47 1.3.2.1 Solvothermal Encapsulation or One Pot 47 1.3.2.2 Co-precipitation Methodologies 49 List of Abbreviations 52 References 53 2 Engineering the Porosity and Active Sites in Metal–Organic Framework 67 Ashish K. Kar, Ganesh S. More, and Rajendra Srivastava 2.1 Introduction 67 2.2 Active Sites in MOF 69 2.2.1 Active Sites Near Pores in MOF 69 2.2.2 Active Sites Near Metallic Nodes in MOF 70 2.2.3 Active Sites Near Ligand Center in MOF 70 2.3 Synthesis and Characterization 70 2.4 Engineering of Active Sites in MOF Structure for Catalytic Transformations 72 2.4.1 Pore Tunability 73 2.4.2 Metal Nodes 77 2.4.3 Ligand Centers 83 2.5 Conclusion 90 References 91 3 Characterization of Organic Linker-Containing Porous Materials as New Emerging Heterogeneous Catalysts 97 Ali R. Oveisi, Saba Daliran, and Yong Peng 3.1 Introduction 97 3.2 Microscopy Techniques 98 3.2.1 Scanning Electron Microscopy (SEM) 98 3.2.2 Transmission Electron Microscopy (TEM) 100 3.2.3 Atomic Force Microscopy (AFM) 103 3.3 Spectroscopy Techniques 104 3.3.1 X-ray Spectroscopy 104 3.3.1.1 X-ray Diffraction (XRD) 104 3.3.1.2 X-ray Photoelectron Spectroscopy (XPS) 105 3.3.1.3 X-ray Absorption Fine Structure (XAFS) Techniques 107 3.3.2 Nuclear Magnetic Resonance (NMR) 109 3.3.3 Electron Paramagnetic Resonance (EPR) 110 3.3.4 Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV–Vis DRS) 111 3.3.5 Inductively Coupled Plasma (ICP) Analysis 112 3.4 Other Techniques 114 3.4.1 Thermogravimetric Analysis (TGA) 114 3.4.2 N2 Adsorption 115 3.4.3 Density Functional Theory (DFT) Calculations 118 3.5 Conclusions 121 Acknowledgments 121 References 121 4 Mixed Linker MOFs in Catalysis 127 Mohammad Y. Masoomi and Lida Hashemi 4.1 Introduction 127 4.1.1 Introduction to Mixed Linker MOFs 127 4.2 Strategies for Synthesizing Mixed-Linker MOFs 128 4.2.1 IML Frameworks 128 4.2.2 HML Frameworks 129 4.2.3 TML Frameworks 130 4.3 Types of Mixed-Linker MOFs 131 4.3.1 Pillared-Layer Mixed-Linker MOFs 131 4.3.2 Cage-Directed Mixed-Linker MOFs 132 4.3.3 Cluster-Based Mixed-Linker MOFs 132 4.3.4 Structure Templated Mixed-Linker MOFs 132 4.4 Introduction to Catalysis with MOFs 133 4.5 Mixed-Linker MOFs as Heterogeneous Catalysts 133 4.5.1 Mixed-Linker MOFs with Similar Size/Directionality Linkers 134 4.5.2 Mixed-Linker MOFs with Structurally Independent Linkers 140 4.6 Conclusion 148 References 148 5 Acid-Catalyzed Diastereoselective Reactions Inside MOF Pores 151 Herme G. Baldoví, Sergio Navalón, and Francesc X. Llabrés I Xamena 5.1 Introduction 151 5.2 Diastereoselective Reactions Catalyzed by MOFs 154 5.2.1 Meerwein–Ponndorf–Verley Reduction of Carbonyl Compounds 154 5.2.2 Aldol Addition Reactions 158 5.2.3 Diels–Alder Reaction 162 5.2.4 Isomerization Reactions 164 5.2.5 Cyclopropanation 168 5.3 Conclusions and Outlook 176 Acknowledgments 176 References 176 6 Chiral MOFs for Asymmetric Catalysis 181 Kayhaneh Berijani and Ali Morsali 6.1 Chiral Metal–Organic Frameworks (CMOFs) 181 6.2 Synthesis Methods of CMOFs with Achiral and Chiral Building Blocks 184 6.2.1 Spontaneous Resolution 185 6.2.2 Direct Synthesis 187 6.2.3 Indirect Synthesis 190 6.3 Chiral MOF Catalysts 192 6.3.1 Brief History of CMOF-Based Catalysts 192 6.3.2 Designing CMOF Catalysts 193 6.4 Examples of Enantioselective Catalysis Using CMOF-Based Catalysts 194 6.4.1 Type I: Chiral MOFs in Simple Asymmetric Reactions 194 6.4.2 Type II: Chiral MOFs in Complex Asymmetric Reactions 206 6.5 Conclusion 210 References 210 7 MOF-Supported Metal Nanoparticles for Catalytic Applications 219 Danyu Guo, liyu Chen, and Yingwei li 7.1 Introduction 219 7.2 Synergistic Catalysis by MNP@MOF Composites 220 7.2.1 The Inorganic Nodes of MOFs Cooperating with Metal NPs 220 7.2.2 The Organic Linkers of MOFs Cooperating with Metal NPs 220 7.2.3 The Nanostructures of MOFs Cooperating with Metal NPs 221 7.3 Electrocatalysis Applications 221 7.3.1 Hydrogen Evolution Reaction 221 7.3.2 Oxygen Evolution Reaction 223 7.3.3 Oxygen Reduction Reaction 224 7.3.4 CO2 Reduction Reaction 224 7.3.4.1 CO 225 7.3.4.2 HCOOH 225 7.3.4.3 C2H4 225 7.3.5 Nitrogen Reduction Reaction 227 7.3.6 Oxidation of Small Molecules 228 7.4 Photocatalytic Applications 229 7.4.1 Photocatalytic Hydrogen Production 229 7.4.2 Photocatalytic CO2 Reduction 232 7.4.2.1 CO2 Photoreduction to CO 232 7.4.2.2 CO2 Photoreduction to CH3OH 233 7.4.2.3 CO2 Photoreduction to HCOO−/HCOOH 234 7.4.3 Photocatalytic Organic Reactions 235 7.4.3.1 Photocatalytic Hydrogenation Reactions 235 7.4.3.2 Photocatalytic Oxidation Reactions 235 7.4.3.3 Photocatalytic Coupling Reaction 236 7.4.4 Photocatalytic Degradation of Organic Pollutants 237 7.4.4.1 Degradation of Pollutants in Wastewater 237 7.4.4.2 Degradation of Gas-Phase Organic Compounds 239 7.5 Thermocatalytic Applications 239 7.5.1 Oxidation Reactions 239 7.5.1.1 Gas-Phase Oxidation Reactions 239 7.5.1.2 Liquid-Phase Oxidation Reactions 240 7.5.2 Hydrogenation Reactions 241 7.5.2.1 Hydrogenation of C=C and C≡C Groups 241 7.5.2.2 The Reduction of −NO2 Group 242 7.5.2.3 The Reduction of C=O Groups 244 7.5.3 Coupling Reactions 244 7.5.3.1 Suzuki–Miyaura Coupling Reactions 244 7.5.3.2 Heck Coupling Reactions 246 7.5.3.3 Glaser Coupling Reactions 246 7.5.3.4 Knoevenagel Condensation Reaction 246 7.5.3.5 Three-Component Coupling Reaction 247 7.5.4 CO2 Cycloaddition Reactions 247 7.5.5 Tandem Reactions 248 7.6 Conclusions and Outlooks 250 References 251 8 Confinement Effects in Catalysis with Molecular Complexes Immobilized into Porous Materials 273 Maryse Gouygou, Philippe Serp, and Jérôme Durand 8.1 Introduction 273 8.2 Immobilization of Molecular Complexes into Porous Materials 279 8.2.1 Confinement of Molecular Complexes in Mesoporous Silica 279 8.2.2 Confinement of Molecular Complexes in Zeolites 281 8.2.3 Confinement of Molecular Complexes in Covalent Organic Frameworks (COF) 282 8.2.4 Confinement of Molecular Complexes in Metal–Organic Frameworks (MOFs) 283 8.2.5 Confinement of Molecular Complexes in Carbon Materials 285 8.3 Characterization of Molecular Complexes Immobilized into Porous Materials 285 8.4 Catalysis with Molecular Complexes Immobilized into Porous Materials and Evidences of Confinement Effects 287 8.4.1 Hydrogenation Reactions 288 8.4.2 Hydroformylation Reactions 289 8.4.3 Oxidation Reactions 290 8.4.4 Ethylene Oligomerization and Polymerization Reactions 291 8.4.5 Metathesis Reactions 291 8.4.6 Miscellaneous Reactions on Various Supports 293 8.4.6.1 Zeolites 293 8.4.6.2 Mesoporous Silica 293 8.4.6.3 MOFs 294 8.4.7 Asymmetric Catalysis Reactions 295 8.5 Conclusion 298 References 299 9 Size-Selective Catalysis by Metal–Organic Frameworks 315 Amarajothi Dhakshinamoorthy and Hermenegildo García 9.1 Introduction 315 9.2 Friedel–Crafts Alkylation 319 9.3 Cycloaddition Reactions 320 9.4 Oxidation of Olefins 323 9.5 Hydrogenation Reactions 325 9.6 Aldehyde Cyanosilylation 326 9.7 Knoevenagel Condensation 328 9.8 Conclusions 329 References 330 10 Selective Oxidations in Confined Environment 333 Oxana A. Kholdeeva 10.1 Introduction 333 10.2 Transition-Metal-Substituted Molecular Sieves 334 10.2.1 Ti-Substituted Zeolites and H2O2 334 10.2.2 Co-Substituted Aluminophosphates and O2 337 10.3 Mesoporous Metal–Silicates 338 10.3.1 Mesoporous Ti-Silicates in Oxidation of Hydrocarbons 339 10.3.2 Mesoporous Ti-Silicates in Oxidation of Bulky Phenols 340 10.3.3 Alkene Epoxidation over Mesoporous Nb-Silicates 342 10.4 Metal–Organic Frameworks 343 10.4.1 Selective Oxidations over Cr- and Fe-Based MOFs 343 10.4.2 Selective Oxidations with H2O2 over Zr- and Ti-Based MOFs 347 10.5 Polyoxometalates in Confined Environment 349 10.5.1 Silica-Encapsulated POM 350 10.5.2 MOF-Incorporated POM 350 10.5.3 POMs Supported on Carbon Nanotubes 352 10.6 Conclusion and Outlook 353 Acknowledgments 354 References 354 11 Tailoring the Porosity and Active Sites in Silicoaluminophosphate Zeolites and Their Catalytic Applications 363 Jacky H. Advani, Abhinav Kumar, and Rajendra Srivastava 11.1 Introduction 363 11.2 Synthesis of SAPO-n Zeolites 365 11.3 Characterization of SAPO Zeolites 370 11.4 SAPO-Based Catalysts in Organic Transformations 370 11.4.1 Acid Catalysis 370 11.4.2 Reductive Transformations 374 11.4.2.1 Selective Catalytic Reduction (SCR) 374 11.4.2.2 Hydroisomerization 379 11.4.2.3 Hydroprocessing 383 11.4.2.4 CO2 Hydrogenation 385 11.5 Conclusion 387 References 388 12 Heterogeneous Photocatalytic Degradation of Pharmaceutical Pollutants over Titania Nanoporous Architectures 397 Surya Kumar Vatti and Parasuraman Selvam 12.1 Introduction 397 12.2 Advanced Oxidation Process 399 12.2.1 Ozonation 401 12.2.2 UV Irradiation (Photolysis) 401 12.2.3 Fenton and Photo-Fenton Process 402 12.2.4 Need for Green Sustainable Heterogeneous AOP 402 12.2.5 Heterogeneous Photocatalysis 402 12.3 Semiconductor Photocatalysis Mechanism 403 12.4 Factors Affecting Photocatalytic Efficiency 404 12.5 Crystal Phases of TiO2 404 12.6 Semiconductor/Electrolyte Interface and Surface Reaction 406 12.7 Visible-Light Harvesting 409 12.8 Photogenerated Charge Separation Strategies 412 12.8.1 TiO2/Carbon Heterojunction 412 12.8.2 TiO2/SC Coupled Heterojunction 412 12.8.3 TiO2/ TiO2 Phase Junction 414 12.8.4 Metal/ TiO2 Schottky Junction 415 12.9 Ordered Mesoporous Materials 415 12.10 Ordered Mesoporous Titania 417 12.10.1 Synthesis and Characterization 418 12.10.2 Photocatalytic Degradation Studies 420 12.10.3 Complete Mineralization Studies 424 12.10.4 Spent Catalyst 425 12.11 Conclusion 427 Acknowledgment 428 References 429 13 Catalytic Dehydration of Glycerol Over Silica and Alumina-Supported Heteropoly Acid Catalysts 433 Sekar Mahendran, Shinya Hayami, and Parasuraman Selvam 13.1 Introduction 433 13.2 Value Addition of Bioglycerol 434 13.3 Interaction Between HPA and Support 437 13.4 Bulk Heteropoly Acid 438 13.5 Silica-Supported HPA 439 13.5.1 Effect of Textural Properties of Support on Product Selectivity 439 13.5.2 Effect of Catalyst Loading 440 13.5.3 Effect of Acid Sites 440 13.5.4 Effect of Type of Heteropoly Acids 443 13.6 Tuning the Acidity 444 13.7 Conclusions 446 Acknowledgments 447 References 447 14 Catalysis with Carbon Nanotubes 451 Mohammad Y. Masoomi and Lida Hashemi 14.1 Introduction 451 14.1.1 Why CNT may be Suitable to be Used as Catalyst Supports? 451 14.1.1.1 From the Point of Structural Features 452 14.1.1.2 From the Point of Electronic Properties 455 14.1.1.3 From the Point of Adsorption Properties 455 14.1.1.4 From the Point of Mechanical and Thermal Properties 456 14.2 Catalytic Performances of CNT-Supported Systems 456 14.2.1 Different Approaches for the Anchoring of Metal-Containing Species on CNT 457 14.2.2 Different Approaches for the Confining NPs Inside CNTs and Their Characterization 457 14.2.2.1 Wet Chemistry Method 458 14.2.2.2 Production of CNTs Inside Anodic Alumina 459 14.2.2.3 Arc-Discharge Synthesis 459 14.2.3 Hydrogenation Reactions 459 14.2.4 Dehydrogenation Reactions 460 14.2.5 Liquid-Phase Hydroformylation Reactions 461 14.2.6 Liquid-Phase Oxidation Reactions 462 14.2.7 Gas-Phase Reactions 464 14.2.7.1 Syngas Conversion 464 14.2.7.2 Ammonia Synthesis and Ammonia Decomposition 464 14.2.7.3 Epoxidation of Propylene in DWCNTs 465 14.2.8 Fuel Cell Electro Catalyst 465 14.2.9 Catalytic Decomposition of Hydrocarbons 466 14.2.10 CNT as Heterogeneous Catalysts 466 14.2.11 Sulfur Catalysis 467 14.3 Metal-Free Catalysts of CNTs 467 14.4 Conclusion 468 References 469 Index 473

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Book SynopsisCO2 Conversion and Utilization Comprehensive overview of current development of various catalysts in CO2 conversion and utilization through photocatalytic and electrochemical methods CO2 Conversion and Utilization systematically summarizes the development of CO2 photo- and electro-conversion and utilization, especially the reaction mechanism, engineering and technology of testing, and preparation methods and physicochemical properties of various catalytic materials. The rational design and preparation of catalysts, development of characterization technologies, and in-depth understanding of catalytic mechanisms are systematically discussed. In particular, the various parameters influencing the photocatalytic and electrochemical CO2 reduction are emphasized. The underlying challenges and perspectives for the future development of efficient catalysts for CO2 reduction to specific chemicals and fuels are discussed at the end of the text. Written by a highly qualified author with significant experience in the field, CO2 Conversion and Utilization includes information on: Measurement systems and parameters for CO2 photo/electro-conversion, CO2 photo/electro-conversion mechanism, and Cu-based and Cu-free metal materials for electrocatalytic CO2 reduction Organic-inorganic, metal organic framework, and covalent organic framework hybrid materials for CO2 photo/electro-conversion Single/dual-atom catalysts, homogeneous catalysts, and high-entropy alloys for CO2 photo/electro-conversion Semiconductor composite and carbon-based materials for photocatalytic CO2 reduction, novel routes for CO2 utilization via metal-CO2 batteries, and CO2 conversion into long-chain compounds Providing comprehensive coverage of the subject, CO2 Conversion and Utilization is of high interest for scientific researchers as well as engineers and technicians in industry, including but not limited to photochemists, electrochemists, environmental chemists, catalytic chemists, chemists in industry, and inorganic chemists.Table of ContentsPreface xiii 1 Measurement Systems and Parameters for CO 2 Photo/Electro-Conversion 1 li li, Zhenwei Zhao, Xinyi Wang, and Zhicheng Zhang 1.1 Introduction 1 1.2 The Measurement Systems for CO 2 Photo/Electro-Conversion 1 1.2.1 The Measurement Systems of Photocatalytic CO 2 Reduction 1 1.2.1.1 CO 2 Reduction System Under Liquid-Phase Reaction System 2 1.2.1.2 CO 2 Reduction System in Gas-Phase Reaction System 2 1.2.1.3 Detection of CO 2 Reduction Products 3 1.2.2 The Measurement Systems of Electrocatalytic CO 2 Reduction 3 1.2.2.1 Electrocatalytic CO 2 Reduction Reaction Test in H-Cell 3 1.2.2.2 Electrocatalytic CO 2 Reduction Reaction Test in Flow Cell 5 1.2.2.3 Electrocatalytic CO 2 Reduction Reaction Test in MEA 5 1.2.3 The Measurement Systems of Photo-Electro-Catalytic CO 2 Reduction 6 1.2.3.1 Basic Device for Photocatalytic CO 2 Reduction Experiment 6 1.2.3.2 Other Devices for Photocatalytic CO 2 Reduction 7 1.2.3.3 Detection of CO 2 Reduction Reaction Products 7 1.3 The Parameters for CO 2 Photo-Conversion 7 1.3.1 The Parameters of Photocatalytic CO 2 Reduction 7 1.3.1.1 Evaluation Parameters of Photocatalytic CO 2 Reduction Activity 8 1.3.1.2 Evaluation Parameters of Photocatalytic CO 2 Reduction Selectivity 10 1.3.1.3 Evaluation Parameters of Photocatalytic CO 2 Reduction Stability 10 1.3.2 The Parameters of Electrocatalytic CO 2 Reduction 10 1.3.3 The Parameters of Photo-Electro-Catalytic CO 2 Reduction 12 1.3.3.1 Overpotential 12 1.3.3.2 Total Photocurrent Density (j ph) and Partial Photocurrent Density (j A) 12 1.3.3.3 Faraday Efficiency (FE) 13 1.3.3.4 Solar Energy Conversion Efficiency 13 1.3.3.5 Apparent Quantum Yield (AQY) 13 1.3.3.6 Electrochemical Active Area (ECSA) 14 1.3.3.7 Electrochemical Impedance (EIS) 14 1.3.3.8 Tafel Slope (Tafel) 14 1.3.3.9 Photocatalytic Stability 14 References 15 2 CO 2 Photo/Electro-Conversion Mechanism 17 Yalin Guo, Shenghong Zhong, and Jianfeng Huang 2.1 Introduction 17 2.2 CO 2 Photo-Conversion Mechanism 18 2.3 CO 2 Electro-Conversion Mechanism 25 2.3.1 Thermodynamics of CO 2 Reduction 25 2.3.2 Pathways of Electrochemical CO 2 Reduction 26 2.3.2.1 Electrochemical CO 2 Reduction to CO 27 2.3.2.2 Electrochemical CO 2 Reduction to Formate 28 2.3.2.3 Electrochemical CO 2 Reduction to Products Beyond CO 29 2.4 Summary and Perspectives 32 References 32 3 Cu-Based Metal Materials for Electrocatalytic CO 2 Reduction 37 Junjun Li, Yongxia Shi, Man Hou, and Zhicheng Zhang 3.1 Introduction 37 3.2 Cu-Based Metal Materials for Electrocatalytic CO 2 Reduction 39 3.2.1 Cu Materials for Electrocatalytic CO 2 Reduction 39 3.2.2 Cu-Based Bimetal Materials for Electrocatalytic CO 2 Reduction 40 3.2.2.1 Cu–Au 40 3.2.2.2 Cu–Ag 42 3.2.2.3 Cu–Pd 43 3.2.2.4 Cu–Sn 44 3.2.2.5 Cu–Bi 46 3.2.2.6 Cu–In 46 3.2.2.7 Cu–Al 49 3.2.2.8 Cu–Zn 49 3.2.3 Cu-Based Trimetallic Materials for Electrocatalytic CO 2 Reduction 50 3.3 Conclusion and Outlook 50 Acknowledgment 53 References 53 4 Cu-Free Metal Materials for Electrocatalytic CO 2 Conversion 61 Zhiqi Huang and Qingfeng Hua 4.1 Introduction 61 4.2 CO-Producing Metals 62 4.2.1 Au-Based Electrocatalysts 62 4.2.2 Ag-Based Electrocatalysts 66 4.2.3 Pd-Based Electrocatalysts 68 4.2.4 Zn-Based Electrocatalysts 70 4.3 HCOOH-Producing Metals 72 4.3.1 Sn-Based Electrocatalysts 72 4.3.2 Bi-Based Electrocatalysts 76 4.3.3 In-Based Electrocatalysts 78 References 80 5 Organic–Inorganic Hybrid Materials for CO 2 Photo/Electro-Conversion 93 Peilei He 5.1 Hybrid Materials for Photocatalytic CO 2 Reduction Reaction (co 2 Rr) 93 5.1.1 Photocatalytic CO 2 RR on p-type Semiconductor/Molecule Catalysts 93 5.1.2 Photocatalytic CO 2 RR on Carbon Nitride (C 3 N 4)-supported Molecular Catalysts 95 5.1.3 Photocatalytic CO 2 RR on Polyoxometalates (POMs)-based Catalysts 97 5.2 Hybrid Materials for Electrochemical CO 2 RR 98 5.2.1 Electrochemical CO 2 RR on Carbon-supported Molecular Catalysts 98 5.2.2 Electrochemical CO 2 RR on TiO 2 -based Hybrid Materials 103 5.3 Hybrid Materials for Photoelectrochemical (PEC) CO 2 RR 104 5.4 Challenge and Opportunity 106 References 107 6 Metal–Organic Framework Materials for CO 2 Photo-/Electro-Conversion 111 Bingqing Yao, Xiaoya Cui, and Zhicheng Zhang 6.1 Introduction 111 6.2 Photocatalysis 112 6.2.1 MOFs with Photoactive Organic Ligands 113 6.2.2 MOFs with Photoactive Metal Nodes 116 6.2.3 MOF-Based Hybrid System 117 6.3 Electrocatalysis 119 6.3.1 MOFs with Active Sites at Organic Ligands 120 6.3.2 MOFs with Active Sites at Metal Nodes 121 6.3.3 MOF-Based Hybrid System 125 6.4 Photoelectrocatalysis 128 6.5 Conclusion and Outlook 129 Acknowledgment 130 References 130 7 Covalent Organic Frameworks for CO 2 Photo/Electro-Conversion 137 Ting He 7.1 Introduction 137 7.2 COFs for Photocatalytic CO 2 Reduction 138 7.2.1 Imine-Linked COFs 138 7.2.2 Ketoenamine COFs 141 7.2.3 Carbon–Carbon Double Bond-Linked COFs 145 7.2.4 Dioxin-Linked COFs 147 7.2.5 Azine-Linked and Hydrazone-Linked COFs 147 7.3 COFs for Electrocatalytic CO 2 Reduction 148 7.3.1 Porphyrin-Based COFs 148 7.3.2 Phthalocyanine-Based COFs 151 7.3.3 Other COFs 152 7.4 Challenges and Perspectives 152 References 154 8 Single/Dual-Atom Catalysts for CO 2 Photo/Electro-Conversion 157 Honghui Ou and Yao Wang 8.1 Introduction 157 8.2 Synthetic Methods of Single/Dual-Atom Catalysts 158 8.2.1 Single-Atom Photocatalysts 158 8.2.2 Dual-Atom Photocatalysts 160 8.2.3 Single-Atom Electro-Catalysts 162 8.2.4 Dual-Atom Electro-Catalysts 164 8.3 CO 2 Photo-Conversion 165 8.4 CO 2 Electro-Conversion 169 8.5 Summary and Perspective 171 References 172 9 Homogeneous Catalytic CO 2 Photo/Electro-Conversion 177 Zhenguo Guo and Houjuan Yang 9.1 Introduction 177 9.2 Homogeneous Catalytic CO 2 Electro-Conversion 177 9.2.1 The Structure Homogeneous Electrocatalytic CO 2 Reduction System 177 9.2.2 Products in Homogeneous Electrocatalytic CO 2 Reduction 178 9.2.3 Characterizing the Performance of Molecular Electrocatalysts 178 9.2.3.1 Selectivity 178 9.2.3.2 Activity 178 9.2.3.3 Overpotential (η) 179 9.2.3.4 Stability 179 9.2.4 Catalysts for Homogeneous Electrocatalytic CO 2 Reduction 179 9.3 Homogeneous Photocatalytic CO 2 Reduction 180 9.3.1 Mechanism of Homogeneous Photocatalytic CO 2 Reduction 180 9.3.2 Characterizing the Performance of Photocatalysis 181 9.3.3 Photosensitizers Used in Homogeneous Photocatalytic CO 2 Reduction 181 9.3.4 Sacrificial Electron Donors in Homogeneous Photocatalytic CO 2 Reduction 181 9.3.5 Catalysts Used in Homogeneous Photocatalytic CO 2 Reduction 182 9.4 Summary and Perspective 186 Acknowledgments 187 References 187 10 High-Entropy Alloys for CO 2 Photo/Electro-Conversion 189 Fengqi Wang, Pei Liu, and Yuchen Qin 10.1 Introduction 189 10.2 Reaction Pathways and Evaluation Parameters of Electrochemical Co 2 Rr 191 10.2.1 Reaction Pathways of CO 2 RR 191 10.2.2 Evaluation Parameters of Electrochemical CO 2 RR 192 10.2.2.1 Faraday Efficiency 192 10.2.2.2 Current Density 193 10.2.2.3 Turnover Number (TON) 194 10.2.2.4 Turnover Frequency (TOF) 194 10.2.2.5 Overpotential 194 10.3 Characteristics and Synthesis of HEAs 194 10.3.1 Characteristics of HEAs 194 10.3.1.1 The Cocktail Effect 194 10.3.1.2 The Sluggish Diffusion Effect 195 10.3.1.3 The High-entropy Effect 195 10.3.1.4 The Lattice Distortion Effect 195 10.3.1.5 The Phase Structure 196 10.3.2 Synthesis of HEAs 196 10.3.2.1 Top-Down Method 196 10.3.2.2 Down–Top Method 198 10.4 High-Entropy Alloys for CO 2 RR 199 10.5 Summary and Outlook 204 References 205 11 Semiconductor Composite Materials for Photocatalytic CO 2 Reduction 215 Shengyao Wang and Bo Jiang 11.1 Introduction 215 11.2 TiO 2 -Based Composite Photocatalysts 216 11.2.1 Mixed-Phase TiO 2 Composites 217 11.2.2 Metal-Modified TiO 2 218 11.2.3 Nonmetallic-Modified TiO 2 219 11.2.4 Organic Photosensitizer-Modified TiO 2 219 11.2.5 Composited TiO 2 Catalyst 220 11.3 Metal Oxides/Hydroxides-Based Composite Photocatalysts 222 11.3.1 Binary Metal Oxide 222 11.3.2 Ternary Metal Oxide 222 11.3.3 Oxide Perovskite 224 11.3.4 Transition Metal Hydroxide 224 11.3.5 Layered Double Hydroxides (LDHs) 226 11.4 Metal Chalcogenides/Nitrides-Based Composite Photocatalysts 226 11.4.1 Metal Chalcogenides-Based Composite Photocatalysts 227 11.4.2 Metal Nitrides-Based Composite Photocatalysts 228 11.5 c 3 N 4 -Based composite Photocatalysts 229 11.5.1 Change the Morphology and Structure 230 11.5.2 Doped Elements and Other Structural Units 231 11.5.3 Influence of Cocatalyst 232 11.5.4 Constructing Heterojunction 233 11.6 MOFs-Derived Composite Photocatalysts 233 11.6.1 Tunable Frame Structure 234 11.6.2 High Specific Surface Area Enhances CO 2 Adsorption 234 11.6.3 MOFs-Derived Composite Photocatalysts 234 11.7 Nonmetal-Based Composite Photocatalysts 236 11.7.1 Graphene Oxide-Based Composite Photocatalysts 236 11.7.2 SiC-Based Composite Photocatalysts 237 11.7.3 BN-Based Composite Photocatalysts 237 11.7.4 Black Phosphorus-Based Composite Photocatalysts 238 11.7.5 COFs-Based Composite Photocatalysts 239 11.7.6 CMPs-Based Composite Photocatalysts 240 11.8 Conclusions and Perspectives 240 References 242 12 Carbon-Based Materials for CO 2 Photo/Electro-Conversion 251 Qing Qin and Lei Dai 12.1 Advances of Carbon-Based Materials 251 12.1.1 Heteroatom-Doped Carbon 251 12.1.2 Metal-Based Carbon Composites 252 12.1.3 Carbon–Carbon Composites 253 12.1.4 Pore Construction 254 12.2 Background of CO 2 Conversion 255 12.3 EC CO 2 Conversion 256 12.3.1 Heteroatom-Doped Carbon in EC CO 2 Conversion 257 12.3.2 Metal-Modified Carbon Materials in EC CO 2 Conversion 259 12.3.3 Carbon–Carbon Composites in EC CO 2 Conversion 261 12.3.4 Pore Engineering in EC CO 2 Conversion 262 12.4 PC CO 2 Reduction 264 12.4.1 Heteroatom-Doped Carbon in PC CO 2 Conversion 265 12.4.2 Metal-Based/Carbon Nanocomposites in PC CO 2 Conversion 266 12.4.3 Carbon–Carbon Composites in PC CO 2 Conversion 268 12.5 Carbon-Based Materials in PEC CO 2 Reduction 269 12.6 Challenge and Opportunity 270 References 272 13 Metal–CO 2 Batteries: Novel Routes for CO 2 Utilization 283 Xiangyu Zhang and Le Yu 13.1 Introduction 283 13.2 The Mechanism for Metal–CO 2 Electrochemistry 284 13.2.1 Discharge/Charge Mechanisms of Li–CO 2 Batteries 284 13.2.1.1 Discharge Mechanisms of Pure Li–CO 2 Batteries 284 13.2.1.2 Charge Mechanisms of Pure Li–CO 2 Batteries 285 13.2.2 Discharge/Charge Mechanisms of Zn–CO 2 Batteries 286 13.3 The Electrocatalysts for Metal–CO 2 Batteries 286 13.3.1 Carbonaceous Materials 286 13.3.2 Noble Metal-based Materials and Transition Metal-based Materials 287 13.4 The Electrolytes for Metal–CO 2 Batteries 290 13.4.1 Nonaqueous Aprotic Liquid Electrolytes for Pure Li–CO 2 Electrochemistry 290 13.4.2 Solid-State Electrolytes for Pure Li–CO 2 Electrochemistry 290 13.5 Conclusion and Outlook 292 References 293 14 CO 2 Conversion into Long-Chain Compounds 297 Tingting Zheng and Chuan Xia 14.1 Introduction 297 14.2 Photobiochemical Synthesis (PBS) 299 14.2.1 Principles in Designing the PBS System 299 14.2.2 Multicarbon Compounds Produced from PBS 301 14.2.3 Challenges and Prospects for PBS 304 14.3 Microbial Electrosynthesis (MES) 306 14.3.1 Extracellular Electron Transfer (EET) 306 14.3.2 Approaches to Optimize MES 309 14.3.2.1 Metabolic Pathways 309 14.3.2.2 Metabolic Engineering 309 14.3.2.3 Culture 311 14.3.2.4 Biocathode 312 14.3.3 Multicarbon Products Derived from MES 313 14.3.4 The Status Quo and Challenges of MES 316 14.4 Decoupling Biotic and Abiotic Processes 318 14.5 Conclusions and Perspectives 322 References 324 15 Conclusions and Perspectives 335 Haiqing Wang 15.1 New CO 2 RR Catalyst 335 15.2 New CO 2 RR Mechanism 336 15.3 Industrial CO 2 RR Perspectives 337 Index 339

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Book SynopsisThe importance of solid base catalysts has come to be recognized for their environmentally benign qualities, and much significant progress has been made over the past two decades in catalytic materials and solid base-catalyzed reactions. The book is focused on the solid base. Because of the advantages over liquid bases, the use of solid base catalysts in organic synthesis is expanding. Solid bases are easier to dispose than liquid bases, separation and recovery of products, catalysts and solvents are less difficult, and they are non-corrosive. Furthermore, base-catalyzed reactions can be performed without using solvents and even in the gas phase, opening up more possibilities for discovering novel reaction systems. Using numerous examples, the present volume describes the remarkable role solid base catalysis can play, given the ever increasing worldwide importance of "green" chemistry. The reader will obtain an overall view of solid base catalysis and gain insight into the versatility of the reactions to which solid base catalysts can be utilized. The concept and significance of solid base catalysis are discussed, followed by descriptions of various methods for the characterization of solid bases, including spectroscopic methods and test reactions. The preparation and properties of base materials are presented in detail, with the two final chapters devoted to surveying the variety of reactions catalyzed by solid bases.Table of ContentsIntroduction.- Characterization of Solid Base Catalysts.- Preparation and Catalytic Properties of Solid Base Catalysts - Metal Oxides.- Preparation and Catalytic Properties of Solid Base Catalysts - Specific Materials for Solid Bases.- Reactions Catalyzed by Solid Bases.- Solid Base Catalysts for Specific Subjects.

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Book SynopsisTransformation and Utilization of Carbon Dioxide shows the various organic, polymeric and inorganic compounds which result from the transformation of carbon dioxide through chemical, photocatalytic, electrochemical, inorganic and biological processes. The book consists of twelve chapters demonstrating interesting examples of these reactions, depending on the types of reaction and catalyst. It also includes two chapters dealing with the utilization of carbon dioxide as a reaction promoter and presents a wide range of examples of chemistry and chemical engineering with carbon dioxide. Transformation and Utilization of Carbon Dioxide is a collective work of reviews illustrative of recent advances in the transformation and utilization of carbon dioxide. This book is interesting and useful to a wide readership in the various fields of chemical science and engineering.Bhalchandra Bhanage is a professor of industrial and engineering chemistry at Institute of Chemical Technology, India.Masahiko Arai is a professor of chemical engineering at Hokkaido University, Japan.Table of ContentsPart I Chemical Reactions.- Addition of CO2 with molecular catalysts (metal complexes).- Addition of CO2 with molecular catalysts (other catalysts).- Direct CO2 fixation over heterogeneous catalysts.- Indirect CO2 fixation over heterogeneous catalysts (using urea and others).- Hydrogenation of CO2 with molecular catalysts (to alcohol, formate and others).- Hydrogenation of CO2 with heterogeneous catalysts (to alcohol, formate and others).- Dry CO2 reforming.- Polymerization.- Part II Photocatalytic, Electrochemical and Inorganic Reactions.- Photocatalytic reaction.- Electrochemical reaction.- Inorganic reaction (including CO2 storage).- Part III Biological Reactions.- Biological reaction.- Part IV Utilization as Reaction Promoter.- Application of CO2 as a reaction promoter in organic synthetic reaction.

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Book SynopsisThis multi-authored book provides a comprehensive overview of the latest developments in porous CO2 capture materials, including ionic liquid–derived carbonaceous adsorbents, porous carbons, metal-organic frameworks, porous aromatic frameworks, micro porous organic polymers. It also reviews the sorption techniques such as cyclic uptake and desorption reactions and membrane separations. In each category, the design and fabrication, the comprehensive characterization, the evaluation of CO2 sorption/separation and the sorption/degradation mechanism are highlighted. In addition, the advantages and remaining challenges as well as future perspectives for each porous material are covered.This book is aimed at scientists and graduate students in such fields as separation, carbon, polymer, chemistry, material science and technology, who will use and appreciate this information source in their research. Other specialists may consult specific chapters to find the latest, authoritative reviews.Dr. An-Hui Lu is a Professor at the State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Faculty of Chemical, Environmental and Biological Science and Technology, Dalian University of Technology, China.Dr. Sheng Dai is a Corporate Fellow and Group Leader in the Chemical Sciences Division at Oak Ridge National Laboratory (ORNL) and a Professor of Chemistry at the University of Tennessee, USA.Table of ContentsIonic Liquid-Derived Carbonaceous Adsorbents for CO2 Capture.- Porous Carbons for Carbon Dioxide Capture.- Metal-Organic Frameworks (MOFs) for CO2 Capture.- Carbon Dioxide Capture in Porous Aromatic Frameworks.- Microporous Organic Polymers for Carbon Dioxide Capture.- CO2 capture via cyclic calcination and carbonation reactions.- Functionalized inorganic membranes for high temperature CO2/N2 separation.

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Book SynopsisThis book illustrates the broad field of enantioselective catalysis by highlighting a few topics, out of myriads, with the double aim to typify selected synthetic achievements and future challenges. Eleven research groups have highlighted topics of interest in either organo- or organometallic catalysis, related to their own expertise. For mature fields, these short chapters, far from being exhaustive, show updated overviews including major recent advances and disclose a few prospects. Other chapters focus on upcoming topics in enantioselective catalysis, i.e. on classes of reactions or families of catalysts that are expected to provide appealing synthetic tools when suitably mastered. For all these areas, recent studies demonstrate highly promising perspectives.

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Book SynopsisThis book provides an overview of plasticizers, from the latest global research developments to the laws and regulations applied to their use. In addition the book details the author's recently developed methodology for a catalytic hydrogenation of phthalate plasticizers. It presents insights into the development of the catalytic phthalate hydrogenation from the reaction mechanism and catalyst characterization to pilot tests and its industrialization. Given its scope, the book will appeal to a broad readership, particularly professionals at universities and scientific research institutes, as well as practitioners in industry.Table of ContentsIntroduction.- Plasticizer Laws and Evolution in Different Regions.- Current Status of Plasticizer Research.- Inventions and Patents in Different Regions.- Catalytic Ring Hydrogenation of Phthalate Plasticizers.- Pilot Demonstrations and Industrialization.

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Book SynopsisThis book introduces readers to the preparation of metal nanocrystals and its applications. In this book, an important point highlighted is how to design noble metal nanocrystals at the atomic scale for energy conversion and storage. It also focuses on the controllable synthesis of water splitting electrode materials including anodic oxygen evolution reaction (OER) and cathode hydrogen evolution reaction (HER) at the atomic level by defect engineering and synergistic effect. In addition, in-situ technologies and theoretical calculations are utilized to reveal the catalytic mechanisms of catalysts under realistic operating condition. The findings presented not only enrich research in the nano-field, but also support the promotion of national and international cooperation.Table of ContentsOverviews of noble metal nanocrystals.- Advanced synthesis methods of noble metal nanocrystals.- Characterization methods for noble metal nanocrystals.- Applications of noble metal nanocrystals.- Electrocatalytic water splitting technology.- Conclusions.

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Book SynopsisThis book describes the development of two kinds of continuous-flow transformation using heterogeneous catalysts, and explains how they can be applied in the multistep synthesis of active pharmaceutical ingredients. It demonstrates and proves that fine chemicals can be synthesized under continuous-flow conditions using heterogeneous catalysis alone. Importantly, the book also proposes a general concept and strategy for achieving multistep flow synthesis and developing heterogeneous catalysts, and shows that commercially available anion exchange resin can be used as a water-tolerant strong base catalyst for various types of continuous-flow aldol-type reaction. Reviewing the state of the art in heterogeneous catalysis in flow chemistry – a “hot topic” and rapidly developing area of organic synthesis – the book will provide readers with a deeper understanding of fine chemical flow synthesis and its future prospects. Table of Contents1. Introduction and Strategy.- 2. Synthesis of Nitro-containing Compounds through Multistep Continuous-flow with Heterogeneous Catalysts.- 3. Polysilane-Supported Pd Catalysts for Continuous-flow Hydrogenations.- 4. Anion Exchange Resins as Catalysts for Direct Aldol-type Reactions of Ketones, Esters and Nitriles under Continuous-flow.- 5. Multistep Continuous-flow Synthesis of APIs Based on Aldol-hydrogenation Strategy.- 6. Summary.- 7. Experimental Section.

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