Presents state-of-the-art knowledge of heterogeneous catalysts including new applications in energy and environmental fields This book focuses on emerging techniques in heterogeneous catalysis, from new methodology for catalysts design and synthesis, surface studies and operando spectroscopies, ab initio techniques, to critical catalytic systems as relevant to energy and the environment. It provides the vision of addressing the foreseeable knowledge gap unfilled by classical knowledge in the field. Heterogeneous Catalysts: Advanced Design, Characterization and Applications begins with an overview on the evolution in catalysts synthesis and introduces readers to facets engineering on catalysts; electrochemical synthesis of nanostructured catalytic thin films; and bandgap engineering of semiconductor photocatalysts. Next, it examines how we are gaining a more precise understanding of catalytic events and materials under working conditions. It covers bridging pressure gap in surface catalytic studies; tomography in catalysts design; and resolving catalyst performance at nanoscale via fluorescence microscopy. Quantum approaches to predicting molecular reactions on catalytic surfaces follows that, along with chapters on Density Functional Theory in heterogeneous catalysis; first principles simulation of electrified interfaces in electrochemistry; and high-throughput computational design of novel catalytic materials. The book also discusses embracing the energy and environmental challenges of the 21st century through heterogeneous catalysis and much more. Presents recent developments in heterogeneous catalysis with emphasis on new fundamentals and emerging techniques Offers a comprehensive look at the important aspects of heterogeneous catalysis Provides an applications-oriented, bottoms-up approach to a high-interest subject that plays a vital role in industry and is widely applied in areas related to energy and environment Heterogeneous Catalysts: Advanced Design, Characterization and Applications is an important book for catalytic chemists, materials scientists, surface chemists, physical chemists, inorganic chemists, chemical engineers, and other professionals working in the chemical industry.

Table of Contents:
Volume 1 Preface xv Section I Heterogeneous Catalysts Design and Synthesis 1 1 Evolution of Catalysts Design and Synthesis: From Bulk Metal Catalysts to Fine Wires and Gauzes, and that to Nanoparticle Deposits, Metal Clusters, and Single Atoms 3 Wey Yang Teoh 1.1 The Cradle of Modern Heterogeneous Catalysts 3 1.2 The Game Changer: High-Pressure Catalytic Reactions 5 1.3 Catalytic Cracking and Porous Catalysts 8 1.4 Miniaturization of Metal Catalysts: From Supported Catalysts to Single-Atom Sites 12 1.5 Perspectives and Opportunities 15 References 16 2 Facets Engineering on Catalysts 21 Jian (Jeffery) Pan 2.1 Introduction 21 2.2 Mechanisms of Facets Engineering 22 2.3 Anisotropic Properties of Crystal Facets 27 2.3.1 Anisotropic Adsorption 27 2.3.2 Surface Electronic Structure 28 2.3.3 Surface Electric Field 29 2.4 Effects of Facets Engineering 32 2.4.1 Optical Properties 32 2.4.2 Activity and Selectivity 33 2.5 Outlook 34 References 35 3 Electrochemical Synthesis of Nanostructured Catalytic Thin Films 39 Hoi Ying Chung and Yun Hau Ng 3.1 Introduction 39 3.2 Principle of Electrochemical Method in Fabricating Thin Film 40 3.2.1 Anodization 42 3.2.1.1 Pulse or Step Anodization 45 3.2.2 Cathodic Electrodeposition 46 3.2.2.1 Pulse Electrodeposition 47 3.2.3 Electrophoretic Deposition 48 3.2.4 Combinatory Methods Involving Electrochemical Process 50 3.2.4.1 Combined Electrophoretic Deposition–Anodization (CEPDA) Approach 51 3.3 Conclusions and Perspective 52 References 53 4 Synthesis and Design of Carbon-Supported Highly Dispersed Metal Catalysts 57 Enrique García-Bordejé 4.1 Introduction 57 4.2 Preparation of Catalysts on New Carbon Supports 58 4.2.1 Catalyst on Graphene Oxide 59 4.2.2 Catalyst on Graphene 60 4.2.2.1 Graphene or rGO as Starting Material 60 4.2.2.2 Graphene Oxide as Precursor of Graphene-Supported Catalyst 61 4.2.2.3 Graphene Derivatives: Doped Graphene and Synthetic Derivatives 62 4.2.3 Catalyst on Nanodiamonds and Onion-Like Carbon 63 4.2.4 SACs on Carbon Nitrides and Covalent Triazine Frameworks 67 4.2.5 Catalyst on Carbon Material from Hydrothermal Carbonization of Biomolecules 68 4.3 Emerging Techniques for Carbon-Based Catalyst Synthesis 69 4.3.1 Deposition of Colloidal Nanoparticles 70 4.3.2 Single-Metal Atom Deposition byWet Chemistry 71 4.3.3 Immobilization of Metal Clusters and SACs by Organometallic Approach 71 4.3.4 Chemical Vapor Deposition Techniques on Carbon Supports 72 4.3.5 Simultaneous Formation of Metallic Catalyst and Porous Carbon Support by Pyrolysis 73 4.3.6 Dry Mechanical Methods 73 4.3.7 Electrodeposition 73 4.3.8 Photodeposition 74 4.4 Conclusions and Outlook 74 References 75 5 Metal Cluster-Based Catalysts 79 Vladimir B. Golovko 5.1 Introduction 79 5.2 Catalysts Made by Deposition of Clusters from the Gas Phase Under Ultrahigh Vacuum 81 5.3 Chemically Synthesized Metal Clusters 85 5.4 Catalysis Using the Chemically Synthesized Metal Clusters 88 5.5 Conclusion 95 References 96 6 Single-Atom Heterogeneous Catalysts 103 Yaxin Chen, ZhenMa, and Xingfu Tang 6.1 Introduction 103 6.2 Concept and Advantages of SACs 104 6.2.1 Concept of SACs 104 6.2.2 Advantages of SACs 105 6.2.2.1 Maximum Atom Efficiency 105 6.2.2.2 Unique Catalytic Properties 105 6.2.2.3 Identification of Catalytically Active Sites 105 6.2.2.4 Establishment of Intrinsic Reaction Mechanisms 106 6.3 Synthesis of SACs 107 6.3.1 Physical Methods 108 6.3.2 Chemical Methods 108 6.3.2.1 Bottom-Up SyntheticMethods 109 6.3.2.2 Top-Down SyntheticMethods 112 6.4 Challenges and Perspective 113 References 114 7 Synthesis Strategies for Hierarchical Zeolites 119 Xicheng Jia, Changbum Jo, and Alex C.K. Yip 7.1 Introduction 119 7.2 Hierarchical Zeolites 122 7.2.1 Increased Intracrystalline Diffusion 123 7.2.2 Reduced Steric Limitation 123 7.2.3 Changed Product Selectivity 124 7.2.4 Decreased Coke Formation 124 7.3 Modern Strategies for the Synthesis of Hierarchical Zeolites 124 7.3.1 Hard Templates 124 7.3.1.1 Confined-Space Method 125 7.3.1.2 Carbon Nanotubes and Nanofibers 127 7.3.1.3 Ordered Mesoporous Carbons 128 7.3.2 Soft Templates 130 7.3.2.1 Templating with Surfactants 130 7.3.2.2 Silanization TemplatingMethods 135 7.3.3 Dealumination 136 7.3.4 Desilication 138 7.4 Conclusion 140 References 141 8 Design of Molecular Heterogeneous Catalysts with Metal–Organic Frameworks 147 Marco Ranocchiari 8.1 Secondary Building Units (SBUs) and IsoreticularMOFs 151 8.2 The Tools to Build Molecular Active Sites: Reticular Chemistry and Beyond 152 8.2.1 Pre-synthetic Methodologies 153 8.2.2 Post-synthetic Methodologies 155 8.2.2.1 Post-synthetic Modification (PSM) 155 8.2.2.2 Post-synthetic Exchange (PSE) 156 8.3 MOFs in Catalysis 156 8.3.1 The Difference Between MOFs and Standard Heterogeneous and Homogeneous Catalysts 157 8.4 Conclusion: Where to Go from Here 158 References 158 9 Hierarchical and Anisotropic Nanostructured Catalysts 161 Hamidreza Arandiyan, YuanWang, Christopher M.A. Parlett, and Adam Lee 9.1 Introduction 161 9.2 Top-Down vs. Bottom-Up Approaches 162 9.3 Shape Anisotropy and Nanostructured Assemblies 162 9.4 Janus Nanostructures 165 9.5 Hierarchical Porous Catalysts 169 9.6 Functionalization of Porous/Anisotropic Substrates 170 9.7 Perspective 174 References 176 10 Flame Synthesis of Simple and Multielemental Oxide Catalysts 183 Wey Yang Teoh 10.1 From Natural Aerosols Formation to Engineered Nanoparticles 183 10.2 Flame Aerosol Synthesis and Reactors 185 10.3 Simple Metal Oxide-Based Catalysts 189 10.4 Multielemental Oxide-Based Catalysts 192 10.4.1 Solid Solution Metal Oxide Catalysts 192 10.4.2 Composite Metal Oxide Catalysts 192 10.4.3 Complex Metal Oxide Catalysts 197 10.5 Perspective and Outlook 197 References 199 11 Band Engineering of Semiconductors Toward Visible-Light-Responsive Photocatalysts 203 Akihide Iwase 11.1 Basis of Photocatalyst Materials 203 11.2 Photocatalyst Material Groups 204 11.2.1 Variety of Photocatalyst Materials 204 11.2.2 Main Constituent Metal Elements in Photocatalyst Materials 205 11.3 Design of Band Structures of Photocatalyst Materials 206 11.3.1 Doped Photocatalysts 206 11.3.2 Valence-Band-Controlled Photocatalysts 208 11.3.3 Solid Solution Photocatalysts 209 11.4 Preparation of Photocatalysts 210 11.4.1 Solid-State Reaction Method 211 11.4.2 Flux Method 211 11.4.3 Hydrothermal Synthesis Method/Solvothermal Synthesis Method 211 11.4.4 Polymerized (Polymerizable) Complex Method 211 11.4.5 PrecipitationMethod 212 11.4.6 Loading of Cocatalysts 212 References 212 Section II Surface Studies and Operando Spectroscopies in Heterogeneous Catalysis 215 12 Toward Precise Understanding of Catalytic Events and Materials Under Working Conditions 217 Atsushi Urakawa References 220 13 Pressure Gaps in Heterogeneous Catalysis 225 Lars Österlund 13.1 Introduction 225 13.2 High-Pressure Studies of Catalysts 226 13.3 Adsorption on Solid Surfaces at Low and High Pressures 229 13.3.1 Kinetically Restricted Adsorbate Structures 229 13.3.2 Thermodynamically Driven Reactions on Solid Surfaces 234 13.3.3 Reactions on Supported Nanoparticle Catalysts 244 13.4 Conclusions and Outlook 246 Acknowledgments 247 References 247 14 In Situ Transmission Electron Microscopy Observation of Gas/Solid and Liquid/Solid Interfaces 253 Ayako Hashimoto 14.1 Introduction 253 14.2 Observation in Gas and Liquid Phases 254 14.2.1 Window-Type System 254 14.2.2 Differential Pumping-Type System 256 14.2.3 Other Systems 257 14.3 Applications and Outlook 259 References 261 15 Tomography in Catalyst Design 263 Dorota Matras, Jay Pritchard, Antonios Vamvakeros, Simon D.M. Jacques, and Andrew M. Beale 15.1 Introduction 263 15.2 Imaging with X-Rays 264 15.3 Conventional Absorption CT to Study Catalytic Materials 265 15.4 X-Ray Diffraction Computed Tomography (XRD-CT) 267 15.5 Pair Distribution Function CT 269 15.6 Multimodal XANES-CT, XRD-CT, and XRF-CT 270 15.7 Atom Probe Tomography 272 15.8 Ptychographic X-Ray CT 273 15.9 Conclusions 274 References 275 16 Resolving Catalyst Performance at Nanoscale via Fluorescence Microscopy 279 Alexey Kubarev and Maarten Roeffaers 16.1 Fluorescence Microscopy as Catalyst Characterization Tool 279 16.2 Basics of Fluorescence and Fluorescence Microscopy 280 16.3 Strategies to Resolve Catalytic Processes in a Fluorescence Microscope 283 16.4 Wide-Field and Confocal Fluorescence Microscopy 284 16.5 Super-resolution Fluorescence Microscopy 285 16.6 What Can We Learn About Catalysts from (Super-resolution) Fluorescence Microscopy: Case Studies 286 16.7 Conclusions and Outlook 291 References 292 17 In Situ Electron Paramagnetic Resonance Spectroscopy in Catalysis 295 Yiyun Liu and RyanWang 17.1 Introduction 295 17.2 Basic Principles of Electron Paramagnetic Resonance (EPR) 296 17.3 Experimental Methods and Setup for In Situ cw-EPR 298 17.4 Applications of In Situ EPR Spectroscopy 302 17.4.1 Cu-Zeolite Systems 303 17.4.2 Radicals and Radical Ions 305 17.5 Conclusions 306 References 307 18 Toward Operando Infrared Spectroscopy of Heterogeneous Catalysts 311 Davide Ferri 18.1 Brief Theory on Infrared Spectroscopy 311 18.2 Different Modes of IR Measurements 314 18.3 Measuring the “Background” 318 18.4 Using Probe Molecules to Identify Heterogeneous Sites 320 18.5 IR Measurements Under Operando Conditions 325 18.6 Case Studies of Operando IR Spectroscopy 328 18.6.1 Selective Catalytic Reduction of NO by NH3 Measured Using Operando Transmission IR 328 18.6.2 Methanation of CO2 Measured Using Operando DRIFTS 329 18.6.3 Selective Oxidation of Alcohols Measured Using Operando ATR-IR 331 18.7 Perspective and Outlook 333 References 334 19 Operando X-Ray Spectroscopies on Catalysts in Action 339 Olga V. Safonova and Maarten Nachtegaal 19.1 Fundamentals of X-Ray Spectroscopy 339 19.2 X-Ray Absorption Spectroscopy Methods 342 19.3 High-Energy-Resolution (Resonant) X-Ray Emission Spectroscopy 347 19.4 In Situ and Operando Cells 351 19.5 Application of Time-Resolved Methods 353 19.6 Limitations and Challenges 356 19.7 Concluding Remarks 357 References 358 20 Methodologies to Hunt Active Sites and Active Species 363 Atsushi Urakawa 20.1 Introduction 363 20.2 Modulation Excitation Technique 365 20.3 Steady-State Isotopic Transient Kinetic Analysis (SSITKA) 369 20.4 Multivariate Analysis 371 20.5 Outlook 373 References 373 21 Ultrafast Spectroscopic Techniques in Photocatalysis 377 Chun Hong Mak, Rugeng Liu, and Hsien-Yi Hsu 21.1 Transient Absorption Spectroscopy 377 21.1.1 Introduction 377 21.1.2 Conventional Heterogeneous Photocatalyst 380 21.1.3 Dye-Sensitized Heterogeneous Photocatalyst 384 21.2 Time-Resolved Photoluminescence 386 21.2.1 Introduction 386 21.2.2 Applications of TRPL in Heterogeneous Catalysis 387 21.3 Time-Resolved Microwave Conductivity 389 21.3.1 Introduction 389 21.3.2 Applications of TRMC in Heterogeneous Catalysis 391 References 393 Volume 2 Preface xv Section III Ab Initio Techniques in Heterogeneous Catalysis 399 22 Quantum Approaches to Predicting Molecular Reactions on Catalytic Surfaces 401 Patrick Sit 23 Density Functional Theory in Heterogeneous Catalysis 405 Patrick Sit and Linghai Zhang 24 Ab InitioMolecular Dynamics in Heterogeneous Catalysis 419 Ye-Fei Li 25 First Principles Simulations of Electrified Interfaces in Electrochemistry 439 Stephen E.Weitzner and Ismaila Dabo 26 Time-Dependent Density Functional Theory for Excited-State Calculations 471 Chi Yung Yam 27 The GW Method for Excited States Calculations 483 Paolo Umari 28 High-Throughput Computational Design of Novel Catalytic Materials 497 Chenxi Guo, Jinfan Chen, and Jianping Xiao Section IV Advancement in Energy and Environmental Catalysis 525 29 Embracing the Energy and Environmental Challenges of the Twenty-First Century Through Heterogeneous Catalysis 527 Yun Hau Ng 30 Electrochemical Water Splitting 533 Guang Liu, Kamran Dastafkan, and Chuan Zhao 31 New Visible-Light-Responsive Photocatalysts for Water Splitting Based on Mixed Anions 557 Kazuhiko Maeda 32 Electrocatalysts in Polymer Electrolyte Membrane Fuel Cells 571 StephenM. Lyth and Albert Mufundirwa 33 Conversion of Lignocellulosic Biomass to Biofuels 593 Cristina García-Sancho, Juan A. Cecilia, and Rafael Luque 34 Conversion of Carbohydrates to High Value Products 617 Isao Ogino 35 Enhancing Sustainability Through Heterogeneous Catalytic Conversions at High Pressure 633 Nat Phongprueksathat and Atsushi Urakawa 36 Electro-, Photo-, and Photoelectro-chemical Reduction of CO2 649 Jonathan Albo,Manuel Alvarez-Guerra, and Angel Irabien 37 Photocatalytic Abatement of Emerging Micropollutants in Water and Wastewater 671 Lan Yuan, Zi-Rong Tang, and Yi-Jun Xu 38 Catalytic Abatement of NOx Emissions over the Zeolite Catalysts 685 Runduo Zhang, Peixin Li, and HaoWang Index 699 9783527344154