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
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