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.

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 NO_x Emissions over the Zeolite Catalysts 685
Runduo Zhang, Peixin Li, and HaoWang

Index 699