Heterogeneous Catalysis at Nanoscale for Energy Applications (eBook, PDF)
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This book presents both the fundamentals concepts and latest achievements of a field that is growing in importance since it represents a possible solution for global energy problems. It focuses on an atomic-level understanding of heterogeneous catalysis involved in important energy conversion processes. It presents a concise picture for the entire area of heterogeneous catalysis with vision at the atomic- and nano- scales, from synthesis, ex-situ and in-situ characterization, catalytic activity and selectivity, to mechanistic understanding based on experimental exploration and theoretical…mehr
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- Produktdetails
- Verlag: John Wiley & Sons
- Seitenzahl: 344
- Erscheinungstermin: 17. Februar 2015
- Englisch
- ISBN-13: 9781118843482
- Artikelnr.: 42365876
- Verlag: John Wiley & Sons
- Seitenzahl: 344
- Erscheinungstermin: 17. Februar 2015
- Englisch
- ISBN-13: 9781118843482
- Artikelnr.: 42365876
Schneider, and Prashant V. Kamat 2 Chemical Synthesis of Nanoscale
Heterogeneous Catalysts 9 Jianbo Wu and Hong Yang 2.1 Introduction 9 2.2
Brief Overview of Heterogeneous Catalysts 10 2.3 Chemical Synthetic
Approaches 11 2.3.1 Colloidal Synthesis 11 2.3.2 Shape Control of Catalysts
in Colloidal Synthesis 12 2.3.3 Control of Crystalline Phase of
Intermetallic Nanostructures 14 2.3.4 Other Modes of Formation for Complex
Nanostructures 17 2.4 Core-Shell Nanoparticles and Controls of Surface
Compositions and Surface Atomic Arrangements 21 2.4.1 New Development on
the Preparation of Colloidal Core-Shell Nanoparticles 21 2.4.2
Electrochemical Methods to Core-Shell Nanostructures 22 2.4.3 Control of
Surface Composition via Surface Segregation 24 2.5 Summary 25 3 Physical
Fabrication of Nanostructured Heterogeneous Catalysts 31 Chunrong Yin, Eric
C. Tyo, and Stefan Vajda 3.1 Introduction 31 3.2 Cluster Sources 34 3.2.1 T
hermal Vaporization Source 34 3.2.2 Laser Ablation Source 36 3.2.3
Magnetron Cluster Source 37 3.2.4 Arc Cluster Ion Source 38 3.3 Mass
Analyzers 39 3.3.1 Neutral Cluster Beams 40 3.3.2 Quadrupole Mass Analyzer
41 3.3.3 Lateral TOF Mass Filter 42 3.3.4 Magnetic Sector Mass Selector 43
3.3.5 Quadrupole Deflector (Bender) 44 3.4 Survey of Cluster Deposition
Apparatuses in Catalysis Studies 44 3.4.1 Laser Ablation Source with a
Quadrupole Mass Analyzer at Argonne National Lab 44 3.4.2 ACIS with a
Quadrupole Deflector at the Universität Rostock 46 3.4.3 Magnetron Cluster
Source with a Lateral TOF Mass Filter at the University of Birmingham 47
3.4.4 Laser Ablation Cluster Source with a Quadrupole Mass Selector at the
Technische Universität München 48 3.4.5 Laser Ablation Cluster Source with
a Quadrupole Mass Analyzer at the University of Utah 49 3.4.6 Laser
Ablation Cluster Source with a Magnetic Sector Mass Selector at the
University of California, Santa Barbara 49 3.4.7 Magnetron Cluster Source
with a Quadrupole Mass Filter at the Toyota Technological Institute 51
3.4.8 PACIS with a Magnetic Sector Mass Selector at Universität Konstanz 52
3.4.9 Magnetron Cluster Source with a Magnetic Sector at Johns Hopkins
University 53 3.4.10 Magnetron Cluster Source with a Magnetic Sector at HZB
53 3.4.11 Magnetron Sputtering Source with a Quadrupole Mass Filter at the
Technical University of Denmark 54 3.4.12 CORDIS with a Quadrupole Mass
Filter at the Lausanne Group 56 3.4.13 Electron Impact Source with a
Quadrupole Mass Selector at the Universität Karlsruhe 56 3.4.14 CORDIS with
a Quadrupole Mass Analyzer at the Universität Ulm 58 3.4.15 Magnetron
Cluster Source with a Lateral TOF Mass Filter at the Universität Dortmund
59 3.4.16 Z-Spray Source with a Quadrupole Mass Filter for Gas-Phase
Investigations at FELIX 60 3.4.17 Laser Ablation Source with an Ion
Cyclotron Resonance Mass Spectrometer for Gas-Phase Investigations at the
Technische Universität Berlin 61 4 Ex Situ Characterization 69 Minghua
Qiao, Songhai Xie, Yan Pei, and Kangnian Fan 4.1 Introduction 69 4.2 Ex
Situ Characterization Techniques 70 4.2.1 X-Ray Absorption Spectroscopy 71
4.2.2 Electron Spectroscopy 72 4.2.3 Electron Microscopy 74 4.2.4 Scanning
Probe Microscopy 75 4.2.5 Mössbauer Spectroscopy 76 4.3 Some Examples on Ex
Situ Characterization of Nanocatalysts for Energy Applications 77 4.3.1
Illustrating Structural and Electronic Properties of Complex Nanocatalysts
77 4.3.2 Elucidating Structural Characteristics of Catalysts at the
Nanometer or Atomic Level 81 4.3.3 Pinpointing the Nature of the Active
Sites on Nanocatalysts 85 4.4 Conclusions 88 5 Applications of Soft X-Ray
Absorption Spectroscopy for In Situ Studies of Catalysts at Nanoscale 93
Xingyi Deng, Xiaoli Gu, and Franklin (Feng) Tao 5.1 Introduction 93 5.2 In
Situ SXAS under Reaction Conditions 96 5.3 Examples of In Situ SXAS Studies
under Reaction Conditions Using Reaction Cells 99 5.3.1 Atmospheric
Corrosion of Metal Films 99 5.3.2 Cobalt Nanoparticles under Reaction
Conditions 101 5.3.3 Electrochemical Corrosion of Cu in Aqueous NaHCO3
Solution 108 5.4 Summary 112 6 First-Principles Approaches to Understanding
Heterogeneous Catalysis 115 Dorrell C. McCalman and William F. Schneider
6.1 Introduction 115 6.2 Computational Models 116 6.2.1 Electronic
Structure Methods 116 6.2.2 System Models 117 6.3 NOx Reduction 118 6.4
Adsorption at Metal Surfaces 119 6.4.1 Neutral Adsorbates 119 6.4.2 Charged
Adsorbates 122 6.5 Elementary Surface Reactions Between Adsorbates 125
6.5.1 Reaction Thermodynamics 125 6.5.2 Reaction Kinetics 129 6.6 Coverage
Effects on Reaction and Activation Energies at Metal Surfaces 131 6.7
Summary 135 7 Computational Screening for Improved Heterogeneous Catalysts
and Electrocatalysts 139 Jeffrey Greeley 7.1 Introduction 139 7.2 T
rends-Based Studies in Computational Catalysis 140 7.2.1 Early Groundwork
for Computational Catalyst Screening 140 7.2.2 Volcano Plots and Rate
Theory Models 141 7.2.3 Scaling Relations, BEP Relations, and Descriptor
Determination 144 7.3 Computational Screening of Heterogeneous Catalysts
and Electrocatalysts 148 7.3.1 Computational Catalyst Screening Strategies
149 7.4 Challenges and New Frontiers in Computational Catalyst Screening
153 7.5 Conclusions 155 8 Catalytic Kinetics and Dynamics 161 Rafael C.
Catapan, Matthew A. Christiansen, Amir A. M. Oliveira, and Dionisios G.
Vlachos 8.1 Introduction 161 8.2 Basics of Catalyst Functionality,
Mechanisms, and Elementary Reactions on Surfaces 163 8.3 T ransition State
Theory, Collision Theory, and Rate Constants 166 8.4 Density Functional
Theory Calculations 168 8.4.1 Calculation of Energetics and Coverage
Effects 169 8.4.2 Calculation of Vibrational Frequencies 172 8.5 T
hermodynamic Consistency of the DFT-Predicted Energetics 172 8.6 State
Properties from Statistical Thermodynamics 176 8.6.1 Strongly Bound
Adsorbates 177 8.6.2 Weakly Bound Adsorbates 177 8.7 Semiempirical Methods
for Predicting Thermodynamic Properties and Kinetic Parameters 178 8.7.1
Linear Scaling Relationships 178 8.7.2 Heat Capacity and Surface Entropy
Estimation 179 8.7.3 Brønsted-Evans-Polanyi Relationships 180 8.8 Analysis
Tools for Microkinetic Modeling 181 8.8.1 Rates in Microkinetic Modeling
181 8.8.2 Reaction Path Analysis and Partial Equilibrium Analysis 181 8.8.3
Rate-Determining Steps, Most Important Surface Intermediates, and Most
Abundant Surface Intermediates 184 8.8.4 Calculation of the Overall
Reaction Order and Apparent Activation Energy 186 8.9 Concluding Remarks
187 9 Catalysts for Biofuels 191 Gregory T. Neumann, Danielle Garcia, and
Jason C. Hicks 9.1 Introduction 191 9.2 Lignocellulosic Biomass 192 9.2.1
Cellulose 192 9.2.2 Hemicellulose 194 9.2.3 Lignin 195 9.3 Carbohydrate
Upgrading 195 9.3.1 Zeolitic Upgrading of Cellulosic Feedstocks 196 9.3.2
Levulinic Acid Upgrading 199 9.3.3 GVL Upgrading 201 9.3.4 Aqueous-Phase
Processing 202 9.4 Lignin Conversion 205 9.4.1 Zeolite Upgrading of Lignin
Feedstocks 206 9.4.2 Catalysts for Hydrodeoxygenation of Lignin 208 9.4.3
Selective Unsupported Catalyst for Lignin Depolymerization 211 9.5
Continued Efforts for the Development of Robust Catalysts 212 10
Development of New Gold Catalysts for Removing CO from H2 217 Zhen Ma,
Franklin (Feng) Tao, and Xiaoli Gu 10.1 Introduction 217 10.2 General
Description of Catalyst Development 218 10.3 Development of WGS catalysts
220 10.3.1 Initially Developed Catalysts 220 10.3.2 Fe2O3-Based Gold
Catalysts 221 10.3.3 CeO2-Based Gold Catalysts 221 10.3.4 TiO2- or
ZrO2-Based Gold Catalysts 223 10.3.5 Mixed-Oxide Supports with 1:1
Composition 223 10.3.6 Bimetallic Catalysts 224 10.4 Development of New
Gold Catalysts for PROX 225 10.4.1 General Considerations 225 10.4.2
CeO2-Based Gold Catalysts 226 10.4.3 TiO2-Based Gold Catalysts 227 10.4.4
Al2O3-Based Gold Catalysts 228 10.4.5 Mixed Oxide Supports with 1:1
Composition 228 10.4.6 Other Oxide-Based Gold Catalysts 229 10.4.7
Supported Bimetallic catalysts 229 10.5 Perspectives 229 11 Photocatalysis
in Generation of Hydrogen from Water 239 Kazuhiro Takanabe and Kazunari
Domen 11.1 Solar Energy Conversion 239 11.1.1 Solar Energy Conversion
Technology for Producing Fuels and Chemicals 239 11.1.2 Solar Spectrum and
STH Efficiency 242 11.2 Semiconductor Particles: Optical and Electronic
Nature 244 11.2.1 Reaction Sequence and Principles of Overall Water
Splitting and Reaction Step Timescales 244 11.2.2 Number of Photons
Striking a Single Particle 245 11.2.3 Absorption Depth of Light Incident on
Powder Photocatalyst 247 11.2.4 Degree of Band Bending in Semiconductor
Powder 248 11.2.5 Band Gap and Flat-Band Potential of Semiconductor 250
11.3 Photocatalyst Materials for Overall Water Splitting: UV to Visible
Light Response 251 11.3.1 UV Photocatalysts: Oxides 251 11.3.2
Visible-Light Photocatalysts: Band Engineering of Semiconductor Materials
Containing Transition Metals 253 11.3.3 Visible-Light Photocatalysts:
Organic Semiconductors as Water-Splitting Photocatalysts 255 11.3.4
Z-Scheme Approach: Two-Photon Process 257 11.3.5 Defects and Recombination
in Semiconductor Bulk 257 11.4 Cocatalysts for Photocatalytic Overall Water
Splitting 259 11.4.1 Metal Nanoparticles as Hydrogen Evolution Cocatalysts:
Novel Core/Shell Structure 259 11.4.2 Reaction Rate Expression on Active
Catalytic Centers for Redox Reaction in Solution 261 11.4.3 Measurement of
Potentials at Semiconductor and Metal Particles Under Irradiation 264
11.4.4 Metal Oxides as Oxygen Evolution Cocatalyst 266 11.5 Concluding
Remarks 268 12 Photocatalysis in Conversion of Greenhouse Gases 271 Kentaro
Teramura and Tsunehiro Tanaka 12.1 Introduction 271 12.2 Outline of
Photocatalytic Conversion of CO2 273 12.3 Reaction Mechanism for the
Photocatalytic Conversion of CO2 276 12.3.1 Adsorption of CO2 and H2 276
12.3.2 Assignment of Adsorbed Species by FT-IR Spectroscopy 279 12.3.3
Observation of Photoactive Species by Photoluminescence (PL) and Electron
Paramagnetic Resonance (EPR) Spectroscopies 281 12.4 Summary 283 13
Electrocatalyst Design in Proton Exchange Membrane Fuel Cells for
Automotive Application 285 Anusorn Kongkanand, Wenbin Gu, and Frederick T.
Wagner 13.1 Introduction 285 13.2 Advanced Electrocatalysts 288 13.2.1
Pt-Alloy and Dealloyed Catalysts 288 13.2.2 Pt Monolayer Catalysts 290
13.2.3 Continuous-Layer Catalysts 293 13.2.4 Controlled Crystal Face
Catalysts 296 13.2.5 Hollow Pt Catalysts 298 13.3 Electrode Designs 299
13.3.1 Dispersed-Catalyst Electrodes 299 13.3.2 NSTF Electrodes 302 13.4
Concluding Remarks 307 Index 315
Schneider, and Prashant V. Kamat 2 Chemical Synthesis of Nanoscale
Heterogeneous Catalysts 9 Jianbo Wu and Hong Yang 2.1 Introduction 9 2.2
Brief Overview of Heterogeneous Catalysts 10 2.3 Chemical Synthetic
Approaches 11 2.3.1 Colloidal Synthesis 11 2.3.2 Shape Control of Catalysts
in Colloidal Synthesis 12 2.3.3 Control of Crystalline Phase of
Intermetallic Nanostructures 14 2.3.4 Other Modes of Formation for Complex
Nanostructures 17 2.4 Core-Shell Nanoparticles and Controls of Surface
Compositions and Surface Atomic Arrangements 21 2.4.1 New Development on
the Preparation of Colloidal Core-Shell Nanoparticles 21 2.4.2
Electrochemical Methods to Core-Shell Nanostructures 22 2.4.3 Control of
Surface Composition via Surface Segregation 24 2.5 Summary 25 3 Physical
Fabrication of Nanostructured Heterogeneous Catalysts 31 Chunrong Yin, Eric
C. Tyo, and Stefan Vajda 3.1 Introduction 31 3.2 Cluster Sources 34 3.2.1 T
hermal Vaporization Source 34 3.2.2 Laser Ablation Source 36 3.2.3
Magnetron Cluster Source 37 3.2.4 Arc Cluster Ion Source 38 3.3 Mass
Analyzers 39 3.3.1 Neutral Cluster Beams 40 3.3.2 Quadrupole Mass Analyzer
41 3.3.3 Lateral TOF Mass Filter 42 3.3.4 Magnetic Sector Mass Selector 43
3.3.5 Quadrupole Deflector (Bender) 44 3.4 Survey of Cluster Deposition
Apparatuses in Catalysis Studies 44 3.4.1 Laser Ablation Source with a
Quadrupole Mass Analyzer at Argonne National Lab 44 3.4.2 ACIS with a
Quadrupole Deflector at the Universität Rostock 46 3.4.3 Magnetron Cluster
Source with a Lateral TOF Mass Filter at the University of Birmingham 47
3.4.4 Laser Ablation Cluster Source with a Quadrupole Mass Selector at the
Technische Universität München 48 3.4.5 Laser Ablation Cluster Source with
a Quadrupole Mass Analyzer at the University of Utah 49 3.4.6 Laser
Ablation Cluster Source with a Magnetic Sector Mass Selector at the
University of California, Santa Barbara 49 3.4.7 Magnetron Cluster Source
with a Quadrupole Mass Filter at the Toyota Technological Institute 51
3.4.8 PACIS with a Magnetic Sector Mass Selector at Universität Konstanz 52
3.4.9 Magnetron Cluster Source with a Magnetic Sector at Johns Hopkins
University 53 3.4.10 Magnetron Cluster Source with a Magnetic Sector at HZB
53 3.4.11 Magnetron Sputtering Source with a Quadrupole Mass Filter at the
Technical University of Denmark 54 3.4.12 CORDIS with a Quadrupole Mass
Filter at the Lausanne Group 56 3.4.13 Electron Impact Source with a
Quadrupole Mass Selector at the Universität Karlsruhe 56 3.4.14 CORDIS with
a Quadrupole Mass Analyzer at the Universität Ulm 58 3.4.15 Magnetron
Cluster Source with a Lateral TOF Mass Filter at the Universität Dortmund
59 3.4.16 Z-Spray Source with a Quadrupole Mass Filter for Gas-Phase
Investigations at FELIX 60 3.4.17 Laser Ablation Source with an Ion
Cyclotron Resonance Mass Spectrometer for Gas-Phase Investigations at the
Technische Universität Berlin 61 4 Ex Situ Characterization 69 Minghua
Qiao, Songhai Xie, Yan Pei, and Kangnian Fan 4.1 Introduction 69 4.2 Ex
Situ Characterization Techniques 70 4.2.1 X-Ray Absorption Spectroscopy 71
4.2.2 Electron Spectroscopy 72 4.2.3 Electron Microscopy 74 4.2.4 Scanning
Probe Microscopy 75 4.2.5 Mössbauer Spectroscopy 76 4.3 Some Examples on Ex
Situ Characterization of Nanocatalysts for Energy Applications 77 4.3.1
Illustrating Structural and Electronic Properties of Complex Nanocatalysts
77 4.3.2 Elucidating Structural Characteristics of Catalysts at the
Nanometer or Atomic Level 81 4.3.3 Pinpointing the Nature of the Active
Sites on Nanocatalysts 85 4.4 Conclusions 88 5 Applications of Soft X-Ray
Absorption Spectroscopy for In Situ Studies of Catalysts at Nanoscale 93
Xingyi Deng, Xiaoli Gu, and Franklin (Feng) Tao 5.1 Introduction 93 5.2 In
Situ SXAS under Reaction Conditions 96 5.3 Examples of In Situ SXAS Studies
under Reaction Conditions Using Reaction Cells 99 5.3.1 Atmospheric
Corrosion of Metal Films 99 5.3.2 Cobalt Nanoparticles under Reaction
Conditions 101 5.3.3 Electrochemical Corrosion of Cu in Aqueous NaHCO3
Solution 108 5.4 Summary 112 6 First-Principles Approaches to Understanding
Heterogeneous Catalysis 115 Dorrell C. McCalman and William F. Schneider
6.1 Introduction 115 6.2 Computational Models 116 6.2.1 Electronic
Structure Methods 116 6.2.2 System Models 117 6.3 NOx Reduction 118 6.4
Adsorption at Metal Surfaces 119 6.4.1 Neutral Adsorbates 119 6.4.2 Charged
Adsorbates 122 6.5 Elementary Surface Reactions Between Adsorbates 125
6.5.1 Reaction Thermodynamics 125 6.5.2 Reaction Kinetics 129 6.6 Coverage
Effects on Reaction and Activation Energies at Metal Surfaces 131 6.7
Summary 135 7 Computational Screening for Improved Heterogeneous Catalysts
and Electrocatalysts 139 Jeffrey Greeley 7.1 Introduction 139 7.2 T
rends-Based Studies in Computational Catalysis 140 7.2.1 Early Groundwork
for Computational Catalyst Screening 140 7.2.2 Volcano Plots and Rate
Theory Models 141 7.2.3 Scaling Relations, BEP Relations, and Descriptor
Determination 144 7.3 Computational Screening of Heterogeneous Catalysts
and Electrocatalysts 148 7.3.1 Computational Catalyst Screening Strategies
149 7.4 Challenges and New Frontiers in Computational Catalyst Screening
153 7.5 Conclusions 155 8 Catalytic Kinetics and Dynamics 161 Rafael C.
Catapan, Matthew A. Christiansen, Amir A. M. Oliveira, and Dionisios G.
Vlachos 8.1 Introduction 161 8.2 Basics of Catalyst Functionality,
Mechanisms, and Elementary Reactions on Surfaces 163 8.3 T ransition State
Theory, Collision Theory, and Rate Constants 166 8.4 Density Functional
Theory Calculations 168 8.4.1 Calculation of Energetics and Coverage
Effects 169 8.4.2 Calculation of Vibrational Frequencies 172 8.5 T
hermodynamic Consistency of the DFT-Predicted Energetics 172 8.6 State
Properties from Statistical Thermodynamics 176 8.6.1 Strongly Bound
Adsorbates 177 8.6.2 Weakly Bound Adsorbates 177 8.7 Semiempirical Methods
for Predicting Thermodynamic Properties and Kinetic Parameters 178 8.7.1
Linear Scaling Relationships 178 8.7.2 Heat Capacity and Surface Entropy
Estimation 179 8.7.3 Brønsted-Evans-Polanyi Relationships 180 8.8 Analysis
Tools for Microkinetic Modeling 181 8.8.1 Rates in Microkinetic Modeling
181 8.8.2 Reaction Path Analysis and Partial Equilibrium Analysis 181 8.8.3
Rate-Determining Steps, Most Important Surface Intermediates, and Most
Abundant Surface Intermediates 184 8.8.4 Calculation of the Overall
Reaction Order and Apparent Activation Energy 186 8.9 Concluding Remarks
187 9 Catalysts for Biofuels 191 Gregory T. Neumann, Danielle Garcia, and
Jason C. Hicks 9.1 Introduction 191 9.2 Lignocellulosic Biomass 192 9.2.1
Cellulose 192 9.2.2 Hemicellulose 194 9.2.3 Lignin 195 9.3 Carbohydrate
Upgrading 195 9.3.1 Zeolitic Upgrading of Cellulosic Feedstocks 196 9.3.2
Levulinic Acid Upgrading 199 9.3.3 GVL Upgrading 201 9.3.4 Aqueous-Phase
Processing 202 9.4 Lignin Conversion 205 9.4.1 Zeolite Upgrading of Lignin
Feedstocks 206 9.4.2 Catalysts for Hydrodeoxygenation of Lignin 208 9.4.3
Selective Unsupported Catalyst for Lignin Depolymerization 211 9.5
Continued Efforts for the Development of Robust Catalysts 212 10
Development of New Gold Catalysts for Removing CO from H2 217 Zhen Ma,
Franklin (Feng) Tao, and Xiaoli Gu 10.1 Introduction 217 10.2 General
Description of Catalyst Development 218 10.3 Development of WGS catalysts
220 10.3.1 Initially Developed Catalysts 220 10.3.2 Fe2O3-Based Gold
Catalysts 221 10.3.3 CeO2-Based Gold Catalysts 221 10.3.4 TiO2- or
ZrO2-Based Gold Catalysts 223 10.3.5 Mixed-Oxide Supports with 1:1
Composition 223 10.3.6 Bimetallic Catalysts 224 10.4 Development of New
Gold Catalysts for PROX 225 10.4.1 General Considerations 225 10.4.2
CeO2-Based Gold Catalysts 226 10.4.3 TiO2-Based Gold Catalysts 227 10.4.4
Al2O3-Based Gold Catalysts 228 10.4.5 Mixed Oxide Supports with 1:1
Composition 228 10.4.6 Other Oxide-Based Gold Catalysts 229 10.4.7
Supported Bimetallic catalysts 229 10.5 Perspectives 229 11 Photocatalysis
in Generation of Hydrogen from Water 239 Kazuhiro Takanabe and Kazunari
Domen 11.1 Solar Energy Conversion 239 11.1.1 Solar Energy Conversion
Technology for Producing Fuels and Chemicals 239 11.1.2 Solar Spectrum and
STH Efficiency 242 11.2 Semiconductor Particles: Optical and Electronic
Nature 244 11.2.1 Reaction Sequence and Principles of Overall Water
Splitting and Reaction Step Timescales 244 11.2.2 Number of Photons
Striking a Single Particle 245 11.2.3 Absorption Depth of Light Incident on
Powder Photocatalyst 247 11.2.4 Degree of Band Bending in Semiconductor
Powder 248 11.2.5 Band Gap and Flat-Band Potential of Semiconductor 250
11.3 Photocatalyst Materials for Overall Water Splitting: UV to Visible
Light Response 251 11.3.1 UV Photocatalysts: Oxides 251 11.3.2
Visible-Light Photocatalysts: Band Engineering of Semiconductor Materials
Containing Transition Metals 253 11.3.3 Visible-Light Photocatalysts:
Organic Semiconductors as Water-Splitting Photocatalysts 255 11.3.4
Z-Scheme Approach: Two-Photon Process 257 11.3.5 Defects and Recombination
in Semiconductor Bulk 257 11.4 Cocatalysts for Photocatalytic Overall Water
Splitting 259 11.4.1 Metal Nanoparticles as Hydrogen Evolution Cocatalysts:
Novel Core/Shell Structure 259 11.4.2 Reaction Rate Expression on Active
Catalytic Centers for Redox Reaction in Solution 261 11.4.3 Measurement of
Potentials at Semiconductor and Metal Particles Under Irradiation 264
11.4.4 Metal Oxides as Oxygen Evolution Cocatalyst 266 11.5 Concluding
Remarks 268 12 Photocatalysis in Conversion of Greenhouse Gases 271 Kentaro
Teramura and Tsunehiro Tanaka 12.1 Introduction 271 12.2 Outline of
Photocatalytic Conversion of CO2 273 12.3 Reaction Mechanism for the
Photocatalytic Conversion of CO2 276 12.3.1 Adsorption of CO2 and H2 276
12.3.2 Assignment of Adsorbed Species by FT-IR Spectroscopy 279 12.3.3
Observation of Photoactive Species by Photoluminescence (PL) and Electron
Paramagnetic Resonance (EPR) Spectroscopies 281 12.4 Summary 283 13
Electrocatalyst Design in Proton Exchange Membrane Fuel Cells for
Automotive Application 285 Anusorn Kongkanand, Wenbin Gu, and Frederick T.
Wagner 13.1 Introduction 285 13.2 Advanced Electrocatalysts 288 13.2.1
Pt-Alloy and Dealloyed Catalysts 288 13.2.2 Pt Monolayer Catalysts 290
13.2.3 Continuous-Layer Catalysts 293 13.2.4 Controlled Crystal Face
Catalysts 296 13.2.5 Hollow Pt Catalysts 298 13.3 Electrode Designs 299
13.3.1 Dispersed-Catalyst Electrodes 299 13.3.2 NSTF Electrodes 302 13.4
Concluding Remarks 307 Index 315