Heterogeneous Catalysis at Nanoscale for Energy Applications

Franklin (Feng) Tao, PhD, is a tenured Miller associate professor of chemical engineering and chemistry at the University of Kansas. He leads a research group focusing on synthesis, evaluation of catalytic performance, and in-situ characterization of heterogeneous catalysts at nanoscale for chemical and energy transformations. He has published almost 100 papers and three books with Wiley and RSC. William F. Schneider, PhD, is a Professor of Chemical and Biomolecular Engineering at the University of Notre Dame. His research interests are in the application of theory and simulation to probe and predict the molecular details of surface chemical reactivity and catalysis.  He has co-authored more than 130 papers and book chapters. Prashant V. Kamat, PhD, is Rev. John A. Zahm Professor of Science in the Department of Chemistry and Biochemistry, and Radiation Laboratory at the University of Notre Dame. For nearly three decades, he has worked to build bridges between physical chemistry and material science by developing semiconductor and metal nanostructure based hybrid assemblies for cleaner and efficient light energy conversion. He has co-authored more than 450 papers, reviews and book chapters.

• Contributors xiii1 Introduction 1Franklin (Feng) Tao, William F. Schneider, and Prashant V. Kamat2 Chemical Synthesis of Nanoscale Heterogeneous Catalysts 9Jianbo Wu and Hong Yang2.1 Introduction 92.2 Brief Overview of Heterogeneous Catalysts 102.3 Chemical Synthetic Approaches 112.3.1 Colloidal Synthesis 112.3.2 Shape Control of Catalysts in Colloidal Synthesis 122.3.3 Control of Crystalline Phase of Intermetallic Nanostructures 142.3.4 Other Modes of Formation for Complex Nanostructures 172.4 Core–Shell Nanoparticles and Controls of Surface Compositions and Surface Atomic Arrangements 212.4.1 New Development on the Preparation of Colloidal Core–Shell Nanoparticles 212.4.2 Electrochemical Methods to Core–Shell Nanostructures 222.4.3 Control of Surface Composition via Surface Segregation 242.5 Summary 253 Physical Fabrication of Nanostructured Heterogeneous Catalysts 31Chunrong Yin, Eric C. Tyo, and Stefan Vajda3.1 Introduction 313.2 Cluster Sources 343.2.1 T hermal Vaporization Source 343.2.2 Laser Ablation Source 363.2.3 Magnetron Cluster Source 373.2.4 Arc Cluster Ion Source 383.3 Mass Analyzers 393.3.1 Neutral Cluster Beams 403.3.2 Quadrupole Mass Analyzer 413.3.3 Lateral TOF Mass Filter 423.3.4 Magnetic Sector Mass Selector 433.3.5 Quadrupole Deflector (Bender) 443.4 Survey of Cluster Deposition Apparatuses in Catalysis Studies 443.4.1 Laser Ablation Source with a Quadrupole Mass Analyzer at Argonne National Lab 443.4.2 ACIS with a Quadrupole Deflector at the Universität Rostock 463.4.3 Magnetron Cluster Source with a Lateral TOF Mass Filter at the University of Birmingham 473.4.4 Laser Ablation Cluster Source with a Quadrupole Mass Selector at the Technische Universität München 483.4.5 Laser Ablation Cluster Source with a Quadrupole Mass Analyzer at the University of Utah 493.4.6 Laser Ablation Cluster Source with a Magnetic Sector Mass Selector at the University of California, Santa Barbara 493.4.7 Magnetron Cluster Source with a Quadrupole Mass Filter at the Toyota Technological Institute 513.4.8 PACIS with a Magnetic Sector Mass Selector at Universität Konstanz 523.4.9 Magnetron Cluster Source with a Magnetic Sector at Johns Hopkins University 533.4.10 Magnetron Cluster Source with a Magnetic Sector at HZB 533.4.11 Magnetron Sputtering Source with a Quadrupole Mass Filter at the Technical University of Denmark 543.4.12 CORDIS with a Quadrupole Mass Filter at the Lausanne Group 563.4.13 Electron Impact Source with a Quadrupole Mass Selector at the Universität Karlsruhe 563.4.14 CORDIS with a Quadrupole Mass Analyzer at the Universität Ulm 583.4.15 Magnetron Cluster Source with a Lateral TOF Mass Filter at the Universität Dortmund 593.4.16 Z-Spray Source with a Quadrupole Mass Filter for Gas-Phase Investigations at FELIX 603.4.17 Laser Ablation Source with an Ion Cyclotron Resonance Mass Spectrometer for Gas-Phase Investigations at the Technische Universität Berlin 614 Ex Situ Characterization 69Minghua Qiao, Songhai Xie, Yan Pei, and Kangnian Fan4.1 Introduction 694.2 Ex Situ Characterization Techniques 704.2.1 X-Ray Absorption Spectroscopy 714.2.2 Electron Spectroscopy 724.2.3 Electron Microscopy 744.2.4 Scanning Probe Microscopy 754.2.5 Mössbauer Spectroscopy 764.3 Some Examples on Ex Situ Characterization of Nanocatalysts for Energy Applications 774.3.1 Illustrating Structural and Electronic Properties of Complex Nanocatalysts 774.3.2 Elucidating Structural Characteristics of Catalysts at the Nanometer or Atomic Level 814.3.3 Pinpointing the Nature of the Active Sites on Nanocatalysts 854.4 Conclusions 885 Applications of Soft X-Ray Absorption Spectroscopy for In Situ Studies of Catalysts at Nanoscale 93Xingyi Deng, Xiaoli Gu, and Franklin (Feng) Tao5.1 Introduction 935.2 In Situ SXAS under Reaction Conditions 965.3 Examples of In Situ SXAS Studies under Reaction Conditions Using Reaction Cells 995.3.1 Atmospheric Corrosion of Metal Films 995.3.2 Cobalt Nanoparticles under Reaction Conditions 1015.3.3 Electrochemical Corrosion of Cu in Aqueous NaHCO3 Solution 1085.4 Summary 1126 First-Principles Approaches to Understanding Heterogeneous Catalysis 115Dorrell C. McCalman and William F. Schneider6.1 Introduction 1156.2 Computational Models 1166.2.1 Electronic Structure Methods 1166.2.2 System Models 1176.3 NOx Reduction 1186.4 Adsorption at Metal Surfaces 1196.4.1 Neutral Adsorbates 1196.4.2 Charged Adsorbates 1226.5 Elementary Surface Reactions Between Adsorbates 1256.5.1 Reaction Thermodynamics 1256.5.2 Reaction Kinetics 1296.6 Coverage Effects on Reaction and Activation Energies at Metal Surfaces 1316.7 Summary 1357 Computational Screening for Improved Heterogeneous Catalysts and Electrocatalysts 139Jeffrey Greeley7.1 Introduction 1397.2 T rends-Based Studies in Computational Catalysis 1407.2.1 Early Groundwork for Computational Catalyst Screening 1407.2.2 Volcano Plots and Rate Theory Models 1417.2.3 Scaling Relations, BEP Relations, and Descriptor Determination 1447.3 Computational Screening of Heterogeneous Catalysts and Electrocatalysts 1487.3.1 Computational Catalyst Screening Strategies 1497.4 Challenges and New Frontiers in Computational Catalyst Screening 1537.5 Conclusions 1558 Catalytic Kinetics and Dynamics 161Rafael C. Catapan, Matthew A. Christiansen, Amir A. M. Oliveira, and Dionisios G. Vlachos8.1 Introduction 1618.2 Basics of Catalyst Functionality, Mechanisms, and Elementary Reactions on Surfaces 1638.3 T ransition State Theory, Collision Theory, and Rate Constants 1668.4 Density Functional Theory Calculations 1688.4.1 Calculation of Energetics and Coverage Effects 1698.4.2 Calculation of Vibrational Frequencies 1728.5 T hermodynamic Consistency of the DFT-Predicted Energetics 1728.6 State Properties from Statistical Thermodynamics 1768.6.1 Strongly Bound Adsorbates 1778.6.2 Weakly Bound Adsorbates 1778.7 Semiempirical Methods for Predicting Thermodynamic Properties and Kinetic Parameters 1788.7.1 Linear Scaling Relationships 1788.7.2 Heat Capacity and Surface Entropy Estimation 1798.7.3 Brønsted-Evans-Polanyi Relationships 1808.8 Analysis Tools for Microkinetic Modeling 1818.8.1 Rates in Microkinetic Modeling 1818.8.2 Reaction Path Analysis and Partial Equilibrium Analysis 1818.8.3 Rate-Determining Steps, Most Important Surface Intermediates, and Most Abundant Surface Intermediates 1848.8.4 Calculation of the Overall Reaction Order and Apparent Activation Energy 1868.9 Concluding Remarks 1879 Catalysts for Biofuels 191Gregory T. Neumann, Danielle Garcia, and Jason C. Hicks9.1 Introduction 1919.2 Lignocellulosic Biomass 1929.2.1 Cellulose 1929.2.2 Hemicellulose 1949.2.3 Lignin 1959.3 Carbohydrate Upgrading 1959.3.1 Zeolitic Upgrading of Cellulosic Feedstocks 1969.3.2 Levulinic Acid Upgrading 1999.3.3 GVL Upgrading 2019.3.4 Aqueous-Phase Processing 2029.4 Lignin Conversion 2059.4.1 Zeolite Upgrading of Lignin Feedstocks 2069.4.2 Catalysts for Hydrodeoxygenation of Lignin 2089.4.3 Selective Unsupported Catalyst for Lignin Depolymerization 2119.5 Continued Efforts for the Development of Robust Catalysts 21210 Development of New Gold Catalysts for Removing CO from H2 217Zhen Ma, Franklin (Feng) Tao, and Xiaoli Gu10.1 Introduction 21710.2 General Description of Catalyst Development 21810.3 Development of WGS catalysts 22010.3.1 Initially Developed Catalysts 22010.3.2 Fe2O3-Based Gold Catalysts 22110.3.3 CeO2-Based Gold Catalysts 22110.3.4 TiO2- or ZrO2-Based Gold Catalysts 22310.3.5 Mixed-Oxide Supports with 1:1 Composition 22310.3.6 Bimetallic Catalysts 22410.4 Development of New Gold Catalysts for PROX 22510.4.1 General Considerations 22510.4.2 CeO2-Based Gold Catalysts 22610.4.3 TiO2-Based Gold Catalysts 22710.4.4 Al2O3-Based Gold Catalysts 22810.4.5 Mixed Oxide Supports with 1:1 Composition 22810.4.6 Other Oxide-Based Gold Catalysts 22910.4.7 Supported Bimetallic catalysts 22910.5 Perspectives 22911 Photocatalysis in Generation of Hydrogen from Water 239Kazuhiro Takanabe and Kazunari Domen11.1 Solar Energy Conversion 23911.1.1 Solar Energy Conversion Technology for Producing Fuels and Chemicals 23911.1.2 Solar Spectrum and STH Efficiency 24211.2 Semiconductor Particles: Optical and Electronic Nature 24411.2.1 Reaction Sequence and Principles of Overall Water Splitting and Reaction Step Timescales 24411.2.2 Number of Photons Striking a Single Particle 24511.2.3 Absorption Depth of Light Incident on Powder Photocatalyst 24711.2.4 Degree of Band Bending in Semiconductor Powder 24811.2.5 Band Gap and Flat-Band Potential of Semiconductor 25011.3 Photocatalyst Materials for Overall Water Splitting: UV to Visible Light Response 25111.3.1 UV Photocatalysts: Oxides 25111.3.2 Visible-Light Photocatalysts: Band Engineering of Semiconductor Materials Containing Transition Metals 25311.3.3 Visible-Light Photocatalysts: Organic Semiconductors as Water-Splitting Photocatalysts 25511.3.4 Z-Scheme Approach: Two-Photon Process 25711.3.5 Defects and Recombination in Semiconductor Bulk 25711.4 Cocatalysts for Photocatalytic Overall Water Splitting 25911.4.1 Metal Nanoparticles as Hydrogen Evolution Cocatalysts: Novel Core/Shell Structure 25911.4.2 Reaction Rate Expression on Active Catalytic Centers for Redox Reaction in Solution 26111.4.3 Measurement of Potentials at Semiconductor and Metal Particles Under Irradiation 26411.4.4 Metal Oxides as Oxygen Evolution Cocatalyst 26611.5 Concluding Remarks 26812 Photocatalysis in Conversion of Greenhouse Gases 271Kentaro Teramura and Tsunehiro Tanaka12.1 Introduction 27112.2 Outline of Photocatalytic Conversion of CO2 27312.3 Reaction Mechanism for the Photocatalytic Conversion of CO2 27612.3.1 Adsorption of CO2 and H2 27612.3.2 Assignment of Adsorbed Species by FT-IR Spectroscopy 27912.3.3 Observation of Photoactive Species by Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) Spectroscopies 28112.4 Summary 28313 Electrocatalyst Design in Proton Exchange Membrane Fuel Cells for Automotive Application 285Anusorn Kongkanand, Wenbin Gu, and Frederick T. Wagner13.1 Introduction 28513.2 Advanced Electrocatalysts 28813.2.1 Pt-Alloy and Dealloyed Catalysts 28813.2.2 Pt Monolayer Catalysts 29013.2.3 Continuous-Layer Catalysts 29313.2.4 Controlled Crystal Face Catalysts 29613.2.5 Hollow Pt Catalysts 29813.3 Electrode Designs 29913.3.1 Dispersed-Catalyst Electrodes 29913.3.2 NSTF Electrodes 30213.4 Concluding Remarks 307Index 315