Chapter
1.2.3. Control of Heterostructures
1.3. Challenges and Opportunities
1.3.1. Improving Synthesis and Translation to Industrial Applications of Nanostructured Catalysts
1.3.2. Improving In Situ and Operando Characterization
1.3.3. Stronger Theory-Experiment Connections
1.3.4. Stability Issues in Nanostructured Catalysts
1.3.5. Cost Issues Related to Well-Defined Nanostructures (Scale-Up Synthesis)
1.3.6. Toxicity Aspects of Nanostructured Catalysts
Chapter 2: Tuning Product Selectivity by Changing the Size of Catalytically Active Metallic Nanoparticles
2.2. Tuning Product Selectivity by Changing the Size of Metallic Nanoparticles
2.2.1. Influence of Platinum Particles Size on Product Selectivity in Pyrrole Hydrogenation Reaction
2.2.2. Influence of Platinum Particles Size on Product Selectivity in 1,3-Butadiene Hydrogenation Reaction
2.2.3. Dendrimer-Encapsulated Metallic Nanoparticles as Catalysts for Pi-Bond Activation Reactions
2.4.1. Formation of Subnanometer Clusters by Metal Atom Deposition on Surfaces
2.4.2. Formation and Stabilization of Atomic Clusters by Their Encapsulation With Strongly Coordinated Surface Ligands
Chapter 3: Achievements, Present Status, and Grand Challenges of Controlled Model Nanocatalysts
3.2. Molecular Fundamentals of Catalysis and Controlled Nanocatalysts
3.3. Overview of Synthetic Strategies for Controlled Nanocatalysts
3.4. Controlled Model Nanocatalysts in Action
3.4.1. Size and Shape Controlled Nanocatalysts
3.4.1.1. Hydrogenation of Aromatics Over Size- and Shape-Controlled Pt NPs
3.4.1.2. Hydrogenative Isomerization of Methylcyclopentane Over Size- and Shape-Controlled Pt NPs
3.4.1.3. Oxidation of CO Over Size-Controlled Oxyphilic Metal NPs
3.4.2. Composition and Architecture Controlled Nanocatalysts
3.4.2.1. Hydrogenative Reforming of Hexane Over Size and Composition Controlled Bimetallic NPs
3.4.2.2. Preferential Oxidation of CO in H2 (PROX) Over Size and Architecture Controlled Bimetallic NPs
3.4.3. Control of Metal-Oxide Interface
3.4.3.1. Size-Controlled Co NPs Supported on TiO2 for Hydrogenation of CO and CO2
3.4.3.2. Pt NPs Supported on Aluminasilicates (Zeolites) for Hydrogenative Reforming
3.4.3.3. Pt NPs Deposited on Transition Metal Oxides
3.4.4. Structure-Performance Correlations of Model Nanocatalysts
3.4.4.1. In Situ Tools and Techniques for Probing Surfaces
3.4.4.2. In Situ Spectroscopy & Microscopy of Model Nanocatalysts
3.4.4.2.1. Size, Composition Support Effects for CO Oxidation
3.4.4.2.2. Size, Architecture and Support Effects During Hydrogenation of CO and CO2
3.5. Grand Challenges of Model-Nanocatalysts
3.5.1. Size and Shape Control of Ultra-Small Metal Clusters
3.5.2. Size- and Shape-Control of Oxyphilic Early Group Transition Metals and Their Bimetallics
3.5.3. Understanding and Cataloging the Functions of Surface Capping and Directing Agents
3.5.4. Techniques for Detection of Single Catalyst Sites and Single Catalytic Turnovers
3.5.5. High-Throughput Synthesis and Combinatorial Discovery of Model Nanocatalysts
3.5.6. Computationally Guided Synthesis of Model Nanocatalysts
Chapter 4: Well-Defined Metal Nanoparticles for Electrocatalysis
4.3. Electrocatalysis of MNPs
4.3.1. Activation of MNPs
4.3.2. MNPs as the Fuel Cell Catalysts
4.3.2.1. MNPs for Oxygen Reduction Reaction
4.3.2.2. MNPs for Methanol and Formic Acid Oxidation
4.3.3. MNPs in Water Splitting
4.3.4. MNPs in Electrochemical Reduction of CO2
4.4. Conclusions and Future Outlooks
Chapter 5: Characterization of Model Nanocatalysts by X-ray Absorption Spectroscopy
5.1.1. Nanocatalysts and Their Applications
5.1.2. Solving the Structure in Model Nanocatalysts
5.2. Characterization of Model Nanocatalysts by EXAFS
5.2.1. EXAFS Application in Nanomaterials Research
5.2.2. Methods of Analysis of Monometallic Nanocatalysts
5.2.2.1. Size, Shape, Morphology of Well-Defined Clusters
5.2.2.2. Adsorbate and Support Effects on Metal-Metal Bond Strains
5.2.3. Methods of Analysis of Bimetallic Nanoparticles
5.2.3.1. Determination of Composition Patterns of Bimetallic Clusters
5.2.3.2. Solving Structures of Bimetallic Clusters With Overlapping Absorption Edges
5.2.4. Limitations of EXAFS Methods for Analysis of Nanoclusters
5.3. Outlook and Perspectives
Chapter 6: Controlling the Number of Atoms on Catalytic Metallic Clusters
6.2. Electron Microscopy of Catalytic Nanoalloys
6.2.1. TEM, STEM, and Spectroscopy Techniques
6.2.2. TEM Imaging of Nanoalloys
6.2.3. HAADF-STEM of Bimetallic Catalysts
6.2.4. HAADF-STEM of Supported Metallic Catalysts
6.2.5. Core-Shell Nanoparticles
6.2.5.1. AuAg Core-Shell Nanocubes
6.2.5.2. AuPd Core-Shell Nanocubes
6.2.5.3. AuPdAu Multishell Truncated Nanocubes
6.2.5.4. AuAgAu Hollow-Like Yolk Shell Cuboctahedra
6.3. Catalytic Activity Studies
6.4. Atom Counting for Metallic Clusters
Chapter 7: Spectroscopic Methods in Catalysis and Their Application in Well-Defined Nanocatalysts
7.1. Brief Historical Introduction and Definitions of the Main Classes of Spectroscopies
7.2. Basic Concepts on the Nature of Electrons, Photons, and Neutrons and on Their Interaction With Matter
7.3. Spectroscopies Classifications
7.3.1. Absorption Spectroscopies
7.3.2. Inelastic Scattering Spectroscopies
7.3.3. Photoelectron Spectroscopies
7.3.4. Decay Spectroscopies
7.4. Selected Examples of Spectroscopic Investigation of Nanostructured Catalysts
7.4.1. Understanding the Deactivation of Methanol-to-Hydrocarbons Process
7.4.1.1. Understanding the Role of Topology in the Deactivation of MTH Process Inside Nanostructured Zeolite Catalysts of ...
7.4.1.2. MTH Reaction Followed by Operando Raman
7.4.2. ETS-10, a Nanostructured Titanosilicate Photocatalyst
7.4.2.1. Stoichiometric and Sodium-Doped Titanium Silicate Molecular Sieve Containing Atomically Defined OTiOTiO Quantum ...
7.4.2.2. Red-Ox Behavior of Ag Nanoparticles Embedded in ETS-10 Inverse Shape-Selective PhotoCatalyst
7.4.3. PE Microtubes From Silica Fiber-Based PE Composites Synthesized by Using an In Situ Catalytic Method and Character ...
7.4.4. Active-Site Generation in ZN Polymerization Catalysts Highlighted by Combined XAS, XES, and UV-vis DRS
7.5. Conclusions and New Perspectives
Chapter 8: Nanoscale Control of Metal Clusters on Templating Supports
8.1.1. Metal Nanoclusters for Model Catalytic Studies: Finite Size Effects
8.1.2. The Role of the Support
8.1.3. Interaction With the Gas Phase
8.2. Investigating Metal Nanoclusters: Experimental and Theoretical Approaches
8.2.1. Experimental Approaches
8.2.1.1. Chemical Vapor Deposition
8.2.1.3. Characterization Techniques
8.2.2. Theoretical Approaches
8.2.2.1. Ab Initio Approaches
8.2.2.2. Atomistic Approaches and Interatomic Potentials
8.2.2.3. Nanoclusters Growth and Dynamical Processes
8.3. Clusters Growth and Characterization
8.3.1. Ultra-Thin Oxide Supports
8.4.2. Activity and Chemical Stability
Chapter 9: 0D, 1D, 2D, and 3D Soft and Hard Templates for Catalysis
9.1. 0D Templates in Metal Nanoparticle Preparation
9.1.1. Surfactant and Polymer as Templates
9.1.2. Di-, and Triblock Copolymers as Templates
9.2. 1D and 2D Hard Templates for Metallic Catalysts
9.3. 3D Templates in Various Sizes and Morphologies
9.3.2. 3D Template Usage for In Situ Metal Nanoparticle Preparation
9.3.3. 3D Hydrogel-Metal Composites as Catalysts
9.3.3.1. Hydrolysis of NaBH4 and NH3BH3 for Hydrogen Production
9.3.3.2. Reduction of Nitro Compounds to Their Corresponding Amino Forms by Soft Templated Metal Nanoparticles
9.3.3.3. Decolorization of Dyes
Chapter 10: Atomically Precise Gold and Bimetal Nanoclusters as New Model Catalysts
10.1. Synthesis of Atomically Precise Aun(SR)m Nanoclusters
10.1.1. From Polydisperse to Monodisperse to Atomic Precision
10.1.2. Size-Focusing Methodology: Principles and Examples
10.1.3. Transformation Chemistry of Gold Nanoclusters
10.1.4. Three Levels of Ligand Effects in Tuning the Sizes and Structures
10.1.5. Total Structures of Aun(SR)m Nanoclusters
10.2. Synthesis of Bimetallic Nanoclusters
10.2.1. Coreduction of Metal Salts: A ``Pretemplate´´ Method
10.2.2. Galvanic and Antigalvanic Replacements: A ``Posttemplate´´ Method
10.3. Catalytic Properties of Atomically Precise Gold Nanoclusters
10.3.1. Catalytic Oxidation
10.3.1.1. Catalytic Oxidation of Carbon Monoxide
10.3.1.2. Selective Oxidation of Styrene
10.3.1.3. Selective Oxidation of Benzyl Alcohol
10.3.1.4. Selective Oxidation of Sulfides
10.3.2. Catalytic Hydrogenation
10.3.2.1. Hydrogenation of Nitrophenol or Nitrobenzene
10.3.2.2. Selective Hydrogenation of Aldehydes and Ketones
10.3.2.3. Selective Hydrogenation of Nitrobenzaldehyde Derivatives
10.3.2.4. Semihydrogenation of Alkynes
10.3.3. Catalytic Carbon-Carbon Coupling Reaction
10.3.3.1. Ullmann-Type Homocoupling Reaction
10.3.3.2. Sonogashira Cross-Coupling Reaction
10.4. Catalytic Properties of Precisely Doped Au-M Bimetal Nanoclusters
10.5. Electrochemical Catalysis
Chapter 11: Fundamental Studies on Photocatalytic Structures With Well-Defined Crystal Facets
11.2. Synthesis of Well-Defined Photocatalytic Structures
11.2.1. General Strategies for Synthesis of Faceted Crystals
11.2.2. Tuning the Facet Exposure Using Bottom-Up Strategy
11.2.3. Tuning the Facet Exposure Using Top-Down Strategy
11.2.4. Mesocrystals With Oriented Alignment of Faceted Nanocrystals
11.3. Unusual Properties of Well-Defined Photocatalytic Structures
11.3.1. Surface Atomic Structure
11.3.1.1. Anisotropic Molecule/Cluster Adsorption
11.3.1.2. Anisotropic Charge Transfer Across the Interface
11.3.2. Surface Electronic Structure
11.3.2.1. Anisotropic Light Harvesting Ability
11.3.2.2. Anisotropic Redox Ability of Photo-Induced e-/h+ Pairs
11.3.2.3. Synergy Between Different Crystal Facets
11.3.3. Surface Defect Structure
11.3.4. Synergy or Competition among Different Surface Factors
11.3.4.1. Equilibrium Among Different Surface Factors
11.3.4.2. Equilibrium Between Surface Factors and Other Factors
11.4. Summary and Future Prospects
Chapter 12: Nanocrystal Catalysts of High-Energy Surface and Activity
Chapter 13: Synthesis and Characterization of Morphology-Controlled TiO2 Nanocrystals: Opportunities and Challenges for t ...
13.1. Introduction: Morphology-Dependent Photocatalytic Properties of TiO2 NCs
13.2. Solution Synthesis: A Powerful Chance for Tailoring Size, Shape, and Exposed Crystal Surfaces of TiO2 NCs
13.2.1. Sol-Gel Synthesis
13.2.1.1. Survey and Examples
13.2.2. Hydrothermal Synthesis
13.2.2.1. Survey and Examples
13.2.3. Solvothermal Synthesis
13.2.3.1. Survey and Examples
13.2.4. Microemulsion and Miniemulsion
13.2.4.1. Survey and Examples
13.2.5. High Temperature Colloidal Synthesis: Hot Injection and Heating Up Methods
13.2.5.1. Survey and Examples
13.3. Characterization of TiO2 NCs: Unraveling the Role of Size, Shape, and Exposed Crystal Surfaces in the Photocatalyti ...
13.3.1. Brief Survey on the Characterization Approaches of Morphology-Controlled TiO2 NCs
13.3.2. Fundamentals of ESR Spectroscopy
13.3.3. ESR Spectroscopy as a Probe of Photoinduced Processes in TiO2 NCs
13.3.4. Charge Trapping in TiO2 Nanocrystals With Different Crystal Phase, Size, and Shape
13.3.5. Photogenerated Defects in Shape-Controlled Anatase NCs With Specific Exposed Crystal Surfaces: Toward a Fine Cont ...
13.3.6. Brief Summary and Perspectives
13.4. Morphology-Controlled TiO2 NCs in Materials for Large-Scale Photocatalytic Applications: Some Examples
13.4.1. TiO2 Immobilized into Flexible Polyester Acrylate Membranes
13.4.2. TiO2 NCs Grafted on Macroporous Silica
13.5. Summary and Perspectives
Chapter 14: Uncertainties in Theoretical Description of Well-Defined Heterogeneous Catalysts
14.2. Background of DFT-Based Catalyst Screening
14.3. Reliability of DFT Calculations
14.4. Slab Model Versus Nanoparticles
14.5. Entropies of Adsorbed Molecules
14.6. Converting DFT Potential Energy Surface to Reaction Rate
14.7. Screening of Potential Catalyst
14.8. Summary and Outlook
Chapter 15: Sn-Substituted Zeolites as Heterogeneous Catalysts for Liquid-Phase Catalytic Technologies
15.2. An Introduction to Zeolites
15.2.2. Conventional Zeolite Synthesis
15.2.3. Conventional Applications of Zeolites Catalysts
15.2.4. Acid-Base and Redox Properties of Zeolites
15.3. State of the Art: Liquid Phase Processes Catalyzed by Lewis-Acidic Zeolites
15.3.1. Lewis Acidic Zeolites
15.3.2. Stannosilicate Zeolites as Liquid Phase Catalysts
15.3.3. Synthesis of Sn-β
15.3.4. Active Site Distributions and Selective Spectroscopic Techniques
15.3.5. Intensification Studies
15.4. Outlook and Pertaining Challenges
15.4.1. Synthetic Challenges
15.4.2. Spectroscopic Challenges
15.4.3. Intensification-Related Challenges
Chapter 16: Discovering and Utilizing Structure Sensitivity: From Chemical Catalysis in the Gas Phase to Electrocatalysis ...
16.2. Single Crystal Surfaces and Catalysis
16.3. Structure Sensitivity of Nanoparticle Catalysts
16.4. Comparing Solid/Gas and Solid/Liquid Catalysis
16.5. Catalyst Structure Design for Electrocatalysis
16.6. Future Perspectives
Chapter 17: Well-Defined Nanostructures for Catalysis by Atomic Layer Deposition
17.1.1. Motivation of ALD in Catalysis
17.2. Tuning Reactivity, Selectivity and Stability of Catalysts by ALD
17.2.1. Support Modification
17.2.3. Acid-Base Catalysis
17.2.5. Bimetallic Catalysis
17.2.5.1. Core-Shell Nanoparticles
17.2.5.2. Well-Mixed Alloy Nanoparticles
17.2.6. Bifunctional Catalysis
17.2.7. Oxide Overcoating to Improve Selectivity
17.2.8. Oxide Overcoating to Prevent Catalyst Deactivation
17.2.9. Electrocatalysis and Photocatalysis
17.3. Challenges and Opportunities for the Field
Morphological, Compositional, and Shape Control of Materials for Catalysis
( Volume 177 )
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