Atomically Precise Nanoclusters

✍ Scribed by Rongchao Jin, Yan Zhu

• Year: 2020
• Tongue: English
• Leaves: 346
• Category: Library

✦ Table of Contents

Cover
Half Title
Title Page
Copyright Page
Contents
Preface
About Editors
Part I Nanocluster Synthesis and Structural Characterization
1. Chemical Synthesis and Physical Isolation of Metal Nanoclusters
1.1 Introduction
1.2 Synthesis Principles of Gold Nanoclusters
1.3 Isolation of Gold Nanoclusters
1.3.1 Fractionated Precipitation
1.3.2 Recrystallization
1.3.3 Solvent Extraction
1.3.4 Polyacrylamide Gel Electrophoresis
1.3.5 Size Exclusion Chromatography
1.3.6 High-Performance Liquid Chromatography
1.3.6.1 Separation of NCs depending on core sizes
1.3.6.2 Separation of NCs depending on the charge
1.3.6.3 Separation of doped NCs
1.3.6.4 Separation of NCs depending on the ligand composition
1.3.6.5 Separation of coordination isomer
1.3.6.6 Separation of enantiomers of intrinsically chiral NCs
1.3.7 Thin-Layer Chromatography
1.3.8 Other Separation Methods
1.4 Summary
2. Nanoparticles with Atomic Resolution: Synthesis and Stable Structures of Atomically Precise Gold Nanoclusters
2.1 Introduction
2.2 Atomically Precise Synthesis of Metal Nanoclusters
2.2.1 Size-Focusing Methodology
2.2.2 Ligand-Exchange-Induced Size/Structure Transformation
2.3 Synthesis and Structure Determination of Large Gold Nanoclusters
2.3.1 Icosahedral Structures
2.3.1.1 Case of Au133(SR)52
2.3.1.2 Case of Au144(SR)60
2.3.2 Decahedral Structures
2.3.2.1 Case of Au102(SR)44
2.3.2.2 Case of Au103S2(SR)41
2.3.2.3 Case of Au130(SR)50
2.3.2.4 Case of Au246(SR)80
2.3.3 Face-Centered Cubic Structures
2.3.3.1 Case of Au146(SR)57
2.3.3.2 Case of Au279(SR)84
2.4 Conclusions and Future Perspectives
3. Synthesis and Structure of Selenolate-Protected Metal Nanoclusters
3.1 Introduction
3.2 Synthetic Methods
3.2.1 Direct Synthesis
3.2.2 Ligand Exchange
3.2.3 Size Focusing
3.3 Structure of Selenolate-Capped Metal Clusters
3.3.1 Metal Nanocluster Protected by Full Selenolate Ligands
3.3.1.1 Case of [Au24(SePh)20] nanocluster
3.3.1.2 Case of [Au25(SePh)18]- nanocluster
3.3.1.3 Case of [Cd12Ag32(SePh)36] nanocluster
3.3.1.4 Case of [MAg20{Se2P(OEt)2}12]+ nanocluster (M = Au or Ag)
3.3.2 Metal Nanocluster Co-capped by Selenolate and Phosphine
3.3.2.1 Case of [Au11(L5)4(SePh)2]+ nanocluster
3.3.2.2 Case of rod-like [Au25(SePh)5(TPP)10Cl2]+/2+ nanoclusters
3.3.2.3 Case of [Au60Se2(SePh)15(TPP)10]+ nanocluster
3.3.2.4 Case of [Au13Cu4(PPyPh2)3(SePh)9] nanocluster
3.4 Summary
4. Strategy for Structural Prediction of Thiolate-Protected Au Nanoclusters Based on Density Functional Theory
4.1 Introduction
4.2 Structural Predictions of RS-AuNPs
4.2.1 Unbiased Prediction Method
4.2.2 Biased Prediction Strategy for RS-AuNPs
4.3 Conclusion
Part II Electronic and Optical Properties of Nanoclusters
5. Toward Understanding the Structure of Gold Nanoclusters
5.1 Introduction
5.2 Theoretical Models of Structures of AuNCs
5.2.1 “Divide and Protect Model” Concept
5.2.2 Inherent Structure Rule
5.2.3 Superatom Complex (SAC) Model
5.2.4 Superatom Network (SAN) Model
5.2.5 Grand Unified Model (GUM)
5.3 Rethinking the Structure of Gold Nanoclusters with fcc-Based Kernel through GUM
5.3.1 Segregation of Sample AuNCs Based on GUM
5.3.2 Validation of Calculations
5.3.3 Bond Length and Bond Order
5.4 Conclusion
6. Optical Properties of Atomically Precise Gold Nanoclusters: Transition from Excitons to Plasmons
6.1 Introduction
6.2 Optical Properties of Small-Sized Gold Nanoclusters
6.2.1 Au25(SR)18 Nanoclusters
6.2.2 Single-Atom Effect on Optical Properties
6.3 Optical Properties of Large-Sized Gold Nanoclusters
6.3.1 Case of Au246(SR)80
6.3.2 Case of Au279(SR)84
6.4 Conclusions and Future Perspectives
7. Gold Nanoclusters with Atomic Precision: Optical Properties
7.1 Introduction
7.2 Optical Properties
7.2.1 Absorption Properties
7.2.2 Photoluminescence
7.2.2.1 Capping the gold core with different ligands
7.2.2.2 Tailoring core size and doping
7.2.2.3 Aggregation-induced emission
7.3 Nonlinear Optical Properties
7.3.1 Two-Photon Absorption/Emission
7.3.2 Second Harmonic Generation
7.3.3 Ultrafast Electron Dynamics
7.3.3.1 Metallic or nonmetallic state of gold nanoparticles
7.3.3.2 Electron and energy transfer
7.4 Optical Stability
7.5 Optical Rotation and Circular Dichroism (CD) of Gold Nanoclusters
7.5.1 Origin of Chirality of Gold Clusters
7.5.2 Optical Properties of Chiral Gold Clusters
7.6 Summary and Prospects
Part III Catalytic Application of Nanoclusters
8. Catalytic Application of Well-Defined Au Nanoparticles: Oxidation, Hydrogenation, and Coupling Reactions
8.1 Introduction
8.2 Homogeneous Catalysis
8.2.1 Hydrogenation of Aldehyde
8.2.2 Photo-oxidation
8.3 Heterogeneous Catalysis
8.3.1 Oxidation
8.3.1.1 CO oxidation
8.3.1.2 Photo-oxidation of amines to imines
8.3.2 Hydrogenation
8.3.2.1 Hydrogenation of aldehydes
8.3.2.2 Semihydrogenation
8.3.3 One-Pot Cascade Coupling
8.4 Conclusions
9. Catalytic Application of Atomically Precise Metal Nanoclusters as Heterogeneous Catalysts in Industrially Important Chemical Reactions
9.1 Introduction
9.2 Catalysis of Surface Active Sites
9.2.1 Selective Oxidation
9.2.2 Selective Hydrogenation
9.2.3 Other Catalytic Reactions
9.3 Catalysis of Non-surface Active Sites
9.3.1 Central Atom Doped by a Foreign Atom
9.3.2 Appearance and Disappearance of Central Atom
10. Density Functional Theory Studies for Catalysis of Atomically Precise Metal Clusters
10.1 Introduction
10.2 DFT-Related Methods for Cluster Catalysis
10.2.1 Determination of Atomistic Structures for Catalysts
10.2.2 Determining Electronic Structures for Catalysts
10.2.3 Predicting Spectra for Catalysts
10.2.4 Adiabatic and Non-adiabatic Molecular Dynamics
10.2.5 Transition State Theory and Microkinetics
10.3 Designing Factors for Atomically Precise Metal Cluster Catalysis from DFT Studies
10.3.1 Charge State of the Catalyst
10.3.2 Point Vacancy
10.3.3 Metal Cluster Surface
10.3.4 Roles of Protective Ligands
10.3.5 Structural Evolution of Catalyst
10.4 Conclusions and Future Perspectives
Index