Atomically Precise Nanoclusters - Atomically Precise Nanoclusters -

I Nanocluster Synthesis and Structural Characterization Chemical Synthesis and Physical Isolation of Metal Nanoclusters Introduction Synthesis Principles of Gold Nanoclusters Isolation of Gold Nanoclusters Fractionated Precipitation Recrystallization Solvent Extraction Polyacrylamide Gel Electrophoresis Size Exclusion Chromatography High-Performance Liquid Chromatography Separation of NCs depending on core sizes Separation of NCs depending on the charge Separation of doped NCs Separation of NCs depending on the ligand composition Separation of coordination isomer Separation of enantiomers of intrinsically chiral NCs Thin-Layer Chromatography Other Separation Methods Summary Nanoparticles with Atomic Resolution: Synthesis and Stable Structures of Atomically Precise Gold Nanoclusters Introduction Atomically Precise Synthesis of Metal Nanoclusters Size-Focusing Methodology Ligand-Exchange-Induced Size/Structure Transformation Synthesis and Structure Determination of Large Gold Nanoclusters Icosahedral Structures Decahedral Structures Face-Centered Cubic Structures Conclusions and Future Perspectives Synthesis and Structure of Selenolate-Protected Metal Nanoclusters Introduction Synthetic Methods Direct Synthesis Ligand Exchange Size Focusing Structure of Selenolate-Capped Metal Clusters Metal Nanocluster Protected by Full Selenolate Ligands Metal Nanocluster Co-capped by Selenolate and Phosphine Summary Strategy for Structural Prediction of Thiolate-Protected Au Nanoclusters Based on Density Functional Theory Introduction Structural Predictions of RS-AuNPs Unbiased Prediction Method Biased Prediction Strategy for RS-AuNPs Conclusion II Electronic and Optical Properties of Nanoclusters Toward Understanding the Structure of Gold Nanoclusters Introduction Theoretical Models of Structures of AuNCs “Divide and Protect Model” Concept Inherent Structure Rule Superatom Complex (SAC) Model Superatom Network (SAN) Model Grand Unified Model (GUM)Rethinking the Structure of Gold Nanoclusters with fcc-Based Kernel through GUM Segregation of Sample AuNCs Based on GUM Validation of Calculations Bond Length and Bond Order Conclusion Optical Properties of Atomically Precise Gold Nanoclusters: Transition from Excitons to Plasmons Introduction Optical Properties of Small-Sized Gold Nanoclusters Au25(SR)18 Nanoclusters Single-Atom Effect on Optical Properties Optical Properties of Large-Sized Gold Nanoclusters Case of Au246(SR)80 Case of Au279(SR)84 Conclusions and Future Perspectives Gold Nanoclusters with Atomic Precision: Optical Properties Introduction Optical Properties Absorption Properties Photoluminescence Capping the gold core with different ligands Tailoring core size and doping Aggregation-induced emission Nonlinear Optical Properties Two-Photon Absorption/Emission Second Harmonic Generation Ultrafast Electron Dynamics Metallic or nonmetallic state of gold nanoparticles Electron and energy transfer Optical Stability Optical Rotation and Circular Dichroism (CD) of Gold Nanoclusters Origin of Chirality of Gold Clusters Optical Properties of Chiral Gold Clusters Summary and Prospects III Catalytic Application of Nanoclusters Catalytic Application of Well-Defined Au Nanoparticles: Oxidation, Hydrogenation, and Coupling Reactions Introduction Homogeneous Catalysis Hydrogenation of Aldehyde Photo-oxidation Heterogeneous Catalysis Oxidation CO oxidation Photo-oxidation of amines to imines Hydrogenation Hydrogenation of aldehydes Semihydrogenation One-Pot Cascade Coupling Conclusions Catalytic Application of Atomically Precise Metal Nanoclusters as Heterogeneous Catalysts in Industrially Important Chemical Reactions Introduction Catalysis of Surface Active Sites Selective Oxidation Selective Hydrogenation Other Catalytic Reactions Catalysis of Non-surface Active Sites Central Atom Doped by a Foreign Atom Appearance and Disappearance of Central Atom Density Functional Theory Studies for Catalysis of Atomically Precise Metal Clusters Introduction DFT-Related Methods for Cluster Catalysis Determination of Atomistic Structures for Catalysts Determining Electronic Structures for Catalysts Predicting Spectra for Catalysts Adiabatic and Non-adiabatic Molecular Dynamics Transition State Theory and Microkinetics Designing Factors for Atomically Precise Metal Cluster Catalysis from DFT Studies Charge State of the Catalyst Point Vacancy Metal Cluster Surface Roles of Protective Ligands Structural Evolution of Catalyst Conclusions and Future Perspectives