☆ 4.8 Review

Structural Engineering toward Gold Nanocluster Catalysis

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Ligand Engineering toward the Trade-Off between Stability and Activity in Cluster Catalysis

Zong-Jie Guan et al.

Summary: We report the structures, stability, and catalytic properties of two Ag-21 nanoclusters with different electronic structures and an identical icosahedral kernel. These clusters exhibit superior stability under ambient conditions and one of them shows higher activity as a catalyst in a reduction reaction.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

A 59-Electron Non-Magic-Number Gold Nanocluster Au99(C=CR)40 Showing Unexpectedly High Stability

Jiao-Jiao Li et al.

Summary: An atomically resolved gold nanocluster Au-99 with an open-shell electronic structure has been synthesized and characterized. It exhibits high stability and good charging-discharging capability, highlighting the crucial role of geometric factors in determining the stability of metal nanoclusters.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Multidisciplinary

Solvent-Controlled Condensation of [Mo2O5(PTC4A)2]6- Metalloligand in Stepwise Assembly of Hexagonal and Rectangular Ag18 Nanoclusters

Zhi Wang et al.

Summary: Stepwise assembly starting from a preassembled metalloligand has been used to obtain silver nanoclusters with convincing evidence. The study shows that different solvents can regulate the structure of silver nanoclusters and the installation of the metalloligand can control the subsequent condensation process.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

An Ultrastable 155-Nuclei Silver Nanocluster Protected by Thiacalix[4]arene and Cyclohexanethiol for Photothermal Conversion

Zhi Wang et al.

Summary: This study reports the single-crystal structure of the largest known mixed-valence silver nanoclusters protected by thiacalix[4]arenes and cyclohexanethiol. The structure consists of a metallic core with four concentric shells, surrounded by an organic skin. This work not only reveals the influence of macrocyclic ligands on the formation of large silver nanoclusters, but also provides a new structural archetype.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Multidisciplinary Sciences

Structural transformation and catalytic hydrogenation activity of amidinate-protected copper hydride clusters

Chun-Yu Liu et al.

Summary: This study uncovers the role of the amidinate ligand in yielding two closely related copper hydride clusters with different catalytic hydrogenation activities. The researchers synthetized stable copper hydride clusters using ligand engineering strategy and observed reversible interconversion between the clusters triggered by solvent. Deuteration experiments demonstrated that the type of hydride in the clusters dictates the catalytic activity.

NATURE COMMUNICATIONS (2022)

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Article Chemistry, Multidisciplinary

Au20(tBu3P)8: A Highly Symmetric Metalloid Gold Cluster in Oxidation State 0

Florian Fetzer et al.

Summary: Metalloid gold clusters, as key intermediates in studying metal phase transitions, possess unique properties. This study reports the synthesis of an all-phosphine protected metalloid cluster solely built from gold atoms. The cluster exhibits a highly symmetric structure resembling gold bulk, and shows molecular-like optical behavior.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Ligand-Shell Engineering of a Au28 Nanocluster Boosts Electrocatalytic CO2 Reduction

Jie Wang et al.

Summary: In this study, a new gold nanocluster Au-28-S was synthesized and compared with alkynyl-protected Au-28-C. It was found that the different ligand shells lead to distinctions in electronic structure and optical properties, and Au-28-S shows better catalytic activity for CO2 electrochemical reduction. Theoretical calculations also revealed the catalytic mechanism behind the different performances.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

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Article Chemistry, Multidisciplinary

Identification of the Active Species in Bimetallic Cluster Catalyzed Hydrogenation

Shang-Fu Yuan et al.

Summary: The identification of the authentic active species in cluster catalysis is challenging, and the direct structural evidence is valuable but difficult to obtain. In this study, two isostructural clusters were isolated and characterized, showing different catalytic activities and providing clear evidence for the modulation of catalytic performance by regulating the oxidation state of metal atoms.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Article Chemistry, Multidisciplinary

A 59-Electron Non-Magic-Number Gold Nanocluster Au-99(C CR)(40) Showing Unexpectedly High Stability

Jiao-Jiao Li et al.

Summary: A chemically synthesized gold nanocluster Au-99 with an unusual 59 valence electrons exhibits high stability in toluene solution at 80 degrees C for over a week, along with good charging-discharging capability under electrochemical conditions. The unique structure and geometric factors play a crucial role in determining the stability of this open-shell gold cluster.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

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Review Chemistry, Multidisciplinary

Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures

Rongchao Jin et al.

Summary: Researchers have successfully synthesized atomically precise metal nanoclusters with well-defined structures, opening up new opportunities for catalysis research. These atomically precise nanoclusters combine the characteristics of homogeneous catalysts and enzymes, holding significant potential for practical applications.

CHEMICAL REVIEWS (2021)

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Article Chemistry, Multidisciplinary

Atomically Precise Preorganization of Open Metal Sites on Gold Nanoclusters with High Catalytic Performance

Shang-Fu Yuan et al.

Summary: A gold nanocluster with well-defined access has been successfully synthesized using a surface geometric mismatch strategy with mixed ligands. This cluster shows excellent performance in selective oxidation reactions and demonstrates good stability due to the protection of a negatively charged multidentate ligand.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Enriching Structural Diversity of Alkynyl-Protected Gold Nanoclusters with Chlorides

Jiao-Jiao Li et al.

Summary: The article describes the synthesis and isolation of alkynyl/chloride-protected gold nanoclusters, and presents the structures of three different clusters, including the new clusters Au-67 and Au-106 with complex surface structures and unique electrochemical properties.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Surface Coordination of Multiple Ligands Endows N-Heterocyclic Carbene-Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity

Hui Shen et al.

Summary: Deciphering the atomic arrangement of hybrid surface ligands on metal nanoparticles is a key step towards understanding their complex geometrical and electronic structures, which can have potential bio-applications.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Physical

Ligand Effects on the Hydrogen Evolution Reaction Catalyzed by Au13 and Pt@Au12: Alkynyl vs Thiolate

Xiang Li et al.

Summary: The effects of alkynyl and thiolate ligands on the catalytic activities of Au-25 and PtAu24 nanoparticles for the hydrogen evolution reaction were studied. It was found that alkynyl ligands significantly enhanced the HER activity of Au-25, while the effect on PtAu24 was negligible.

JOURNAL OF PHYSICAL CHEMISTRY C (2021)

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Article Chemistry, Multidisciplinary

Precisely Constructed Silver Active Sites in Gold Nanoclusters for Chemical Fixation of CO2

Guangjun Li et al.

Summary: In this study, tailor-made catalytic sites for the cycloaddition of CO2 to epoxides were introduced by implementing Ag atoms at different levels of liberation in atomically precise Au nanoclusters. Structural tunability imparted by the atom-by-atom tailoring seemed to be crucial for promoting challenging bond cleavages and formations in the chemical utilization of CO2.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Molecular Gold Nanocluster Au156 Showing Metallic Electron Dynamics

Feng Hu et al.

Summary: The study focuses on the boundary between molecular and metallic gold nanoclusters, presenting the synthesis and structural determination of the largest all-alkynyl-protected gold nanocluster, Au-156. The cluster's rod shape with concentric core structure displays metal-like electron dynamics, suggesting Au-156 as a key crossover cluster for the transition from molecular to metallic state. The shape of the cluster is identified as one of the crucial factors in determining the molecular or metallic nature of a gold nanocluster.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Robust Gold Nanocluster Protected with Amidinates for Electrocatalytic CO2 Reduction

Shang-Fu Yuan et al.

Summary: The first amidinate-protected gold nanocluster Au-28 has a compact core-shell structure of T symmetry, fully protected by bridging formamidinate ligands. It shows excellent catalytic performance for CO2 electroreduction with 96.5% FE. Superior stability is attributed to strong gold-ligand binding and geometric shell closure.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Cluster From Cluster: A Quantitative Approach to Magic Gold Nanoclusters [Au25(SR)18]-

Zhen Lei et al.

Summary: The study introduces a novel cluster to cluster approach for assembling gold nanoclusters using preformed atomically precise Au-13 precursors, successfully synthesizing the well-known [Au-25(SR)(18)](-) magic cluster at high yield (overall yield close to 100%) and large scale (gram-scale based on gold). This method can be extended to the high-yield and large-scale synthesis of other metal nanoclusters.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

Ligand-Protected Au55 with a Novel Structure and Remarkable CO2 Electroreduction Performance

Xian-Kai Wan et al.

Summary: The study successfully synthesized an Au-55 nanocluster, which exhibited high catalytic activity and selectivity for the electrochemical reduction of CO2 to CO. The research also demonstrated that carrying out synthetic reactions in the absence of halide can lead to the formation of phosphine/thiolate co-protected metal nanoclusters.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

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Article Chemistry, Multidisciplinary

The role of ligands in atomically precise nanocluster-catalyzed CO2 electrochemical reduction

Site Li et al.

Summary: This study investigates the effects of different protecting ligands on Au nanoclusters in the CO2 electrochemical reduction reaction, revealing that the sulfur site acts as the active site supporting CO selectivity, while the selenium site shows a higher tendency for hydrogen evolution. Energy calculations demonstrate that the sulfur-based Au nanocluster exhibits lower energy penalties for key reaction steps, leading to improved catalytic performance.

NANOSCALE (2021)

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Review Chemistry, Multidisciplinary

Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties

Yuanxin Du et al.

CHEMICAL REVIEWS (2020)

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Article Chemistry, Multidisciplinary

Structure Determination of Alkynyl-Protected Gold Nanocluster Au22(tBuC≡C)18 and Its Thermochromic Luminescence

Xu-Shuang Han et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Review Chemistry, Multidisciplinary

Importance of Size and Contact Structure of Gold Nanoparticles for the Genesis of Unique Catalytic Processes

Tamao Ishida et al.

CHEMICAL REVIEWS (2020)

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Article Chemistry, Multidisciplinary

Isomerization in Alkynyl-Protected Gold Nanoclusters

Zong-Jie Guan et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

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A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

Zhi Wang et al.

NATURE COMMUNICATIONS (2020)

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Review Chemistry, Inorganic & Nuclear

New protective ligands for atomically precise silver nanoclusters

Geng-Geng Luo et al.

DALTON TRANSACTIONS (2020)

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Homoleptic alkynyl-protected gold nanoclusters with unusual compositions and structures

Zong-Jie Guan et al.

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Unlocking the catalytic activity of an eight-atom gold cluster with a Pd atom

Jiayu Xu et al.

NANOSCALE (2020)

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A Ligand-Protected Golden Fullerene: The Dipyridylamido Au328+ Nanocluster

Shang-Fu Yuan et al.

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Highly Robust but Surface-Active: An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster

Hui Shen et al.

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Alkynyl-Protected Au22(CCR)18 Clusters Featuring New Interfacial Motifs and R-Dependent Photoluminescence

Shun Ito et al.

JOURNAL OF PHYSICAL CHEMISTRY LETTERS (2019)

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Same Magic Number but Different Arrangement: Alkynyl-Protected Au25 with D3 Symmetry

Jiao-Jiao Li et al.

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Chiroptical Activity Enhancement via Structural Control: The Chiral Synthesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters

Jia-Qi Wang et al.

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An Au22(L8)6 nanocluster with in situ uncoordinated Au as a highly active catalyst for O2 activation and CO oxidation

Fuhua Li et al.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2019)

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Toward Total Synthesis of Thiolate-Protected Metal Nanoclusters

Qiaofeng Yao et al.

ACCOUNTS OF CHEMICAL RESEARCH (2018)

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Isolation and Total Structure Determination of an All-Alkynyl-Protected Gold Nanocluster Au144

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Liang Xu et al.

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Roles of thiolate ligands in the synthesis, properties and catalytic application of gold nanoclusters

Ricca Rahman Nasaruddin et al.

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Au-25(SR)(18): the captain of the great nanocluster ship

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Stronger-than-Pt hydrogen adsorption in a Au-22 nanocluster for the hydrogen evolution reaction

Guoxiang Hu et al.

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Structurally Precise Dichalcogenolate-Protected Copper and Silver Superatomic Nanoclusters and Their Alloys

Sachil Sharma et al.

ACCOUNTS OF CHEMICAL RESEARCH (2018)

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Surface Chemistry of Atomically Precise Coinage-Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

Juanzhu Yan et al.

ACCOUNTS OF CHEMICAL RESEARCH (2018)

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Alkynyl Approach toward the Protection of Metal Nanoclusters

Zhen Lei et al.

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Reversible Control of Chemoselectivity in Au38(SR)24 Nanocluster-Catalyzed Transfer Hydrogenation of Nitrobenzaldehyde Derivatives

Jianbo Zhao et al.

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Unraveling the long-pursued Au144 structure by x-ray crystallography

Nan Yan et al.

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Ligands Modulate Reaction Pathway in the Hydrogenation of 4-Nitrophenol Catalyzed by Gold Nanoclusters

Ricca Rahman Nasaruddin et al.

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Ligand effects in catalysis by atomically precise gold nanoclusters

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Homoleptic Alkynyl-Protected Gold Nanoclusters: Au44(PhCC)28 and Au36( PhCC)24

Xian-Kai Wan et al.

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ZnAl-Hydrotalcite-Supported Au25 Nanoclusters as Precatalysts for Chemoselective Hydrogenation of 3-Nitrostyrene

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Tailoring the Electronic and Catalytic Properties of Au25 Nanoclusters via Ligand Engineering

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Formation of Superlattices of Gold Nanoparticles Using Ostwald Ripening in Emulsions: Transition from fcc to bcc Structure

Julien Schmitt et al.

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Amplification of the Optical Activity of Gold Clusters by the Proximity of BINAP

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Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal Nanoparticles

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Atomic Structure of Self-Assembled Monolayer of Thiolates on a Tetragonal Au92 Nanocrystal

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Gold Quantum Boxes: On the Periodicities and the Quantum Confinement in the Au28, Au36, Au44, and Au52 Magic Series

Chenjie Zeng et al.

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Diphosphine-Protected Au22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal

Zili Wu et al.

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Zong-Jie Guan et al.

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Anuj S. Sharma et al.

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Experimental and Mechanistic Understanding of Aldehyde Hydrogenation Using Au25 Nanoclusters with Lewis Acids: Unique Sites for Catalytic Reactions

Gao Li et al.

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Nonscalable Oxidation Catalysis of Gold Clusters

Seiji Yamazoe et al.

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Balancing the Rate of Cluster Growth and Etching for Gram- Scale Synthesis of Thiolate- Protected Au25 Nanoclusters with Atomic Precision

Xun Yuan et al.

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Controlling Gold Nanoclusters by Diphospine Ligands

Jing Chen et al.

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Crystal Structure of Selenolate-Protected Au24(SeR)20 Nanocluster

Yongbo Song et al.

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Thiolate Ligands as a Double-Edged Sword for CO Oxidation on CeO2 Supported Au25(SCH2CH2Ph)18 Nanoclusters

Zili Wu et al.

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Size Dependence of Atomically Precise Gold Nanoclusters in Chemoselective Hydrogenation and Active Site Structure

Gao Li et al.

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Scalable and Precise Synthesis of Thiolated Au10-12, Au15, Au18, and Au25 Nanoclusters via pH Controlled CO Reduction

Yong Yu et al.

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Following the Thermal Activation of Au25(SR)18 Clusters for Catalysis by X-ray Absorption Spectroscopy

Atal Shivhare et al.

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Protected but Accessible: Oxygen Activation by a Calixarene-Stabilized Undecagold Cluster

Xi Chen et al.

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CO Oxidation Catalyzed by Oxide-Supported Au25(SR)18 Nanoclusters and Identification of Perimeter Sites as Active Centers

Xiaotao Nie et al.

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Total Structure and Electronic Properties of the Gold Nanocrystal Au36(SR)24

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Yan Zhang et al.

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Ligand-Induced Stability of Gold Nanoclusters: Thiolate versus Selenolate

Wataru Kurashige et al.

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A New Binding Motif of Sterically Demanding Thiolates on a Gold Cluster

Jun-ichi Nishigaki et al.

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Supported Gold and Silver Nanoparticles for Catalytic Deoxygenation of Epoxides into Alkenes

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A. Stephen K. Hashmi

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Avelino Corma et al.

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W Ngantsoue-Hoc et al.

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