Exposing the Delocalized Cu−S π Bonds on the Au24Cu6(SPhtBu)22 Nanocluster and Its Application in Ring‐Opening Reactions
Authors:
- 22 August 2019
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 58 (44) , 15671-15674
Abstract
Bimetallic nanomaterials are of major importance in catalysis. A Au‐Cu bimetallic nanocluster was synthesized that is effective in catalyzing the epoxide ring‐opening reaction. The catalyst was analyzed by SCXRD and ESI‐MS and found to be Au24Cu6(SPhtBu)22 (Au24Cu6 for short). Six copper atoms exclusively occupy the surface positions in two groups with three atoms for each, and each group was bonded with three thiolate ligands to give a planar motif reminiscent of a benzene ring. In the epoxide‐ring opening reaction, Au24Cu6 exhibited superior catalytic activity compared to other homometallic and Au‐Cu alloy NCs, such as Au25 and Au38−xCux. Control experiments and DFT calculations revealed that the π conjugation among the Cu−S bonds played a pivotal role. This study demonstrates a unique π conjugation established among the Cu−S bonds as a critical structural motif in the nanocluster, which facilitates the catalysis of a ring‐opening reaction.Keywords
Funding Information
- National Natural Science Foundation of China (21631001, 21871001, 21672001, and U1532141)
This publication has 40 references indexed in Scilit:
- Shape-Controlled Synthesis of Pd Nanocrystals and Their Catalytic ApplicationsAccounts of Chemical Research, 2012
- Enhancement in Aerobic Alcohol Oxidation Catalysis of Au25 Clusters by Single Pd Atom DopingACS Catalysis, 2012
- Atomic‐Distribution‐Dependent Electrocatalytic Activity of Au–Pd Bimetallic NanocrystalsAngewandte Chemie International Edition, 2011
- Atomic‐Distribution‐Dependent Electrocatalytic Activity of Au–Pd Bimetallic NanocrystalsAngewandte Chemie, 2011
- Trialkylphosphine-Stabilized Copper(I) Phenylchalcogenolate Complexes - Crystal Structures and Copper–Chalcogenolate BondingInorganic Chemistry, 2011
- Continuous modulation of electronic structure of stable thiolate-protected Au25 cluster by Ag dopingChemical Communications, 2010
- Atomically Precise Au25(SR)18 Nanoparticles as Catalysts for the Selective Hydrogenation of α,β‐Unsaturated Ketones and AldehydesAngewandte Chemie International Edition, 2010
- Atomically Precise Au25(SR)18 Nanoparticles as Catalysts for the Selective Hydrogenation of α,β‐Unsaturated Ketones and AldehydesAngewandte Chemie, 2010
- Mass Spectrometry of Small Bimetal Monolayer-Protected ClustersLangmuir, 2009
- Correlating the Crystal Structure of A Thiol-Protected Au25 Cluster and Optical PropertiesJournal of the American Chemical Society, 2008