Structure Distortion Endows Copper Nanoclusters with Surface-Active Uncoordinated Sites for Boosting Catalysis

作者：Jing Sun, Qingyuan Wu, Xiaodan Yan, Lei Li, Xiongkai Tang, Xuekun Gong, Bingzheng Yan, Qinghua Xu, Qingxiang Guo, Jinlu He, Hui Shen · 发表于：JACS Au · 年份：2024 · DOI：10.1021/jacsau.4c00574 · 被引用次数：11 · 研究领域：Nanocluster Synthesis and Applications、Advanced Nanomaterials in Catalysis、Gold and Silver Nanoparticles Synthesis and Applications

High Resolution Image Download MS PowerPoint Slide The utilization of structure distortion to modulate the electronic structure and alter catalytic properties of metallic nanomaterials is a well-established practice, but accurately identifying and comprehensively understanding these distortions present significant challenges. Ligand-stabilized metal nanoclusters with well-defined structures serve as exemplary model systems to illustrate the structure chemistry of nanomaterials, among which few studies have investigated nanocluster models that incorporate structural distortions. In this work, a novel copper hydride nanocluster, Cu 42 (PPh 3 ) 8 (RS) 4 (CF 3 COO) 10 (CH 3 O) 4 H 10 (Cu 42; PPh 3 is triphenylphosphine and RSH is 2,4-dichlorophenylthiol), with a highly twisted structure has been synthesized in a simple way. Structural analysis reveals Cu 42 comprises two Cu 25 units that are conjoined in a nearly orthogonal manner. The dramatic distortion in the metal framework, which is driven by multiple interactions from the surface ligands, endows the cluster with a rich array of uncoordinated metal sites on the surface. The resulting cluster, as envisioned, exhibits remarkable activity in catalyzing carbonylation of anilines. The findings from this study not only provides atomically precise insights into the structural distortions that are pertinent to nanoparticle catalysts but also underscores the potential of structurally distorted NCs as a burgeoning generation of cataly...