Array-Based Clusters of Copper with Largely Exposed Metal Sites for Promoting Catalysis

Most ligand-stabilized metal nanoclusters feature a core–shell or polyhedron-derived metal framework, in which the metal active sites would be blocked by either metal–ligand interfacial shells or surface passive units. We report, in this work, a strategy of largely exposing metal sites and thus prom...

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Published in:Chemistry of materials 2023-09, Vol.35 (18), p.7588-7596
Main Authors: Xu, Xiaoxuan, Liu, Ying, Sun, Fang, Jia, Yanyuan, Xu, Qinghua, Tang, Jiaqi, Xie, Zhenlang, Sun, Jing, Li, Simin, Tang, Qing, Guo, Shuo, Shen, Hui, Zheng, Nanfeng
Format: Article
Language:English
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Summary:Most ligand-stabilized metal nanoclusters feature a core–shell or polyhedron-derived metal framework, in which the metal active sites would be blocked by either metal–ligand interfacial shells or surface passive units. We report, in this work, a strategy of largely exposing metal sites and thus promoting catalysis via constructing metal nanoclusters with array-based geometry. Exampled here are a pair of Cu8 clusters with polyhedron-derived ([Cu8(RS)6(PPh3)4(MeCN)4H]+, where RS is 3,5-bis­(trifluoromethyl)­benzenethiol) and array-based ([Cu8(Tf-dpf)4(NO3)2]­(NO3)2, Tf-dpf is N,N′-di­(5-trifluoromethyl-2-pyridyl) formamidinate) structure, respectively. In sharp contrast to the cubic Cu8 cluster whose metal core has been totally covered by ligands, the array-based analogue displays largely uncoordinated metal sites. As a result, the array-based Cu8 cluster exhibits significantly enhanced activity in catalytic hydrogenation reactions in comparison to the cubic one. In addition, the array-based Cu8 cluster shows excellent catalytic performance in the “aldehyde–acetylene–amine” A3-coupling reaction for the synthesis of propargylamines. The reaction can be converted almost perfectly with a rather low amount of cluster, which further reflects its potential catalytic application.
ISSN:0897-4756
1520-5002
DOI:10.1021/acs.chemmater.3c01277