Dramatic Difference Between Cu_(20)H_(8)and Cu_(20)H_(9)Clusters in Catalysis  

作　　者：Chun-Yu Liu Tong-Yu Liu Zong-Jie Guan Song Wang Yuan-Yuan Dong Feng Hu De-en Jiang Quan-Ming Wang 

机构地区：[1]Department of Chemistry,Engineering Research Center of Advanced Rare Earth Materials(Ministry of Education),Tsinghua University,Beijing 100084 [2]Jiangsu Engineering Research Centre for Digital Textile Inkjet Printing Key Laboratory of Eco-Textile,Jiangnan University,Ministry of Education,Wuxi,Jiangsu 214122 [3]Department of Chemical and Biomolecular Engineering,Vanderbilt University,Nashville,Tennessee 37235 [4]Department of Chemistry,Vanderbilt University,Nashville,Tennessee 37235 [5]College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082 [6]Hefei National Research Center for Physical Sciences at the Microscale,School of Chemistry and Materials Science,University of Science and Technology of China,Hefei,Anhui 230026

出　　处：《CCS Chemistry》2024年第6期1581-1590,共10页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant nos.91961201 and 21973116);the Beijing Natural Science Foundation(grant no.2234087);the China Postdoctoral Science Foundation(grant nos.2023T160357 and 2022M721797).

摘　　要：Sensitivity to structure and composition is very challenging to establish in nanocatalysis due to inadequate definition of structures that are very close in composition.We synthesized a pair of atomically precise copper clusters that are very close in composition,[Cu_(20)H_(9)(Tf-dpf)_(10)]·BF4(Cu_(20)H_(9))and[Cu_(20)H_(8)(Tf-dpf)_(10)]·(BF_(4))_(2)(Cu_(20)H_(8)),by using a pyridyl-functionalized flexible amidinate ligand,N,N′-di(5-trifluoromethyl-2-pyridyl)formamidinate.The one-hydride difference in their composition leads to significant variation in geometric and electronic structures and,consequently,distinctly different optical and catalytic properties.Cu_(20)H_(8)exhibits 25 times higher catalytic activity than Cu_(20)H_(9)(96.7%vs 3.7%in yield)in the selective hydrogenation of anα,β-unsaturated aldehyde(cinnamaldehyde)to saturated aldehyde(3-phenylpropanal).Electrospray ionization mass spectrometry combined with density functional theory calculations reveal that the greater ease of dissociation of one Tf-dpf ligand compared to Cu_(20)H_(8)is the key to its higher activity.This work demonstrates a clear case of structure and composition sensitivity in nanocatalysis and that one hydride,out of∼330 atoms in the nanoclusters,can make a huge difference in the catalytic activity.These insights will be useful in the design and synthesis of atomically precise nanocatalysts.

关 键 词：copper cluster HYDRIDE amidinate ligand structural transformation hydrogenation catalysis 

分 类 号：O64[理学—物理化学]