Regulating interaction with surface ligands on Au_(25)nanoclusters by multivariate metal-organic framework hosts for boosting catalysis  

作　　者：He Wang Xiaokang Liu Yulong Zhao Zhihu Sun Yue Lin Tao Yao Hai-Long Jiang 

机构地区：[1]Hefei National Research Center for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei 230026,China [2]Department of Chemistry,University of Science and Technology of China,Hefei 230026,China [3]National Synchrotron Radiation Laboratory,University of Science and Technology of China,Hefei 230029,China

出　　处：《National Science Review》2024年第10期257-265,共9页国家科学评论（英文版）

基　　金：supported by the National Key Research and Development Program of China(2021YFA1500402);the National Natural Science Foundation of China(22331009 and U22A20401);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450302 and XDB0540000);the Fundamental Research Funds for the Central Universities(WK2060000038).

摘　　要：Whi le atomical ly precise metal nanoclusters(NCs)with unique structures and reactivity are very promising in catalysis,the spatial resistance caused by the surface ligands and structural instability poses significant challenges.In this work,Au_(25)(Cys)_(18)NCs are encapsulated in multivariate metal-organic frameworks(MOFs)to afford Au_(25)@M-MOF-74(M=Zn,Ni,Co,Mg).By the MOF confinement,the Au_(25)NCs showcase highly enhanced activity and stability in the intramolecular cascade reaction of 2-nitrobenzonitrile.Notably,the interaction between the metal nodes in M-MOF-74 and Au_(25)(Cys)_(18)is able to suppress the free vibration of the surface ligands on the Au_(25)NCs and thereby improve the accessibility of Au sites;meanwhile,the stronger interactions lead to higher electron density and core expansion within Au_(25)(Cys)_(18).As a result,the activity exhibits the trend of Au_(25)@Ni-MOF-74>Au_(25)@Co-MOF-74>Au_(25)@Zn-MOF-74>Au_(25)@Mg-MOF-74,highlighting the crucial roles of microenvironment modulation around the Au_(25)NCs by interaction between the surface ligands and MOF hosts.

关 键 词：metal nanoclusters metal-organic frameworks heterogeneous catalysis microenvironment modulation 

分 类 号：TB383[一般工业技术—材料科学与工程]