Regulating interaction with surface ligands on Au25 nanoclusters by multivariate metal–organic framework hosts for boosting catalysis

Author:

Wang He12,Liu Xiaokang3,Zhao Yulong12,Sun Zhihu3,Lin Yue1,Yao Tao3,Jiang Hai-Long12ORCID

Affiliation:

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

Abstract

ABSTRACT While atomically 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, Au25(Cys)18 NCs are encapsulated in multivariate metal–organic frameworks (MOFs) to afford Au25@M-MOF-74 (M = Zn, Ni, Co, Mg). By the MOF confinement, the Au25 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 Au25(Cys)18 is able to suppress the free vibration of the surface ligands on the Au25 NCs and thereby improve the accessibility of Au sites; meanwhile, the stronger interactions lead to higher electron density and core expansion within Au25(Cys)18. As a result, the activity exhibits the trend of Au25@Ni-MOF-74 > Au25@Co-MOF-74 > Au25@Zn-MOF-74 > Au25@Mg-MOF-74, highlighting the crucial roles of microenvironment modulation around the Au25 NCs by interaction between the surface ligands and MOF hosts.

Funder

National Key Research and Development Program of China

National Natural Science Foundation of China

Chinese Academy of Sciences

Fundamental Research Funds for the Central Universities

Publisher

Oxford University Press (OUP)

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