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Proc Natl Acad Sci U S A. 2018 Oct 16;115(42):10588-10593. doi: 10.1073/pnas.1805711115. Epub 2018 Oct 1.

Unique size-dependent nanocatalysis revealed at the single atomically precise gold cluster level.

Zhang Y1,2, Song P1,2, Chen T3, Liu X1,2,4, Chen T1,2,4, Wu Z5,6, Wang Y5,6, Xie J7, Xu W8,2.

Author information

1
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
2
Jilin Province Key Laboratory of Low Carbon Chemical Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
3
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585.
4
University of Chinese Academy of Sciences, Beijing 100049, China.
5
Center of Electron Microscopy, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China.
6
State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China.
7
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585; chexiej@nus.edu.sg weilinxu@ciac.ac.cn.
8
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China; chexiej@nus.edu.sg weilinxu@ciac.ac.cn.

Abstract

Atomically precise metal clusters have attracted increasing interest owing to their unique size-dependent properties; however, little has been known about the effect of size on the catalytic properties of metal clusters at the single-cluster level. Here, by real-time monitoring with single-molecule fluorescence microscopy the size-dependent catalytic process of individual Au clusters at single-turnover resolution, we study the size-dependent catalytic behaviors of gold (Au) clusters at the single-cluster level, and then observe the strong size effect on the catalytic properties of individual Au clusters, in both catalytic product formation and dissociation processes. Surprisingly, indicated by both experiments and density functional theory (DFT) calculations, due to such a unique size effect, besides observing the different product dissociation behaviors on different-sized Au clusters, we also observe that small Au clusters [i.e., Au15(MPA)13; here, MPA denotes 3-mercaptopropionic acid] catalyze the product formation through a competitive Langmuir-Hinshelwood mechanism, while those relatively larger Au clusters [e.g., Au18(MPA)14 and Au25(MPA)18] or nanoparticles catalyze the same process through a noncompetitive Langmuir-Hinshelwood mechanism. Such a size effect on the nanocatalysis could be attributed intrinsically to the size-dependent electronic structure of Au clusters. Further analysis of dynamic activity fluctuation of Au clusters reveals more different catalytic properties between Au clusters and traditional Au nanoparticles due to their different size-dependent structures.

KEYWORDS:

gold clusters; quantum effect; single-molecule fluorescence microscopy; single-molecule nanocatalysis; size dependence

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