Ligand effect on switching the rate-determining step of water oxidation in atomically precise metal nanoclusters

Zhihe Liu, Hua Tan, Bo Li, Zehua Hu, Jiang De-en, Qiaofeng Yao (), Lei Wang () and Jianping Xie ()
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Zhihe Liu: Joint School of National University of Singapore and Tianjin University International Campus of Tianjin University Binhai New City Fuzhou
Hua Tan: School of Physical and Mathematical Sciences Nanyang Technological University
Bo Li: Vanderbilt University
Zehua Hu: School of Physical and Mathematical Sciences Nanyang Technological University
Jiang De-en: Vanderbilt University
Qiaofeng Yao: Joint School of National University of Singapore and Tianjin University International Campus of Tianjin University Binhai New City Fuzhou
Lei Wang: Department of Chemical and Biomolecular Engineering National University of
Jianping Xie: Joint School of National University of Singapore and Tianjin University International Campus of Tianjin University Binhai New City Fuzhou

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract The ligand effects of atomically precise metal nanoclusters on electrocatalysis kinetics have been rarely revealed. Herein, we employ atomically precise Au25 nanoclusters with different ligands (i.e., para-mercaptobenzoic acid, 6-mercaptohexanoic acid, and homocysteine) as paradigm electrocatalysts to demonstrate oxygen evolution reaction rate-determining step switching through ligand engineering. Au25 nanoclusters capped by para-mercaptobenzoic acid exhibit a better performance with nearly 4 times higher than that of Au25 NCs capped by other two ligands. We deduce that para-mercaptobenzoic acid with a stronger electron-withdrawing ability establishes more partial positive charges on Au(I) (i.e., active sites) for facilitating feasible adsorption of OH– in alkaline media. X-ray photo-electron spectroscopy and theoretical study indicate a profound electron transfer from Au(I) to para-mercaptobenzoic acid. The Tafel slope and in situ Raman spectroscopy suggest different ligands trigger different rate-determining step for these Au25 nanoclusters. The mechanistic insights reported here can add to the acceptance of atomically precise metal nanoclusters as effective electrocatalysts.

Date: 2023
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DOI: 10.1038/s41467-023-38914-7

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