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

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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
    Department of Chemical and Biomolecular Engineering National University of)

  • 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)

  • De-en Jiang

    (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
    Department of Chemical and Biomolecular Engineering National University of)

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.

Suggested Citation

  • Zhihe Liu & Hua Tan & Bo Li & Zehua Hu & De-en Jiang & Qiaofeng Yao & Lei Wang & Jianping Xie, 2023. "Ligand effect on switching the rate-determining step of water oxidation in atomically precise metal nanoclusters," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-38914-7
    DOI: 10.1038/s41467-023-38914-7
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    References listed on IDEAS

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