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Title: Stronger-than-Pt hydrogen adsorption in a Au 22 nanocluster for the hydrogen evolution reaction

Abstract

Atomically precise metal nanoclusters have recently emerged as a novel class of catalysts for the hydrogen evolution reaction. From first-principles density functional theory, we show in this paper that the eight coordinatively unsaturated (cus) Au atoms in the Au 22(L 8) 6 cluster [L 8 = 1,8-bis(diphenylphosphino) octane] can adsorb H stronger than Pt, thereby being a potentially promising catalyst for the hydrogen evolution reaction (HER). We find that up to six H atoms can adsorb onto the Au 22(L 8) 6 cluster and they have close-to-zero Gibbs free adsorption energies (ΔG H). From the HOMO–LUMO gaps, frontier orbitals, and Bader charge analysis, we conclude that H behaves as a hydride or electron-withdrawing ligand in the Au 22(L 8) 6 clusters, in contrast to the metallic H in thiolate-protected Au nanoclusters. Finally, our study demonstrates that ligand-protected Au clusters with cus Au sites will be the most promising candidates for realizing Au–H nanoclusters and can act as excellent electrocatalysts for the HER.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468196
Alternate Identifier(s):
OSTI ID: 1434104
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 17; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hu, Guoxiang, Wu, Zili, and Jiang, De-en. Stronger-than-Pt hydrogen adsorption in a Au22 nanocluster for the hydrogen evolution reaction. United States: N. p., 2018. Web. doi:10.1039/C8TA00461G.
Hu, Guoxiang, Wu, Zili, & Jiang, De-en. Stronger-than-Pt hydrogen adsorption in a Au22 nanocluster for the hydrogen evolution reaction. United States. doi:10.1039/C8TA00461G.
Hu, Guoxiang, Wu, Zili, and Jiang, De-en. Mon . "Stronger-than-Pt hydrogen adsorption in a Au22 nanocluster for the hydrogen evolution reaction". United States. doi:10.1039/C8TA00461G. https://www.osti.gov/servlets/purl/1468196.
@article{osti_1468196,
title = {Stronger-than-Pt hydrogen adsorption in a Au22 nanocluster for the hydrogen evolution reaction},
author = {Hu, Guoxiang and Wu, Zili and Jiang, De-en},
abstractNote = {Atomically precise metal nanoclusters have recently emerged as a novel class of catalysts for the hydrogen evolution reaction. From first-principles density functional theory, we show in this paper that the eight coordinatively unsaturated (cus) Au atoms in the Au22(L8)6 cluster [L8 = 1,8-bis(diphenylphosphino) octane] can adsorb H stronger than Pt, thereby being a potentially promising catalyst for the hydrogen evolution reaction (HER). We find that up to six H atoms can adsorb onto the Au22(L8)6 cluster and they have close-to-zero Gibbs free adsorption energies (ΔGH). From the HOMO–LUMO gaps, frontier orbitals, and Bader charge analysis, we conclude that H behaves as a hydride or electron-withdrawing ligand in the Au22(L8)6 clusters, in contrast to the metallic H in thiolate-protected Au nanoclusters. Finally, our study demonstrates that ligand-protected Au clusters with cus Au sites will be the most promising candidates for realizing Au–H nanoclusters and can act as excellent electrocatalysts for the HER.},
doi = {10.1039/C8TA00461G},
journal = {Journal of Materials Chemistry. A},
number = 17,
volume = 6,
place = {United States},
year = {2018},
month = {3}
}

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