Stronger-than-Pt hydrogen adsorption in a Au22 nanocluster for the hydrogen evolution reaction

Hu, Guoxiang; Wu, Zili; Jiang, De-en

doi:10.1039/C8TA00461G

Title: Stronger-than-Pt hydrogen adsorption in a Au₂₂ nanocluster for the hydrogen evolution reaction

Journal Article · Mon Mar 19 00:00:00 EDT 2018 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/C8TA00461G· OSTI ID:1468196

Hu, Guoxiang ^[1];

^[2];

^[1]

Univ. of California, Riverside, CA (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences

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 (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 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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1468196

Alternate ID(s):: OSTI ID: 1434104

Journal Information:: Journal of Materials Chemistry. A, Vol. 6, Issue 17; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 55 works

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Title: Stronger-than-Pt hydrogen adsorption in a Au₂₂ nanocluster for the hydrogen evolution reaction