Stronger-than-Pt hydrogen adsorption in a Au22 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 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.
- Authors:
-
[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
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of California, Riverside, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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. https://doi.org/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. https://doi.org/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 = {Mon Mar 19 00:00:00 EDT 2018},
month = {Mon Mar 19 00:00:00 EDT 2018}
}
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