Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst
Abstract
Electrocatalytic activity of a water-soluble nickel complex, [Ni(DHMPE)2]2+ (DHMPE = 2-bis(di(hydroxymethyl)phosphino)ethane), for the hydrogen evolution reaction (HER) at pH 1 is reported. The catalyst functions at a rate of ~103 s-1 (kobs) with high Faradaic efficiency. Quantification of the complex before and after 18+ hours of electrolysis reveals negligible decomposition under catalytic conditions. Although highly acidic conditions are common in electrolytic cells, this is a rare example of a homogeneous catalyst for HER that functions with high stability at low pH. The stability of the compound and proposed catalytic intermediates enabled detailed mechanistic studies. The thermodynamic parameters governing electron and proton transfer were used to determine the appropriate reductants and acids to access the catalytic cycle in a stepwise fashion, permitting direct spectroscopic identification of intermediates. Finally, these studies support a mechanism for proton reduction that proceeds through two-electron reduction of the nickel(II) complex, protonation to generate [HNi(DHMPE)2]+, and further protonation to initiate hydrogen bond formation.
- Authors:
-
- Department of Chemistry, University of California, Irvine, California 92697, United States
- Publication Date:
- Research Org.:
- Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1415252
- Alternate Identifier(s):
- OSTI ID: 1474066
- Grant/Contract Number:
- SC0012150
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 43; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Tsay, Charlene, and Yang, Jenny Y. Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b05851.
Tsay, Charlene, & Yang, Jenny Y. Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst. United States. https://doi.org/10.1021/jacs.6b05851
Tsay, Charlene, and Yang, Jenny Y. Fri .
"Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst". United States. https://doi.org/10.1021/jacs.6b05851.
@article{osti_1415252,
title = {Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst},
author = {Tsay, Charlene and Yang, Jenny Y.},
abstractNote = {Electrocatalytic activity of a water-soluble nickel complex, [Ni(DHMPE)2]2+ (DHMPE = 2-bis(di(hydroxymethyl)phosphino)ethane), for the hydrogen evolution reaction (HER) at pH 1 is reported. The catalyst functions at a rate of ~103 s-1 (kobs) with high Faradaic efficiency. Quantification of the complex before and after 18+ hours of electrolysis reveals negligible decomposition under catalytic conditions. Although highly acidic conditions are common in electrolytic cells, this is a rare example of a homogeneous catalyst for HER that functions with high stability at low pH. The stability of the compound and proposed catalytic intermediates enabled detailed mechanistic studies. The thermodynamic parameters governing electron and proton transfer were used to determine the appropriate reductants and acids to access the catalytic cycle in a stepwise fashion, permitting direct spectroscopic identification of intermediates. Finally, these studies support a mechanism for proton reduction that proceeds through two-electron reduction of the nickel(II) complex, protonation to generate [HNi(DHMPE)2]+, and further protonation to initiate hydrogen bond formation.},
doi = {10.1021/jacs.6b05851},
journal = {Journal of the American Chemical Society},
number = 43,
volume = 138,
place = {United States},
year = {Fri Jul 22 00:00:00 EDT 2016},
month = {Fri Jul 22 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/jacs.6b05851
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Catalytic Activity of Thiolate-Bridged Diruthenium Complexes Bearing Pendent Ether Moieties in the Oxidation of Molecular Dihydrogen
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