Electrochemical CO Reduction: A Property of the Electrochemical Interface

Bagger, Alexander; Arnarson, Logi; Hansen, Martin H.; Spohr, Eckhard; Rossmeisl, Jan

doi:10.1021/jacs.8b08839

Electrochemical CO Reduction: A Property of the Electrochemical Interface

Journal Article · Tue Jan 08 00:00:00 EST 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b08839· OSTI ID:1503404

Bagger, Alexander ^[1]; Arnarson, Logi ^[1]; ^[2]; Spohr, Eckhard ^[3]; ^[1]

Univ. of Copenhagen, Copenhagen (Denmark)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Duisburg-Essen, Essen (Germany)

Electrochemical CO reduction holds the promise to be a cornerstone for sustainable production of fuels and chemicals. However, the underlying understanding of the carbon–carbon coupling toward multiple-carbon products is not complete. Here we present thermodynamically realistic structures of the electrochemical interfaces, determined by explicit ab initio simulations. We investigate how key CO reduction reaction intermediates are stabilized in different electrolytes and at different pH values. We find that the catalytic trends previously observed experimentally can be explained by the interplay between the metal surface and the electrolyte. For the Cu(100) facet with a phosphate buffer electrolyte, the energy efficiency is found to be limited by blocking of a phosphate anion, while in alkali hydroxide solutions (MOH, M = Na, K, Cs), OH* intermediates may be present, and at high overpotential the H* coverage limits the reaction. Furthermore the results provide insight into the electrochemical interface structure, revealing the limitations for multiple-carbon products, and offer a direct comparison to experiments.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1503404

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 141; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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