skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on January 8, 2020

Title: Electrochemical CO Reduction: A Property of the Electrochemical Interface

Abstract

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.

Authors:
 [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [1]
  1. Univ. of Copenhagen, Copenhagen (Denmark)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Univ. of Duisburg-Essen, Essen (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1503404
Grant/Contract Number:  
AC02-76SF00515; CF15-0165; 5124-00003A
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 4; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bagger, Alexander, Arnarson, Logi, Hansen, Martin H., Spohr, Eckhard, and Rossmeisl, Jan. Electrochemical CO Reduction: A Property of the Electrochemical Interface. United States: N. p., 2019. Web. doi:10.1021/jacs.8b08839.
Bagger, Alexander, Arnarson, Logi, Hansen, Martin H., Spohr, Eckhard, & Rossmeisl, Jan. Electrochemical CO Reduction: A Property of the Electrochemical Interface. United States. doi:10.1021/jacs.8b08839.
Bagger, Alexander, Arnarson, Logi, Hansen, Martin H., Spohr, Eckhard, and Rossmeisl, Jan. Tue . "Electrochemical CO Reduction: A Property of the Electrochemical Interface". United States. doi:10.1021/jacs.8b08839.
@article{osti_1503404,
title = {Electrochemical CO Reduction: A Property of the Electrochemical Interface},
author = {Bagger, Alexander and Arnarson, Logi and Hansen, Martin H. and Spohr, Eckhard and Rossmeisl, Jan},
abstractNote = {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.},
doi = {10.1021/jacs.8b08839},
journal = {Journal of the American Chemical Society},
number = 4,
volume = 141,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on January 8, 2020
Publisher's Version of Record

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Structure‐Sensitivity and Electrolyte Effects in CO 2 Electroreduction: From Model Studies to Applications
journal, June 2019

  • Sebastián‐Pascual, Paula; Mezzavilla, Stefano; Stephens, Ifan E. L.
  • ChemCatChem, Vol. 11, Issue 16
  • DOI: 10.1002/cctc.201900552