Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)
Abstract
Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C1 pathway proceeds through COH to CHOH to form CH4 while C2 (C3) pathways are kinetically blocked; (2) at neutral pH, the C1 and C2 (C3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.
- Authors:
-
- Materials and Process Simulation Center (MSC) and Joint Center for Artificial Photosynthesis (JCAP), California Institute of Technology, Pasadena, California 91125, United States
- Publication Date:
- Research Org.:
- California Institute of Technology (CalTech), Pasadena, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1328819
- Alternate Identifier(s):
- OSTI ID: 1436113
- Grant/Contract Number:
- SC0004993
- 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: 2; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Xiao, Hai, Cheng, Tao, Goddard, III, William A., and Sundararaman, Ravishankar. Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111). United States: N. p., 2016.
Web. doi:10.1021/jacs.5b11390.
Xiao, Hai, Cheng, Tao, Goddard, III, William A., & Sundararaman, Ravishankar. Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111). United States. https://doi.org/10.1021/jacs.5b11390
Xiao, Hai, Cheng, Tao, Goddard, III, William A., and Sundararaman, Ravishankar. Mon .
"Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)". United States. https://doi.org/10.1021/jacs.5b11390.
@article{osti_1328819,
title = {Mechanistic Explanation of the pH Dependence and Onset Potentials for Hydrocarbon Products from Electrochemical Reduction of CO on Cu (111)},
author = {Xiao, Hai and Cheng, Tao and Goddard, III, William A. and Sundararaman, Ravishankar},
abstractNote = {Energy and environmental concerns demand development of more efficient and selective electrodes for electrochemical reduction of CO2 to form fuels and chemicals. Since Cu is the only pure metal exhibiting reduction to form hydrocarbon chemicals, we focus here on the Cu (111) electrode. We present a methodology for density functional theory calculations to obtain accurate onset electrochemical potentials with explicit constant electrochemical potential and pH effects using implicit solvation. We predict the atomistic mechanisms underlying electrochemical reduction of CO, finding that (1) at acidic pH, the C1 pathway proceeds through COH to CHOH to form CH4 while C2 (C3) pathways are kinetically blocked; (2) at neutral pH, the C1 and C2 (C3) pathways share the COH common intermediate, where the branch to C-C coupling is realized by a novel CO-COH pathway; and (3) at high pH, early C-C coupling through adsorbed CO dimerization dominates, suppressing the C1 pathways by kinetics, thereby boosting selectivity for multi-carbon products.},
doi = {10.1021/jacs.5b11390},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 138,
place = {United States},
year = {Mon Jan 04 00:00:00 EST 2016},
month = {Mon Jan 04 00:00:00 EST 2016}
}
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