Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO2 in Electrochemical CO2 Reduction
Abstract
In the aqueous electrochemical reduction of CO2, the choice of electrolyte is responsible for the catalytic activity and selectivity, although there remains a need for more in-depth understanding of electrolyte effects and mechanisms. In this study, using both experimental and simulation approaches, we report how the buffer capacity of the electrolytes affects the kinetics and equilibrium of surface reactant species and the resulting reaction rate of CO2 with varying partial CO2 pressure. Electrolytes investigated include KCl (nonbuffered), KHCO3 (buffered by bicarbonate), and phosphate-buffered electrolytes. Assuming 100% methane production, the simulation successfully explains the experimental trends in maximum CO2 flux in KCl and KHCO3 and also highlights the difference between KHCO3 and phosphate in terms of pKaas well as the impact of the buffer capacity. To examine the electrolyte impact on selectivity, the model is run with a constant total current density. Using this model, several factors are elucidated, including the importance of local pH, which is not in acid/base equilibrium, the impact of buffer identity and kinetics, and the mass-transport boundary-layer thickness. The gained understanding can help to optimize CO2 reduction in aqueous environments.
- Authors:
-
- Panasonic Corporation, Sōraku-gun, Kyoto (Japan). Advanced Research Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
- California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1476629
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 7; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Hashiba, Hiroshi, Weng, Lien-Chun, Chen, Yikai, Sato, Hiroki K., Yotsuhashi, Satoshi, Xiang, Chengxiang, and Weber, Adam Z. Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO2 in Electrochemical CO2 Reduction. United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.7b11316.
Hashiba, Hiroshi, Weng, Lien-Chun, Chen, Yikai, Sato, Hiroki K., Yotsuhashi, Satoshi, Xiang, Chengxiang, & Weber, Adam Z. Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO2 in Electrochemical CO2 Reduction. United States. https://doi.org/10.1021/acs.jpcc.7b11316
Hashiba, Hiroshi, Weng, Lien-Chun, Chen, Yikai, Sato, Hiroki K., Yotsuhashi, Satoshi, Xiang, Chengxiang, and Weber, Adam Z. Fri .
"Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO2 in Electrochemical CO2 Reduction". United States. https://doi.org/10.1021/acs.jpcc.7b11316. https://www.osti.gov/servlets/purl/1476629.
@article{osti_1476629,
title = {Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO2 in Electrochemical CO2 Reduction},
author = {Hashiba, Hiroshi and Weng, Lien-Chun and Chen, Yikai and Sato, Hiroki K. and Yotsuhashi, Satoshi and Xiang, Chengxiang and Weber, Adam Z.},
abstractNote = {In the aqueous electrochemical reduction of CO2, the choice of electrolyte is responsible for the catalytic activity and selectivity, although there remains a need for more in-depth understanding of electrolyte effects and mechanisms. In this study, using both experimental and simulation approaches, we report how the buffer capacity of the electrolytes affects the kinetics and equilibrium of surface reactant species and the resulting reaction rate of CO2 with varying partial CO2 pressure. Electrolytes investigated include KCl (nonbuffered), KHCO3 (buffered by bicarbonate), and phosphate-buffered electrolytes. Assuming 100% methane production, the simulation successfully explains the experimental trends in maximum CO2 flux in KCl and KHCO3 and also highlights the difference between KHCO3 and phosphate in terms of pKaas well as the impact of the buffer capacity. To examine the electrolyte impact on selectivity, the model is run with a constant total current density. Using this model, several factors are elucidated, including the importance of local pH, which is not in acid/base equilibrium, the impact of buffer identity and kinetics, and the mass-transport boundary-layer thickness. The gained understanding can help to optimize CO2 reduction in aqueous environments.},
doi = {10.1021/acs.jpcc.7b11316},
journal = {Journal of Physical Chemistry. C},
number = 7,
volume = 122,
place = {United States},
year = {Fri Feb 09 00:00:00 EST 2018},
month = {Fri Feb 09 00:00:00 EST 2018}
}
Web of Science
Figures / Tables:
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