Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO2 in Electrochemical CO2 Reduction

Hashiba, Hiroshi; Weng, Lien-Chun; Chen, Yikai; Sato, Hiroki K.; Yotsuhashi, Satoshi; Xiang, Chengxiang; Weber, Adam Z.

doi:10.1021/acs.jpcc.7b11316

Title: Effects of Electrolyte Buffer Capacity on Surface Reactant Species and the Reaction Rate of CO₂ in Electrochemical CO₂ Reduction

Journal Article · Fri Feb 09 00:00:00 EST 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b11316· OSTI ID:1476629

Hashiba, Hiroshi ^[1]; Weng, Lien-Chun ^[2]; Chen, Yikai ^[3]; Sato, Hiroki K. ^[1]; Yotsuhashi, Satoshi ^[1]; Xiang, Chengxiang ^[3];

^[4]

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

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1476629

Journal Information:: Journal of Physical Chemistry. C, Vol. 122, Issue 7; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 63 works

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