Hydronium-Induced Switching between CO2 Electroreduction Pathways
Abstract
Over a broad range of operating conditions, many CO2 electroreduction catalysts can maintain selectivity toward certain reduction products, leading to materials and surfaces being categorized according to their products; here we ask, is product selectivity truly a property of the catalyst? Silver is among the best electrocatalysts for CO in aqueous electrolytes, where it reaches near-unity selectivity. We consider the hydrogenations of the oxygen and carbon atoms via the two proton-coupled-electron-transfer processes as chief determinants of product selectivity; and find using density functional theory (DFT) that the hydronium (H3O+) intermediate plays a key role in the first oxygen hydrogenation step and lowers the activation energy barrier for CO formation. When this hydronium influence is removed, the activation energy barrier for oxygen hydrogenation increases significantly, and the barrier for carbon hydrogenation is reduced. These effects make the formate reaction pathway more favorable than CO. Experimentally, we then carry out CO2 reduction in highly concentrated potassium hydroxide (KOH), limiting the hydronium concentration in the aqueous electrolyte. The product selectivity of a silver catalyst switches from entirely CO under neutral conditions to over 50% formate in the alkaline environment. The simulated and experimentally observed selectivity shift provides new insights into the role of hydronium on CO2 electroreduction processes and the ability for electrolyte manipulation to directly influence transition state (TS) kinetics, altering favored CO2 reaction pathways. We argue that selectivity should be considered less of an intrinsic catalyst property, and rather a combined product of the catalyst and reaction environment.
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As pH is increased, the selectivity of CO decreases in favor of formate formation on Ag catalysts.
“however, as the pH is increased, the selectivity of CO decreases in favor of formate formation. [47,131]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [47]
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- Authors
- Seifitokaldani, A., Gabardo, C. M., Burdyny, T., Dinh, C.-T., Edwards, J. P., Kibria, M. G., Bushuyev, O. S., Kelley, S. O., Sinton, D., & Sargent, E. H.
- Affiliations
- University of Toronto (CA)
- Corresponding author
- Sargent, Edward H.
- ORCID
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2018-03-05
- Volume
- 140
- Issue
- 11
- Pages
- 3833-3837
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2790006205
- Cited by
- 179
- References
- 34
- Citations by year
- 2026: 11 · 2025: 12 · 2024: 20 · 2023: 24 · 2022: 19 · 2021: 25 · 2020: 32 · 2019: 23 · 2018: 13
- FWCI
- 5.36
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Government of Canada
- Fonds de Recherche du Qu?bec - Nature et Technologies
- Natural Sciences and Engineering Research Council of Canada
- Ontario Research Fund
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Keywords
- electrochemical CO2 reduction, hydronium ion, product selectivity, silver electrocatalyst, formate formation, CO formation, activation barrier, KOH electrolyte, alkaline water electrolysis, proton-coupled electron transfer
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