Mechanistic Insights for Low-Overpotential Electroreduction of CO2 to CO on Copper Nanowires
Abstract
Recent developments of copper (Cu)-based nanomaterials have enabled the electroreduction of CO 2 at low overpotentials. The mechanism of low-overpotential CO 2 reduction on these nanocatalysts, however, largely remains elusive. We report here a systematic investigation of CO 2 reduction on highly dense Cu nanowires, with the focus placed on understanding the surface structure effects on the formation of *CO (* denotes an adsorption site on the catalyst surface) and the evolution of gas-phase CO product (CO(g)) at low overpotentials (more positive than −0.5 V). Cu nanowires of distinct nanocrystalline and surface structures are studied comparatively to build up the structure–property relationships, which are further interpreted by performing density functional theory (DFT) calculations of the reaction pathway on the various facets of Cu. A kinetic model reveals competition between CO(g) evolution and *CO poisoning depending on the electrode potential and surface structures. Open and metastable facets such as (110) and reconstructed (110) are found to be likely the active sites for the electroreduction of CO 2 to CO at the low overpotentials.
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Cavalca et al. determined that the stabilization of subsurface oxygen under the reaction conditions is possible due to the abundant defects present in the OD Cu electrodes.
“Moreover, Cavalca et al. determined that the stabilization of subsurface oxygen under the reaction conditions is possible due to the abundant defects present in the OD Cu electrodes.[108]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [108]
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- Authors
- Cao, L., Raciti, D., Li, C., Livi, K. J. T., Rottmann, P. F., Hemker, K. J., Mueller, T., & Wang, C.
- Affiliations
- Johns Hopkins University (US)
- Corresponding author
- Mueller, Tim
- Wang, Chao
- ORCID
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-11-17
- Volume
- 7
- Issue
- 12
- Pages
- 8578-8587
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2767984731
- Cited by
- 122
- References
- 49
- Citations by year
- 2026: 4 · 2025: 12 · 2024: 5 · 2023: 9 · 2022: 15 · 2021: 19 · 2020: 27 · 2019: 17 · 2018: 14
- FWCI
- 4.24
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Catalysis (publishedVersion)
- Funders
- Division of Chemistry (1437396)
- Basic Energy Sciences (DE-FG02-07ER46437)
- Johns Hopkins University
- 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 › Catalysis › Catalysts for Methane Reforming
- Keywords
- electrochemical CO2 reduction, CO2 to CO conversion, copper nanowires, low overpotential, reaction mechanism, CO adsorption, CO poisoning, surface structure effects, kinetic model, structure-property relationships, nanocrystalline catalysts
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