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Selective Enhancement of Methane Formation in Electrochemical CO₂ Reduction Enabled by a Raman-Inactive Oxygen-Containing Species on Cu

He, Ming and Chang, Xiaoxia and Chao, Tzu-Hsuan and Li, Chunsong and Goddard, William A., III and Cheng, Mu-Jeng and Xu, Bingjun and Lu, Qi (2022) Selective Enhancement of Methane Formation in Electrochemical CO₂ Reduction Enabled by a Raman-Inactive Oxygen-Containing Species on Cu. ACS Catalysis, 12 (10). pp. 6036-6046. ISSN 2155-5435. doi:10.1021/acscatal.2c00087.

[img] PDF (CO₂ electrolysis results; LSV curves of co-electrolysis; AFM images of the Cu electrode; SER spectra; TEM images of Au@SiO₂ NPs; MD simulation results; and structures for DFT calculation) - Supplemental Material
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The role of oxygen-containing species on Cu catalysts in the electrochemical CO₂ reduction reaction (CO₂RR) remains unclear due to the difficulty in its stabilization under reaction conditions. Co-electrolysis of CO₂ with an oxidant is an effective strategy to introduce oxygen-containing species on Cu during the CO₂RR. In this work, we present concrete evidence demonstrating that an oxygen-containing species is able to not only enhance the rate of the CO₂RR but also tune selectivities for certain products. Co-electrolysis of CO₂ with H₂O₂ on Cu selectively accelerates the CH4 production rate by up to a factor of 200, but with only a slight enhancement of C₂₊ products. Combined investigations using in situ Raman spectroscopy with density functional theory calculations reveal that a Raman-inactive Cu oxide species is responsible for the improved CH₄ production. Results reported in this work highlight the possibility of enhancing Cu-based CO₂RR catalysts by introducing stable oxygen-containing catalytic structures.

Item Type:Article
Related URLs:
URLURL TypeDescription
He, Ming0000-0001-5392-503X
Chang, Xiaoxia0000-0001-6598-6083
Li, Chunsong0000-0002-8016-1896
Goddard, William A., III0000-0003-0097-5716
Cheng, Mu-Jeng0000-0002-8121-0485
Xu, Bingjun0000-0002-2303-257X
Lu, Qi0000-0002-0380-2629
Additional Information:© 2022 American Chemical Society. Received 6 January 2022. Revised 23 March 2022. Published online 6 May 2022. Published in issue 20 May 2022. This work is supported by the National Key Research and Development Program of China (grant number 2017YFA0208200) and the National Natural Science Foundation of China (grant number 21872079). X.C. and B.X. acknowledge the support of Beijing National Laboratory for Molecular Sciences, as well as the National Science Foundation CAREER Program (Award No. CBET-1651625). W.A.G. thanks the Department of Energy (DE-SC0021266) for support. All NMR experiments were performed at the BioNMR facility, Tsinghua University Branch of China National Center for Protein Sciences (Beijing). The authors thank Dr. Ning Xu for assistance in NMR data collection. The authors thank Zenan Wang for assistance in AFM measurement. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Key Research and Development Program of China2017YFA0208200
National Natural Science Foundation of China21872079
Department of Energy (DOE)DE-SC0021266
Subject Keywords:CO₂ electroreduction; oxygen-containing species; co-electrolysis; CH₄ formation; in situ SERS; DFT calculation
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Issue or Number:10
Record Number:CaltechAUTHORS:20220520-388227000
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Official Citation:Selective Enhancement of Methane Formation in Electrochemical CO2 Reduction Enabled by a Raman-Inactive Oxygen-Containing Species on Cu Ming He, Xiaoxia Chang, Tzu-Hsuan Chao, Chunsong Li, William A. Goddard, Mu-Jeng Cheng, Bingjun Xu, and Qi Lu ACS Catalysis 2022 12 (10), 6036-6046 DOI: 10.1021/acscatal.2c00087
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114837
Deposited By: George Porter
Deposited On:20 May 2022 23:02
Last Modified:14 Aug 2022 23:49

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