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Small alkali cations direct CO electroreduction to hydrocarbons rather than oxygenates

Nature Chemistry volume 18, pages 774–781 (2026) Cite this article

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Abstract

Electrochemical CO reduction has the potential to enable low-carbon-intensity chemicals and fuels, but the reaction yields a mixture of multi-carbon products, and the underlying selectivity-driving mechanisms are unclear. Here we explore trends in alkali cations and find, in contradistinction to carbon dioxide electroreduction, that lithium promotes ethylene production. We study the electrolyte–catalyst interface using operando Raman spectroscopy and simulations and find that hydrated Li+ on the electrode surface has the greatest hydrogen bonding and the least cation–dipole interaction with the oxygen site on intermediates. These interactions suppress hydrogenation on carbon and promote the competing hydrodeoxygenation reaction that leads to hydrocarbons. We leverage this understanding and reduce the oxygen affinity of copper via antimony doping, suppressing the formation of the O-tethered CHCHO* intermediate on the surface that would otherwise lead to oxygenates. Combining these strategies, we achieve an ethylene faradaic efficiency of 79% at 150 mA cm−2 and an energy efficiency of 39% in a membrane electrode assembly electrolyser.

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Fig. 1: Influence of cations on activity versus selectivity in C2+ electroproduction in a flow cell.
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Fig. 2: Raman spectra and MD simulations of the distribution of H2O and cations at the electrode–electrolyte interface.
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Fig. 3: DFT studies of the cation effect on COR product selectivity.
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Fig. 4: Optimization of catalyst and system for COR to C2H4.
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All data are available in the main text or the Supplementary Information. Correspondence and requests for materials should be addressed to the corresponding authors. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the Ontario Research Fund – Research Excellence program, the Natural Sciences and Engineering Research Council of Canada and TotalEnergies SE. All MD and DFT computations were carried out at the Shenzhen Bay Laboratory Supercomputing Center. W.N. gratefully acknowledges the financial support from the Swiss National Science Foundation (Postdoc.Mobility fellowship no. 202906). G.C.S. was supported by US Department of Energy grant no. DE-SC0004752. We thank Q. Xiao, M. Shakouri and A. Paterson at the SXRMB beamline of the Canadian Light Source, and D. Meira and Y. Chen at beamline 20-BM of the Advanced Photon Source for technical assistance in XAS measurements.

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Author notes

  1. Weiyan Ni

    Present address: Department of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, China

  2. These authors contributed equally: Weiyan Ni, Yongxiang Liang, Yufei Cao, Zhu Chen.

Authors and Affiliations

  1. The Edward S. Rogers Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Weiyan Ni, Yongxiang Liang, Yufei Cao, Zhu Chen, Yanjiang Liu, Xiao Wang, Dongha Kim, Sungjin Park, Muhammad Imran, Pengfei Ou, Xiao-Yan Li, Ke Xie, Roham Dorakhan, Erfan Shirzadi & Edward H. Sargent

  2. Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, P.R. China

    Yongxiang Liang & Jie Zeng

  3. Lab of Applied Biocatalysis, School of Food Science and Engineering, South China University of Technology, Guangzhou, China

    Yufei Cao

  4. Key Lab for Industrial Biocatalysis, Ministry of Education, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Yufei Cao & Jun Ge

  5. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    Rui Kai Miao, Panos Papangelakis, Qiyou Wang & David Sinton

  6. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Bosi Peng, Zeyan Liu, Huajie Ze, Jiaqi Yu & George C. Schatz

  7. Interdisciplinary Center for Electron Microscopy, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Victor Boureau

  8. Institute of Biomedical Health Technology and Engineering, Shenzhen Bay Laboratory, Shenzhen, China

    Jun Ge

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Contributions

E.H.S. and J.G. supervised this project. W.N. conceived the idea of this project. W.N. and Y. Liang carried out the electrochemical measurements with the help of R.K.M., X.W., Z.C. and Q.W.; Y.C. performed the MD and DFT calculations. W.N. designed and synthesized the Cu–Sb catalyst. W.N., Z.C. and H.Z. performed the Raman experiments. B.P., Z.L., V.B. and M.I. carried out the electron microscopy characterization. Y. Liu performed the X-ray diffraction and XPS measurements. D.K., S.P., W.N., Y. Liu, Jiaqi Yu, P.P., R.D. and E.S. conducted the XAS measurements. P.O., X.-Y.L., K.X., D.S. and G.C.S. contributed to the data analysis. W.N. and E.H.S. co-wrote the manuscript with input from all the co-authors. All authors contributed to the discussion of the results and the final manuscript preparation.

Corresponding authors

Correspondence to Jun Ge or Edward H. Sargent.

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Competing interests

E.H.S., W.N., Y. Liang and Z.C. have submitted a US provisional patent application titled ‘Techniques for favoring CO electroreduction (COR) into ethylene’.

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Nature Chemistry thanks Ludmilla Steier and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Ni, W., Liang, Y., Cao, Y. et al. Small alkali cations direct CO electroreduction to hydrocarbons rather than oxygenates. Nat. Chem. 18, 774–781 (2026). https://doi.org/10.1038/s41557-025-02061-x

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