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Emerging roles of cations in electrocatalytic reduction of CO2 and CO

Nature Energy volume 11, pages 387–399 (2026)Cite this article

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Abstract

The electrochemical CO2 and CO reduction reactions (CO(2)RR) represent a promising strategy for enabling a circular carbon economy. Cations have been shown to have a substantial impact on catalytic activity and selectivity in CO(2)RR; however, the mechanisms in play remain debated. In this Review we explore the multifaceted roles of cations in CO(2)RR, categorizing their effects based on the degree of involvement at the molecular level: as indirect mediators, energetic modulators and participants in electron-transfer processes. At each level, we critically evaluate the key mechanistic hypotheses, supporting evidence and existing contradictions of cation effects. Furthermore, we highlight critical knowledge gaps and potential future research directions, in particular regarding cation effects on specific elementary steps in reaction pathways and catalyst-dependent behaviours, to advance our understanding of the interfacial chemistry and to enable the rational design and optimization of CO(2)RR.

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Fig. 1: Proposed roles of cations in electrocatalysis grouped by the degree of involvement in reactions.
Fig. 2: Cations as indirect modulators in the microenvironment.
Fig. 3: Cations as energetic regulators of the RDS.
Fig. 4: Cations as participants in elementary reactions with electron transfers.

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (grant number: 22532002), the Beijing Natural Science Foundation Key Research Program (grant number: Z240026) and the Beijing National Laboratory for Molecular Sciences. We acknowledge the support of the Innovation Centre for Chemical Engineering at Peking University.

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  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Yifei Xu, Kaiyue Zhao, Xiaoxia Chang & Bingjun Xu

  2. Beijing National Laboratory for Molecular Sciences, Beijing, China

    Yifei Xu, Kaiyue Zhao, Xiaoxia Chang & Bingjun Xu

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Y.X. and B.X. conceived the work and wrote the initial draft. Y.X., K.Z., X.C. and B.X. contributed to the editing of the manuscript.

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Correspondence to Bingjun Xu.

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Xu, Y., Zhao, K., Chang, X. et al. Emerging roles of cations in electrocatalytic reduction of CO2 and CO. Nat Energy 11, 387–399 (2026). https://doi.org/10.1038/s41560-026-01973-3

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