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<p>The electrochemical CO<sub>2</sub> and CO reduction reactions (CO<sub>(2)</sub>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<sub>(2)</sub>RR; however, the mechanisms in play remain debated. In this Review we explore the multifaceted roles of cations in CO<sub>(2)</sub>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<sub>(2)</sub>RR.</p>

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Emerging roles of cations in electrocatalytic reduction of CO2 and CO

  • 期刊论文

  • 发表日期：

    2026年2月27日

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  • Yifei Xu,
  • Kaiyue Zhao,
  • Xiaoxia Chang,
  • Bingjun Xu

摘要

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.