Progress and Perspectives for Efficient Electrochemical Carbon Dioxide Reduction to Methane

The electrochemical carbon dioxide reduction reaction (ECO2RR) provides a promising route for synthesizing high‐value chemicals and fuels for sustainable economies development. Methane, one of the potential reduction products of ECO2RR, plays a crucial role in chemical production and energy storage. Recent advancements in ECO2RR have led to significant progress in methane production. However, existing research findings remain substantially distant from practical industrial applications. In this paper, we systematically review the recent research progress in ECO2RR for methane production. First, we elaborate on the theoretical foundations of ECO2RR and the key reaction mechanisms involved in methane production. Then summarize catalyst design strategies aimed at enhancing methane selectivity and activity, including (1) fine‐tuning of crystal surface, morphology, and size; (2) defects engineering; and (3) tandem catalysis. In addition, the role of modulating microenvironment is reviewed, focusing on the effects of pH, ionic effects, and CO2 concentration. Finally, some insights for the industrial application of ECO2RR to methane are presented in the light of existing studies and practical needs.