Electrochemical Carbon Dioxide Reduction to Methanol on Copper‐Based Catalysts: Mechanistic Insights and Industrial Prospects

Electrochemical CO₂ reduction (ECO₂R) offers a promising route to convert CO₂ into high-value-added chemicals using renewable energy. Among the diverse ECO₂R products, the selective conversion of CO₂ to methanol (CH₃OH) holds significant industrial importance as a fuel and chemical feedstock. This review provides a comprehensive overview of recent progress in Copper (Cu)-based catalysts for selective ECO₂R to CH₃OH. Key advancements in catalyst design and synthesis are discussed, followed by mechanistic insights obtained through computational modeling and advanced characterization techniques. Special focus is given to the structure-activity relationship that controls CH₃OH selectivity, disclosing the importance of intermediate stabilization and electronic structure tuning. Further, state-of-the-art Cu-based materials and benchmarking their performances under various operating conditions, including the role of electrolyzer configurations, electrolytes, and ion-exchange membranes, is summarized. Moreover, we analyze challenges in upscaling, such as stability, selectivity under high current densities, and integration with renewable energy sources. Besides, the potential of tandem and hybrid systems to improve reaction pathways is also emphasized. Finally, techno-economic considerations are explored to evaluate the feasibility of large-scale CH₃OH production. By combining fundamental understanding with practical implementation, this review provides strategic direction toward the rational design of Cu-based electrocatalysts and the development of commercially viable ECO₂R systems for sustainable CH₃OH synthesis.