Emerging Cu-MOFs Catalyst Architectures for Selective Electrochemical CO2 Reduction to C1 Products

Electrochemical CO2 reduction reactions (CO2RR) offer a viable approach to mitigating anthropogenic CO2 while simultaneously generating value-added chemicals. Among diverse electrocatalyst classes, metal–organic framework (MOF)-based materials have been extensively explored owing to their excellent tunability of chemical structure, high surface area, and the ability to tailor the coordination/electronic environment of active centers. This state-of-the-art review provides a critical assessment of recent progress in the development of pristine Cu-based MOFs, Cu MOF-derived catalysts, and hybrid Cu@MOFs for the selective production of C1 products such as CO, CH4, and formate/formic acid. Theoretical investigations into the roles of the copper center, ligands, pore structures, and interfacial effects reveal that product selectivity is influenced by more than just the oxidation state of Cu sites. Mixed-valence Cu+/Cu0 junctions, defect-rich surfaces, conductive frameworks, and coordination site tuning constitute fundamental design strategies for steering CO2 reduction pathways. In addition to electrocatalytic performance, this review emphasizes the importance of life cycle assessment (LCA). Current studies identify electricity demand, separation steps, and operational lifetime as the dominant environmental impact factors in LCA analyses. Combining molecular-level catalyst design with systems-level sustainability considerations, this review highlights key challenges and future prospects for advancing Cu-MOF electrocatalysts toward efficient and sustainable C1 formation from CO2.