Metal‐Organic Frameworks‐Based Copper Catalysts for CO2 Electroreduction Toward Multicarbon Products

Copper (Cu) is the most promising catalyst for electrochemical CO₂-to-C₂₊ conversion, whereas performance remains below practical thresholds due to the high energy barrier of C-C coupling and lack of effective approaches to steer the reaction pathway. Recent advances show that metal-organic frameworks (MOF) could be a promising platform as support, pre-catalyst, and co-catalyst to modify the electronic structure and local reaction environment of Cu catalysts for promoting CO₂-to-C₂₊ reduction by virtue of their great tunability over compositions and pore architectures. In this review, we discussed general design principles, catalytic mechanisms, and performance achievements of MOF-based Cu catalysts, aiming to boost catalyst refinement for steering CO₂ reduction pathway to C₂₊ products. The fundamentals and challenges of CO₂-to-C₂₊ reduction are first introduced. Then, we summarized design conceptions of MOF-based Cu catalysts from three aspects: engineering the electronic properties of Cu, regulating the local reaction environment, and managing site exposure and mass transport. Further, the latest progress of CO₂ reduction to C₂₊ products over MOF-based Cu catalysts, namely Cu-based MOF, MOF-derived Cu, and Cu@MOF hybrid catalysts, are discussed. Finally, future research opportunities and strategies are suggested to innovate the rational design of advanced MOF-based Cu catalysts for electrifying CO₂-to-C₂₊ transformation.