Controlled One‐Step Synthesis of MOF‐on‐MOF Cocatalysts for Two‐Channel Electrocatalytic Conversion of CO₂ to Formic Acid

Abstract The synthesis of efficient and highly selective catalysts and rational reactor design play decisive roles in the industrial application of the electrocatalytic carbon dioxide reduction reaction (CO 2 RR). In this study, a dual‐metal–organic framework (MOF) copper‐based catalytic electrode is designed and prepared in one step by in situ synthesis on a foamed copper substrate. The MOF‐on‐MOF structure can effectively inhibit the generation of H 2 and CO, and further enhance the selectivity of HCOOH. Furthermore, by using cheap and durable poly(tetrafluoroethylene) (PTFE) instead of an expensive and fragile GDE, the optimized reactor design improves the stability and durability of the gas channel and the replaceability of the electrode. The structure‐optimized reactor has a maximum Faradaic efficiency of 89.2% in neutral medium, and an average current density of 26.1 mA cm −2 in the flow cell, which has comparable performance to a GDE and can continue to operate stably. The use of PTFE improves the service life of the gas mass transfer channel, and the independent catalytic electrode can provide good catalytic efficiency. These results provide new insights into the reaction mechanism of structurally recombined double MOFs and PTFE‐optimized CO 2 RR reactor designs, providing technical support for the practical industrial application of the CO 2 RR.