Mimicking natural photosynthesis to convert CO 2 with H 2O into value-added fuels achieving overall reaction is a promising way to reduce the atmospheric CO 2 level. Casting the catalyst of two or more catalytic sites with rapid electron transfer and interaction may be an effective strategy for coupling photocatalytic CO 2 reduction and H 2O oxidation. Herein, based on the MOF ∪ COF collaboration, we have carefully designed and synthesized a crystalline hetero-metallic cluster catalyst denoted MCOF-Ti 6Cu 3 with spatial separation and functional cooperation between oxidative and reductive clusters. It utilizes dynamic covalent bonds between clusters to promote photo-induced charge separation and transfer efficiency, to drive both the photocatalytic oxidative and reductive reactions. MCOF-Ti 6Cu 3 exhibits fine activity in the conversion of CO 2 with water into HCOOH (169.8 μmol g −1h −1). Remarkably, experiments and theoretical calculations reveal that photo-excited electrons are transferred from Ti to Cu, indicating that the Cu cluster is the catalytic reduction center.
A crystalline hetero-metallic cluster catalyst based on a covalent organic framework strategy is reported. The catalyst can facilitate both photocatalytic oxidative and reductive reactions leading to efficient production of HCOOH from CO2 and H2O.