Linking oxidative and reductive clusters to prepare crystalline porous catalysts for photocatalytic CO2 reduction with H2O

Mimicking natural photosynthesis to convert CO2 with H2O into value-added fuels achieving overall reaction is a promising way to reduce the atmospheric CO2 level. Casting the catalyst of two or more catalytic sites with rapid electron transfer and interaction may be an effective strategy for coupling photocatalytic CO2 reduction and H2O oxidation. Herein, based on the MOF ? COF collaboration, we have carefully designed and synthesized a crystalline hetero-metallic cluster catalyst denoted MCOF-Ti6Cu3 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-Ti6Cu3 exhibits fine activity in the conversion of CO2 with water into HCOOH (169.8 mu mol g(-1)h(-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.