Linking oxidative and reductive clusters to prepare crystalline porous catalysts for photocatalytic CO 2 reduction with H 2 O.

Mimicking natural photosynthesis to convert CO 2 with H 2 O 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 2 O oxidation. Herein, based on the MOF ∪ COF collaboration, we have carefully designed and synthesized a crystalline hetero-metallic cluster catalyst denoted MCOF-Ti 6 Cu 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 6 Cu 3 exhibits fine activity in the conversion of CO 2 with water into HCOOH (169.8 μmol 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.