A Fully Conjugated Covalent Organic Framework with Oxidative and Reductive Sites for Photocatalytic Carbon Dioxide Reduction with Water

Abstract Constructing a powerful photocatalytic system that can achieve the carbon dioxide (CO 2 ) reduction half‐reaction and the water (H 2 O) oxidation half‐reaction simultaneously is a very challenging but meaningful task. Herein, a porous material with a crystalline topological network, named viCOF‐bpy‐Re, was rationally synthesized by incorporating rhenium complexes as reductive sites and triazine ring structures as oxidative sites via robust −C=C− bond linkages. The charge‐separation ability of viCOF‐bpy‐Re is promoted by low polarized π‐bridges between rhenium complexes and triazine ring units, and the efficient charge‐separation enables the photogenerated electron–hole pairs, followed by an intramolecular charge‐transfer process, to form photogenerated electrons involved in CO 2 reduction and photogenerated holes that participate in H 2 O oxidation simultaneously. The viCOF‐bpy‐Re shows the highest catalytic photocatalytic carbon monoxide (CO) production rate (190.6 μmol g −1 h −1 with about 100 % selectivity) and oxygen (O 2 ) evolution (90.2 μmol g −1 h −1 ) among all the porous catalysts in CO 2 reduction with H 2 O as sacrificial agents. Therefore, a powerful photocatalytic system was successfully achieved, and this catalytic system exhibited excellent stability in the catalysis process for 50 hours. The structure–function relationship was confirmed by femtosecond transient absorption spectroscopy and density functional theory calculations.