The Reduced Barrier for the Photogenerated Charge Migration on Covalent Triazine‐Based Frameworks for Boosting Photocatalytic CO₂ Reduction Into Syngas

Abstract Photocatalytic CO₂ reduction together with hydrogen generation is a promising approach to generate syngas, the photogenerated electron migration from photosensitizers to the catalytic active sites is the rate‐determining step. Herein, an integrative strategy is presented by covalently grafting metal complexes into donor–acceptor covalent triazine‐based frameworks. The catalytic active sites are integrated with the photosensitizer units by covalent linkages to form an extended π‐conjugated framework, which significantly reduces the energy barrier for the migration of the photogenerated charge carriers, resulting in high activity and durability in photocatalytic CO₂ reduction into syngas under visible light irradiation. The CO and H₂ evolution amounts in 1.5 h are 1086 and 1042 µmol g⁻¹, respectively, which greatly surpass those in the host‐guest counterparts. Furthermore, selective adsorption for CO₂ over N₂ renders this photocatalytic system to be effective for syngas production from the simulated flue gas. This study provides new approaches to construct the integrative photocatalytic systems for solar‐to‐chemical energy conversion.