Metalloporphyrin-Based Metal–Organic Frameworks for Photocatalytic Carbon Dioxide Reduction: The Influence of Metal Centers

Photocatalysis is one of the most promising technologies to achieve efficient carbon dioxide reduction reaction (CO2RR) under mild conditions. Herein, metalloporphyrin-based metal–organic frameworks (MOFs) with different metal centers, denoted as PCN-222, were utilized as visible-light photocatalysts for CO2 reduction. Due to the combination of the conjugated planar macrocyclic structures of metalloporphyrins and the stable porous structures of MOFs, all PCN-222 materials exhibited excellent light-harvesting and CO2-adsorbing abilities. Among the studied MOFs of varied metal centers (M = Pt, Fe, Cu, Zn, Mn), PCN-222(2H&Zn) exhibited the highest photocatalytic CO2RR performance, with an average CO yield of 3.92 μmol g−1 h−1 without any organic solvent or sacrificial agent. Furthermore, this was three and seven times higher than that of PCN-222(Zn) (1.36 μmol g−1 h−1) and PCN-222(2H) (0.557 μmol g−1 h−1). The superior photocatalytic activity of PCN-222(2H&Zn) was attributed to its effective photoexcited electron–hole separation and transportation compared with other PCN-222(2H&M) materials. The obtained results indicate that Zn ions in the porphyrin’s center played an important role in the reaction of active sites for the adsorption–activation of CO2. In addition, PCN-222(2H&Zn) showed the highest CO2 selectivity (almost 100%) and stability. This work provides a clear guide for the design of efficient photocatalysts.