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