| 초록 |
A porphyrinic metal-organic framework (PMOF) known as PCN-222(Zn) was surface-modified by the molecular Re(I) catalyst through anchoring to the PMOF with carboxylate to form a new type of MOF hybrid photocatalyst. The porphyrinic MOF-based hybrid (PMOF/Re(I)) prepared with an archetypical CO2 reduction catalyst, (L)ReI(CO)3Cl (Re(I); L = 4,4′-dicarboxylic-2,2′-bipyridine), in the presence of 3 vol% water produced CO with no leveling-off tendency for 59 h to give a turnover number of ≥1,133 ± 142 (639 ± 80 μmol h–1 (g MOF)–1). The high catalytic activity should mainly arise from efficient exciton migration and funneling from photoexcited porphyrin linkers (ZnPs*) to the periphery Re(I) catalytic sites, which is in line with the observed fast exciton (energy) migration (~(20–30 ps) between porphyrin pho-toreceptors and funneling into Re(I) catalytic centers in Re(I)-doped PMOF sample. |
