Rapid Exciton Migration and Amplified Funneling Effects of Multi-Porphyrin Arrays in a Re(I)-Porphyrinic MOF Hybrid for Photocatalytic CO<SUB>2</SUB> Reduction
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초록
내용
A porphyrinic metal-organic framework (PMOF) known as PCN-222(Zn) was chemically doped by with the molecular Re(I) catalyst bearing carboxylate anchoring group to form a new type of MOF-Re(I) hybrid photocatalyst. The porphyrinic MOF-sensitized hybrid (PMOF/Re) 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 ≥1893 (1,070 ± 80 μmol h–1 (g MOF)–1). The high catalytic activity arises mainly from efficient exciton migration and funneling from photoexcited porphyrin linkers to the peripheral Re(I) catalytic sites, which is in accordance with the observed fast exciton (energy) migration (≈1 ps) in highly ordered porphyrin photoreceptors and the effective funneling into Re(I) catalytic centers in Re(I)-doped PMOF sample.