The combination of covalent organic framework(COF)photosensitizers with molecular cocatalysts is a promising avenue for photocatalytic carbon dioxide(CO_(2))reduction.Here,a series of isostructural COFs was synthesize...The combination of covalent organic framework(COF)photosensitizers with molecular cocatalysts is a promising avenue for photocatalytic carbon dioxide(CO_(2))reduction.Here,a series of isostructural COFs was synthesized using linkers of different lengths,with or without partial fluorination.These COFs were investigated for photocatalytic CO_(2)reduction under visible-light irradiation when combined with cobalt(II)bipyridine complexes as a cocatalyst.Fluorination was found to enhance both CO_(2)affinity and catalytic activity,and a partially fluorinated COF,FBP-COF,achieved the highest CO_(2)-to-CO conversion efficiency,showing a carbon monoxide(CO)generation rate of 2.08 mmol h−1 g−1 and a 90%CO selectivity.FBP-COF also showed good stability under sacrificial conditions,generating CO for 50 h with a turnover number of 91.5.This activity is much higher than a homogeneous system using ruthenium bipyridine complexes as the photosensitizer combined with the same cobalt bipyridine complexes.展开更多
文摘The combination of covalent organic framework(COF)photosensitizers with molecular cocatalysts is a promising avenue for photocatalytic carbon dioxide(CO_(2))reduction.Here,a series of isostructural COFs was synthesized using linkers of different lengths,with or without partial fluorination.These COFs were investigated for photocatalytic CO_(2)reduction under visible-light irradiation when combined with cobalt(II)bipyridine complexes as a cocatalyst.Fluorination was found to enhance both CO_(2)affinity and catalytic activity,and a partially fluorinated COF,FBP-COF,achieved the highest CO_(2)-to-CO conversion efficiency,showing a carbon monoxide(CO)generation rate of 2.08 mmol h−1 g−1 and a 90%CO selectivity.FBP-COF also showed good stability under sacrificial conditions,generating CO for 50 h with a turnover number of 91.5.This activity is much higher than a homogeneous system using ruthenium bipyridine complexes as the photosensitizer combined with the same cobalt bipyridine complexes.
