Photocatalytic CO_(2) reduction with H_(2)O of chemicals without H2 generation is interesting but challenging.Herein,we report temporally separated CO_(2) photoreduction and H_(2)O photooxidation that are achieved ove...Photocatalytic CO_(2) reduction with H_(2)O of chemicals without H2 generation is interesting but challenging.Herein,we report temporally separated CO_(2) photoreduction and H_(2)O photooxidation that are achieved over redox-active o-hydroxyazo-based conjugated organic polymer films(HAzo-COPFs),affording CO with high efficiency as the sole reduction product.HAzo-COPFs are prepared via interfacial diazo-coupling reactions of aromatic diamines and diphenols,and HAzo-COPF-1 from 4,4′-biphenol and benzidine shows the best performance with a CO generation rate of 53.6μmol g−1 h−1 under visible-light irradiation(>420 nm).Interestingly,we discovered that diphenol(DP-OH)moieties in HAzo-COPFs,serving as electron and proton donors to participate in CO_(2) photoreduction,are oxidized into quinone(DP=O)moieties,which are subsequently photoreduced to regenerate DP-OH in H_(2)O photooxidation.Consequently,CO_(2) photoreduction and H_(2)O photooxidation are temporally separated and perfectly coupled via redox transformation between DP-OH and DP=O that form in situ,affording enhanced charge carrier separation and inhibiting the hydrogen evolution reaction.This work provides new insights for the design of COP photocatalysts and artificial photosynthesis.展开更多
基金the National Natural Science Foundation of China(grant nos.22121002 and 21890761)the Chinese Academy of Sciences(grant no.121111KYSB20200057)for their financial support.
文摘Photocatalytic CO_(2) reduction with H_(2)O of chemicals without H2 generation is interesting but challenging.Herein,we report temporally separated CO_(2) photoreduction and H_(2)O photooxidation that are achieved over redox-active o-hydroxyazo-based conjugated organic polymer films(HAzo-COPFs),affording CO with high efficiency as the sole reduction product.HAzo-COPFs are prepared via interfacial diazo-coupling reactions of aromatic diamines and diphenols,and HAzo-COPF-1 from 4,4′-biphenol and benzidine shows the best performance with a CO generation rate of 53.6μmol g−1 h−1 under visible-light irradiation(>420 nm).Interestingly,we discovered that diphenol(DP-OH)moieties in HAzo-COPFs,serving as electron and proton donors to participate in CO_(2) photoreduction,are oxidized into quinone(DP=O)moieties,which are subsequently photoreduced to regenerate DP-OH in H_(2)O photooxidation.Consequently,CO_(2) photoreduction and H_(2)O photooxidation are temporally separated and perfectly coupled via redox transformation between DP-OH and DP=O that form in situ,affording enhanced charge carrier separation and inhibiting the hydrogen evolution reaction.This work provides new insights for the design of COP photocatalysts and artificial photosynthesis.
