Temporally Separated CO_(2) Photoreduction and H_(2)O Photooxidation over Redox-Active Conjugated Organic Polymer Films

查看全文 作　　者：Guipeng [1]Ji;Yuepeng [1,2]Wang;Wenqiang [1,3]Ye;Meifang [1]Chen;Fengtao [1,2]Zhang;Yanfei [1,2]Zhao;Shengrui [1,2]Tong;Buxing [1,2]Han;Zhimin [1,2]Liu 机构地区：[1]Beijing National Laboratory for Molecular Sciences,Key Laboratory of Colloid,Interface,and Thermodynamics,CAS Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences(CAS),100190 Beijing;[2]University of Chinese Academy of Sciences,100049 Beijing;[3]School of Science,China University of Geosciences,100083 Beijing 出　　处：《CCS Chemistry》索引2023年第5卷第8期,共12页 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. 摘　　要：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. 关 键 词：CO_(2)photoreduction conjugated organic polymers carbon monoxide redox transformation artificial photosynthesis