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

作　　者：Guipeng Ji Yuepeng Wang Wenqiang Ye Meifang Chen Fengtao Zhang Yanfei Zhao Shengrui Tong Buxing Han Zhimin 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》2023年第8期1854-1865,共12页中国化学会会刊（英文）

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 

分 类 号：O62[理学—有机化学]