Polarization engineering in porous organic polymers for charge separation efficiency and its applications in photocatalytic aerobic oxidations  

作　　者：Kun Wu Pei-Wen Cheng Xin-Yi Liu Ji Zheng Xiao-Wei Zhu Mo Xie Puxin Weng Weigang Lu Dan Li 

机构地区：[1]College of Chemistry and Materials Science,Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications,Jinan University,Guangzhou 510632,China [2]Guangdong Rare Earth Photofunctional Materials Engineering Technology Research Center,School of Chemistry and Environment,Jiaying University,Meizhou 514015,China

出　　处：《Science China Chemistry》2024年第3期1000-1007,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21731002,21975104,22101099,22150004,22271120);Guangdong Major Project of Basic and Applied Research(2019B030302009);the Outstanding Innovative Talents Cultivation Funded Programs for Doctoral Students of Jinan University(2022CXB007);the Fundamental Research Funds for the Central Universities and Jinan University(21621035)。

摘　　要：Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.

关 键 词：porous organic polymer local polarization photocatalytic aerobic oxidation charge separation reactive oxygen species exciton binding energy 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]