Designed polymeric conjugation motivates tunable activation of molecular oxygen in heterogeneous organic photosynthesis  

聚合物共轭度设计驱动可控分子氧活化促进非均相有机光合成反应

作　　者：Wenhao Sun Yonggang Xiang Zhihui Jiang Shengyao Wang Nan Yang Shangbin Jin Linhao Sun Huailong Teng Hao Chen 孙文浩;项勇刚;蒋志慧;汪圣尧;杨楠;金尚彬;孙林浩;滕怀龙;陈浩(College of Science,Huazhong Agricultural University,Wuhan 430070,China;Key Laboratory of Environment Correlative Dietology(Ministry of Education),Huazhong Agricultural University,Wuhan 430070,China;Key Laboratory of Material Chemistry for Energy Conversion and Storage(Ministry of Education),School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074,China)

机构地区：[1]College of Science,Huazhong Agricultural University,Wuhan 430070,China [2]Key Laboratory of Environment Correlative Dietology(Ministry of Education),Huazhong Agricultural University,Wuhan 430070,China [3]Key Laboratory of Material Chemistry for Energy Conversion and Storage(Ministry of Education),School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074,China

出　　处：《Science Bulletin》2022年第1期61-70,M0004,共11页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(51902121,52073110,22071072,51872107,21975090,and 21801086);the Fundamental Research Funds for the Central Universities of China(2662018QD011,2662018PY052,and 2662019PY023);the Natural Science Foundation of Hubei Province(2019CFB322)。

摘　　要：Photocatalytic oxidative organic reactions are important synthetic transformations,and research on reaction selectivity by reactive oxygen species(ROS)is significant.To date,however,there has rarely been any focus on the directed generation of ROSs.Herein,we report the first identification of tunable molecular oxygen activation induced by polymeric conjugation in nonmetallic conjugated microporous polymers(CMP).The conjugation between these can be achieved by the introduction of alkynyl groups.CMP-A with an alkynyl bridge facilitates the intramolecular charge mobility while CMP-D,lacking an alkynyl group enhances the photoexcited carrier build-up on the surface from diffusion.These different processes dominate the directed ROS generation of the superoxide radical(·O_(2)^(-))and singlet oxygen(^(1)O_(2)),respectively.This theory is substantiated by the different performances of these CMPs in the aerobic oxidation of sulfides and the dehydrogenative coupling of amines,and could provide insight into the rational design of CMPs for various heterogeneous organic photosynthesis.光催化氧化有机反应是绿色催化合成转化的重要途径之一.这其中,分子氧活化过程产生活性氧物种(ROS)对促进非均相有机光合成反应选择性具有重要作用,但光催化可控分子氧活化定向生成ROS的研究尚不多见.本研究发现了共轭微孔聚合物(CMPs)的共轭度设计可诱导分子氧活化的选择性.通过CMPs共轭度的设计调控,具有强共轭结构CMP-A材料可促进分子内光生载流子的转移,而弱共轭结构CMP-D材料则会增强光生载流子在其表面的局部积累,使得CMP-A与CMP-D在光催化反应苄胺脱氢偶联与硫醚氧化方面表现出不同性能.研究证实了共轭度诱导的差异化载流子迁移过程可有效促进超氧自由基(·O_(2)^(-))和单线态氧(^(1)O_(2))的定向生成,为理性设计CMPs用以提高多种光催化有机反应的选择性提供新的思路.

关 键 词：PHOTOCATALYSIS Conjugated polymers Molecular oxygen activation Aerobic oxidation Polymeric conjugation 

分 类 号：TQ203.2[化学工程—有机化工]