光催化可控分子氧活化过程中，活性氧物种的定向生成

论文概述

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关键词

Photocatalysis

Conjugated polymers

Molecular oxygen activation

Aerobic oxidation

Polymeric conjugation

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导读

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(•O²⁻)和单线态氧(¹O₂)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.

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图文速览 

Figure 1  (a) Illustration of synthesis and strategy of designed polymeric conjugation processes. (b) SEM and TEM images of CMP-D and CMP-A. (c) Solid-state ¹³C CP/MAS NMR spectroscopy. (d) FT-IR spectroscopy and (e) UV-visDRS spectra and normalized Tauc plots created from UV-vis measurements (inset of (e)) of CMPs.

Figure 2  Diagram of electrons distribution in (a) CMP-D and (b) CMP-A. (c) TPV spectra over CMP-D and CMP-A under the irradiation of a laser beam of 355 nm. Steady-stated fluorescence (d) and phosphorescence (e) for CMP-A and CMP-D, and phosphorescence spectra at 77 K (delay time 0.1 s) for CMP-D (inset of (e)). TR-PL under different atmosphere over (f) CMP-A and CMP-D (inset of (f)).

Figure 3  (a) The heterogeneous organic photosynthesis of methyl phenyl sulfoxide and (b) N-benzylidene benzylamine by different cooperative photocatalyst. Visible-light-induced selective oxidation of primary (c) thioethers into sulfoxides and (d) amines into imines over CMPs.

Figure 4  The ESR spectra of different samples in the presence of (a) TEMP and (b) TEMPB with or without quencher under visible light irradiation in the solvent of CH₃CN. The performed spin-trapping experiments over (c) the dehydrogenation of amines into imines and (d) oxygenation of thioether into sulfoxide.

Figure 5  The mechanism of photocatalytic aerobic oxidation reactions induced by tunable molecular oxygen activation.

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文章信息 

Wenhao Sun, Yonggang Xiang, Zhihui Jiang, Shengyao Wang, Nan Yang, Shangbin Jin, Linhao Sun, Huailong Teng, Hao Chen. Designed polymeric conjugation motivates tunable activation of molecular oxygen in heterogeneous organic photosynthesis. ScienceBulletin, 2022, 67(1): 61–70, doi: 10.1016/j.scib.2021.07.016

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