影像科学与光化学 ›› 2017, Vol. 35 ›› Issue (5): 675-685.DOI: 10.7517/j.issn.1674-0475.2017.04.028

• 论文 • 上一篇    下一篇

苝衍生物光催化氧化硫醚的研究

彭成云1,2, 陈勇1   

  1. 1. 中国科学院 理化技术研究所, 北京 100190;
    2. 中国科学院大学, 北京 100049
  • 收稿日期:2017-05-31 修回日期:2017-06-09 出版日期:2017-09-15 发布日期:2017-09-15
  • 通讯作者: 陈勇
  • 基金资助:

    国家自然科学基金项目(21371175)资助

Photocatalytic Oxidation of Sulfides with Perylene-based Derivatives as Photosensitizers

PENG Chengyun1,2, CHEN Yong1   

  1. 1. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China;
    2. University of Chinese Academy of Sciences, Beijing 100049, P. R. China
  • Received:2017-05-31 Revised:2017-06-09 Online:2017-09-15 Published:2017-09-15

摘要:

本文通过对苝酐进行化学修饰,合成了两种具有较好溶解性和强可见光吸收的苝衍生物:PMI-(iPr)2An(PSⅡ)和PMI-((iPr)2An)2(PSⅢ)。在可见光照射下,以PSⅡ和PSⅢ作为光敏剂,氧气为氧化剂,实现了高转化率和高选择性的硫醚到亚砜的氧化。在优化反应条件下,PSⅢ对苯基硫醚衍生物光催化氧化的转化率和选择性均接近100%。活性中间体的清除实验和电子顺磁共振实验表明,该体系中单重态氧(1O2)和超氧自由基同时对硫醚的氧化起作用。

关键词: 苝衍生物, 光催化, 硫醚氧化, 单线态氧, 超氧自由基

Abstract:

PMI-(iPr)2An (PSⅡ) and PMI-((iPr)2An)2(PSⅢ)) with strong visible light absorption and good solubility are successfully synthesized through the chemically modifications of Perylene-3,4,9,10-tetracarboxylicdianhydride. Under visible light irradiation, sulfides are transformed to sulfoxides with relatively high selectivity and yield, in which PSⅡ or PSⅢ act as the photosensitizer and oxygen plays the role of oxidant. Under optimized conditions, both the yield and selectivity can reach up to 100% for sulfides oxidation by using PSⅢ as the photosensitizer. Active species trapping experiments and electron spin resonance (ESR) demonstrate that the singlet oxygen and superoxide radical anion are the effective oxidants during the photocatalyticreaction.

Key words: perylene derivative, photocatalysis, sulfides oxidation, singlet oxygen, superoxide radical anion