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A Carbazolyl Porphyrin‐Based Conjugated Microporous Polymer for Metal‐Free Photocatalytic Aerobic Oxidation Reactions
ChemCatChem ( IF 4.5 ) Pub Date : 2020-03-31 , DOI: 10.1002/cctc.202000199
Jun Jiang 1 , Zhongxiu Liang 1 , Xiaoyan Xiong 1 , Xiantai Zhou 2 , Hongbing Ji 3
Affiliation  

Herein, a carbazolyl porphyrin‐based π‐conjugated microporous polymer was prepared via simple FeCl3‐catalyzed oxidative polymerization. The resulting polymer (TCPP‐CMP) exhibits high surface area, permanent pores, good stability, broad light absorption range and suitable redox potentials. As expected, TCPP‐CMP is a highly effective metal‐free and heterogeneous photocatalyst for a variety of aerobic oxidation reactions, including oxidative coupling of primary amines, oxidative dehydrogenation of secondary amines, and oxidation of sulfides into sulfoxides using molecular oxygen under visible light irradiation. Importantly, natural sunlight is able to promote the aerobic oxidation of benzylamine and thioanisole via TCPP‐CMP photocatalyst with high conversion and selectivity, which are comparable with reactions conducted under artificial light. In addition, heterogeneous TCPP‐CMP has good recyclability, which retained its activity even after four cycles. The current work lays the foundation for future applications of TCPP‐CMP as metal‐free heterogeneous photocatalyst for aerobic oxidation reactions.

中文翻译:

基于咔唑基卟啉的共轭微孔聚合物,用于无金属的光催化需氧氧化反应

本文中,通过简单的FeCl 3制备了咔唑基卟啉的π共轭微孔聚合物。催化氧化聚合。所得聚合物(TCPP-CMP)具有高表面积,永久孔,良好的稳定性,宽广的光吸收范围和合适的氧化还原电势。不出所料,TCPP-CMP是一种高效的无金属多相光催化剂,适用于多种需氧氧化反应,包括伯胺的氧化偶联,仲胺的氧化脱氢以及在可见光照射下使用分子氧将硫化物氧化为亚砜。重要的是,自然阳光能够通过TCPP-CMP光催化剂以高的转化率和选择性来促进苄胺和硫代茴香醚的好氧氧化,这与在人造光下进行的反应相当。此外,异构TCPP-CMP具有良好的可回收性,甚至在四个周期后仍保持其活动。当前的工作为TCPP-CMP作为有氧氧化反应的无金属多相光催化剂的未来应用奠定了基础。
更新日期:2020-03-31
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