Liu Xiao-Hui, Guo Xiao-Xuan, Zheng Shuo-Yun, Zhou Xian-Tai
School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519082, China.
Huizhou Research Institute, Sun Yat-sen University, Huizhou, 516081, P.R. China.
Chempluschem. 2025 Jan;90(1):e202400460. doi: 10.1002/cplu.202400460. Epub 2024 Oct 29.
Porphyrins-based porous organic polymers (POP) were widely used in photocatalytic oxidation under visible light owing to their superiority in the activation of oxygen. In contrast, the efficiency is usually limited due to the fast recombination and slow electron transfer. Herein, we report the use of a trioporphyrins-based covalent triazine framework (Por-CTF) as visible-light-active photocatalyst for the coupling oxidative of amines to imines at room temperature. By incorporating the π-conjugated porphyrin building block led to the enhanced electron transport between molecules, and the extended recombination time of excited electrons. The photocatalytic efficiency of Por-CTF is superior to that of polymer in absence of triazine framework (POP-TSP), which was prepared by radical polymerization using tetra-(4-vinylphenyl) porphyrin (TSP) as monomer. Por-CTF catalyst presented excellent efficiency for various primary amines and stability. This work provides a reasonable guidance of catalyst molecular structure design for enhancing efficiency in the photocatalytic oxidation.
基于卟啉的多孔有机聚合物（POP）由于其在激活氧方面的优势而被广泛用于可见光下的光催化氧化。相比之下，由于快速复合和缓慢的电子转移，其效率通常受到限制。在此，我们报道了使用基于三卟啉的共价三嗪框架（Por-CTF）作为可见光活性光催化剂，用于在室温下将胺偶联氧化为亚胺。通过引入π共轭卟啉结构单元，导致分子间电子传输增强，激发电子的复合时间延长。Por-CTF的光催化效率优于不含三嗪框架的聚合物（POP-TSP），后者是使用四（4-乙烯基苯基）卟啉（TSP）作为单体通过自由基聚合制备的。Por-CTF催化剂对各种伯胺表现出优异的效率和稳定性。这项工作为提高光催化氧化效率的催化剂分子结构设计提供了合理的指导。
