三(4-乙炔苯基)胺类共轭微孔聚合物及其光催化水分解性能研究

Tris(4-ethynylphenyl)amine-Based Conjugated Microporous Polymers and Its Photocatalytic Water Splitting Hydrogen Evolution

共轭微孔聚合物(CMPs)由于良好的稳定性和性能可调性已在光催化水分解制氢领域显示出诱人的应用前景.为了开发新型的CMPs类光催化剂多官能团构筑砌块,探索有效的材料性能调节手段,通过Sonogashira-Hagihara偶联反应合成了4种基于三(4-乙炔苯基)胺(TEA)单元和具有不同连接位置的苯并噻二唑(BT)单元的CMPs:FS1、FS2、FS3和FS4,其中,BT单元的连接位置分别为:5,6、4,5、4,6、4,7.研究发现:可见光驱动下,四种聚合物均具有稳定的光催化析氢性能,其中4,7-位连接的聚合物FS4性能最好,析氢效率高达115.74×10μmol·mg^(-1)·h^(-1),为FS1的近3倍.说明TEA为一种性能优异的CMPs类光催化剂多官能团构筑砌块, BT单元的连接位置调控是一种有效的TEA类CMPs的性能调节手段.

Conjugated microporous polymers(CMPs) have shown attractive application prospects in the field of photocatalytic water splitting hydrogen evolution because of their excellent stability and adjustable properties. To develop novel multi-functional building blocks for CMPs photocatalysts and explore effective methods to tune their properties, based on tris-(4-ethynylphenyl) amine(TEA) unit and benzothiadiazole(BT) unit with different linking positions, four CMPs FS1, FS2,FS3 and FS4 have been synthesized with Sonogashira-Hagihara coupling reaction. The linking positions of BT units in them are 5,6, 4,5, 4,6 and 4,7, respectively. It suggests that the four polymers all have stable photocatalytic hydrogen evolution performance under visible light driving. FS4 with 4,7-linked polymer has the best performance, and its hydrogen evolution efficiency is as high as 115.74×10μmol·mg^(-1)·h^(-1), nearly three times than that of FS1. It shows that TEA is an excellent multi-functional building block of CMPs photocatalyst, and the linking position regulation of BT unit is an effective means to tune the performance of TEA based CMPs.