Wu Chongbei, Yu Guanhang, Yin Yue, Wang Yuze, Chen Li, Han Qing, Tang Junwang, Wang Bo
Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, P. R. China.
Department of Chemical Engineering, University College London, London, WC1E 7JE, UK.
Small. 2020 Sep;16(37):e2003162. doi: 10.1002/smll.202003162. Epub 2020 Aug 12.
Conjugated polymers are promising light harvesters for water reduction/oxidation due to their simple synthesis and adjustable bandgap. Herein, both cyanamide and triazole functional groups are first incorporated into a heptazine-based carbon nitride (CN) polymer, resulting in a mesoporous conjugated cyanamide-triazole-heptazine polymer (CTHP) with different compositions by increasing the quantity of cyanamide/triazole units in the CN backbone. Varying the compositions of CTHP modulates its electronic structures, mesoporous morphologies, and redox energies, resulting in a significantly improved photocatalytic performance for both H and O evolution under visible light irradiation. A remarkable H evolution rate of 12723 µmol h g is observed, resulting in a high apparent quantum yield of 11.97% at 400 nm. In parallel, the optimized photocatalyst also exhibits an O evolution rate of 221 µmol h g , 9.6 times higher than the CN counterpart, with the value being the highest among the reported CN-based bifunctional photocatalysts. This work provides an efficient molecular engineering approach for the rational design of functional polymeric photocatalysts.
由于共轭聚合物合成简单且带隙可调，它们是用于水还原/氧化的很有前景的光捕获剂。在此，氰胺基和三唑官能团首次被引入到基于七嗪的氮化碳（CN）聚合物中，通过增加CN主链中氰胺/三唑单元的数量，得到了具有不同组成的介孔共轭氰胺 - 三唑 - 七嗪聚合物（CTHP）。改变CTHP的组成可调节其电子结构、介孔形态和氧化还原能，从而在可见光照射下显著提高其对氢气和氧气析出的光催化性能。观察到显著的氢气析出速率为12723 μmol h g，在400 nm处产生了11.97%的高表观量子产率。同时，优化后的光催化剂还表现出221 μmol h g的氧气析出速率，比CN对应物高9.6倍，该值是已报道的基于CN的双功能光催化剂中最高的。这项工作为功能性聚合物光催化剂的合理设计提供了一种有效的分子工程方法。
