School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240 Shanghai, P. R. China.
ACS Macro Lett. 2022 Apr 19;11(4):434-440. doi: 10.1021/acsmacrolett.2c00035. Epub 2022 Mar 15.
Porphyrin-based photocatalytic materials have received great attention, and the effect of the substituents, central ions, and aggregated structure on the catalysis performance has been studied up to now. Herein, we report the effect of porphyrin isomerism on their aggregated structures as well as the photocatalytic activity. Two - and -porphyrin-based alternating copolymers with the same compositions ( and ) are successfully synthesized. It is found that self-assembles into propeller-like nanoparticles and into multilayer hollow nanospheres. Furthermore, the hydrogen production rate of (5533 μmol g h) is 30 times higher than that of (173 μmol g h). Mechanism studies reveal that the high photocatalytic properties of originate from the more ordered arrangement of porphyrins than , which facilitates the mobility and separation of photoinduced carriers. We believe the covalent and noncovalent polymer self-assembly process as well as the isomerism effect as disclosed here will shed new light on the design of high performance photocatalysts.
基于卟啉的光催化材料受到了广泛关注，目前已经研究了取代基、中心离子和聚集结构对催化性能的影响。在此，我们报告了卟啉异构对其聚集结构以及光催化活性的影响。成功合成了两种具有相同组成的卟啉-和-卟啉交替共聚物（和）。研究发现，自组装成桨叶状纳米颗粒，而自组装成多层空心纳米球。此外，（5533 μmol g h）的产氢速率是（173 μmol g h）的 30 倍。机理研究表明，比具有更高光催化性能源于其卟啉排列更有序，这有利于光生载流子的迁移和分离。我们相信，这里所揭示的共价和非共价聚合物自组装过程以及异构效应将为设计高性能光催化剂提供新的思路。
