Ye Dongnai, Liu Lei, Peng Qimin, Qiu Jiabin, Gong Hao, Zhong Aiguo, Liu Shiyong
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China.
School of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000, China.
Molecules. 2023 Jun 1;28(11):4507. doi: 10.3390/molecules28114507.
Conjugated polymer photocatalysts for hydrogen production have the advantages of an adjustable structure, strong response in the visible light region, adjustable energy levels, and easy functionalization. Using an atom- and step-economic direct C-H arylation method, dibromocyanostilbene was polymerized with thiophene, dithiophene, terthiophene, and fused thienothiophene and dithienothiophene, respectively, to produce donor-acceptor (D-A)-type linear conjugated polymers containing different thiophene derivatives with different conjugation lengths. Among them, the D-A polymer photocatalyst constructed from dithienothiophene could significantly broaden the spectral response, with a hydrogen evolution rate up to 12.15 mmol h g. The results showed that the increase in the number of fused rings on thiophene building blocks was beneficial to the photocatalytic hydrogen production of cyanostyrylphene-based linear polymers. For the unfused dithiophene and terthiophene, the increase in the number of thiophene rings enabled more rotation freedom between the thiophene rings and reduced the intrinsic charge mobility, resulting in lower hydrogen production performance accordingly. This study provides a suitable process for the design of electron donors for D-A polymer photocatalysts.
用于制氢的共轭聚合物光催化剂具有结构可调节、在可见光区域响应强、能级可调节以及易于功能化等优点。采用原子经济和步骤经济的直接C-H芳基化方法，分别将二溴氰基芪与噻吩、二噻吩、三噻吩以及稠合噻吩并噻吩和二噻吩并噻吩聚合，以制备含有不同共轭长度的不同噻吩衍生物的供体-受体（D-A）型线性共轭聚合物。其中，由二噻吩并噻吩构建的D-A聚合物光催化剂可显著拓宽光谱响应，析氢速率高达12.15 mmol h g。结果表明，噻吩结构单元上稠环数量的增加有利于基于氰基苯乙烯基的线性聚合物的光催化产氢。对于未稠合的二噻吩和三噻吩，噻吩环数量的增加使得噻吩环之间具有更多的旋转自由度，并降低了本征电荷迁移率，从而相应地导致较低的产氢性能。本研究为D-A聚合物光催化剂的电子供体设计提供了合适的方法。
