Effect of Controlling Thiophene Rings on D-A Polymer Photocatalysts Accessed via Direct Arylation for Hydrogen Production
Dongnai Ye,
Lei Liu,
Qimin Peng,
Jiabin Qiu,
Hao Gong,
Aiguo Zhong,
Shiyong Liu
Affiliations
Dongnai Ye
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
Lei Liu
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
Qimin Peng
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
Jiabin Qiu
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
Hao Gong
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
Aiguo Zhong
Department of Pharmacy & Chemistry, Taizhou University, Taizhou 318000, China
Shiyong Liu
Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry, College of Materials, Metallurgical and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
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−1 g−1. 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.
