Side-chain-extended conjugation: a strategy for improving the photocatalytic hydrogen production performance of a linear conjugated polymer

Wen-Rui Wang; Jia Li; Qian Li; Zi-Wen Xu; Li-Na Liu; Xue-Qiang Chen; Wen-Jing Xiao; Jianhua Yao; Fang Zhang; Wei-Shi Li

doi:10.1039/D0TA12425G

Side-chain-extended conjugation: a strategy for improving the photocatalytic hydrogen production performance of a linear conjugated polymer†

Wen-Rui Wang,^ab Jia Li,^c Qian Li,^ab Zi-Wen Xu,^a Li-Na Liu,^a Xue-Qiang Chen,^a Wen-Jing Xiao,^a Jianhua Yao,*^cd Fang Zhang

*^b and Wei-Shi Li

*^ad

Author affiliations

* Corresponding authors

^a CAS Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Centre for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
E-mail: liws@mail.sioc.ac.cn

^b The Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University, Shanghai 200234, China
E-mail: zhangfang@shnu.edu.cn

^c CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
E-mail: yaojh@mail.sioc.ac.cn

^d Engineering Research Center of Zhengzhou for High Performance Organic Functional Materials, Zhengzhou Institute of Technology, 6 Yingcai Street, Huiji District, Zhengzhou 450044, China

Abstract

A side-chain-extended conjugation strategy is demonstrated here to improve the photocatalytic performance of a linear conjugated polymer for hydrogen production from water. For this, polymers P0, P1, and P2 were designed and synthesized based on benzodithiophene and dibenzothiophene S,S-dioxide. Compared with P0, P1 and P2 have two additional thiophene units conjugated in the polymer skeleton along the main-chain and side-chain directions, respectively. Studies found that side chain-conjugated functionalization in P2 enhances thermal stability, redshifts light-absorption bands, narrows the polymer bandgap, prolongs the exciton lifetime, enlarges the photocatalytic over-potential, increases charge mobility, reduces charge transport resistance, and thus improves the hydrogen evolution rate (HER) by a factor of 160 fold. Although performance improvement is still observed in P1, the factor is only 3.6 fold. Thus, P2 exhibits the most promising performance among the three polymers with a HER of 20 314 μmol g⁻¹ h⁻¹ in the presence of 3 wt% Pt cocatalyst and a record apparent quantum yield of 7.04% at 500 nm, rendering it an excellent green light photocatalyst.

Journal of Materials Chemistry A

Side-chain-extended conjugation: a strategy for improving the photocatalytic hydrogen production performance of a linear conjugated polymer†

Abstract

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Side-chain-extended conjugation: a strategy for improving the photocatalytic hydrogen production performance of a linear conjugated polymer

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