Molecular Engineering of Fully Conjugated sp2 Carbon‐Linked Polymers for High‐Efficiency Photocatalytic Hydrogen Evolution. Issue 4 (21st January 2020)

• Record Type: Journal Article
• Authors: Huang, Tao; Lin, Xi; Liu, Yang; Zhao, Jiwu; Lin, Huan; Xu, Ziting; Zhong, Shuncong; Zhang, Chunjie; Wang, Xuxu; Fu, Xianzhi; Long, Jinlin
• Is Part Of: ChemSusChem. Volume 13:Issue 4(2020)
• Page Start: 672
• Page End: 676
• Publication Date: 2020-01-21
• Subjects: conjugation -- donor–acceptor systems -- hydrogen evolution -- photocatalysis -- polymers; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.201903334
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: The diverse nature of organic precursors offers a versatile platform for precisely tailoring the electronic properties of semiconducting polymers. In this study, three fully conjugated sp 2 carbon‐linked polymers have been designed and synthesized for photocatalytic hydrogen evolution under visible‐light illumination, by copolymerizing different C 3 ‐symmetric aromatic aldehydes as knots with the 1, 4‐phenylene diacetonitrile (PDAN) linker through a C=C condensation reaction. The hydrogen evolution (HER) is achieved at a maximum rate of 30.2 mmol g −1 h −1 over a polymer based on 2, 4, 6‐triphenyl‐1, 3, 5‐triazine units linked by cyano‐substituted phenylene, with an apparent quantum yield (AQY) of 7.20 % at 420 nm. Increasing the degree of conjugation and planarity not only extends visible‐light absorption, but also stabilizes the fully conjugated sp 2 ‐carbon‐linked donor–acceptor (D–A) polymer. Incorporating additional electron‐withdrawing triazine units into the D–A polymer to form multiple electron donors and acceptors can greatly promote exciton separation and charge transfer, thus significantly enhancing the photocatalytic activity. Abstract : A bigger piece of the π : By extension of the π‐conjugated structure and introduction of electron‐withdrawing triazine units into the fully conjugated donor–acceptor (D–A) polymers bearing sp 2 carbon linkages, a highly efficient and stable polymeric photocatalyst is obtained for visible‐light‐induced H2 evolution.