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Modulating Benzothiadiazole‐Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting
Author(s) -
Chen Weiben,
Wang Lei,
Mo Daize,
He Feng,
Wen Zhilin,
Wu Xiaojun,
Xu Hangxun,
Chen Long
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202006925
Subject(s) - photocatalysis , moiety , covalent bond , halogenation , halogen , energy conversion efficiency , materials science , quantum efficiency , covalent organic framework , chemistry , photochemistry , chemical engineering , nanotechnology , organic chemistry , catalysis , optoelectronics , alkyl , engineering
Two‐dimensional covalent organic frameworks (2D COFs), an emerging class of crystalline porous polymers, have been recognized as a new platform for efficient solar‐to‐hydrogen energy conversion owing to their pre‐designable structures and tailor‐made functions. Herein, we demonstrate that slight modulation of the chemical structure of a typical photoactive 2D COF (Py‐HTP‐BT‐COF) via chlorination (Py‐ClTP‐BT‐COF) and fluorination (Py‐FTP‐BT‐COF) can lead to dramatically enhanced photocatalytic H 2 evolution rates (HER=177.50 μmol h −1 with a high apparent quantum efficiency (AQE) of 8.45 % for Py‐ClTP‐BT‐COF). Halogen modulation at the photoactive benzothiadiazole moiety can efficiently suppress charge recombination and significantly reduce the energy barrier associated with the formation of H intermediate species (H*) on polymer surface. Our findings provide new prospects toward design and synthesis of highly active organic photocatalysts toward solar‐to‐chemical energy conversion.