Modulating Benzothiadiazole‐Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting.
- Resource Type
- Article
- Authors
- Chen, Weiben; Wang, Lei; Mo, Daize; He, Feng; Wen, Zhilin; Wu, Xiaojun; Xu, Hangxun; Chen, Long
- Source
- Angewandte Chemie. 9/21/2020, Vol. 132 Issue 39, p17050-17057. 8p.
- Subject
- *HALOGENATION
*POROUS polymers
*ACTIVATION energy
*CRYSTALLINE polymers
*ENERGY conversion
*ORGANIC water pollutants
*PHOTOCATALYSTS
- Language
- ISSN
- 0044-8249
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 H2 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. [ABSTRACT FROM AUTHOR]