Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting

Chen, Weiben1; Wang, Lei2; Mo, Daize3,4; He, Feng3,4; Wen, Zhilin2; Wu, Xiaojun2; Xu, Hangxun2; Chen, Long1

2020-08-25

10.1002/anie.202006925

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

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 mu mol 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.

charge transfer HYDROGEN-PRODUCTION covalent organic frameworks H-2 EVOLUTION halogenation METAL-FREE photocatalytic water splitting EFFICIENT solar energy conversion CHLORINATION CRYSTALLINE

SCI ; EI

英语

NI论文 ; ESI高被引

其他

Chemistry

Chemistry, Multidisciplinary

WOS:000562258200001

WILEY-V C H VERLAG GMBH

20203509100761

Organic polymers ; Photocatalytic activity ; Solar energy ; Solar energy conversion ; Halogenation ; Modulation ; Solar power generation

Solar Power:615.2 ; Solar Energy and Phenomena:657.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Polymers:815.1.1

CHEMISTRY

1.Tianjin Univ, Dept Chem, Inst Mol Plus, Tianjin Key Lab Mol Optoelect Sci, Tianjin 300072, Peoples R China;
2.Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, CAS Key Lab Soft Matter Chem, Dept Polymer Sci & Engn, Hefei 230026, Anhui, Peoples R China;
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China;
4.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Chen, Weiben,Wang, Lei,Mo, Daize,et al. Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2020,59(39):16902-16909.

Chen, Weiben.,Wang, Lei.,Mo, Daize.,He, Feng.,Wen, Zhilin.,...&Chen, Long.(2020).Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,59(39),16902-16909.

Chen, Weiben,et al."Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 59.39(2020):16902-16909.