Donor-acceptor moiety functionalized covalent organic frameworks for boosting charge separation and H2 photogeneration

Chang-Cheng Gu; Chen-Quan Ni; Run-Juan Wu; Lu Deng; Jun Zou; Hao Li; Chun-Yi Tong; Feng-Hua Xu; Bai-Cheng Weng; Ri-Long Zhu

doi:10.1016/j.jcis.2023.12.109

Donor-acceptor moiety functionalized covalent organic frameworks for boosting charge separation and H₂ photogeneration

J Colloid Interface Sci. 2024 Mar 15:658:450-458. doi: 10.1016/j.jcis.2023.12.109. Epub 2023 Dec 18.

Authors

Chang-Cheng Gu¹, Chen-Quan Ni², Run-Juan Wu¹, Lu Deng¹, Jun Zou¹, Hao Li¹, Chun-Yi Tong¹, Feng-Hua Xu³, Bai-Cheng Weng⁴, Ri-Long Zhu⁵

Affiliations

¹ Advanced Catalytic Engineering Research Center of the Ministry of Education, Department of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
² Key Laboratory of Biohydrometallurgy of Ministry of Education, School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China.
³ Department of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China.
⁴ Department of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China. Electronic address: bcweng@mail.csu.edu.cn.
⁵ Advanced Catalytic Engineering Research Center of the Ministry of Education, Department of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China. Electronic address: zrlden@hnu.edu.cn.

PMID: 38118191
DOI: 10.1016/j.jcis.2023.12.109

Abstract

Covalent organic frameworks (COFs) have a broad prospect to be used as a photocatalytic platform to convert solar energy into valuable chemicals due to their tunable structures and rich active catalytic sites. However, constructing COFs with tuned sp²-carbon donor-acceptor moiety remains an enormous challenge. Herein, we synthesized two new fully π-conjugated cyano-ethylene-linked COFs containing benzotrithiophene as functional group by Knoevenagel polycondensation reaction. The accetpor 2,2'-bipyridine unit in BTT-BpyDAN-COF skeleton favored the formation of a intermolecular specific electron transport pathway with the donor benzotrithiophene, and thereby promoted charge separation and transfer efficiency. Specifically, a donor-acceptor (D-A) type BTT-BpyDAN-COF exhibited high hydrogen evolution rate of 10.1 mmol g^-1h^-1 and an excellent apparent quantum efficiency of 4.83 % under visible light irradiation.

Keywords: Charge separation; Covalent organic frameworks; Donor-acceptor moiety; Knoevenagel polycondensation reaction; Photocatalytic hydrogen evolution.