Fabrication of electron-acceptor staggered AB Covalent triazine-based frameworks for enhanced visible-light-driven H2 evolution

Yinyin Li; Rui Zhang; Cuiyan Li; Hui Li; Qianrong Fang; Tengfeng Xie

doi:10.1016/j.jcis.2021.10.100

Fabrication of electron-acceptor staggered AB Covalent triazine-based frameworks for enhanced visible-light-driven H₂ evolution

J Colloid Interface Sci. 2022 Feb 15;608(Pt 2):1449-1456. doi: 10.1016/j.jcis.2021.10.100. Epub 2021 Oct 20.

Authors

Yinyin Li¹, Rui Zhang¹, Cuiyan Li², Hui Li³, Qianrong Fang⁴, Tengfeng Xie⁵

Affiliations

¹ Institute of Physical Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China.
² State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China.
³ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China. Electronic address: postlh@jlu.edu.cn.
⁴ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China. Electronic address: qrfang@jlu.edu.cn.
⁵ Institute of Physical Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China. Electronic address: xietf@jlu.edu.cn.

PMID: 34742064
DOI: 10.1016/j.jcis.2021.10.100

Abstract

Covalent triazine-based frameworks (CTFs) have been emerged as a promising organic material for photocatalytic water splitting. However, all of the CTFs only are in the form of AA stacking model to participate in water splitting. Herein, two CTF-1 isomers with different stacking models (eclipsed AA, staggered AB) were obtained by modulating the reaction temperature. Interestingly, experimental and theoretical calculations showed that the crystalline AB stacking CTF-1 possessed a much higher activity for photochemical hydrogen evolution (362 μmol g^-1 h^-1) than AA stacking CTF-1 (70 µmol h^-1 g^-1) for the first time. The outstanding photochemical performance could be attributed to its distinct structural feature that allows more N atoms with higher electron-withdrawing property to be involved in the water reduction reaction. Notably, as a cathode material for PEC water reduction, AB stacking CTF-1 also demonstrated an excellent saturated photocurrent density up to 77 µA cm^-2 at 0 V vs. RHE, which was superior to the AA stacking CTF-1 (47 µA cm^-2). Furthermore, the correlation between stacking models and photocatalytic H₂ evolution of CTF-1 were investigated. This study thus paves the path for designing optimal photocatalyst and extending the novel applications of CTF-based materials.

Keywords: AB stacking; Charge separation; Covalent triazine-based frameworks; H(2) evolution; Photocatalyst.