Constructing a novel family of halogen-doped covalent triazine-based frameworks as efficient metal-free photocatalysts for hydrogen production.

Halogens, as typical non-metal dopants, have attracted intensive interests for developing highly active photocatalysts. However, the essential factors and underlying mechanism of halogen modification are still unclear. Herein, we systematically report the development of halogen (F, Cl and Br)-doped covalent triazine-based frameworks (CTFs) via a facile thermal treatment of CTFs and an excess of ammonium halide. The introduction of halogen atoms endowed CTFs with multiple superior effects such as improved optical absorption, promoted charge migration, narrowed band gaps and tuned band positions. The newly developed halogen-doped CTFs showed remarkable photocatalytic activities for H2 evolution under visible-light irradiation. Notably, the most enhanced photocatalytic performance was obtained with Cl-doped CTFs, which exhibited 7.1- and 2.4-fold enhancements compared to un-doped CTFs and Cl-doped g-C3N4, respectively. The electronegativity and atomic radius of the halogen atoms affected the modification of the optical and electronic properties, leading to different photocatalytic performances of F-, Cl- and Br-doped CTFs. The conclusions presented in this work will provide some new insights into the understanding of the doping effect for the improvement of the photocatalytic activity of halogen-doped CTF photocatalysts.