In-situ doping strategy for improving the photocatalytic hydrogen evolution performance of covalent triazine frameworks

A highly conjugated network of covalent triazine frameworks (CTFs) on the one hand promotes light-harvesting, but on the other hand, also results in high carrier recombination which eventually limits their photocatalytic hydrogen evolution reaction (HER) rates. Thus, strategies to favorably tune the electronic configuration of CTFs for efficient photocatalytic HERs need to be developed, but still remain challenging. Herein, a simple in-situ defect strategy involving element doping is developed for the first time to introduce a heteroatom including S and Se into CTF-1 via the condensation of aldehydes with the mixture of the terephthalimidamide and the S- or Se-substituted terephthalimidamide under mild conditions. The doping content ( X ) is varied, resulting in a series of S- and Se-doped CTFs, named CTFS-1- X and CTFSe-1- X , respectively. Interestingly, for the S-doped CTFs, CTFS-1-10 shows the most excellent HER rate (4,992.3 µmol g −1 h −1 ) from water splitting, while for the Se-doped ones, CTFSe-1-10 exhibits a photocatalytic HER rate of 5,792.8 µmol g −1 h −1 , both of which far surpass undoped CTFs (693.3 µmol g −1 h −1 ). In-depth studies indicate that the introduction of S or Se atoms into CTFs could extend the light absorption and promote photo-generated electron-hole pairs migration. Meanwhile, S- or Se-doping could create heterogeneous electronic configuration in CTFs, which can help to suppress carrier recombination.