Crystalline covalent triazine frameworks manipulated by aliphatic amine modulator

Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks (CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystalline CTFs via the introduction of aliphatic amine as a dynamic modulator is reported. By optimizing the amount of aliphatic amine, the crystallization process can be controlled in an open system, resulting in the synthesis of crystalline CTFs. These crystalline CTFs exhibit much better photocatalytic hydrogen evolution performance, with highly ordered CTF-1-C3 demonstrating superior performance (10 mmol g −1 h −1 ) compared with most reported CTF-1. This approach also allows for the preparation of various crystalline CTFs.