Rapid, Ordered Polymerization of Crystalline Semiconducting Covalent Triazine Frameworks

The rapid synthesis of crystalline covalent triazine frameworks (CTFs) and exploration of the polymerization mechanism are highly desired for the research of crystalline porous polymers, but have not yet been reported. Herein, we demonstrate a scalable microwave-assisted synthetic strategy to successfully prepare a series of highly crystalline and semiconducting CTFs within 20 minutes for the first time. By in situ imaging and time-dependent characterization, we proposed an ordered two-dimensional (2D) polymerization mechanism for crystalline CTFs, in which the monomers rapidly polymerize into periodic 2D molecular sheets within 10 s and then grow into more ordered framework structures. Photocatalytic study of CTF with different crystallinity revealed that large crystalline domain could significantly improve the photocatalytic performance. Single-layer and few-layer crystalline 2D triazine polymer nanosheets could be obtained through simple ball-milling exfoliation of the bulk layered CTFs and exhibit nearly fivefold improved photocatalytic hydrogen evolution rate up to 7971 μmol g^-1 h^-1 .