High pressure and high temperature phase transformations of covalent triazine-based frameworks

A monolithic two-dimensional (2D) biphenyl-linked triazine-based framework (CTF-2) showing merely slight crystallinity was prepared by Lewis acid-promoted polymerisation of 4,4′-biphenyldicarbonitrile in liquid TiCl4 at moderate temperature to avoid unwanted carbonization. The transformations of CTF-2 induced by high pressure (up to 60 GPa) and temperature (up to 2400 K) were studied by IR and in situ Raman spectroscopy as well as TEM microscopy. In contrast to graphitic C3N4 materials, CTF-2 exhibits high optical density and reduced fluorescence at high pressure, allowing laser-induced sample heating. Spectral data show the formation of sp3 hybridised carbon atoms and triazine ring distortion in CTF-2 material at pressures above 17 GPa. According to the pressure Raman effect, the bulk modulus of the high-pressure phase of CTF-2 (high-pressure phase CTF-2) was found to be 570 ± 10 GPa, which is a typical value for superhard carbon materials. Structural studies revealed nitrogen preservation in the specimen after high-pressure treatment and stability of the disordered sp3 states of the high-pressure phase CTF-2 in the quenched specimen. This behaviour is quite different from that of the quenched disordered sp3 states of high pressure pure carbon phases, which convert to the sp2 state at pressures below 3–7 GPa.