In Situ-Doped Superacid in the Covalent Triazine Framework Membrane for Anhydrous Proton Conduction in a Wide Temperature Range from Subzero to Elevated Temperature.

Synthesis of solid-state proton-conducting membranes with low activation energy and high proton conductivity under anhydrous conditions is a great challenge. Here, we show a simple and convenient way to prepare covalent triazine framework membranes (CTF-Mx) with acid in situ doping for anhydrous proton conduction in a wide temperature range from subzero to elevated temperature (160 °C). The low proton dissociation energy and continuous hydrogen bond network in CTF-Mx make the membrane achieve high proton conductivity from 1.21×10 ^-3 S cm ^-1 (-40 °C) to 2.08×10 ^-2 S cm ^-1 (160 °C) under anhydrous conditions. Molecular dynamics and proton relaxation time analyses reveal proton hopping at low activation energies with greatly enhanced mobility in the CTF membranes.