Pore Geometry and Surface Engineering of Covalent Organic Frameworks for Anhydrous Proton Conduction

Developing new materials for anhydrous proton conduction under high-temperature conditions is significant and challenging. Herein, we create a series of highly crystalline covalent organic frameworks (COFs) via a pore engineering approach. We simultaneously engineer the pore geometry (generating concave dodecagonal nanopores) and pore surface (installing multiple functional groups such as -C=N-, -OH, -N=N- and -CF₃ ) to improve the utilization efficiency and host-guest interaction of proton carriers, hence benefiting the enhancement of anhydrous proton conduction. Upon loading with H₃ PO₄ , COFs can realize a proton conductivity of 2.33×10^-2  S cm^-1 under anhydrous conditions, among the highest values of all COF materials. These materials demonstrate good stability and maintain high proton conductivity over a wide temperature range (80-160 °C). This work paves a new way for designing COFs for anhydrous proton conduction applications, which shows great potential as high-temperature proton exchange membranes.