Synergism of orderly intrinsic and extrinsic proton-conducting sites in covalent organic framework membranes

• NUS-9 nanosheets with well-defined sulfonic acid groups possess intrinsic proton conductivity. • DNA with plentiful linear arranged phosphate groups provide extrinsic proton-conducting sites. • Synergism of orderly intrinsic and extrinsic proton-conducting sites facilitates the proton conduction. • DNA@COF-X membranes exhibit enhanced proton conductivity in different humidity. Development of high proton-conducting membranes is the major demand in energy conversion, sensing, and catalysis. The emerging ionic covalent organic frameworks (iCOFs) with abundant and well-arranged proton-conducting groups offer new materials for efficient proton conduction. However, the poor processability of iCOFs makes it difficult to fabricate defect-free membranes. Herein, we use the interfacial reaction method to synthesize high crystalline iCOF nanosheets (NUS-9) which are then processed into defect-free membranes by vacuum-assisted assembly method. The plenty of intrinsic orderly aligned sulfonic acid groups in the iCOF skeletons endows the nanosheets with intrinsic high proton conductivity. Furthermore, the deoxyribonucleic acid molecules (DNA) with sequential linear arranged phosphate groups are intercalated into the iCOF membrane. The synergetic effect of orderly intrinsic and extrinsic proton-conducting sites gives the resulting DNA@iCOF membranes high proton conductivity of up to 494.7 mS cm −1 (98% RH, 80 °C), which is among the highest values of the state-of-the-art COF-based proton conductors. Besides, it also retains high conductivity over a wide range of RH (40–100%) and temperature (30−80 °C).