Enhanced Proton Transfer in Proton‐Exchange Membranes with Interconnected and Zwitterion‐Functionalized Covalent Porous Material Structures

Excellent proton-conductive accelerators are indispensable for efficient proton-exchange membranes (PEMs). Covalent porous materials (CPMs), with adjustable functionalities and well-ordered porosities, show much promise as effective proton-conductive accelerators. In this study, an interconnected and zwitterion-functionalized CPM structure based on carbon nanotubes and a Schiff-base network (CNT@ZSNW-1) is constructed as a highly efficient proton-conducting accelerator by in situ growth of SNW-1 onto carbon nanotubes (CNTs) and subsequent zwitterion functionalization. A composite PEM with enhanced proton conduction is acquired by integrating CNT@ZSNW-1 with Nafion. Zwitterion functionalization offers additional proton-conducting sites and promotes the water retention capacity. Moreover, the interconnected structure of CNT@ZSNW-1 induces a more consecutive arrangement of ionic clusters, which significantly relieves the proton transfer barrier of the composite PEM and increases its proton conductivity to 0.287 S cm^-1 under 95 % RH at 90 °C (about 2.2 times that of the recast Nafion, 0.131 S cm^-1 ). Furthermore, the composite PEM displays a peak power density of 39.6 mW cm^-2 in a direct methanol fuel cell, which is significantly higher than that of the recast Nafion (19.9 mW cm^-2 ). This study affords a potential reference for devising and preparing functionalized CPMs with optimized structures to expedite proton transfer in PEMs.