Hydroxide Ion Conduction through Viologen-Based Covalent Organic Frameworks (vCOFs): An Approach toward the Advancement

Alkaline fuel cells rely on the movement of hydroxide anions (OH–) for their operation, yet these anions face challenges in efficient conduction due to their limited diffusion coefficient and substantial mass compared to proton (H+) transport. Within the covalent organic framework structure, ordered channels offer a promising solution for the OH– ion transport. Herein, we synthesized a cationic covalent organic framework (vTAPA) via the solvothermal-assisted Zincke reaction. vTAPA showcases excellent stability in harsh basic solution (12 M) and a wide range of pH. This framework facilitates OH– conduction through its one-dimensional network through the anion exchange process. We employed various tertiary ammonium salts (tetramethyl, tetraethyl, and tetrabutyl ammonium hydroxide) to exchange trapped anionic chloride ions inside the vTAPA structure with OH– ions. The density functional theory (DFT) study exhibited that the anion exchange process is very favorable, as the vTAPA framework offers preferable interaction sites for OH– ions. The impact of steric hindrance from these tertiary ammonium salts on the OH– conduction performance was extensively investigated. Butyl@vTAPA exhibited a high OH– ion conductivity of 1.05 × 10–4 S cm–1 at 90 °C under 98% relative humidity (RH). Our uniquely designed cationic covalent organic frameworks (COF) created a platform for a preferential transport network of hydroxide ions, and this is the first report of directly used COFs for hydroxide ion conduction without any vigorous postsynthetic modification.