Electrostatic Repulsion Facilitated Ion Transport in Covalent−Organic Framework Membranes

Abstract Covalent−organic framework (COF) membranes are increasingly used for many potential applications including ion separation, fuel cells, and ion batteries. It is of central importance to fundamentally and quantitatively understand ion transport in COF membranes. In this study, a series of COF membranes is designed with different densities and arrangements of functional groups and subsequently utilize molecular simulation to provide microscopic insights into ion transport in these membranes. The membrane with a single‐sided layer exhibits the highest chloride ion (Cl ⁻ ) conductivity of 77.2 mS cm ⁻¹ at 30 °C. Replacing the single‐sided layer with a double‐sided layer or changing layer arrangement leads to a decrease in Cl ⁻ conductivity up to 33% or 53%, respectively. It is revealed that the electrostatic repulsion between ions serves as a driving force to facilitate ion transport and the positions of functional groups determine the direction of electrostatic repulsion. Furthermore, the ordered pores generate concentrated ions and allow rapid ion transport. This study offers bottom‐up inspiration on the design of new COF membranes with moderate density and proper arrangement of functional groups to achieve high ion conductivity.