Short hydrogen-bond network confined on COF surfaces enables ultrahigh proton conductivity

Abstract

The idea of spatial confinement has gained widespread interest in myriad applications. Especially, the confined short hydrogen-bond (SHB) network could afford an attractive opportunity to enable proton transfer in a nearly barrierless manner, but its practical implementation has been challenging. Herein, we report a SHB network confined on the surface of ionic covalent organic framework (COF) membranes decorated by densely and uniformly distributed hydrophilic ligands. Combined experimental and theoretical evidences have pointed to the confinement of water molecules allocated to each ligand, achieving the local enrichment of hydronium ions and the concomitant formation of SHBs in water-hydronium domains. These overlapped water-hydronium domains create an interconnected SHB network, which yields an unprecedented ultrahigh proton conductivity of 1389 mS cm⁻¹ at 90 °C, 100% relative humidity.

When hydronium ions are enriched in confined water, short hydrogen bonds (SHBs) form due to the constrained space of excess protons between pairs of water molecules. Here authors demonstrate a SHB network confined on the surface of ionic COF membranes with tunable -SO₃H groups, with proton conductivity of 1389 mS cm^-1 at 90 ^oC.