Proton conductive materials are of significant importance and highly desired for clean energy-related applications. Discovery of practical metal-organic frameworks (MOFs) with high proton conduction remains a challenge due to the use of toxic chemicals, inconvenient ligand preparation and complication of production at scale for the state-of-the-art candidates. Herein, we report a zirconium-MOF, MIP-202(Zr), constructed from natural α-amino acid showing a high and steady proton conductivity of 0.011 S cm−1 at 363 K and under 95% relative humidity. This MOF features a cost-effective, green and scalable preparation with a very high space-time yield above 7000 kg m−3 day−1. It exhibits a good chemical stability under various conditions, including solutions of wide pH range and boiling water. Finally, a comprehensive molecular simulation was carried out to shed light on the proton conduction mechanism. All together these features make MIP-202(Zr) one of the most promising candidates to approach the commercial benchmark Nafion.

A hydrolytically stable metal-organic framework (MOF) material, named KAUST-7', was derived from a structural phase change of KAUST-7 upon exposure to conditions akin to protonic conduction (363 K/95% relative humidity). KAUST 7' exhibited a superprotonic conductivity as evidenced by the impedance spectroscopic measurement revealing an exceptional conductivity up to 2.0 × 10 S cm at 363 K and under 95% RH, a performance maintained over 7 days. Ab initio molecular dynamics simulations suggested that the water-mediated proton transport mechanism is governed by water assisted reorganization of the H-bond network involving the fluorine moieties in KAUST-7' and the guest water molecules. The notable level of performances combined with a very good hydrolytic stability positions KAUST-7' as a prospective proton-exchange membrane alternative to the commercial benchmark Nafion. Furthermore, the remarkable RH sensitivity of KAUST-7' conductivity, substantially higher than previously reported MOFs, offers great opportunities for deployment as a humidity sensor.