Synthesis of Proton Conductive Zirconium Metal–Organic Framework Glasses

The emerging class of metal-organic framework glasses (MOF glasses) holds promise for achieving high proton conductivity due to their disordered structure, which enhances proton mobility. However, designing the properties of MOF glasses remains challenging because they are mostly prepared using top-down approaches, and only a few selected MOFs show a stable liquid state while most of them decompose upon heating. Moreover, proton-conductive MOF glasses, to date, are not water-stable, which limits their applications. Here we propose an entirely novel bottom-up strategy to synthesize tailored Zr-MOF glasses for achieving proton conductivity and water stability. The MOF glasses were synthesized by crosslinking Zr-clusters, leveraging modular building blocks such as pre-designed functional linkers, precise control over local geometry, and post-synthesis modifications to achieve proton conductivity, thermal stability, processability, and water stability.