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.

新兴的金属有机框架玻璃（metal-organic framework glasses，简称MOF玻璃）凭借无序结构提升质子迁移率的特性，在实现高质子传导性能方面极具应用潜力。然而，调控MOF玻璃的性能仍颇具挑战：这类材料大多通过自上而下法制备，仅有少量筛选得到的金属有机框架能够保持稳定液态，绝大多数则会在受热时发生分解。此外，截至目前已报道的质子传导型MOF玻璃均不具备水稳定性，这极大限制了其实际应用。本研究提出了一种全新的自下而上合成策略，用于制备兼具质子传导性与水稳定性的定制化锆基金属有机框架玻璃（Zr-MOF glasses）。该类MOF玻璃通过交联锆簇合成得到，依托模块化构筑单元（如预先设计的功能性连接配体）、对局部几何结构的精准调控以及后合成修饰手段，同时实现质子传导性、热稳定性、可加工性与水稳定性的优化。