Hopping Diffusion in Wiggling Nanopore Architecture of MOF Enabling Synergistic Equilibrium‐Kinetic Separation of Fluorinated Propylene and Propane

The separation of octafluoropropane (C₃F₈) from hexafluoropropylene (C₃F₆) is an industrially important yet challenging process due to their similar physicochemical properties and stringent purity demands in industrial applications. Herein, we address this task through precise pore architecture in a zirconium-based metal-organic framework (Zr-PMA), which exhibits unique "wiggling nanopores" with narrow windows and large cavities. The narrow windows act as diffusion barriers, selectively restricting C₃F₈ transport, while the large cavities provide strong adsorption sites for C₃F₆, enabling an equilibrium-kinetic synergistic separation. This dual functionality results in a ∼450-fold difference in diffusion rates and exceptional kinetic selectivity for C₃F₆ over C₃F₈, as demonstrated by adsorption isotherms, time-resolved kinetics, and dynamic breakthrough experiments. Theoretical calculations coupled with in situ spectroscopy elucidate the pore geometry-dependent hopping diffusion mechanism responsible for the separation. This work establishes wiggling pore geometry as a versatile paradigm for advanced adsorbents targeting energy-efficient separations of structurally similar fluorocarbon mixtures.