Vapor‐Mediated Metal–Organic Framework Topology Transition for Continuous Crystalline Membranes With Excellent Pervaporative Performance

ABSTRACT Despite their high porosity and abundant interaction sites, continuous crystalline metal–organic framework (MOF) membranes remain hindered by solvent‐intensive syntheses, uncontrollable homogeneous nucleation, and anisotropic crystal growth on the substrate. Here we report a solvent‐minimal route where a continuous csq ‐net Zr‐MOF membrane was achieved using its scu ‐net isomer nanoparticles as seeds under formic acid vapor, which triggers epitaxial intergrowth at particle interfaces, healing intergranular gaps, and yielding vertically aligned intact membranes. The evolution from scu ‐net nanoparticles to csq ‐net membranes has been sophisticatedly investigated under varied conditions. Benefiting from the inherent large porosity of csq ‐net, the optimized membrane achieves an extremely high separation factor of 21 215, and a water flux of 1.18 kg m ^{− 2} h ^{− 1} for n ‐butanol/water pervaporation, outperforming state‐of‐the‐art MOF and mixed‐matrix membranes. This formic‐acid‐vapor‐mediated topology transition strategy abolishes bulk solvent and homogeneous nucleation, offering a sustainable platform for crystalline porous membranes.