Vapor-Mediated Metal-Organic Framework Topology Transition for Continuous Crystalline Membranes With Excellent...

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.