Solvent Polarity Engineering in Low-DMF ZIF-7 Membrane Growth: Crystallization Behavior, Heterogeneous Intergrowth,...

Molecular transport membranes are promising alternatives to conventional cryogenic separation processes. Here, solvent polarity effects were investigated by varying the DMF/MeOH ratio during the solvothermal synthesis of supported ZIF-7 membranes. A DMF:MeOH ratio of 1:3 preserved the characteristic sodalite topology while suppressing dense-phase formation. Methanol incorporation modified heterogeneous crystallization behavior, intercrystalline organization, membrane morphology, and film densification on α-alumina supports while reducing DMF consumption by approximately 75%. These effects are associated with solvent-mediated precursor solvation, Zn²⁺-benzimidazole coordination equilibria, and heterogeneous nucleation at the support-solution interface. Although low BET surface areas were obtained from N₂ adsorption at 77 K, these values were interpreted cautiously considering the known limitations of nitrogen physisorption in flexible ultramicroporous frameworks. Overall, the results support solvent polarity engineering as a physicochemical strategy for regulating membrane microstructural evolution under reduced DMF conditions. Accordingly, the transport behavior discussed herein is interpreted primarily from a solvent-mediated microstructural perspective rather than as a direct quantitative descriptor of accessible porosity.