Anisotropic Gas Separation in Oriented ZIF-95 Membranes Prepared by Vapor-Assisted In-Plane Epitaxial Growth

Control of the microstructure grain orientation, grain boundaries and thickness are crucial for MOF membranes. We report a novel synthesis strategy to prepare highly c-oriented ZIF-95 membranes through vapor-assisted in-plane epitaxial growth. In a mixed DMF/water vapor atmosphere, in-plane epitaxial growth of a ZIF-95 seeds layer was achieved to obtain an oriented and well-intergrown ZIF-95 membrane with a thickness of only 600 nm. Demonstrated by both experimental and simulation studies, the c-oriented ZIF-95 membrane displayed superior separation performance because a perfectly oriented structure resulted in a notable reduction of intercrystalline defects and transport pathways. For the separation of equimolar binary mixtures at 100 °C and 1 bar, the mixture separation factors of H₂/CO₂ and H₂/CH₄ were 32.2 and 53.7, respectively, with an H₂ permeance of over 7.9×10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹, which was 4.6 times higher than that of a randomly oriented ZIF-95 membrane.