Abstract
AbstractControl 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.
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