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Metal‐organic framework (MOF) ‐based membranes excel in molecular separation, attracting significant research interest. The crystallographic microstructure and selective adsorption capacity of MOFs closely correlate with their gas separation performance. Here, aniline was added to the ZIF‐8 synthesis in varying concentrations. Aniline, encapsulated within ZIF‐8 cavities, interacts strongly with the 2‐methylimidazole linker, resulting in both a shift in crystallographic phase from I₄3m to Cm in Rietveld refinement of X‐ray diffraction (XRD) patterns and the selective adsorption behavior between propylene and propane. Consequently, an aniline decorative ZIF‐8 (Anix‐ZIF‐8) membrane was prepared using a fast current‐driven synthesis method, which exhibits good propylene/propane separation selectivity of up to 85. Calculation of the interaction energy between aniline and the various crystallographic phases of ZIF‐8 using density functional theory (DFT) further verifies that aniline not only promotes the formation of crystallographic Cm phase, but also enhances the adsorption selectivity of propylene over propane. Aniline modification effectively tunes the crystallographic microstructure of ZIF‐8, thereby, improving molecular sieving capabilities.
Zhang et al. (Wed,) studied this question.