Metal-organic framework (MOF) membranes exhibit great potential for molecular separations, but it remains a considerable challenge to achieve precise pore aperture regulation, typically requiring the synthesis of distinct MOF structures for each targeted separation. Herein, the first multivariate MOF (MTV-MOF) hollow fiber membranes with precision-tuned subnanometer channels have been fabricated by leveraging the heterogeneous spatial distribution of ligands, where reduced coordination energy barriers drive the formation of alternating narrow (local-path limited) and wide channels, simultaneously addressing the critical permeability-selectivity trade-off in membrane separations. The alternating narrow-wide channel architecture has been systematically investigated through combined density functional theory calculation, molecular dynamics simulation and mathematical modeling, with direct experimental validation provided by low-dose high-resolution scanning transmission electron microscopy and quantitative adsorption analysis. These MTV-MOF membranes demonstrated the ability to selectively separate aromatic hydrocarbons achieving highly selective separation while reduce the molecular transport barriers, offering significant potential for industrial separation processes.
Keywords: Coordination; Membranes; Multivariate metal‐organic frameworks; Separation.
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