Multivariate MOF Hollow Fiber Membranes with Precision‐Tuned Subnanometer Channels Toward Aromatic Hydrocarbon Separation

Abstract 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.