Tailorable Multi‐Modular Pore‐Space‐Partitioned Vanadium Metal‐Organic Frameworks for Gas Separation

Abstract Currently, few porous vanadium metal‐organic frameworks (V‐MOFs) are known and even fewer are obtainable as single crystals, resulting in limited information on their structures and properties. Here this work demonstrates remarkable promise of V‐MOFs by presenting an extensible family of V‐MOFs with tailorable pore geometry and properties. The synthesis leverages inter‐modular synergy on a tri‐modular pore‐partitioned platform. New V‐MOFs show a broad range of structural features and sorption properties suitable for gas storage and separation applications for C₂H₂/CO₂, C₂H₆/C₂H₄, and C₃H₈/C₃H₆. The c/a ratio of the hexagonal cell, a measure of pore shape, is tunable from 0.612 to 1.258. Other tunable properties include pore size from 5.0 to 10.9 Å and surface area from 820 to 2964 m² g⁻¹. With C₂H₂/CO₂ selectivity from 3.3 to 11 and high uptake capacity for C₂H₂ from 65.2 to 182 cm³ g⁻¹ (298K, 1 bar), an efficient separation is confirmed by breakthrough experiments. The near‐record high uptake for C₂H₆ (166.8 cm³ g⁻¹) contributes to the promise for C₂H₆‐selective separation of C₂H₆/C₂H₄. The multi‐module pore expansion enables transition from C₃H₆‐selective to more desirable C₃H₈‐selective separation with extraordinarily high C₃H₈ uptake (254.9 cm³ g⁻¹) and high separation potential (1.25 mmol g⁻¹) for C₃H₈/C₃H₆ (50:50 v/v) mixture.