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

Abstract

AbstractCurrently, 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.