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

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 we demonstrate 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 to1.258. 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. This article is protected by copyright. All rights reserved.