Two Solvent-Induced In(III)-Based Metal-Organic Frameworks with Controllable Topology Performing High-Efficiency...

For pure acetylene manufacturing and natural gas purification, the development of porous materials displaying highly selective C₂H₂/CH₄ and CO₂/CH₄ separation is greatly important but remains a major challenge. In this work, a plausible strategy involving solvent-induced effects and using the flexibility of the ligand conformation to make two In(III) metal-organic frameworks (MOFs) is developed, showing topological diversity and different stability. The X-shaped tetracarboxylic ligand H₄TPTA ([1,1':3',1″-terphenyl]-4,4',4″,6'-tetracarboxylic acid) was selected to construct two new heteroid In MOFs, namely, {[CH₃NH₃][In(TPTA)]·2(NMF)} (MOF 1) and {[In₂(TPTA)(OH)₂]·2(H₂O)·(DMF)} (MOF 2). MOF 1 is a (4, 4)-connected net showing a pts topology with a large channel that is not conducive to fine gas separation. By contrast, with the reduction of SBU from uninucleated In to an {In-OH-In} chain, MOF 2 has a (4, 6)-connected net with the fsc topology with an ∼5 Å suitable micropore to confine matching small gas. The permanent porosity of MOF 2 leads to the preferential adsorption of C₂H₂ over CO₂ with superior C₂H₂/CH₄ (332.3) and CO₂/CH₄ (31.2) separation selectivities. Meanwhile, the cycling dynamic breakthrough experiments showed that the high-purity C₂H₂ (>99.8%) capture capacities of MOF 2 were >1.92 mmol g^-1 from a binary C₂H₂/CH₄ mixture, and its separation factor reached 10.