Three-in-One C₂ H₂ -Selectivity-Guided Adsorptive Separation across an Isoreticular Family of Cationic Square-Lattice MOFs

Energy-efficient selective physisorption driven C₂ H₂ separation from industrial C2-C1 impurities such as C₂ H₄ , CO₂ and CH₄ is of great importance in the purification of downstream commodity chemicals. We address this challenge employing a series of isoreticular cationic metal-organic frameworks, namely iMOF-nC (n=5, 6, 7). All three square lattice topology MOFs registered higher C₂ H₂ uptakes versus the competing C2-C1 gases (C₂ H₄ , CO₂ and CH₄ ). Dynamic column breakthrough experiments on the best-performing iMOF-6C revealed the first three-in-one C₂ H₂ adsorption selectivity guided separation of C₂ H₂ from 1:1 C₂ H₂ /CO₂ , C₂ H₂ /C₂ H₄ and C₂ H₂ /CH₄ mixtures. Density functional theory calculations critically examined the C₂ H₂ selective interactions in iMOF-6C. Thanks to the abundance of square lattice topology MOFs, this study introduces a crystal engineering blueprint for designing C₂ H₂ -selective layered metal-organic physisorbents, previously unreported in cationic frameworks.