Improving Ethane/Ethylene Separation Performance of Isoreticular Metal-Organic Frameworks via Substituent Engineering

The preferential capture of ethane (C₂H₆) over ethylene (C₂H₄) presents a very cost-effective and energy-saving means applied to adsorptive separation and purification of C₂H₄ with a high product purity, which is however challenged by low selectivity originating from their similar molecular sizes and physical properties. Substituent engineering has been widely employed for selectivity regulation and improvement, but its effect on C₂H₆/C₂H₄ separation has been rarely explored to date. In this work, four isoreticular coordination framework compounds based on 5-(pyridin-3-yl)isophthalate ligands bearing different substituents were rationally constructed. As revealed by isotherm measurements, thermodynamic studies, and IAST computations, they exhibited promising utility for C₂H₆/C₂H₄ separation with moderate adsorption heat and a high uptake amount at a relatively low-pressure domain. Furthermore, the C₂H₆/C₂H₄ separation potential can be finely tuned and optimized via purposeful substituent alteration. Most remarkably, functionalization with a nonpolar methyl group yielded an improved separation efficiency compared to its parent compound. This work offers a good reference value for enhancing the C₂H₆/C₂H₄ separation efficiency of MOFs by engineering the pore microenvironment and dimensions via substituent manipulation.