Assessing CH4/N2 separation potential of MOFs, COFs, IL/MOF, MOF/Polymer, and COF/Polymer composites

Separating CH4/N2 mixture is challenging, and performance of the existing materials is still open to improvement. In this study, we examined both the adsorption- and membrane-based CH4/N2 separation performances of 5034 different materials, including metal organic frameworks (MOFs), covalent organic frameworks (COFs), ionic liquid (IL)/MOF composites, MOF/polymer composites, and COF/polymer composites by performing high-throughput computational screening and molecular simulations. The top performing adsorbents and membranes were identified by computing several performance evaluation metrics. Investigation of the interactions between the gas molecules, the IL, and the top MOF was performed by density functional theory (DFT) calculations. Results pointed out that the interactions between the gas molecules and the linker fragments of the MOF are stronger than their interactions with the IL. Thus, as the IL molecules are loaded into the selected top MOF, they occupy the adsorption sites of the gases, decreasing CH4 and N2 uptakes and increasing the CH4/N2 selectivity. Our results revealed that MOFs offer great potential for adsorption-based CH4/N2 separation, and IL incorporation into MOFs remarkably increases their CH4/N2 selectivities. More than 25% of MOF and 70% of the COF membranes surpassed Robeson's upper bound because of high N2 permeabilities and outperformed conventional polymeric membranes. N2 permeabilities and selectivities of MOF/polymer and COF/polymer composites were found to be significantly higher than those of pure polymers. Our results emphasize the promises of the design and development of new MOF and COF adsorbents, membranes, and their composites with ILs and polymers for efficient CH4/N2 separation.