Computational investigation of multifunctional MOFs for adsorption and membrane-based separation of CF4/CH4, CH4/H2, CH4/N2, and N2/H2 mixtures†

The ease of functionalization of metal–organic frameworks (MOFs) can unlock unprecedented opportunities for gas adsorption and separation applications as the functional groups can impart favorable/unfavorable regions/interactions for the desired/undesired adsorbates. In this study, the effects of the presence of multiple functional groups in MOFs on their CF₄/CH₄, CH₄/H₂, CH₄/N₂, and N₂/H₂ separation performances were computationally investigated combining grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. The most promising adsorbents showing the best combinations of selectivity, working capacity, and regenerability were identified for each gas separation. 15, 13, and 16 out of the top 20 MOFs identified for the CH₄/H₂, CH₄/N₂, and N₂/H₂ adsorption-based separation, respectively, were found to have –OCH₃ groups as one of the functional groups. The biggest improvements in CF₄/CH₄, CH₄/H₂, CH₄/N₂, and N₂/H₂ selectivities were found to be induced by the presence of –OCH₃–OCH₃ groups in MOFs. For CH₄/H₂ separation, MOFs with two and three functionalized linkers were the best adsorbent candidates while for N₂/H₂ separation, all the top 20 materials involve two functional groups. Membrane performances of the MOFs were also studied for CH₄/H₂ and CH₄/N₂ separation and the results showed that MOFs having –F–NH₂ and –F–OCH₃ functional groups present the highest separation performances considering both the membrane selectivity and permeability.