Department of Chemical and Biological Engineering2024-11-0920232058-968910.1039/d2me00130f2-s2.0-85139848577https://hdl.handle.net/20.500.14288/391The 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/H-2, CH4/N-2, and N-2/H-2 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/H-2, CH4/N-2, and N-2/H-2 adsorption-based separation, respectively, were found to have -OCH3 groups as one of the functional groups. The biggest improvements in CF4/CH4, CH4/H-2, CH4/N-2, and N-2/H-2 selectivities were found to be induced by the presence of -OCH3-OCH3 groups in MOFs. For CH4/H-2 separation, MOFs with two and three functionalized linkers were the best adsorbent candidates while for N-2/H-2 separation, all the top 20 materials involve two functional groups. Membrane performances of the MOFs were also studied for CH4/H-2 and CH4/N-2 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.pdfChemistry, physicalEngineering, chemicalNanoscience and nanotechnologyMaterials science, multidisciplinaryJournal Articlehttps://doi.org/10.1039/d2me00130f857442400001N/ANOIR03959