Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Covalent organic frameworks (COFs) are promising materials for gas storage and separation; however, the potential of COFs for separation of CH₄ from industrially relevant gases such as H₂, N₂, and C₂H₆ is yet to be investigated. In this work, we followed a multiscale computational approach to unlock both the adsorption- and membrane-based CH₄/H₂, CH₄/N₂, and C₂H₆/CH₄ separation potentials of 572 COFs by combining grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations and density functional theory (DFT) calculations. Adsorbent performance evaluation metrics of COFs, adsorption selectivity, working capacity, regenerability, and adsorbent performance score were calculated for separation of equimolar CH₄/H₂, CH₄/N₂, and C₂H₆/CH₄ mixtures at vacuum swing adsorption (VSA) and pressure swing adsorption (PSA) conditions to identify the best-performing COFs for each mixture. Results showed that COFs could achieve selectivities of 2-85, 1-7, and 2-23 for PSA-based CH₄/H₂, CH₄/N₂, and C₂H₆/CH₄ separations, respectively, outperforming conventional adsorbents such as zeolites and activated carbons for each mixture. Structure-performance relations revealed that COFs with pore sizes <10 Å are promising adsorbents for all mixtures. We identified the gas adsorption sites in the three top-performing COFs commonly identified for each mixture by DFT calculations and computed the binding strength of gases, which were found to be on the order of C₂H₆ > CH₄ > N₂ > H₂, supporting the GCMC results. Nucleus-independent chemical shift (NICS) indexes of aromaticity for adsorption sites were calculated, and the results revealed that the degree of linker aromaticity could be a measure for the selection or design of highly alkane-selective COF adsorbents over N₂ and H₂. Finally, COF membranes were shown to achieve high H₂ permeabilities, 4.57 × 10³ -1.25 × 10⁶ Barrer, and decent membrane selectivities, as high as 4.3, outperforming polymeric and MOF-based membranes for separation of H₂ from CH₄.