Molecular Simulations of MOF Membranes and Performance Predictions of MOF/Polymer Mixed Matrix Membranes for CO/CH Separations.

Efficient separation of CO from CO/CH mixtures using membranes has economic, environmental and industrial importance. Membrane technologies are currently dominated by polymers due to their processing abilities and low manufacturing costs. However, polymeric membranes suffer from either low gas permeabilities or low selectivities. Metal organic frameworks (MOFs) are suggested as potential membrane candidates that offer both high selectivity and permeability for CO/CH separation. Experimental testing of every single synthesized MOF material as membranes is not practical due to the availability of thousands of different MOF materials. A multilevel, high-throughput computational screening methodology was used to examine the MOF database for membrane-based CO/CH separation. MOF membranes offering the best combination of CO permeability (>10 Barrer) and CO/CH selectivity (>80) were identified by combining grand canonical Monte Carlo and molecular dynamics simulations. Results revealed that the best MOF membranes are located above the Robeson's upper bound indicating that they outperform polymeric membranes for CO/CH separation. The impact of framework flexibility on the membrane properties of the selected top MOFs was studied by comparing the results of rigid and flexible molecular simulations. Relations between structures and performances of MOFs were also investigated to provide atomic-level insights into the design of novel MOFs which will be useful for CO/CH separation processes. We also predicted permeabilities and selectivities of the mixed matrix membranes (MMM) in which the best MOF candidates are incorporated as filler particles into polymers and found that MOF-based MMMs have significantly higher CO permeabilities and moderately higher selectivities than pure polymers.