Molecular Simulations of MOF Membranes and PerformancePredictions of MOF/Polymer Mixed Matrix Membranes for CO2/CH4 Separations

摘要

Efficient separation of CO2 from CO2/CH4 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 CO2/CH4 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 CO2/CH4 separation. MOF membranes offering the best combination of CO2 permeability (>10⁶ Barrer) and CO2/CH4 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 forCO2/CH4 separation. The impact of frameworkflexibility on the membrane properties of the selected top MOFs wasstudied by comparing the results of rigid and flexible molecular simulations.Relations between structures and performances of MOFs were also investigatedto provide atomic-level insights into the design of novel MOFs whichwill be useful for CO2/CH4 separation processes.We also predicted permeabilities and selectivities of the mixed matrixmembranes (MMM) in which the best MOF candidates are incorporatedas filler particles into polymers and found that MOF-based MMMs havesignificantly higher CO2 permeabilities and moderatelyhigher selectivities than pure polymers.