Large-Scale Computational Screening of Metal Organic Framework (MOF) Membranes and MOF-Based Polymer Membranes for H(2)/N(2) Separations

[Image: see text] Several thousands of metal organic frameworks (MOFs) have been reported to date, but the information on H(2)/N(2) separation performances of MOF membranes is currently very limited in the literature. We report the first large-scale computational screening study that combines state-of-the-art molecular simulations, grand canonical Monte Carlo (GCMC) and molecular dynamics (MD), to predict H(2) permeability and H(2)/N(2) selectivity of 3765 different types of MOF membranes. Results showed that MOF membranes offer very high H(2) permeabilities, 2.5 × 10(3) to 1.7 × 10(6) Barrer, and moderate H(2)/N(2) membrane selectivities up to 7. The top 20 MOF membranes that exceed the polymeric membranes’ upper bound for H(2)/N(2) separation were identified based on the results of initial screening performed at infinite dilution condition. Molecular simulations were then carried out considering binary H(2)/N(2) and quaternary H(2)/N(2)/CO(2)/CO mixtures to evaluate the separation performance of MOF membranes under industrial operating conditions. Lower H(2) permeabilities and higher N(2) permeabilities were obtained at binary mixture conditions compared to the ones obtained at infinite dilution due to the absence of multicomponent mixture effects in the latter. Structure–performance relations of MOFs were also explored to provide molecular-level insights into the development of new MOF membranes that can offer both high H(2) permeability and high H(2)/N(2) selectivity. Results showed that the most promising MOF membranes generally have large pore sizes (>6 Å) as well as high surface areas (>3500 m(2)/g) and high pore volumes (>1 cm(3)/g). We finally examined H(2)/N(2) separation potentials of the mixed matrix membranes (MMMs) in which the best MOF materials identified from our high-throughput screening were used as fillers in various polymers. Results showed that incorporation of MOFs into polymers almost doubles H(2) permeabilities and slightly enhances H(2)/N(2) selectivities of polymer membranes, which can advance the current membrane technology for efficient H(2) purification.