Zeolitic Imidazolate Framework Membranes for Organic Solvent Nanofiltration: A Molecular Simulation Exploration.

Organic solvents are intensively used in chemical and pharmaceutical industries. Their separation and recovery account for a significant portion of energy consumption and capital cost in many industrial processes. In this study, three microporous crystalline zeolitic imidazolate frameworks (ZIF-25, ZIF-71, and ZIF-96) are investigated as organic solvent nanofiltration (OSN) membranes by molecular simulations. The fluxes of five solvents (methanol, ethanol, acetone, acetonitrile, and n-hexane) are predicted. Despite the smallest aperture size among the three ZIFs, ZIF-25 exhibits the highest flux for polar solvents (methanol, ethanol, acetone, and acetonitrile) because of its hydrophobic nature, whereas hydrophilic ZIF-96 shows the highest flux for nonpolar n-hexane. The analysis of structural information and interaction energy reveals that the solvent-framework interaction is crucial to determine solvent permeation. Good correlations between solvent permeances and a combination of solvent properties are found. In the presence of a model solute (paracetamol), solvent permeances are marginally affected; moreover, the rejection of paracetamol is 100% for the three ZIF membranes in all five solvents. This study highlights that the pore chemistry, in addition to pore size, plays an important role in solvent permeation, and it suggests that ZIFs are potential OSN membranes for the recovery of organic solvents.