Dynamical and electronic properties of anion-pillared metal–organic frameworks for natural gas separation

Abstract

The increasing demand for natural gas as a clean energy source has emphasized the need for efficient gas separation technologies. Metal–organic frameworks (MOFs) have emerged as a promising class of materials for gas separation, with anion-pillared MOFs (APMOFs) gaining attention for their fine-tuned pore design and shape/size selectivity. In this study, we investigate the dynamical and electronic properties of three APMOFs, SIFSIX-3-Cu, SIFSIX-2-Cu-i, and SIFSIX-2-Cu, for the separation of methane from ethane, ethene, propane, propene, and N using computational simulations. Our simulations employ Grand Canonical Monte Carlo (GCMC) and Molecular Dynamics (MD) techniques combined with Density Functional Theory (DFT) calculations. We find that that all three APMOFs exhibit promising separation capabilities for methane from propane and propene based on both thermodynamics and kinetics parameters. In addition, we use Noncovalent Interaction (NCI) analysis to investigate intermolecular interactions and find that the fluorine atoms in the MOF can polarize gas molecules and establish electrostatic interactions with hydrogen atoms in the molecule. Finally, we show that SIFSIX-2-Cu-i is a potential candidate for separating N₂/CH₄ due to its interpenetration.