Gas Adsorption and Diffusion Behaviors in Interfacial Systems Composed of a Polymer of Intrinsic Microporosity and Amorphous Silica: A Molecular Simulation Study

Abstract

We investigate the adsorption and diffusion behaviors of CO 2 , CH 4 , and N 2 in interfacial systems composed of a polymer of intrinsic microporosity (PIM-1) and amorphous silica using grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. We build model systems of mixed matrix membranes (MMMs) with PIM-1 chains sandwiched between silica surfaces. Gas adsorption analysis using GCMC simulations shows that gas molecules are preferentially adsorbed in microcavities distributed near silica surfaces, resulting in an increase in the solubility coefficients of CO 2 , CH 4 , and N 2 compared to bulk PIM-1. In contrast, diffusion coefficients obtained from MD simulations and then calibrated using the dual-mode sorption model show different tendencies depending on gas species: CO 2 diffusivity decreases in MMMs compared to PIM-1, whereas CH 4 and N 2 diffusivities increase. These differences are attributed to competing effects of silica surfaces: the emergence of larger pores as a result of chain packing disruption, which enhances gas diffusion, and a quadrupole−dipole interaction between gas molecules and silica surface hydroxyl groups, which retards gas diffusion. The former has a greater impact on CH 4 and N 2 diffusivities, whereas the latter has a greater impact on CO 2 diffusivity due to the strong quadrupole−dipole interaction between CO 2 and surface hydroxyls. These findings add to our understanding of gas adsorption and diffusion behaviors in the vicinity of PIM-1/silica interfaces, which are unobtainable in experimental studies.

Molecular simulation study on permeation behavior of small molecules in graphyne/polypyrrole mixed matrix membrane

“…It was found that due to the competition effect on the silica surface, the MMMs formed larger pores and promoted the diffusion of CH 4 and N 2 gases. 33 Studies of the gas permeability and diffusion properties of these MMMs have shown that the doping of new carbon materials such as graphene or modified graphene, carbon nanotubes, and so forth, greatly improves the diffusion and permeation properties of common small molecules. [34][35][36] In this study, the focus will be on the factors influencing the gas permeability of MMMs through a time-saving and economical computer simulation method.…”

“…Yoshimoto investigated the adsorption and diffusion behaviors of CO 2 , CH 4 , and N 2 in interfacial systems composed of a polymer of intrinsic microporosity (PIM‐1) and amorphous silica. It was found that due to the competition effect on the silica surface, the MMMs formed larger pores and promoted the diffusion of CH 4 and N 2 gases 33 . Studies of the gas permeability and diffusion properties of these MMMs have shown that the doping of new carbon materials such as graphene or modified graphene, carbon nanotubes, and so forth, greatly improves the diffusion and permeation properties of common small molecules 34–36 …”