Mixture Adsorption in Nanoporous Zeolite and at Its External Surface: In-Pore and Surface Selectivity

Using toluene, ethylene, and water as gas compounds with different representative molecular interactions, we perform atom-scale simulations for their mixtures to investigate the selectivity of the core nanoporosity and external surface in a prototypical zeolite. As expected, the overall behavior suggests that increasing the pressure of a given component promotes the desorption of the coadsorbing species. However, for water-toluene mixtures, we identify that the pseudohydrogen bonding between water and toluene leads to beneficial coadsorption as toluene adsorption in the low-pressure range promotes water adsorption. Moreover, when the zeolite is completely filled with water, toluene adsorption does not occur due to steric repulsion, and ethylene shows oversolubility as the amount of ethylene per water molecule is significantly larger than in bulk water. The underlying oversolubility mechanism is found to be due to localized ethylene adsorption in the density minima arising from the layering of water in nanoconfinement. Despite these specific effects, the relatively weak coadsorption effects in the zeolite nanoporosity, which are found to be reasonably captured using the ideal adsorbed solution theory, arise from the fact that adsorption of these gases having different molecular sizes occurs in distinct pore regions (channel type, channel intersection). Finally, in contrast to confinement in the nanoporosity, mixture adsorption at the external surface does not show coadsorption effects as it mostly follows the Henry regime. These results show that selectivity is mostly governed by the confinement effects as the external surface leads to a selectivity loss.