A Classical Molecular Dynamics Study On The Effect Of Si/Al Ratio And Silanol Nest Defects On Water Diffusion In Zeolite Hy

The diffusion of water confined in zeolite HY has been studied using classical molecular dynamics at 300 K to probe the effects of water loading, Si/Al ratio, and silanol nest defect presence on the behavior of water confined in Bronsted acidic faujasite (FAU) zeolites. Water loading, ranging from 5 to 33 wt %, is shown to have a significant effect on diffusivity, showing an increase by a factor of similar to 7 over the loading range, toward a maximum diffusivity. Upon probing the effect of Si/Al ratio (in a range of Si/Al = 5 to fully siliceous), water diffusivity tends to decrease with the concentration of Bronsted acid sites which show strong interactions with the water molecules and thus hinder molecular mobility. The average residence time of water adsorbed to each Bronsted acid site also decreased with both water loading and Si/Al ratio. Water diffusivity shows the highest dependency on Si/Al ratio at 18 wt % loading, as a lack of total mobility in the systems at the lowest loadings is observed (due to significant populations of water molecules being immobilized via interaction with the framework and Bronsted acid sites), and less of a dependence is observed at the highest loadings due to the prevalence of sorbate-sorbate interactions. Notably, silanol nest presence (at a concentration of 1 per unit cell) had no significant effect on the diffusivity of water in HY at any water loading or Si/Al ratio. Reasons considered for this lack of influence include silanol geometry and flexibility at ambient temperature and potentially a lower effective charge density of the defect site.