The Hidden Role of the Dielectric Effect in Nanofiltration: A Novel Perspective to Unravel New Ion Separation Mechanisms.

Nanofiltration (NF) membranes play a critical role in separation processes, necessitating an in-depth understanding of their selective mechanisms. Existing NF models predominantly include steric and Donnan mechanisms as primary mechanisms. However, these models often fail in elucidating the NF selectivity between ions of similar dimensions and the same valence. To address this gap, an innovative methodology was proposed to unravel new selective mechanisms by quantifying the nominal dielectric effect isolated from steric and Donnan exclusion through fitted pore dielectric constants by regression analysis. We demonstrated that the nominal dielectric effect encompassed unidentified selective mechanisms of significant relevance by establishing the correlation between the fitted pore dielectric constants and these hindrance factors. Our findings revealed that dehydration-induced ion-membrane interaction, rather than ion dehydration, played a pivotal role in ion partitioning within NF membranes. This interaction was closely linked to the nondeformable fraction of hydrated ions. Further delineation of the dielectric effect showed that favorable interactions between ions and membrane functional groups contributed to entropy-driven selectivity, which is a key factor in explaining ion selectivity differences between ions sharing the same size and valence. This study deepens our understanding of NF selectivity and sheds light on the design of highly selective membranes for water and wastewater treatment.