The dynamics of ions and solvent molecules in polyelectrolyte desalination membranes is key to water purification technologies in which selective transport of the different components is desired. Recent experimental and our computational results have shown that nontrivial mechanisms underlie the transport properties of salt ions and water in charged polymer membranes. Explicitly, in polymer electrolytes, we found a reversal in the salt concentration dependence of the mobilities of Na+, Cl– salt ions and water molecules when compared with aqueous solutions. Motivated by such results, in this study, we have used atomistic molecular dynamics simulations to probe whether the mechanisms deduced in our earlier work apply to other salt systems and to mixtures of salts. Specifically, we report results for the ion diffusivities in aqueous KCl, MgCl2, and a 1:1 mixture of NaCl and MgCl2 salt solutions at different concentrations (ranging from 0.06 to 1 M) and investigate, at the molecular level, the mechanisms underlying the behaviors of salt and water transport properties. Our results show that diffusion of salt ions and water in charged polymer membranes are in general influenced by their association with polymer charge groups and ion pairing effects. Divalent ions are more strongly coupled with the polymeric ionic groups than monovalent salt ions and exhibit diffusivity trends that are distinct relative to monovalent salts. Further, we demonstrate that the mobilities of water molecules are influenced by coordination of water with polymer charge groups and their ion pairing tendencies and also exhibit distinct trends in monovalent and divalent salt solutions.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): OSR-2016-CRG5-2993-1
Acknowledgements: We thank Prof. Benny Freeman and Dr. Jovan Kamcev for many useful discussions on this topic, and also for sharing a preprint of their article in advance of submission. We acknowledge funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (CBET-17069698 and DMR-lol1721512), King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). The authors acknowledge the Texas Advanced Computing Center (TACC) for computing resources.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.