Document Type
Article
Original Publication Date
2015
Journal/Book/Conference Title
J. Phys. Chem. C
Volume
119
First Page
20416
DOI of Original Publication
10.1021/acs.jpcc.5b04725
Date of Submission
May 2022
Abstract
Permeation of electrolytes in nanoporous materials underlies many applications in energy and materials technologies. Wetting of apolar nanopores can be enhanced by electric !eld, attracting water and ions from unperturbed electrolyte bath. We study absorption of water and NaCl in the pores by Expanded Ensemble Grand Canonical Monte Carlo simulation, which implements particle insertions and deletions through incremental changes in particles’ coupling with the system. We determine the uptake of water and ions in the pores, and concomitant changes in pore thermodynamics, as functions of !eld strength in the pore and salinity in the external bath. Pressure increase and reduction of wetting free energy, !, in the pore intensify near-quadratically with the !eld. Surprisingly, the in"uence of bulk salinity on ! can change qualitatively with pore width and !eld strength. Conforming to Gibbs adsorption isotherm, narrow pores with salt molality below that of the bath experience an increase in ! with rising bulk salinity. The !eld can change salt depletion to excess and consequently reverse the salinity dependence of wetting free energy from increasing to declining function of bulk molality. Field polarity continues to play a role, leading to asymmetric wettability at opposing walls as we previously observed in the absence of ions.
Rights
© 2015 American Chemical Society
Is Part Of
VCU Chemistry Publications
Comments
This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of Physical Chemistry C, copyright © 2015 American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.5b04725