Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials
Abstract
Understanding ion transport in porous carbons is critical for a wide range of technologies, including supercapacitors and capacitive deionization for water desalination, yet many details remain poorly understood. For instance, an atomistic understanding of how ion selectivity is influenced by the molecular shape of ions, morphology of the micropores and applied voltages is largely lacking. In this work, we combined molecular dynamics simulations with enhanced sampling methods to elucidate the mechanism of nitrate and chloride selectivity in subnanometer graphene slit-pores. We demonstrate that nitrate is preferentially adsorbed over chloride in the slit-like micropores. This preferential adsorption was found to stem from the weaker hydration energy and unique anisotropy of the ion solvation of nitrate. Beside the effects of ion dehydration, we found that applied potential plays an important role in determining the ion selectivity, leading to a lower selectivity of nitrate over chloride at a high applied potential. We conclude that the measured ion selectivity results from a complex interplay between voltage, confinement, and specific ion effects-including ion shape and local hydration structure.
- Authors:
-
[1];
[1];
[1];
[1];
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)A
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1765288
- Alternate Identifier(s):
- OSTI ID: 1669179
- Report Number(s):
- LLNL-JRNL-811539
Journal ID: ISSN 2040-3364; 1018409; TRN: US2206230
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 39; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Aydin, Fikret, Cerón, Maira R., Hawks, Steven A., Oyarzun, Diego I., Zhan, Cheng, Pham, Tuan Anh, Stadermann, Michael, and Campbell, Patrick G. Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials. United States: N. p., 2020.
Web. doi:10.1039/d0nr04496b.
Aydin, Fikret, Cerón, Maira R., Hawks, Steven A., Oyarzun, Diego I., Zhan, Cheng, Pham, Tuan Anh, Stadermann, Michael, & Campbell, Patrick G. Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials. United States. https://doi.org/10.1039/d0nr04496b
Aydin, Fikret, Cerón, Maira R., Hawks, Steven A., Oyarzun, Diego I., Zhan, Cheng, Pham, Tuan Anh, Stadermann, Michael, and Campbell, Patrick G. Fri .
"Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials". United States. https://doi.org/10.1039/d0nr04496b. https://www.osti.gov/servlets/purl/1765288.
@article{osti_1765288,
title = {Selectivity of nitrate and chloride ions in microporous carbons: the role of anisotropic hydration and applied potentials},
author = {Aydin, Fikret and Cerón, Maira R. and Hawks, Steven A. and Oyarzun, Diego I. and Zhan, Cheng and Pham, Tuan Anh and Stadermann, Michael and Campbell, Patrick G.},
abstractNote = {Understanding ion transport in porous carbons is critical for a wide range of technologies, including supercapacitors and capacitive deionization for water desalination, yet many details remain poorly understood. For instance, an atomistic understanding of how ion selectivity is influenced by the molecular shape of ions, morphology of the micropores and applied voltages is largely lacking. In this work, we combined molecular dynamics simulations with enhanced sampling methods to elucidate the mechanism of nitrate and chloride selectivity in subnanometer graphene slit-pores. We demonstrate that nitrate is preferentially adsorbed over chloride in the slit-like micropores. This preferential adsorption was found to stem from the weaker hydration energy and unique anisotropy of the ion solvation of nitrate. Beside the effects of ion dehydration, we found that applied potential plays an important role in determining the ion selectivity, leading to a lower selectivity of nitrate over chloride at a high applied potential. We conclude that the measured ion selectivity results from a complex interplay between voltage, confinement, and specific ion effects-including ion shape and local hydration structure.},
doi = {10.1039/d0nr04496b},
journal = {Nanoscale},
number = 39,
volume = 12,
place = {United States},
year = {Fri Sep 25 00:00:00 EDT 2020},
month = {Fri Sep 25 00:00:00 EDT 2020}
}
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