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Title: Breakdown of electroneutrality in nanopores

Abstract

Ion transport in extremely narrow nanochannels has gained increasing interest in recent years due to unique physical properties at the nanoscale and the technological advances that allow us to study them. It is tempting to approach this confined regime with the theoretical tools and knowledge developed for membranes and microfluidic devices, and naively apply continuum models, such as the Poisson-Nernst-Planck and Navier-Stokes equations. However, it turns out that some of the most basic principles we take for granted in larger systems, such as the complete screening of surface charge by counter-ions, can break down under extreme confinement. Additionally, we show that in a truly one-dimensional system of ions interacting with three-dimensional electrostatic interactions, the screening length is exponentially large, and can easily exceed the macroscopic length of a nanotube. Without screening, electroneutrality breaks down within the nanotube, with fundamental consequences for ion transport and electrokinetic phenomena. In this work, we build a general theoretical framework for electroneutrality breakdown in nanopores, focusing on the most interesting case of a one-dimensional nanotube, and show how it provides an elegant interpretation for the peculiar scaling observed in experimental measurements of ionic conductance in carbon nanotubes.

Authors:
 [1];  [2];  [3]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Physics
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Mathematics
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1852823
Alternate Identifier(s):
OSTI ID: 1775884
Grant/Contract Number:  
SC0019112; 1122374
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Colloid and Interface Science
Additional Journal Information:
Journal Volume: 579; Journal Issue: C; Journal ID: ISSN 0021-9797
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Double layer; Nanopores; Electroneutrality breakdown; Poisson-Boltzmann; Confinement

Citation Formats

Levy, Amir, de Souza, J. Pedro, and Bazant, Martin Z. Breakdown of electroneutrality in nanopores. United States: N. p., 2020. Web. doi:10.1016/j.jcis.2020.05.109.
Levy, Amir, de Souza, J. Pedro, & Bazant, Martin Z. Breakdown of electroneutrality in nanopores. United States. https://doi.org/10.1016/j.jcis.2020.05.109
Levy, Amir, de Souza, J. Pedro, and Bazant, Martin Z. Tue . "Breakdown of electroneutrality in nanopores". United States. https://doi.org/10.1016/j.jcis.2020.05.109. https://www.osti.gov/servlets/purl/1852823.
@article{osti_1852823,
title = {Breakdown of electroneutrality in nanopores},
author = {Levy, Amir and de Souza, J. Pedro and Bazant, Martin Z.},
abstractNote = {Ion transport in extremely narrow nanochannels has gained increasing interest in recent years due to unique physical properties at the nanoscale and the technological advances that allow us to study them. It is tempting to approach this confined regime with the theoretical tools and knowledge developed for membranes and microfluidic devices, and naively apply continuum models, such as the Poisson-Nernst-Planck and Navier-Stokes equations. However, it turns out that some of the most basic principles we take for granted in larger systems, such as the complete screening of surface charge by counter-ions, can break down under extreme confinement. Additionally, we show that in a truly one-dimensional system of ions interacting with three-dimensional electrostatic interactions, the screening length is exponentially large, and can easily exceed the macroscopic length of a nanotube. Without screening, electroneutrality breaks down within the nanotube, with fundamental consequences for ion transport and electrokinetic phenomena. In this work, we build a general theoretical framework for electroneutrality breakdown in nanopores, focusing on the most interesting case of a one-dimensional nanotube, and show how it provides an elegant interpretation for the peculiar scaling observed in experimental measurements of ionic conductance in carbon nanotubes.},
doi = {10.1016/j.jcis.2020.05.109},
journal = {Journal of Colloid and Interface Science},
number = C,
volume = 579,
place = {United States},
year = {Tue Jun 09 00:00:00 EDT 2020},
month = {Tue Jun 09 00:00:00 EDT 2020}
}

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