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Title: Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores

Abstract

Measured apparent activation energies, $$E_A$$, of ion transport (K + and Cl ) in conical glass nanopores are reported as a function of applied voltage (-0.5 to 0.5 V), pore size (20–2000 nm), and electrolyte concentration (0.1–50 mM). $$E_A$$ values for transport within an electrically charged conical glass nanopore differ from the bulk values due to the voltage and temperature-dependent distribution of the ions within the double layer. Remarkably, nanopores that display ion current rectification also display a large decrease in $$E_A$$ under accumulation mode conditions (at applied negative voltages versus an external ground) and a large increase in $$E_A$$ under depletion mode conditions (at positive voltages). Finite element simulations based on the Poisson–Nernst–Planck model semiquantitatively predict the measured temperature-dependent conductivity and dependence of $$E_A$$ on applied voltage. The results highlight the relationships between the distribution of ions with the nanopore, ionic current, and $$E_A$$ and their dependencies on pore size, temperature, ion concentration, and applied voltage.

Authors:
 [1];  [1];  [1];  [1]
  1. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1386251
Grant/Contract Number:  
SC0001160
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 43; Related Information: NEES partners with University of Maryland (lead); University of California, Irvine; University of Florida; Los Alamos National Laboratory; Sandia National Laboratories; Yale University; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bio-inspired; energy storage (including batteries and capacitors); defects; charge transport; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Perera, Rukshan T., Johnson, Robert P., Edwards, Martin A., and White, Henry S. Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b08194.
Perera, Rukshan T., Johnson, Robert P., Edwards, Martin A., & White, Henry S. Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores. United States. https://doi.org/10.1021/acs.jpcc.5b08194
Perera, Rukshan T., Johnson, Robert P., Edwards, Martin A., and White, Henry S. Wed . "Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores". United States. https://doi.org/10.1021/acs.jpcc.5b08194. https://www.osti.gov/servlets/purl/1386251.
@article{osti_1386251,
title = {Effect of the Electric Double Layer on the Activation Energy of Ion Transport in Conical Nanopores},
author = {Perera, Rukshan T. and Johnson, Robert P. and Edwards, Martin A. and White, Henry S.},
abstractNote = {Measured apparent activation energies, $E_A$, of ion transport (K+ and Cl–) in conical glass nanopores are reported as a function of applied voltage (-0.5 to 0.5 V), pore size (20–2000 nm), and electrolyte concentration (0.1–50 mM). $E_A$ values for transport within an electrically charged conical glass nanopore differ from the bulk values due to the voltage and temperature-dependent distribution of the ions within the double layer. Remarkably, nanopores that display ion current rectification also display a large decrease in $E_A$ under accumulation mode conditions (at applied negative voltages versus an external ground) and a large increase in $E_A$ under depletion mode conditions (at positive voltages). Finite element simulations based on the Poisson–Nernst–Planck model semiquantitatively predict the measured temperature-dependent conductivity and dependence of $E_A$ on applied voltage. The results highlight the relationships between the distribution of ions with the nanopore, ionic current, and $E_A$ and their dependencies on pore size, temperature, ion concentration, and applied voltage.},
doi = {10.1021/acs.jpcc.5b08194},
url = {https://www.osti.gov/biblio/1386251}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 43,
volume = 119,
place = {United States},
year = {2015},
month = {9}
}

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Cited by: 23 works
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