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Title: Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes

Abstract

Proton transfer and local structures in 3M (EW 825) and Nafion (EW 890) membranes are investigated in this study by both standard nonreactive molecular dynamics and the self-consistent iterative multistate empirical valence bond method, which is capable of simulating multiple reactive protons and accounting for the Grotthuss mechanism of proton transport. The Nafion and 3M systems have the same backbone, so we can isolate and compare the effect of the different side chains by calculating the radial distribution functions (RDFs), self-diffusion constants, and other properties for three hydration levels at 5, 9, and 14 at 300 and 353 K. The conformations of the 3M and Nafion side chains are also compared. We found that even though many results are similar for both F3C and SPC/Fw water models, certain trends such as the sulfonate clustering can depend on the water model selected. The relationship between the different RDFs for the sulfonate, water, and hydronium is discussed. The self-diffusion constants of water for both membranes are found to be close with respect to each water model selected, even though the experimental values for 3M at 300 K are higher. The calculated self-diffusion constants of the excess protons are found to be highermore » for 3M than Nafion for hydration levels 9 and 14 at 300 K but statistically the same at 353 K.« less

Authors:
 [1];  [2];  [3];  [4]
  1. Colorado School of Mines, Golden, CO (United States). Renewable Energy Materials Research Science and Engineering Center; Univ. of Chicago, IL (United States). James Franck Inst., and Computation Inst., Dept. of Chemistry
  2. Colorado School of Mines, Golden, CO (United States). Renewable Energy Materials Research Science and Engineering Center, Dept. of Chemical and Biological Engineering
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States). Computational Science Center
  4. Univ. of Chicago, IL (United States). James Franck Inst., and Computation Inst., Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1512303
Alternate Identifier(s):
OSTI ID: 1582232
Grant/Contract Number:  
SC0005418; FG02-10ER16171; DMR-0820518
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 117; Journal Issue: 16; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tse, Ying-Lung Steve, Herring, Andrew M., Kim, Kwiseon, and Voth, Gregory A. Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes. United States: N. p., 2013. Web. doi:10.1021/jp400693g.
Tse, Ying-Lung Steve, Herring, Andrew M., Kim, Kwiseon, & Voth, Gregory A. Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes. United States. doi:10.1021/jp400693g.
Tse, Ying-Lung Steve, Herring, Andrew M., Kim, Kwiseon, and Voth, Gregory A. Mon . "Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes". United States. doi:10.1021/jp400693g. https://www.osti.gov/servlets/purl/1512303.
@article{osti_1512303,
title = {Molecular Dynamics Simulations of Proton Transport in 3M and Nafion Perfluorosulfonic Acid Membranes},
author = {Tse, Ying-Lung Steve and Herring, Andrew M. and Kim, Kwiseon and Voth, Gregory A.},
abstractNote = {Proton transfer and local structures in 3M (EW 825) and Nafion (EW 890) membranes are investigated in this study by both standard nonreactive molecular dynamics and the self-consistent iterative multistate empirical valence bond method, which is capable of simulating multiple reactive protons and accounting for the Grotthuss mechanism of proton transport. The Nafion and 3M systems have the same backbone, so we can isolate and compare the effect of the different side chains by calculating the radial distribution functions (RDFs), self-diffusion constants, and other properties for three hydration levels at 5, 9, and 14 at 300 and 353 K. The conformations of the 3M and Nafion side chains are also compared. We found that even though many results are similar for both F3C and SPC/Fw water models, certain trends such as the sulfonate clustering can depend on the water model selected. The relationship between the different RDFs for the sulfonate, water, and hydronium is discussed. The self-diffusion constants of water for both membranes are found to be close with respect to each water model selected, even though the experimental values for 3M at 300 K are higher. The calculated self-diffusion constants of the excess protons are found to be higher for 3M than Nafion for hydration levels 9 and 14 at 300 K but statistically the same at 353 K.},
doi = {10.1021/jp400693g},
journal = {Journal of Physical Chemistry. C},
number = 16,
volume = 117,
place = {United States},
year = {2013},
month = {4}
}

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Cited by: 47 works
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Figures / Tables:

Figure 1 Figure 1: Structures of Nafion 890 (left) and 3M 825 (right). The number next to an atom is the partial charge used in the simulations.

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Works referencing / citing this record:

Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport
journal, January 2013

  • Komarov, Pavel V.; Khalatur, Pavel G.; Khokhlov, Alexei R.
  • Beilstein Journal of Nanotechnology, Vol. 4
  • DOI: 10.3762/bjnano.4.65

Molecular Dynamics Modeling of the Conductivity of Lithiated Nafion Containing Nonaqueous Solvents
journal, January 2016

  • Burlatsky, Sergei; Darling, Robert M.; Novikov, Dmitri
  • Journal of The Electrochemical Society, Vol. 163, Issue 10
  • DOI: 10.1149/2.0461610jes

Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport
journal, January 2013

  • Komarov, Pavel V.; Khalatur, Pavel G.; Khokhlov, Alexei R.
  • Beilstein Journal of Nanotechnology, Vol. 4
  • DOI: 10.3762/bjnano.4.65

Effects of water nanochannel diameter on proton transport in proton‐exchange membranes
journal, May 2019

  • Mabuchi, Takuya; Tokumasu, Takashi
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 13
  • DOI: 10.1002/polb.24842

Elucidating the morphological aspects and proton dynamics in a hybrid perfluorosulfonic acid membrane for medium-temperature fuel cell applications
journal, January 2018

  • Akbari, Saeed; Hamed Mosavian, Mohammad Taghi; Moosavi, Fatemeh
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 47
  • DOI: 10.1039/c8cp05377d