Nanoscale structure and morphology of sulfonated polyphenylenes via atomistic simulations

Abbott, Lauren J.; Frischknecht, Amalie L.

doi:10.1021/acs.macromol.6b02232

Nanoscale structure and morphology of sulfonated polyphenylenes via atomistic simulations

Journal Article · Mon Jan 23 00:00:00 EST 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b02232· OSTI ID:1371479

^[1]; ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

We performed atomistic simulations on a series of sulfonated polyphenylenes systematically varying the degree of sulfonation and water content to determine their effect on the nanoscale structure, particularly for the hydrophilic domains formed by the ionic groups and water molecules. We found that the local structure around the ionic groups depended on the sulfonation and hydration levels, with the sulfonate groups and hydronium ions less strongly coupled at higher water contents. In addition, we characterized the morphology of the ionic domains employing two complementary clustering algorithms. At low sulfonation and hydration levels, clusters were more elongated in shape and poorly connected throughout the system. As the degree of sulfonation and water content were increased, the clusters became more spherical, and a fully percolated ionic domain was formed. As a result, these structural details have important implications for ion transport.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1371479

Report Number(s):: SAND--2017-1157J; 655053

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 3 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

The Chemical and Structural Nature of Proton Exchange Membrane Fuel Cell Properties Hickner, M. A.; Pivovar, B. S. Fuel Cells, Vol. 5, Issue 2 https://doi.org/10.1002/fuce.200400064	journal	April 2005
Water-mediated transport in ion-containing polymers Hickner, Michael A. Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 1 https://doi.org/10.1002/polb.22381	journal	October 2011
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Polymatic: a generalized simulated polymerization algorithm for amorphous polymers Abbott, Lauren J.; Hart, Kyle E.; Colina, Coray M. Theoretical Chemistry Accounts, Vol. 132, Issue 3 https://doi.org/10.1007/s00214-013-1334-z	journal	January 2013
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C. Journal of Computational Physics, Vol. 23, Issue 3 https://doi.org/10.1016/0021-9991(77)90098-5	journal	March 1977
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
A review of polymer electrolyte membrane fuel cells: Technology, applications, and needs on fundamental research Wang, Yun; Chen, Ken S.; Mishler, Jeffrey Applied Energy, Vol. 88, Issue 4 https://doi.org/10.1016/j.apenergy.2010.09.030	journal	April 2011
Anion exchange membranes for alkaline fuel cells: A review Merle, Géraldine; Wessling, Matthias; Nijmeijer, Kitty Journal of Membrane Science, Vol. 377, Issue 1-2, p. 1-35 https://doi.org/10.1016/j.memsci.2011.04.043	journal	July 2011
Transport in sulfonated poly(phenylene)s: Proton conductivity, permeability, and the state of water Hickner, Michael A.; Fujimoto, Cy H.; Cornelius, Chris J. Polymer, Vol. 47, Issue 11, p. 4238-4244 https://doi.org/10.1016/j.polymer.2006.02.034	journal	May 2006
Sulfonated aromatic hydrocarbon polymers as proton exchange membranes for fuel cells Higashihara, Tomoya; Matsumoto, Kazuya; Ueda, Mitsuru Polymer, Vol. 50, Issue 23 https://doi.org/10.1016/j.polymer.2009.09.001	journal	November 2009
Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs) Park, Chi Hoon; Lee, Chang Hyun; Guiver, Michael D. Progress in Polymer Science, Vol. 36, Issue 11 https://doi.org/10.1016/j.progpolymsci.2011.06.001	journal	November 2011
Effect of Superacidic Side Chain Structures on High Conductivity Aromatic Polymer Fuel Cell Membranes Chang, Ying; Mohanty, Angela D.; Smedley, Sarah B. Macromolecules, Vol. 48, Issue 19 https://doi.org/10.1021/acs.macromol.5b01739	journal	September 2015
Characterization of Biaryl Torsional Energetics and its Treatment in OPLS All-Atom Force Fields Dahlgren, Markus K.; Schyman, Patric; Tirado-Rives, Julian Journal of Chemical Information and Modeling, Vol. 53, Issue 5 https://doi.org/10.1021/ci4001597	journal	April 2013
Alternative Polymer Systems for Proton Exchange Membranes (PEMs) Hickner, Michael A.; Ghassemi, Hossein; Kim, Yu Seung Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020711a	journal	October 2004
Ionic Aggregate Structure in Ionomer Melts: Effect of Molecular Architecture on Aggregates and the Ionomer Peak Hall, Lisa M.; Seitz, Michelle E.; Winey, Karen I. Journal of the American Chemical Society, Vol. 134, Issue 1 https://doi.org/10.1021/ja209142b	journal	December 2011
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Structurally-Defined, Sulfo-Phenylated, Oligophenylenes and Polyphenylenes Skalski, Thomas J. G.; Britton, Benjamin; Peckham, Timothy J. Journal of the American Chemical Society, Vol. 137, Issue 38, p. 12223-12226 https://doi.org/10.1021/jacs.5b07865	journal	September 2015
Molecular Dynamics Simulation of Swollen Membrane of Perfluorinated Ionomer Urata, Shingo; Irisawa, Jun; Takada, Akira The Journal of Physical Chemistry B, Vol. 109, Issue 9 https://doi.org/10.1021/jp046434o	journal	March 2005
Molecular Dynamics Study of a Surfactant-Mediated Decane−Water Interface: Effect of Molecular Architecture of Alkyl Benzene Sulfonate Jang, Seung Soon; Lin, Shiang-Tai; Maiti, Prabal K. The Journal of Physical Chemistry B, Vol. 108, Issue 32 https://doi.org/10.1021/jp048773n	journal	August 2004
A Molecular Dynamics Study of a Nafion Polyelectrolyte Membrane and the Aqueous Phase Structure for Proton Transport Cui, Shengting; Liu, Junwu; Selvan, Myvizhi Esai The Journal of Physical Chemistry B, Vol. 111, Issue 9 https://doi.org/10.1021/jp066388n	journal	March 2007
Atomistic Simulation of Nafion Membrane: I. Effect of Hydration on Membrane Nanostructure Devanathan, R.; Venkatnathan, A.; Dupuis, M. The Journal of Physical Chemistry B, Vol. 111, Issue 28 https://doi.org/10.1021/jp0726992	journal	July 2007
Detailed Molecular Dynamics Simulations of a Model NaPSS in Water Carrillo, Jan-Michael Y.; Dobrynin, Andrey V. The Journal of Physical Chemistry B, Vol. 114, Issue 29 https://doi.org/10.1021/jp101978k	journal	July 2010
A Comparative Ab Initio Study of the Primary Hydration and Proton Dissociation of Various Imide and Sulfonic Acid Ionomers Clark, Jeffrey K.; Paddison, Stephen J.; Eikerling, Michael The Journal of Physical Chemistry A, Vol. 116, Issue 7 https://doi.org/10.1021/jp209822k	journal	February 2012
Influence of Hydrogen Bonding Effects on Methanol and Water Diffusivities in Acid–Base Polymer Blend Membranes of Sulfonated Poly(ether ether ketone) and Base Tethered Polysulfone Mahajan, Chetan V.; Ganesan, Venkat The Journal of Physical Chemistry B, Vol. 117, Issue 17 https://doi.org/10.1021/jp3121512	journal	April 2013
Molecular Dynamics Simulations of Water Sorption in a Perfluorosulfonic Acid Membrane Daly, Kevin B.; Benziger, Jay B.; Debenedetti, Pablo G. The Journal of Physical Chemistry B, Vol. 117, Issue 41 https://doi.org/10.1021/jp405440r	journal	October 2013
Molecular Force Field for Ionic Liquids IV: Trialkylimidazolium and Alkoxycarbonyl-Imidazolium Cations; Alkylsulfonate and Alkylsulfate Anions Canongia Lopes, José N.; Pádua, Agílio A. H.; Shimizu, Karina The Journal of Physical Chemistry B, Vol. 112, Issue 16 https://doi.org/10.1021/jp800281e	journal	April 2008
Probing Selected Morphological Models of Hydrated Nafion Using Large-Scale Molecular Dynamics Simulations Knox, Craig K.; Voth, Gregory A. The Journal of Physical Chemistry B, Vol. 114, Issue 9 https://doi.org/10.1021/jp9112409	journal	March 2010
On the Relationship between Polymer Electrolyte Structure and Hydrated Morphology of Perfluorosulfonic Acid Membranes Liu, Junwu; Suraweera, Nethika; Keffer, David J. The Journal of Physical Chemistry C, Vol. 114, Issue 25 https://doi.org/10.1021/jp911972e	journal	June 2010
Temperature-Dependent Elasticity of a Semicrystalline Interphase Composed of Freely Rotating Chains in 't Veld, Pieter J.; Rutledge, Gregory C. Macromolecules, Vol. 36, Issue 19 https://doi.org/10.1021/ma0346658	journal	September 2003
Detailed Atomistic Simulation of the Segmental Dynamics and Barrier Properties of Amorphous Poly(ethylene terephthalate) and Poly(ethylene isophthalate) Karayiannis, Nikos Ch.; Mavrantzas, Vlasis G.; Theodorou, Doros N. Macromolecules, Vol. 37, Issue 8 https://doi.org/10.1021/ma0352577	journal	April 2004
Ionomeric Poly(phenylene) Prepared by Diels−Alder Polymerization: Synthesis and Physical Properties of a Novel Polyelectrolyte Fujimoto, Cy H.; Hickner, Michael A.; Cornelius, Christopher J. Macromolecules, Vol. 38, Issue 12, p. 5010-5016 https://doi.org/10.1021/ma0482720	journal	June 2005
Block Copolymers for Fuel Cells Elabd, Yossef A.; Hickner, Michael A. Macromolecules, Vol. 44, Issue 1 https://doi.org/10.1021/ma101247c	journal	January 2011
Cation Coordination and Motion in a Poly(ethylene oxide)-Based Single Ion Conductor Lin, Kan-Ju; Maranas, Janna K. Macromolecules, Vol. 45, Issue 15 https://doi.org/10.1021/ma300716h	journal	July 2012
Influence of Cation Type on Ionic Aggregates in Precise Ionomers Bolintineanu, Dan S.; Stevens, Mark J.; Frischknecht, Amalie L. Macromolecules, Vol. 46, Issue 13 https://doi.org/10.1021/ma400848m	journal	June 2013
Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers Li, Nanwen; Guiver, Michael D. Macromolecules, Vol. 47, Issue 7 https://doi.org/10.1021/ma402254h	journal	February 2014
Exploring the hydrated microstructure and molecular mobility in blend polyelectrolyte membranes by quantum mechanics and molecular dynamics simulations Bahlakeh, Ghasem; Hasani-Sadrabadi, Mohammad Mahdi; Jacob, Karl I. RSC Advances, Vol. 6, Issue 42 https://doi.org/10.1039/C6RA05513C	journal	January 2016
Modelling of morphology and proton transport in PFSA membranes Elliott, James A.; Paddison, Stephen J. Physical Chemistry Chemical Physics, Vol. 9, Issue 21 https://doi.org/10.1039/b701234a	journal	January 2007
Poly(p-phenylene sulfone)s with high ion exchange capacity: ionomers with unique microstructural and transport features de Araujo, C. C.; Kreuer, K. D.; Schuster, M. Physical Chemistry Chemical Physics, Vol. 11, Issue 17 https://doi.org/10.1039/b822069g	journal	January 2009
A general purpose model for the condensed phases of water: TIP4P/2005 Abascal, J. L. F.; Vega, C. The Journal of Chemical Physics, Vol. 123, Issue 23 https://doi.org/10.1063/1.2121687	journal	December 2005
Specifics of solvation of sulfonated polyelectrolytes in water, dimethylmethylphosphonate, and their mixture: A molecular simulation study Vishnyakov, Aleksey; Neimark, Alexander V. The Journal of Chemical Physics, Vol. 128, Issue 16 https://doi.org/10.1063/1.2899327	journal	April 2008
Clustering by fast search and find of density peaks Rodriguez, A.; Laio, A. Science, Vol. 344, Issue 6191 https://doi.org/10.1126/science.1242072	journal	June 2014
Characterization of Vanadium Ion Uptake in Sulfonated Diels Alder Poly(phenylene) Membranes Lawton, Jamie S.; Jones, Amanda M.; Tang, Zhijiang Journal of The Electrochemical Society, Vol. 163, Issue 1 https://doi.org/10.1149/2.0291601jes	journal	November 2015
Characterization of Sulfonated Diels-Alder Poly(phenylene) Membranes for Electrolyte Separators in Vanadium Redox Flow Batteries Tang, Zhijiang; Lawton, Jamie S.; Sun, Che-Nan Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0631412jes	journal	January 2014

Cited By (3)

Scaling Behavior of Nafion with Different Model Parameterizations in Dissipative Particle Dynamics Simulations Liu, Hongjun; Cavaliere, Sara; Jones, Deborah J. Macromolecular Theory and Simulations, Vol. 27, Issue 4 https://doi.org/10.1002/mats.201800003	journal	April 2018
Self-assembled highly ordered acid layers in precisely sulfonated polyethylene produce efficient proton transport Trigg, Edward B.; Gaines, Taylor W.; Maréchal, Manuel Nature Materials, Vol. 17, Issue 8 https://doi.org/10.1038/s41563-018-0097-2	journal	May 2018
Morphology and proton diffusion in a coarse-grained model of sulfonated poly(phenylenes) Clark, Jennifer A.; Santiso, Erik E.; Frischknecht, Amalie L. The Journal of Chemical Physics, Vol. 151, Issue 10 https://doi.org/10.1063/1.5116684	journal	September 2019

Similar Records

Morphology and proton diffusion in a coarse-grained model of sulfonated poly(phenylenes)

Journal Article · Fri Sep 13 20:00:00 EDT 2019 · Journal of Chemical Physics · OSTI ID:1570275

Impact of Hydration and Sulfonation on the Morphology and Ionic Conductivity of Sulfonated Poly(phenylene) Proton Exchange Membranes

Journal Article · Mon Jan 14 19:00:00 EST 2019 · Macromolecules · OSTI ID:1492390

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Nanoscale structure and morphology of sulfonated polyphenylenes via atomistic simulations

Citation Formats

References (43)

Cited By (3)

Similar Records

Related Subjects