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Impacts of Organic Sorbates on the Ionic Conductivity and Nanostructure of Perfluorinated Sulfonic-Acid Ionomers

Cite this: Macromolecules 2021, 54, 11, 5187–5195
Publication Date (Web):May 19, 2021
https://doi.org/10.1021/acs.macromol.1c00494
Copyright © 2021 American Chemical Society

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    Abstract

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    This study provides insights into structure–property relationships of Nafion membranes swollen with organic sorbates, revealing correlations between sorbate polarity, ionomer domain structure, and ionic conductivity. Swelling, nanostructure, and ionic conductivity of Nafion in the presence of short-chain alcohols and alkanes were studied by infrared spectroscopy, X-ray scattering, and voltammetry. Nafion equilibrated with alkanes exhibited negligible uptake and nanoswelling, while alcohols induced nanoscopic- to macroscopic-swelling exponents that increased with alcohol polarity. In mixed-sorbate environments including organics and water, alcohols preserved the overall ionomer domain structure but altered the matrix to enable higher sorbate uptake. Alkanes did not demonstrably alter the hydrated nanostructure or conductivity. Identifying the impacts of organic sorbates on structure–property relationships in ionomers such as Nafion is imperative as membrane-based electrochemical devices find applications in emerging areas ranging from organic fuel cells to the synthesis of fuels and chemicals.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.1c00494.

    • Sorbate mass, molar, and volume uptake; ATR–FTIR spectra collection; ATR–FTIR spectral regression; and SAXS (PDF)

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    Cited By

    This article is cited by 8 publications.

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    2. Jung Min Kim, Yi-hung Lin, Sean M. Bannon, Geoffrey M. Geise, Bryan S. Beckingham. Improved Structural Stability of Charged Hydrogels under Organic CO2 Reduction Products: Effect of Acrylate and Methacrylate Backbone Linkages. The Journal of Physical Chemistry C 2023, 127 (22) , 10826-10832. https://doi.org/10.1021/acs.jpcc.3c01854
    3. Panpan Guan, Jianlong Lei, Xundao Liu, Kangwei Xu, Supeng Pei, Han Ding, Yecheng Zou, Wei Feng, Feng Liu, Yongming Zhang. Origins of Water State and Ionic Cluster Morphology for High Proton Conductivity of Short Side-Chain Perfluorinated Sulfonic Acid Membranes. Chemistry of Materials 2022, 34 (17) , 7845-7857. https://doi.org/10.1021/acs.chemmater.2c01445
    4. Yu. A. Zakharova, V. G. Sergeyev. Modification of Nafion Membranes by Polycation in the Presence of Lower Alyphatic Alcohols and Salt. Membranes and Membrane Technologies 2023, 5 (3) , 168-177. https://doi.org/10.1134/S2517751623030095
    5. Patrizia Gartner, Gisela Lanza, Jens Rudat, Maximilian Bilger, Tom Grünert, Alexander Nesterov-Mueller, Nadine Zimmerer, Philipp Quarz, Philip Scharfer, Wilhelm Schabel, André P. Jung, Mareen Stahlberger, Stefan Bräse. Self-healing Fuel Cells by Biological Actuators. Procedia CIRP 2023, 116 , 161-166. https://doi.org/10.1016/j.procir.2023.02.028
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    7. Zhenghao Zhu, Stephen J. Paddison. Perspective: Morphology and ion transport in ion-containing polymers from multiscale modeling and simulations. Frontiers in Chemistry 2022, 10 https://doi.org/10.3389/fchem.2022.981508
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