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Effects of Interchain Crosslinking by Alkyl Dihalides on the Electrochemical Performance of Nanoscale Polypyrrole Films

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    Effects of Interchain Crosslinking by Alkyl Dihalides on the Electrochemical Performance of Nanoscale Polypyrrole Films
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    • Ryan C. Gettler
      Ryan C. Gettler
      Department of Biomedical, Biological and Chemical Engineering, University of Missouri, Columbia, Missouri 65211, United States
      More by Ryan C. Gettler
    • Naresh Alaal
      Naresh Alaal
      Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States
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    • Kurt R. Brorsen
      Kurt R. Brorsen
      Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States
      More by Kurt R. Brorsen
      Orcidhttps://orcid.org/0000-0003-3351-4975
    • Matthias J. Young*
      Matthias J. Young
      Department of Biomedical, Biological and Chemical Engineering, University of Missouri, Columbia, Missouri 65211, United States
      Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States
      *Email: [email protected]
      More by Matthias J. Young
      Orcidhttps://orcid.org/0000-0001-7384-4333
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    Chemistry of Materials

    Cite this: Chem. Mater. 2022, 34, 17, 8065–8076
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    https://doi.org/10.1021/acs.chemmater.2c02225
    Published August 29, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    Nanoscale films of redox-active amine polymers such as polypyrrole (Ppy) are of interest for aqueous energy storage, water treatment, and chemical sensors. Unfortunately, the electrochemical properties of Ppy are constrained by the local material structures that form during typical synthesis. In this study, we examine how crosslinking Ppy postsynthesis with short-chain bifunctional alkyl-halide crosslinkers influences the charge storage properties of Ppy. Specifically, we employ dibromoethane (EtBr2), dibromopropane (PrBr2), and dibromobutane (BuBr2) crosslinkers to link amines from adjacent Ppy polymer chains in nanoscale Ppy films formed by electrodeposition. We study the electrochemical performance of the resulting structures using an electrochemical quartz crystal microbalance complemented by density-functional theory studies. We identify that the shortest (ethyl) crosslinker sterically traps free anions from the electrolyte within the Ppy structure. These trapped anions lead to a qualitative shift in the electrochemical mechanism from anion-insertion to cation-insertion behavior. We identify that the propyl crosslinker, with just one carbon more than ethyl, allows for more rapid anion motion than intrinsic Ppy, accessing electrochemical capacities up to 60% higher than that with no crosslinker. These results reveal the strong impact of the local molecular structure on the electrochemical properties of redox-active polymers and demonstrate the use of short-chain bifunctional crosslinkers to control their qualitative electrochemical response.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.2c02225.

    • Additional characterization following Ppy alkylation reaction and EQCM studies during fluoride anion insertion in the Ppy-Et polymer film (PDF)

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    This article is cited by 6 publications.

    1. Ryan C. Gettler, Shima Mehregan, Henry D. Koenig, Andie M. Kaess, Matthias J. Young. Nonequilibrium Anion Detection in Solid-Contact Ion-Selective Electrodes. ACS Omega 2024, 9 (14) , 16443-16457. https://doi.org/10.1021/acsomega.4c00131
    2. Clara Capparelli, Charles Rafalko, Harrison J. Cassady, Megan E. Matta, Benjamin J. Stovall, Michael A. Hickner. Nonporous Cation Exchange Membranes with pH-Responsive Properties as Chemical Valves. ACS Applied Polymer Materials 2024, 6 (1) , 879-887. https://doi.org/10.1021/acsapm.3c02472
    3. Shuaijun Yu, Yazhen Jiang, Geting Xu, Edison Huixiang Ang, Zhipeng Xu, Junbin Liao, Jiangnan Shen. Innovative low-energy enrichment of sulfuric acid using PVDF-HFP anion exchange membranes with acid-blocking properties. Desalination 2024, 580 , 117510. https://doi.org/10.1016/j.desal.2024.117510
    4. Tatyana S. Zyubina, Alexander S. Zyubin, Olga I. Istakova, Nataliia V. Talagaeva, Mikhail A. Vorotyntsev, Dmitry V. Konev. C-C coupling of polymer chains in thin films of oxidized polypyrrole doped by BF4− and PF6− anions: Quantum chemical modeling. Journal of Solid State Electrochemistry 2024, 28 (5) , 1585-1599. https://doi.org/10.1007/s10008-023-05756-8
    5. Taehyun Park, Minseo Kim, Eun Kwang Lee, Jaehyun Hur, Hocheon Yoo. Overcoming Downscaling Limitations in Organic Semiconductors: Strategies and Progress. Small 2024, 20 (9) https://doi.org/10.1002/smll.202306468
    6. Ryan C. Gettler, Patrick J. Kinlen, Emad Renfroe, Yangchuan Xing, Matthias J. Young. Postprocessing of solution-cast polyaniline for enhanced electrochemical properties. Journal of Power Sources 2023, 583 , 233557. https://doi.org/10.1016/j.jpowsour.2023.233557
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    Chemistry of Materials

    Cite this: Chem. Mater. 2022, 34, 17, 8065–8076
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.2c02225
    Published August 29, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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