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Modulation of the Electrochemical Reactivity of Solubilized Redox Active Polymers via Polyelectrolyte Dynamics

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† § Department of Chemistry, §Beckman Institute for Advanced Science and Technology, and Department of Mechanical Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
Joint Center for Energy Storage Research, Argonne, Illinois 60439, United States
Cite this: J. Am. Chem. Soc. 2018, 140, 6, 2093–2104
Publication Date (Web):January 25, 2018
Copyright © 2018 American Chemical Society

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    Redox active polymers (RAPs) are electrochemically versatile materials that find key applications in energy storage, sensing, and surface modification. In spite of the ubiquity of RAP-modified electrodes, a critical knowledge gap exists in the understanding of the electrochemistry of soluble RAPs and their relation to polyelectrolyte dynamics. Here, we explore for the first time the intersection between polyelectrolyte behavior and the electrochemical response that highly soluble and highly substituted RAPs with viologen, ferrocene, and nitrostyrene moieties elicit at electrodes. This comprehensive study of RAP electrolytes over several orders of magnitude in concentration and ionic strength reveals distinct signatures consistent with surface confined, colloidal, and bulk-like electrochemical behavior. These differences emerge across polyelectrolyte packing regimes and are strongly modulated by changes in RAP coil size and electrostatic interactions with the electrode. We found that, unlike monomer motifs, simple changes in the ionic strength caused variations over 1 order of magnitude in the current measured at the electrode. In addition, the thermodynamics of adsorbed RAP films were also affected, giving rise to standard reduction potential shifts leading to redox kinetic effects as a result of the mediating nature of the RAP film in equilibrium with the solution. Full electrochemical characterization via transient and steady-state techniques, including the use of ultramicroelectrodes and the rotating disk electrode, were correlated to dynamic light scattering, ellipsometry, and viscometric analysis. These methods helped elucidate the relationship between electrochemical behavior and RAP coil size, film thickness, and polyelectrolyte packing regime. This study underscores the role of electrostatics in modulating the reactivity of redox polyelectrolytes.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b08353.

    • Synthetic details, additional electrochemical and optical characterization experiments, ellipsometry, and rheology experiments (PDF)

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