Electrochemical current rectification with cross reaction at a TEMPO/viologen-substituted polymer thin-layer heterojunction

H. Tokue, K. Kakitani, Hiroyuki Nishide, Kenichi Oyaizu

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    Abstract

    Totally reversible redox-active polymers, 4-amino-2,2,6,6-tetramethylpiperidin-1-oxyl functionalized polyacrylic acid (PTAm-A) and poly(tripyridiniomesitylene) (PTPM), both of which possessed rapid charge transport properties in an aqueous electrolyte, were applied to a polymer-sandwiched device to offer an electrochemical current rectification functionality. Single-layer and bilayer devices were fabricated employing the PTAm-A and/or PTPM thin layer(s) as charge transport media. Single-layer devices with a 1 cm2 electrode area demonstrated large currents in the order of several milliamperes, which were established by redox mediation based on a fast electron self-exchange reaction between adjacent redox sites in the polymer layers. A current-voltage response obtained from the bilayer device exhibited a rectification effect due to thermodynamically favoured cross reaction at the polymer/polymer interface, retaining the large current densities. The observed currents were comparable to those predicted from the diffusion-controlled charge transport kinetics. Potentiostatic measurements revealed that the rectified current readily achieved a steady state in response to the applied voltage. These results demonstrate that the PTAm-A/PTPM thin-layer heterojunction enabled a large current rectification based on the redox mediation process, providing insight into ideal charge flow systems in various electrochemical devices.

    Original languageEnglish
    Pages (from-to)99195-99201
    Number of pages7
    JournalRSC Advances
    Volume6
    Issue number101
    DOIs
    Publication statusPublished - 2016

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    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)

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