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Issue 44, 2016
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Permselectivity and thickness-dependent ion transport properties of overoxidized polyaniline: a mechanistic investigation

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Abstract

We report here the permselectivity of overoxidized polyaniline obtained using anodic polarization of polyaniline on glassy carbon electrodes. The contrasting redox behavior of overoxidized polyaniline coated electrodes towards [Fe(CN)6]3− and [Ru(NH3)6]3+ has been analyzed using cyclic voltammetry, hydrodynamic voltammetry and electrochemical impedance spectroscopy. This permselectivity vis a vis anion exclusivity arises from the incorporation of counter anions rather than by the formation of new functional groups in the polymer upon overoxidation – as inferred from FT Raman and UV-Visible spectral data. The surface charges of the polymeric films are also deduced from the zeta potential analysis. The thickness-dependent anion exclusion behavior of overoxidized polyaniline is quantitatively interpreted using diffusion coefficient measurements with rotating disc electrodes. The mechanism pertaining to the non-trivial role of film thickness in influencing anion exclusion is confirmed by additional impedance spectroscopy carried out during the overoxidation of polyaniline.

Graphical abstract: Permselectivity and thickness-dependent ion transport properties of overoxidized polyaniline: a mechanistic investigation

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The article was received on 17 Jul 2016, accepted on 16 Oct 2016 and first published on 17 Oct 2016


Article type: Paper
DOI: 10.1039/C6CP04975C
Citation: Phys. Chem. Chem. Phys., 2016,18, 30705-30720
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    Permselectivity and thickness-dependent ion transport properties of overoxidized polyaniline: a mechanistic investigation

    S. Mondal and M. V. Sangaranarayanan, Phys. Chem. Chem. Phys., 2016, 18, 30705
    DOI: 10.1039/C6CP04975C

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