Permselectivity and thickness-dependent ion transport properties of overoxidized polyaniline: a mechanistic investigation
文献信息
Subrata Mondal, M. V. Sangaranarayanan
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.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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