Medium effects on the electro-deposition of MnO2 on glassy carbon electrode: A comparative study in alkane, perfluoro alkane carboxylic acids and methanesulphonic acid

Voltammetric studies of Mn(II) were carried out in acetic acid (AA), trifluoroacetic acid (TFA), butyric acid (BA), perfluorobutyric acid (PFBA) and methanesulphonic acid (MSA) media. Influence of anodic limit and the nature of acids were investigated. Oxidation of Mn(II) shows two anodic peaks in weak acids namely acetic acid and butyric acid media due to the formation of insoluble Mn(III) and Mn(IV) species. Reduction of these species were also observed as two peaks in the cathodic region. Formation and reduction of solid oxide phases are the dominant electrode processes in such weak acid media. In strong acids like MSA and TFA media sharp anodic and cathodic peaks were obtained due to the formation and reduction of stable soluble Mn(III) species. SEM studies reveal the formation of thicker oxide phases in weak acid media and much thinner oxide layers in strong acid media. γ-MnO₂ phase was formed from AA and TFA while -MnO₂ phase was formed from BA and PFBA, suggesting a relationship between phase structure and anionic size.