Effects of reaction parameters on the electrochemical formation of multilayer films composed of manganese oxides and tetra-alkylammonium ions

Multilayered manganese oxide films were prepared on a platinum electrode by potentiostatic oxidation of aqueous Mn^<2+> ions in the presence of n-tetra-alkylammonium compounds. Alkylammonium cations were intercalated between manganese oxide layers to balance the negative layer charge. Effects of several preparative parameters such as the size of alkylammonium molecules, counteranions, and bath composition on the structure of products were investigated. The interlayer distance of the products increased with increasing alkyl chain length up to C4, and the change became obviously small among C4?C6 compounds. The multilayer formation was achieved only when the manganese concentration was lower than 10 mM, and the highest crystallinity was obtained from a bath composed of 2 mM manganese sulfate and 50 mM alkylammonium chloride. At low concentrations of alkylammonium (<10 mM), a product intercalated with hydrated protons was formed, in which the protons were generated by anodic oxidation of Mn<2+> with H_2O