Abstract.
Diphenylamine solid crystals have been mechanically attached to platinum or gold electrodes by four different methods and investigated by cyclic voltammetry in the presence of aqueous acidic media. It is demonstrated that the oxidative dimerization and polymerization (observed in non-aqueous solutions or mixed solvent systems) can also be accomplished by using diphenylamine microcrystals in contact with the electrode metal in the presence of aqueous solutions. Formation of a thin polymer layer has been observed even in the areas of the electrode that were not in direct contact with the diphenylamine microparticles. This finding can be explained by surface diffusion of the organic molecules or by oversaturation of the solution close to the diphenylamine microcrystals. A gradual growth of the voltammetric peaks characteristic of the polymer has been observed, while the irreversible wave due to the formation of cation radicals and their dimerization has shown a stationary behaviour. The redox transformation of the oligomeric compound formed at the surface is accompanied by a clear colour change: at pH 0 the colourless reduced form is converted to the bright-blue (violet) oxidized form.
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Inzelt, G. Cyclic voltammetry of solid diphenylamine crystals immobilized on an electrode surface and in the presence of an aqueous solution. J Solid State Electrochem 6, 265–271 (2002). https://doi.org/10.1007/s100080100223
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DOI: https://doi.org/10.1007/s100080100223