Templating Effect of Polymeric Electrolytes on the Electropolymerization of Aniline

Preparation of polyaniline (PANI) in the presence of polymeric electrolytes is known to produce the polymer with improved characteristics such as mechanical properties, thermal stability, adherence, controlled morphology, wide pH-range of electroactivity, etc. This contribution describes the results of systematic studies on the influence of the structure of water-soluble polymeric sulfonic acids on PANI electrodeposition and properties. The course of polymerization in potentiostatic, galvanostatic and potential sweep regimes was traced by chronoamperometry, chronopotentiometry, cyclic voltammetry and in situ AFM measurements. It was shown that the structure of polyacid, namely, the rigidity of the polymer backbone, the distance between sulfonic groups on the backbone, the length and rigidity of the side chains containing sulfonic groups, strongly affect the onset potential of aniline oxidation, the character and the rate of the initial stages of PANI/polyacid film growth. The in situ AFM studies performed during potentiostatic polymerization showed that the structure of polyacid (primarily the backbone rigidity) has a direct influence on the shape of PANI “nuclei” and the morphology of the film in the early stages of the electropolymerization (Fig. 1). The obtained films were also characterized by UV-Vis-NIR spectroscopy and spectroelectrochemistry and cyclic voltammetry.

This work was supported by the Russian Foundation for Basic Research (grant No.12-03-01087).