Electrodes covered with thin, permeable polymer films

Abstract

Because of the recent interest in electrodes modified with thin polymer films the question of permeability of such films to electrolytes and electroactive species is discussed. Glow-discharge polymer films prepared on platinum electrodes from 4-vinylpyridine were used as model systems. They were investigated mainly with electrochemical techniques. ln particular, the analysis of the electrode impedance over a frequency range of 10–3000 Hz gave valuable information about the structure of the metal—polymer interface in presence of the electrolyte. The films prepared on the anode of the glow discharge were found to act as semi-permeable membranes. Hydrogen could be oxidized on the platinum—polymer interface of these polymer covered electrodes at rates comparable to uncovered platinum, while the films were impermeable to iron ions. The matrix prepared on the cathode was more rigid due to cross-links, and thus less permeable. The polymer matrix was more or less electroactive itself. This was probably due to quinone-type groups formed with oxygen and water after the glow-discharge polymerization process. The oxidation and reduction of these groups gave rise to a Warburg-type contribution to the electrode impedance.