The electrochemical behavior of the cation exchange polymer Nafion containing tetrathiafulvalenium (TTF + ) on a platinum substrate is described. The polymer electrode shows cyclic voltammetric behavior similar to that of solid films of TTF on platinum. In the oxidized form of the electroactive molecules in the polymer (TTF + ) forms nonstoichiometric complexes with Br − . The peak potentials in cyclic voltammetry shift with changes in concentration of supporting electrolyte, temperature, and anion of the supporting electrolyte. Very narrow cyclic voltammetric waves are observed that result in part from attractive interactions between the electroactive molecules. The separation in peak potential of the reduction and oxidation waves is explained by formation of which stabilizes the oxidized form (TTF + ) and makes it harder to reduce. Peak potentials for the oxidation and reduction shift closer together as the scan rate is lowered, which is explained by a "square (reaction) scheme."
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Henning et al. (1983) studied this question.