Polymer Films on Electrodes. 10. Electrochemical Behavior of Solution Species at Nafion-Tetrathiafulvalenium Bromide Polymers

Article abstract of DOI:10.1021/ja00386a002

The electrochemical behavior of solution species at electrodes consisting of a conductive polymer layer, produced by incorporation of tetrathiafulvalenium (TTF⁺) bromide into the cation-exchange polymer Nafion, on various substrates (Pt, Ta, SnO2, n-Si) is described.The votlammetric behavior of the solution species Fe(CN)6^3- and FeY^2- (where Y^4- = ethylenediaminetetraacetate) at the Nafion-TTF⁺ electrodes was consistent with models of electrodes partially covered with electronically conductive sites.Microscopic investigation of the electrode showed that the incorporated TTF⁺ forms electroactive domains and conductive nonelectroactive crystals from electrochemical cycling.The nonelectroactive crystals have the same stoichiometry as the one-dimensional organic conductor TTFBr_0.7.In the electrodeposition of copper onto the TTF⁺ polymer electrode, most deposited on the TTFBr_0.7, indicating that they were the major source of electronic conduction within the polymer.When the TTF⁺ polymer was applied to the surface of an n-type Si electrode, the lifetime of the semiconductor electrode for the photooxydation of Fe(II) species was improved.