Dark electrochemistry and photoelectrochemistry of molecularly doped ion-exchange polymer blends

Abstract

Ion-exchange polymer blends have been shown to produce modified electrode surfaces with high affinities for ionic reactants. The main feature of these blends is their spontaneous tendency to segregate into hydrophilic and hydrophobic domains. It is now believed that, when appropriate dye molecules are incorporated into such films and then illuminated, these systems operate under both ionic and dry electronic conduction mechanisms. The dark electrochemical measurements performed on an ion-exchange polymer containing ZnTPPS/sup 4 -/, ZnTPP, ZnPc(OPh)/sub 4/, or CuPcTS/sub 4-/, in contact with a Fe(CN)/sub 6//sup 3-/4-/ redox solution, show that the dye molecules within the film are immobile and that the high ion-exchange capability is maintained. The photoelectrochemical results obtained with the dye-loaded films indicate that electrons may be transferred from the photoexcited dyes to the polymer matrix and transported to the SnO/sub 2/ substrate electrode. The oxidized dye molecules are reduced by accepting electrons from the Fe(CN)/sub 6//sup 4 -/ species. The electronic conduction following charge separation is assumed to be intimately related to the ion-exchange polymer's tendency to segregate into hydrophilic and hydrophobic domains and also the excited-state energetics of the dye. A model which invokes the existence of large distributions of molecular ion states ismore » proposed to explain the conduction of electrons through the hydrophobic domains of the polymer film and a detailed energy level diagram is presented to summarize the overall situation.« less