Electrochemical and photosensitized redox reactions of a prussian blue film layered on a WO3/[Ru(bpy)3]2+/polymer hybrid film.

A hybrid film of WO(3)/tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)](2+))/poly(sodium 4-styrenesulfonate) (PSS) (denoted as a WRP hybrid film) was prepared as a base layer on an indium tin oxide electrode substrate by cathodic electrodeposition from a colloidal ternary solution containing peroxotungstic acid, Ru(bpy)(3)](2+), and PSS. Prussian blue, Fe(III) (4)Fe(II)(CN)(6)](3) (Fe(II)-Fe(III)) was cathodically electrodeposited on the WRP hybrid film from a Berlin brown (Fe(III)-Fe(III)) colloidal solution to give a WRP/Fe(II)-Fe(III) bilayer film. Spectrocyclic voltammetry measurement of the WRP/Fe(II)-Fe(III) bilayer film reveals that Prussian white (Fe(II)-Fe(II)) is oxidized to Fe(II)-Fe(III) by electrogenerated Ru(III), and Fe(II)-Fe(III) is re-reduced to Fe(II)-Fe(II) by electrogenerated H(x)WO(3). Visible-light irradiation of the WRP hybrid film generates a small photocurrent (approximately 8 nA cm(-2)) at 0.4 V of an applied potential, whereas irradiation of the WRP/Fe(II)-Fe(II) bilayer film (Fe(II)-Fe(III) is electrochemically reduced to the Fe(II)-Fe(II) state) significantly generates a steady photoanodic current of 2.0-1.1 microA cm(-2) under the same conditions, thus demonstrating that the photoanodic current is produced by the layered Fe(II)-Fe(II) film. The photoaction spectrum of the bilayer film reveals that the photoanodic current is based on the photoexcitation of Ru(bpy)(3)](2+). The photogeneration of Fe(II)-Fe(III) from Fe(II)-Fe(II) is shown by the absorption spectral change of the bilayer film on irradiation. These results corroborate the notion that Fe(II)-Fe(II) is oxidized by photogenerated Ru(III) to generate Fe(II)-Fe(III). However, the rate of photogeneration of Fe(II)-Fe(III) is slow, which could be ascribed to the fast back electron transfer (ET) from WO(3) to Ru(III), comparable with the forward ET from Fe(II)-Fe(II) to Ru(III). The fast back ET could be a crucial problem for the Ru(bpy)(3)](2+)-sensitized reaction in the hybrid film.