title: Electrochromic hysteresis performance of a prussian blue film arising from electron-transfer control by a tris(2,2'-bipyridine)ruthenium(II)-doped WO(3) film as studied by a spectrocyclic voltammetry technique.
abstract: A [Ru(bpy)(3)](2+) (bpy=2,2'-bipyridine)-doped WO(3) film was prepared as a base layer on a substrate by cathodic electrodeposition from a colloidal triad solution containing peroxotungstic acid (PTA), [Ru(bpy)(3)](2+), and poly(sodium 4-styrenesulfonate) (PSS). A Prussian blue (PB; Fe(II)-Fe(III)) film was cathodically electrodeposited on the [Ru(bpy)(3)](2+)-doped WO(3) film or neat WO(3) film from an aqueous Berlin brown (BB; Fe(III)-Fe(III)) colloid solution to yield a [Ru(bpy)(3)](2+)-doped WO(3)/PB bilayer film or WO(3)/PB bilayer film. For the spectrocyclic voltammogram (SCV) of the WO(3)/PB film, a redox response of Prussian white (PW; Fe(II)-Fe(II))/PB was observed at 0.11 V, however, further oxidation of PB to BB was not allowed by the interfacial n-type Schottky barrier between the WO(3) and PB layers. For the [Ru(bpy)(3)](2+)-doped WO(3)/PB film, any electrochemical response assigned to the redox of PB was not observed in the cyclic voltammogram, however, the in situ absorption spectral change recorded simultaneously showed the significant redox reactions based on PB. The SCV revealed that PW on the [Ru(bpy)(3)](2+)-doped WO(3) film is completely oxidized to PB by a geared reaction of Ru(II)/Ru(III) at 1.05 V, and that 32 % of PB formed is further oxidized to BB by the same geared reaction in the potential scan to 1.5 V. PB was completely re-reduced to PW by a geared reaction of H(x)WO(3)/WO(3) at -0.5 V in the reductive potential scan. These geared electrochemical reactions produced an electrochromic hysteresis performance of the PB film layered on the [Ru(bpy)(3)](2+)-doped WO(3) film.
authors.affiliation: Faculty of Education and Human Sciences and Center for Transdisciplinary Research, Niigata University, 8050 Ikarashi-2, Niigata 950-2181, Japan.
authors.forename: Koji
authors.initials: K
authors.lastname: Sone
authors.forename: Kanae
authors.initials: K
authors.lastname: Konishi
authors.forename: Masayuki
authors.initials: M
authors.lastname: Yagi