title: Chemically modified electrode with a film of nano ruthenium oxides stabilizing high valent RuO(4)(-) species and its redox-selective sequential transformation to polynuclear ruthenium oxide-metallocyanates.
abstract: High-valent Ru(VII)O(4)(-) (perruthenate) is a short-lived species in aqueous solutions (pH 1-14) and has scarcely been studied through electrochemistry. By a potential-controlled oxidative deposition method at 1 V vs Ag/AgCl using RuCl(3) in a pH 2 KCl-HCl buffer solution, chemically modified glassy carbon (GCE) and indium tin oxide (ITO) electrodes were successfully prepared with a film of hydrous nano ruthenium oxides RuO(2) and RuO(3), stabilizing the high-valent perruthenate anion (Ru(VII)-RuO(x)-CME, x = 2 and 3, CME = chemically modified electrode). The electrodes showed three distinct redox peaks corresponding to Ru(2)O(3)/RuO(2), RuO(2)/RuO(3), and RuO(4)(2-)/RuO(4)(-) redox processes at pH 2, like the classical RuO(2) electrodes in alkaline conditions. Solid state UV-visible spectra of the ITO/Ru(VII)-RuO(x)-CME showed characteristic absorption very close to chemically generated authentic RuO(4)(-) species in alkaline solution. Further, redox-controlled sequential procedures yielded polynuclear ruthenium oxide-hexacyanometallate films (RuO-MCN-CME, M = Fe and Ru), in which Ru(VII)-RuO(x)-CME acted as a specific template. A controlled-potential activation (>1 V) of Ru(VII)-RuO(x)-CME, stabilizing the key RuO(4)(-) species, in a solution of [Fe(CN)(6)](3-) or [Ru(CN)(6)](4-), should be a critical step for the formation of polynuclear RuO-MCN matrix.
authors.affiliation: Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya-higashi-machi, Nara 630-8285, Japan. askumarchem@yahoo.com
authors.forename: Annamalai Senthil
authors.initials: AS
authors.lastname: Kumar
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Tanase
authors.forename: Jyh-Myng
authors.initials: JM
authors.lastname: Zen