Chemically Modified Electrode with a Film of Nano Ruthenium Oxides Stabilizing High Valent RuO4 - Species and Its Redox-Selective Sequential Transformation to Polynuclear Ruthenium Oxide-Metallocyanates

摘要

High-valent RuVIIO4 - (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 Vvs Ag/AgCl using RuCl3 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 RuO2 and RuO3, stabilizing the high-valent perruthenate anion (Ru(VII)-RuOx-CME, x=2 and 3, CME=chemically modified electrode). The electrodes showed three distinct redox peaks corresponding to Ru2O3/RuO2, RuO2/RuO3, and RuO4 2-/RuO4 - redox processes at pH 2,like the classical RuO2 electrodes in alkaline conditions. Solid stateUV-visible spectra of the ITO/Ru(VII)-RuOx-CME showed characteristic absorption very close to chemically generated authentic RuO4 - species in alkaline solution.Further, redox-controlled sequential procedures yielded polynuclear ruthenium oxide-hexacyanometallate films (RuOMCN-CME, M=Fe and Ru), in which Ru(VII)-RuOx-CME acted as a specific template. A controlled-potential activation (>1 V) of Ru(VII)-RuOx-CME, stabilizing the key RuO4 - 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.