Ultrathin Films of Ruthenium on Low Index Platinum Single Crystal Surfaces:  An Electrochemical Study

We report on electrochemical properties of ultrathin films of ruthenium on platinum single crystal surfaces, Pt(100), Pt(111) and Pt(110), and demonstrate that such films can be obtained by spontaneous deposition. We also show that the spontaneously deposited ruthenium coverage is surface structure dependent. Using the spontaneous deposition process and a constant potential electrolysis, a variety of Pt/Ru surfaces up to ca. 0.4 monolayer of ruthenium were prepared. All such Ru films are stable in the electrode potential range that precedes platinum oxidation. A strong surface structure effect in the electrochemical properties of these thin films was found. On Pt(100)/Ru at a fixed Ru coverage, there is a transition from a reversible to irreversible surface redox behavior that is not observed on other platinum single crystal faces. In contrast to Pt(100)/Ru and Pt(110)/Ru, the individual voltammetric phases of the Pt(111)/Ru electrode are not resolved, and ruthenium surface oxides appear to be the most stable on the Pt(111) electrode.