Bulk CO oxidation on platinum electrodes vicinal to the Pt(111) surface

Bulk CO oxidation has been studied on platinum stepped surfaces belonging to the series Pt(S)[n(111)x(111)], using a hanging meniscus rotating disk electrode (HMRDE) configuration. The general shape of the voltammograms is not significantly affected by the presence of the steps. However, the curves shift towards negative values as the step density increases. Thus, in the positive-going scan, a linear relationship is observed for the dependence of the potential for the ignition peak vs the step density for surfaces with terraces wider than five atoms, shorter terraces deviate from this behavior. In the negative-going scan, a similar situation is observed for the potential where the current drops to zero. In this case, Pt(111) electrode also deviates from the expected behavior because of the formation of the ordered bisulfate adlayer on the electrode. The anion readsorption process is also observed by recording the HRMDE voltammograms at a high scan rate. All these results have been analyzed in light of a common mechanism, discussing the possible role of the steps in the stability and reactivity of the CO adlayer.