Oxygen reduction on nanostructured platinum surfaces in acidic media: Promoting effect of surface steps and ideal response of Pt(111)

In this paper, the role of surface steps on the electrocatalytic activity of platinum nanostructured surfaces for the oxygen reduction reaction (ORR) in acidic medium is evaluated by using stepped surfaces of structure Pt(S)[n(1 1 1) x (1 1 1)] with large terraces (20 <= n <= 50). It is realized that the inclusion of an even low amount of surface steps enhances the ORR, and linear activity trends are measured when currents at constant potential are plotted vs. the step density. As a consequence, an ideal ORR curve for a defect-free Pt(1 1 1) surface is extrapolated at zero defect density from experimental data and can be compared to that of a quasi-perfect Pt(1 1 1) electrode. It is clearly shown that surface steps promote the electrode activity toward ORR in acid medium. Results are discussed in light of available theoretical and experimental data. (C) 2014 Elsevier B. V. All rights reserved.