Electrochemical Stripping of Atomic Oxygen on Single-Crystalline Platinum: Bridging Gas-Phase and Electrochemical Oxidation

To understand the interaction between Pt and surface oxygenated species in electrocatalysis, this paper correlates the electrochemistry of atomic oxygen on Pt formed in the gas phase with electrochemically generated oxygen species on a variety of single-crystal platinum surfaces. The atomic oxygen adsorbed on single-crystalline Pt electrodes, made by thermal dissociation of molecular oxygen, is used for voltammetry measurements in acidic electrolytes (HClO₄ and H₂SO₄). The essential knowledge of coverage, binding energy, and surface construction of atomic oxygen is correlated with the charge, potential, and shape of voltammograms, respectively. The differences of the voltammograms between the oxide made by thermal dissociation of molecular oxygen and electrochemical oxidation imply that atomic oxygen is not an intermediate of the electrochemical oxidation of Pt(111). The reconstruction of (100) terrace and step and the low-potential stripping of atomic oxygen on (111) step site provide insight into the first stages of degradation of Pt-based electrocatalysts.