Alternative view of anodic surface oxidation of noble metals

Abstract The idea of underpotential oxidation of water, taking place on the surface of noble metals in the range of potentials preceding molecular oxygen evolution, is more than 40-years old. Chemisorbed oxygen atom—O chem is considered to be the main intermediate in the underpotential oxidation of H 2 O, leading eventually to chemical oxidation of noble metals and formation of anhydrous surface oxides of MeO type. This concept is still used for the evaluation of the real surface area of the noble metal electrodes and also for the interpretation of new experimental results. The existence of reversible metal-oxide electrodes demonstrated experimentally for Pt, Pd, Rh, Ir and Au electrodes, oxidized anodically in the range of potentials preceding O 2 evolution, shows that noble metals do have electrochemistry of their own. Nanometric layers of amorphous, slightly soluble hydroxides, hydrous oxides or oxides can form electrochemically on the electrode surface during the anodic process and be reduced during the cathodic one. Such alternative concept admits the reversibility of anodic and cathodic processes and changes essentially the understanding and interpretation of the phenomena of anodic oxidation of noble metals.