In Situ EC-AFM Study of the Initial Stages of Cathodic Corrosion of Pt(111) and Polycrystalline Pt in Acid Solution

[Image: see text] An atomic scale understanding of the surface degradation mechanism during cathodic corrosion of a platinum electrode is still lacking. Here, we present results of surface structural changes observed during cathodic polarization of a polycrystalline Pt electrode and single crystalline Pt(111) in acid electrolytes in the absence and presence of cations (Na(+)) by in situ electrochemical atomic force microscopy (EC-AFM) imaging. The electrolyte cation is proved to be a prerequisite to trigger cathodic etching of the polycrystalline Pt surface. Further examination of the evolution of electrochemical signals and distinct surface structural transformations of an atomically defined Pt(111) single-crystal electrode during cathodic corrosion reveals clearly that the roughening process commences at the under-coordinated sites of the Pt(111) surface. The created triangular-shape pattern, actually a 100-oriented pit in a 111-terrace, grows primarily laterally in the initial regime, while prolonged cathodic corrosion leads to the existing etching pits growing in depth until ultimately they coalesce with each other, generating a highly roughened surface.