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

Abstract

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.