Alkali Metal Cation Effects in Structuring Pt, Rh, and Au Surfaces through Cathodic Corrosion

Cathodic corrosion is an electrochemical etching process that alters metallic surfaces by creating nanoparticles and a variety of etching features. Because these features typically have a preferential orientation, cathodic corrosion can be applied to modify and nanostructure electrode surfaces. However, this application of cathodic corrosion is currently limited by an insufficient chemical understanding of its underlying mechanism. This includes the role of alkali metal cations, which are thought to be crucial in both enabling cathodic corrosion and controlling its final facet preference. This work addresses this knowledge gap by exploring the cathodic corrosion of Pt, Rh, and Au in LiOH, NaOH, and KOH through both experimental and theoretical methods. These methods demonstrate that cations are adsorbed during cathodic corrosion and play a major role in controlling the onset potential and final surface morphology in cathodic corrosion. Interestingly, an equally significant role appears to be played by adsorbed hydrogen, based on calculations using literature density functional theory data. Considering the significance of both hydrogen and electrolyte cations, it is hypothesized that cathodic corrosion might proceed via an intermediate ternary metal hydride. This fundamental insight leads to both metal-specific recommendations and more general guidelines for applying cathodic corrosion to structure metallic surfaces.