Controlling surface wetting in high-alkaline electrolytes for single facet Pt oxygen evolution electrocatalytic activity mapping by scanning electrochemical cell microscopy.

Scanning electrochemical cell microscopy (SECCM) has been used to explore structure-electrocatalytic activity relationships through high-resolution mapping of local activities of electrocatalysts. However, utilizing SECCM in strongly alkaline conditions presents a significant challenge due to the high wettability of the alkaline electrolyte leading to a substantial instability of the droplet in contact with the sample surface, and hence to unpredictable wetting and spreading of the electrolyte. The spreading phenomena in SECCM is confirmed by the electrochemical response of a free-diffusing redox probe and finite element method (FEM) simulations. Considering the significance of alkaline electrolytes in electrocatalysis, these wetting issues restrict the application of SECCM for electrocatalyst elucidation in highly alkaline electrolytes. We resolve this issue by incorporating a small percentage of polyvinylpyrrolidone (PVP) in the electrolyte inside the SECCM capillary to increase the surface tension of the electrolyte. To demonstrate successful wetting mitigation and stable SECCM mapping, we performed oxygen evolution reaction (OER) mapping on polycrystalline Pt by using 1 M KOH with an optimized PVP concentration. The OER activity maps correlated with the orientation of the exposed facets determined by electron backscatter diffraction and reveal different activities between Pt facets, hence confirming our methodology for exploring electrocatalytic activities in single facet scale in concentrated alkaline media. Interestingly, the maximum OER current density was highest for (110) and (111) which contradicts the activity trends in acidic electrolyte for which (100) is most active for the OER.