Effect of alkali-metal cation on oxygen adsorption at Pt single-crystal electrodes in non-aqueous electrolytes.

The effect of Group 1 alkali-metal cations (Na+ , K+ , and Cs+ ) on the oxygen reduction and evolution reactions (ORR and OER) using dimethyl sulfoxide (DMSO)-based electrolytes was investigated. Cyclic voltammetry (CV) utilising different Pt-electrode surfaces (polycrystalline Pt, Pt(111) and Pt(100)) was undertaken to investigate the influence of surface structure upon the ORR and OER. For K+ and Cs+ , negligible variation in the CV response (in contrast to Na+ ) was observed using Pt(111), Pt(100) and Pt(poly) electrodes, consistent with a weak surface-metal/superoxide complex interaction. Indeed, changes in the half-wave potentials ( E 1/2 ) and relative intensities of the redox peaks corresponding to superoxy (O2 - ) and peroxy (O2 2- ) ion formation were consistent with a solution-mediated mechanism for larger cations, such as Cs+ . Support for this finding was obtained via in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). During the ORR and in the presence of Cs+ , O2 - and weakly adsorbed caesium superoxide (CsO2 ) species were detected. Because DMSO was found to strongly interact with the surface at potentials associated with the ORR, CsO2 was readily displaced at more negative potentials via increased solvent adsorption at the surface. This finding highlights the important impact of the solvent during ORR/OER reactions.