Related Experiment Video
Updated: Jul 15, 2025

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance
Published on: April 27, 2018
Effect of alkali-metal cation on oxygen adsorption at Pt single-crystal electrodes in non-aqueous electrolytes
Julia Fernández-Vidal1, Laurence J Hardwick1, Gema Cabello1
1Stephenson Institute for Renewable Energy, Department of Chemistry, University of Liverpool, Peach Street, L69 7ZF Liverpool, UK.
Abstract:
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 (E1/2) and relative intensities of the redox peaks corresponding to superoxy (O2-) and peroxy (O22-) 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.
Related Concept Videos
Alkali Metals
Table 1: Properties of the alkali metals
Ionic Strength: Effects on Chemical Equilibria
In this solution, the primary...
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Formation of Complex Ions
Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
Electrodeposition
Electrodeposition can...

