Detection of Hydrogen Peroxide Produced during Electrochemical Oxygen Reduction Using Scanning Electrochemical Microscopy

The substrate-generation/tip-collection mode of scanning electrochemical microscopy was used to detect hydrogen peroxide formed as an intermediate during oxygen reduction at various electrodes. The experiment is conceptually similar to rotating ring−disk experiments but does not require the production of a ring−disk assembly for the specific electrode material in question. In order to limit the extension of the diffusion layer above the sample, the sample electrode potential is pulsed while the Pt ultramicroelectrode probe (UME) is held at a constant potential for oxidative amperometric detection of hydrogen peroxide. The signal at UME is influenced by the sample region within the diffusion length of hydrogen peroxide during the pulse of 2.5 s. The method is tested with three model electrodes showing different behavior with respect to the oxygen reduction reaction (ORR) in acidic solution. Simple analytical models were used to extract effective rate constants for the most important reaction paths of ORR at gold and palladium−cobalt samples from the chronoamperometric response of the UME to a reduction pulse at the sample electrode.