Role of oxygen-containing species at Pt(111) on the oxygen reduction reaction in acid media

Abstract

The oxygen reduction reaction (ORR) is one of the fundamental reactions in electrochemistry and has been widely studied, but the mechanistic details of ORR still remain elusive. In this work, the role of electrochemically oxygenated species, such as adsorbed hydroxide, OHads, adsorbed oxygen, Oads, and Pt(111) oxide, PtO, in the ORR dynamics is studied by employing electrochemical techniques, i.e., combining rotating disk mass-transport control with potential sweep rate perturbation. In this framework, a reduction peak at 0.85 V, E ORR, is detected. This peak shows a different electrochemical dynamics than that of Pt(111) oxides. The data analysis suggests that neither OHads nor Oads are the main bottleneck in the mechanism. Instead, results support the reduction of a soluble intermediate species as the rate determining step in the mechanism. On the other hand, PtO species, which are generated at relatively high potentials and are responsible of surface disordering, strongly inhibit the ORR as long as they are adsorbed in the electrode surface.