Surface and Subsurface Oxygen on Platinum in a 0.5 M H2SO4Solution

The oxidation of polycrystalline platinum in 0.5 M H2SO4 is studied by cyclic voltammetry at potential scan rates of 5–500 mV s–1 while varying the potential cycling range. The scheme, which is proposed for explaining the observed acceleration and deceleration of oxygen sorption at 0.75–1.0 V, accounts for the presence of oxygen in the subsurface layers of platinum (Oss) and the formation of a barrier layer comprising complexes Oss–Pt n –SO4. Cycling platinum secures certain steady-state contents of Oss at 0.01–1.35 V. In an anodic scan, Oss accumulates at E > 0.85 V (slow post-electrochemical stage) due to exchange of platinum and oxygen atom sites. In a cathodic scan, the desorption of most oxygen gives way to the adsorption of anions, which prevent residual Oss from appearing on the surface. The residual Oss disappears at E < 0.1 V after a sufficiently complete desorption of anions and the destruction of stable complexes Oss–Pt n –SO4. Varying the potential cyclic limit leads, after a delay, to other steady-state Oss contents.