Oscillatory dynamics during the methanol electrooxidation reaction on Pt(111)

Abstract

Despite several papers describing the oscillatory methanol electrooxidation reaction (OMOR) catalyzed by polycrystalline Pt, these dynamic instabilities are less explored on single crystalline surfaces. Herein, we observed and mapped for the first time the OMOR on Pt(111) in non-adsorbing anion solutions as well as in the presence of small amounts of sulfate anions. Period 1 oscillations with oscillation frequencies from 1.2 to 2.0 Hz were observed for methanol concentrations higher than 1.0 M, with no evolution to more complex patterns. These oscillations occur in the potential range in which PtOH is partially covering the surface without irreversible oxidation processes. Small changes in both the mean potential (E_m) and the poisoning rate along the time-series were observed, the so-called drift, and were explained in terms of the accumulation of intermediates at the interface. The presence of sulfate strongly inhibits the OMOR, and the results are discussed in terms of sulfate adlayer formation on {111} domains.