Scanning electrochemical microscopy (SECM): Study of the formation and reduction of oxides on platinum electrode surfaces in Na2SO4 solution (pH = 7)

The formation and reduction of oxides on polycrystalline platinum were studied in a neutral solution with a scanning electrochemical microscope (SECM). Experiments were carried out with tip—substrate voltammetry where the faradaic current flowing to the tip is recorded while cycling the potential of the substrate, and with tip—substrate chronoamperometry where the faradaic tip current is recorded against time following the application of a potential step to the substrate. The tip current was made pH sensitive by holding the tip potential in a region where a pH dependent reaction occurs. Hydrogen evolution was used to probe pH decreases, oxygen evolution was used for the detection of pH increases and Pt oxide formation was used to detect both pH increases and decreases. The results showed that oxide formation occurs in two stages, each involving the transfer of electrons and the release of protons into the solution. During the first stage the release of H⁺ precedes the transfer of electrons. while in the second stage H⁺ release and electron transfer proceed simultaneously. Results are analysed in terms of the formation of PtOH during stage I and PtO during stage 2. However stage 2 behaves differently under slow potential changes and the release of protons lags behind the transfer of electrons. This is interpreted as the result of a place-exchange mechanism from PtOH to HOPt prior to stage 2, followed by the oxidation of HOPt to OPt during stage 2. Similarly, Oxide reduction was found to occur in two stages, each involving the transfer of electrons and the consumption of protons. During the first stage, the consumption of H⁺ precedes the transfer of electrons. The results suggest that during the transfer of electrons, protons diffuse from the outer layer of the oxide (OPt) into the inner layer to form HOPt. For the second stage results are analysed in terms of a place exchange mechanism from HOPt to PtOH running in parallel with the consumption of H⁺ followed by a surface reduction from PtOH₂⁺ to Pt metal.