Diagnosis of the Mechanism of Anodic Oxide FilmGrowth on Platinum in KOH

Abstract Diagnostic criteria for growth of the anodic oxide film on platinum in KOH are reported. In this work, the analytical analysis of oxide film growth demonstrated that the electric field in the passive film formed anodically on platinum in KOH is constant, independent of the applied voltage and barrier layer thickness. This criterion intrinsically distinguishes the Point Defect Model (PDM) from the High Field Model (HFM). Unequivocally, the PDM provides a superior theoretical framework than does the HFM for interpreting oxide film growth on platinum. Importantly, we argue that the diagnostic criteria also apply to metal interstitial conduction, which is the mechanism proposed in the HFM for formation of the PtO oxide film on platinum, but with film growth occurring at the film/solution interface and with a thickness-dependent electric field, rather than being restricted to oxygen vacancy conductors alone, as originally derived for the PDM. Thus, the ability of the diagnostic criteria to differentiate between the HFM and the PDM, in this case, is a direct assessment of the dependence of the electric field strength on the applied voltage and barrier layer thickness, with the experimental results coming down unequivocally on the side of the PDM.