Nucleation and growth of anodic oxide films on bismuth—I. Cyclic voltammetry

The early stages in the formation of a continuous anodic layer of bismuth oxide on a solid bismuth electrode, in the pH range 5–14, were studied. The oxide covered the surface by the simultaneous thickening and spreading of patches. The metal surface was classified into two different areas with different overvoltage for oxide nucleation. The ratio of the two areas varied according to the history of the surface.The thickening of the newly formed layer (final thickness ～20 nm) followed the high-field growth law i = $\text{A}$exp(B$\text{E}$) where $\text{E}$ is the field in the oxide layer, with B = (2.0 ± 0.5) × 10^?6 V^?1 cm. This value of B gives an activation distance for high-field ion transport of 0.2 nm, comparable to the radius of a lattice site and much smaller than that obtained previously, for much thicker films.Dissolution of the film, giving breakdown of the oxide layer and pitting of the metal, occurred for pH<8. The thickness of the anodic film was thus limited to only 4 nm at pH 5.Cathodic reduction of the anodic oxide resulted in a porous metal surface. The current—voltage curve for the reduction often had a complex shape, which was related to the morphology of the original anodic layer.