The process of Ag2O formation has been investigated in 0.1M, 0.3 M, 1.0Mand 2.0 M NaOH solutions on polycrystalline Ag electrodes by cyclic voltammetry potentiostatic pulse and SEM techniques. The SEM micrographs of the chemically polished Ag surface and the surface after oxide formation revealed considerable roughening of the Ag surface after Ag2O formation and reduction. The roughening was more pronounced at higher NaOH concentrations, indicating that only the first cycle or pulse applied on a freshly polished Ag electrode should be considered in mechanistic studies of Ag2O formation. In the given range of NaOH concentrations, it was shown that the process is not controlled simply by the diffusion of the reacting species.Anucleation phenomenon was clearly detected in all the examined solutions. The SEM micrographs confirm that the two anodic peaks, present on the voltammograms of Ag2O formation correspond to two types of oxide film, i.e., non-homogeneously and homogeneously distributed ones. Potentiostatic formation of the oxide at potentials corresponding to the first and second anodic peak yielded simple cubic Ag2O but of very different grain size.
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