Caracterização eletroquímica e ótica de filmes de óxido espesso crescidos sobre ouro. / Eletrochemical and optical characterization of thick oxide films on gold electrodes.

AUTOR(ES)
DATA DE PUBLICAÇÃO

1995

RESUMO

Potentiostatic polarization of polycrystalline Au electrodes at various polarization potentials, 1.8, ..., 2.4 V, RHE, for polarization times up to 72h, in acid and basic solutions, leads to formation of four oxide states, OC1, OC2, OC3 and OC4, distinguished, in reduction, using linear-sweep voltammetry. The quasi-2d state (OC1) tends to the limit of two monolayers in acid solution and one monolayer in basic solution of AuOads, while the quasi-3d state (OC2-OC4, Au2O3) does not reach any limit in its extent. The cathodic total charge log polarization time plots reveal two linear regions: (a) slow, up to 1 mC cm-2, and (b) fast, beyond 1 mC cm-2. This behavior is attributed to a new oxide growth mechanism. During growth of the oxide film at high anodic potentials through the various stages identifiable in cyclic voltammetry, small but significant changes in the kinetics of O2, evolution arise. Tafel slopes for the oxygen evolution reaction, OER, reveal two linear region in acid and alkaline medium. The mechanism of the OER is preliminarily discussed. Finally, studies of the thick anodic oxide films on Au is done in situ by spectroscopic ellipsometry. The spectrum of the oxide film in the wavelength range 300 to 800 nm, at various stages of film growth is obtained. It is shown that both film thickness and optical spectrum can be solved at each stage in oxide growth assuming a highly absorbing thin film adjacent to the metal surface, and, on the top of it, a second film, which is most probably a hydrous form of "Au2O3". The latter film reaches thicknesses of severa1 hundreds A± up to 72h of anodization.

ASSUNTO(S)

thick oxides eletroquímica Óxidos espessos gold ouro eletrochemistry

ACESSO AO ARTIGO

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