The electrochemical behavior of tin dioxide based electrodes and electrochemical decomposition of cyanides / Comportamento eletroquímico de eletrodos a base de dióxido de estanho e sua aplicação na oxidação do cianeto

AUTOR(ES)
DATA DE PUBLICAÇÃO

1997

RESUMO

Tin dioxide based electrodes have a high overpotential for the OER and are relatively cheap. Due to these characteristics, they have a potential application is waste water treatment as anodes for electrochemical destruction of organics and inorganics. However, the service life of such electrodes are relatively short due to corrosion of the oxide layer during electrolysis. Thus, the knowledge of the physical and electrochemical characteristic of the material is highly desirable for future development of SnO2-based anodes with a better electrochemical performance. This work reports on the electrochemical studies of SnO2-SbOx, layers thermally deposited on Ti, in 0.5 M H2SO4. This work also reports on the cyanide ion electrooxidation using those oxide anodes. The electrochemical behavior and physical characteristics of SnO2-SbOx based electrodes, with and without the addition of RuO2, were studied by means of cyclic voltammetry, service life measurements, electrochemical irnpedance spectroscopy, scanning electron microscopy, EDX and X-rays diffraction. The resulting cyclic voltammograms obtained using SnO2-SbOx, and SnO2-SbOx-RuO2(x), x = 30, 5, 1 and 0.4 %) showed that the OER overpotential decreased with the addition of RuO2. Service life studies, evaluated by the application of a constant current of 10 mAcm-2 to the electrodes revealed that the potential of a SnO2 electrode after 1 hour departed fom its initial value, 3 V, reaching a value of 5 V elapsed 7 hours. Using a SnO2-RuO2 (1 %) electrode, the potential remained constant at 3.0 V for 10 hours and increased slowly afterwards. However, addition of 30% RuO2 to the oxide film resulted in a decrease in the electrode potential to 1.3 V, which remained constant for at least 8 hours. Repetitive triangular potential voltammetry applied to the SnO2 electrode revealed that during the first potential scan appeared and anodic current, which is higher than the corresponding for the SnO2-RuO2 (1 %) electrode. This is explained in terms of the oxidation of the Ti substrate and the lesser porosity of the latter. AC I mpedance diagrams obtained for the Ti/ SnO2-SbOx and Ti/ SnO2-SbOx-RuO2 electrodes at the rest potential and at a potential in the OER region can be explained by a single equivalent circuit containing tvm elements in series. These elements being attributed to the effect of the surface charge transfer and an effect of the difíusion process in the tin oxide layer. The results showed that the charge transfer resistance and the resistance of the oxide film are lower in the containing Ruo2 oxide film. Surface analysis of the electrodes Ti/ SnO2-SbOx, revealed that they are relatively porous and formed by clusters of small particles, while the Ti/SnO2-SbOx-RuO2 (1 %) film is more compact. X-rays diffraction analysis showed that a Sn1-xTixO2 oxide is formed on the Ti/SnO2-SbOx, electrode. With the addition of 1% RuO2 the percentage of that oxide decreased from 12.9 to 5.2 %. An explanation to this fact is given.

ASSUNTO(S)

physical chemistry eletroquímica físico-química tin dioxide eletrodes electrochemistry eletrodos de oxido de estanho

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