Towards a higher photostability of ZnO photo-electrocatalysts in the degradation of organics by using MMO substrates

• Published in: Chemosphere (Oxford) 2021-05, Vol.271, p.129451-129451, Article 129451
• Main Authors: Goulart, Lorena A., Santos, Géssica O.S., Eguiluz, Katlin I.B., Salazar-Banda, Giancarlo R., Lanza, Marcos R.V., Saez, Cristina, Rodrigo, Manuel A.
• Format: Article
• Language: English
• Subjects: Clopyralid; Electrodeposition; Electrodes; Electrolysis; Oxidation-Reduction; Oxides; Photoanode; Photoelectrocatalysis; Ti/MMO/ZnO; Ti/ZnO; Zinc Oxide
• ISSN: 0045-6535; 1879-1298
• DOI: 10.1016/j.chemosphere.2020.129451

In this work, it is proposed a novel strategy to increase the photostability of the ZnO photoelectrocatalyst under prolonged light irradiation, without the addition or deposition of metals and/or semiconductor oxides during their synthesis. This strategy is based on the use of a mixed metal oxide (MMO-Ru0.3Ti0.7O2) coating as the substrate for the electrodeposition of ZnO. To assess it, the electrodeposition of ZnO films on Ti and Ti/MMO substrates and the photoelectrocatalytic activity of these materials for the degradation of the herbicide clopyralid were studied. The results showed that the substrate directly influenced the photo-stability of the ZnO film. Under the incidence of UV light and polarization, the novel Ti/MMO/ZnO electrode showed greater photocurrent stability as compared to Ti/ZnO, which is a very important outcome because the behavior of these electrodes was similar when compared in terms of the degradation of clopyralid. Single electrolysis was not able to degrade efficiently clopyralid at the different potentials studied. However, the irradiation of UV light on the polarized surface of the Ti/ZnO and Ti/MMO/ZnO electrodes increased markedly the degradation rate of clopyralid. A synergistic effect was observed between light and electrode polarization, since the rate of degradation of clopyralid was twice as high in photoelectrocatalysis (PhEC) than in photocatalysis (PhC) and different intermediates were formed. From these results, mechanisms of degradation of clopyralid for the PhC and PhEC systems with the Ti/ZnO and Ti/MMO/ZnO electrodes were presented. Therefore, the Ti/MMO/ZnO electrode could be a cheap and simple alternative to be applied in the efficient photodegradation of organic pollutants, presenting the great advantage of having a facile synthesis and high capacity to work at relatively low potentials. [Display omitted] •Deposition of ZnO on Ti/MMO improves the adhesion and stability of the film.•ZnO deposited on Ti/MMO results in a more porous electrode with large surface area.•Insignificant differences in photoactivity between Ti/ZnO and Ti/MMO/ZnO.•Photoelectrocatalysis present high clopyralid degradation efficiency for both anodes.•Clopyralid oxidation mechanism was dependent on the oxidizing species and UV light.