H2O2-assisted photoelectrocatalytic degradation of Mitoxantrone using CuO nanostructured films: Identification of by-products and toxicity

• Published in: The Science of the total environment Vol. 651; pp. 2845 - 2856
• Main Authors: da Rosa, Ana Paula Pereira, Cavalcante, Rodrigo Pereira, da Silva, Débora Antonio, da Silva, Lucas de Melo, da Silva, Thalita Ferreira, Gozzi, Fábio, McGlynn, Enda, Brady-Boyd, Anita, Casagrande, Gleison Antônio, Wender, Heberton, de Oliveira, Silvio César, Junior, Amilcar Machulek
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.02.2019
• Subjects: Anticancer drug; Chemical synthesis; CuO/Si heterojunctions; Degradation pathways; Needle-like CuO nanostructures; Photoelectrocatalytic activity; Photoelectrocatalytic activity; Anticancer drug; CuO/Si heterojunctions; Chemical synthesis; Degradation pathways; Needle-like CuO nanostructures
• ISSN: 0048-9697; 1879-1026
• DOI: 10.1016/j.scitotenv.2018.10.173

CuO nanostructured thin films supported on silicon with 6.5 cm2 area (geometric area greater than the studies reported in the literature) were synthesized by a chemical bath deposition technique. The electrodes were characterized by MEV, XRD, XPS, contact angle, cyclic voltammetry and electrochemical impedance spectroscopy analyses. To evaluate the photoelectrochemical properties of the CuO films, photocurrent–voltage measurements were performed using linear voltammetry. The catalytic activities of CuO nanostructures were evaluated by monitoring photodegradation of Mitoxantrone (MTX) under UV-A light irradiation. The method of photoelectrocatalysis (PEC), applying a voltage of 1.5 V and assisted by adding H2O2, was undertaken. To the best of our knowledge, no studies on the degradation of anticancer agents using PEC process have been found in the literature. For comparison purposes, experiments were performed under the same conditions by assisted photocatalysis (PC) with H2O2 and direct photolysis. CuO deposits consist of a needle-like morphology. The presence of CuO in the tenorite phase was evidenced by XRD and the XPS spectra showed the presence of copper(II) oxide. The increase in current under illumination shows that CuO exhibits photoactivity. The PEC system showed a 75% level of MTX degradation, while the level achieved using PC was 50%. Under UV-A light alone only 3% removal was obtained after 180 min. Up to 10 by-products were identified by chromatography-mass spectrometry (LC-MS) with m/z values ranging between 521 and 285 and a plausible degradation route has been proposed. It is worth mentioning that 9 by-products identified in this work, were not found in the literature in other studies of degradation or products generated as metabolites. The toxicity tests of MTX before and after PEC treatment with Artemia Salina and Allium cepa showed a decrease in the acute toxicity of the medium as the antineoplastic was degraded. [Display omitted] •Needle-like CuO nanostructures were grown on Si substrates using a CBD method.•High photoelectrocatalytic performance of CuO film is related to its needle-like nanostructure.•Enhanced H2O2-assisted PEC degradation by CuO film electrodes it was demonstrated.•The MTX drug exhibits high acute toxicity against Artemia salina and Allium cepa.•By-products generated by photoelectrocatalysis are substantially less toxic.