Investigating the reactivity of TiOx and BDD anodes for electro-oxidation of organic pollutants by experimental and modeling approaches

• Published in: Electrochimica acta 2023-01, Vol.439, p.141513, Article 141513
• Main Authors: Ma, Jing, Trellu, Clément, Skolotneva, Ekaterina, Oturan, Nihal, Oturan, Mehmet A., Mareev, Semyon
• Format: Article
• Language: English
• Subjects: Anodic oxidation; Chemical Sciences; Environmental Sciences; Hydroxyl radical; Mass transport; Modeling; Paracetamol; Terephthalic acid
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2022.141513

•Model took into consideration mass transport, ⋅OH-mediated oxidation and DET.•Reactivity of BDD and TiOx for degradation and mineralization was compared.•The role of each phenomenon was discussed in different experimental configurations.•The predominant mechanism depends on ⋅OH scavengers and reaction rates.•100 mM ethanol was necessary for relevant ⋅OH quenching experiment. The reactivity of two non-active anodes (BDD and TiOx) for the removal of organic pollutants from water was investigated and compared. A mathematical model for electro-oxidation of organic compounds was developed by considering (i) an analytical expression of the spatial distribution of •OH concentration at non-active anodes, (ii) mass transport through the diffusion boundary layer and (iii) both direct electron transfer and •OH-mediated oxidation for degradation of organic pollutants. The model was calibrated from experimental data using, for example, terephthalic acid as •OH probe molecule or ethanol as •OH quencher during paracetamol degradation. Calculation of the fraction of current ascribed to the different possible reactions as well as a sensitivity analysis allowed for highlighting the key mechanisms and limiting phenomena. Degradation of organics occurs almost exclusively through •OH-mediated oxidation under mass transport limitation and for sufficiently high reaction rate constants. Improvement of degradation kinetics strongly depends on mass transport enhancement of organic compounds to the reaction zone at the electrode surface. Competition between the mother molecule and degradation by-products for reaction with •OH did not significantly affect degradation kinetics under mass transport limitation. Direct electron transfer can potentially become important in presence of large amounts of •OH scavengers or for organic compounds that react slowly with •OH (k