Sara Feijoo

Electrochemical wastewater treatment is a promising technique to remove recalcitrant pollutants from wastewater. However, the complexity of elucidating the underlying degradation mechanisms hinders its optimisation not only from a techno-economic perspective, as it is desirable to maximise removal efficiencies at low energy and chemical requirements, but also in environmental terms, as the generation of toxic by-products is an ongoing challenge. In this work, we propose a novel combined experimental and computational approach to (i) estimate the contribution of radical and non-radical mechanisms as well as their synergistic effects during electrochemical oxidation and (ii) identify the optimal conditions that promote specific degradation pathways. As a case study, the distribution of the degradation mechanisms involved in the removal of benzoic acid (BA) via boron-doped diamond (BDD) anodes was elucidated and analysed as a function of several operating parameters, i.e., the initial sulfate and nitrate content of the wastewater and the current applied. Subsequently, a multivariate optimisation study was conducted, where the influence of the electrode nature was investigated for two commercial BDD electrodes and a customised silver-decorated BDD electrode. Optimal conditions were identified for each degradation mechanism as well as for the overall BA degradation rate constant. BDD selection was found to be the most influential factor favouring any mechanism (i.e., 52–85% contribution), given that properties such as its boron doping and the presence of electrodeposited silver could dramatically affect the reactions taking place. In particular, decorating the BDD surface with silver microparticles significantly enhanced BA degradation via sulfate radicals, whereas direct oxidation, reactive oxygen species and radical synergistic effects were promoted when using a commercial BDD material with higher boron content and on a silicon substrate. Consequently, by simplifying the identification and quantification of underlying mechanisms, our approach facilitates the elucidation of the most suitable degradation route for a given electrochemical wastewater treatment together with its optimal operating conditions.