FeS2/carbon felt as an efficient electro-Fenton cathode for carbamazepine degradation and detoxification: In-depth discussion of reaction contribution and empirical kinetic model

Highlights: • A novel FeS₂/CF cathode was fabricated and used in EF. • The fabricated cathode could accelerate the generation rate of • OH. • The contribution of oxidation reactions in EF was calculated specifically. • The exposures of • OH in EP and EF were calculated by quenching experiment. • An inconsecutive empirical model of EF was firstly established to predict reaction. Carbamazepine (CBZ) decay by electro-Fenton (EF) oxidation using a novel FeS₂/carbon felt (CF) cathode, instead of a soluble iron salt, was studied with the aim to accelerate the reaction between H₂O₂ and ferrous ions, which helps to produce more hydroxyl radicals (^• OH) and eliminate iron sludge. First, fabricated FeS₂ and its derived cathode were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. Anodes were then screened, with DSA (Ti/IrO₂–RuO₂) showing the best performance under EF oxidation regarding CBZ degradation and electrochemical characterization. Several operating parameters of this EF process, such as FeS₂ loading, current density, gap between electrodes (GBE), initial [CBZ], and electrolyte type, were also investigated. Accordingly, a nonconsecutive empirical kinetic model was established to predict changes in CBZ concentration under the given operational parameters. The contribution of different oxidation types to the EF process was calculated using kinetic analysis and quenching experiments to verify the role of the FeS₂-modified cathode. The reaction contributions of anodic oxidation (AO), H₂O₂ electrolysis (EP), and EF oxidation to CBZ removal were 12.81%, 7.41%, and 79.77%, respectively. The ^• OH exposure of EP and EF oxidation was calculated, confirming that ^• OH exposure was approximately 22.45-fold higher using FeS₂-modified CF. Finally, the 19 intermediates formed by CBZ degradation were identified by ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry. Accordingly, four CBZ degradation pathways were proposed. ECOSAR software was used to assess the ecotoxicity of intermediates toward fish, daphnia, and green algae, showing that this novel EF oxidation process showed good toxicity reduction performance. A prolonged EF retention time was proposed to be necessary to obtain clean and safe water, even if the targeted compound was removed at an earlier time.