Rapid degradation and detoxification of metronidazole using calcium sulfite activated by CoCu two-dimensional layered bimetallic hydroxides: Performance, mechanism, and degradation pathway

Abstract

In this study, cobalt copper-layered double hydroxides (CoCu-LDHs) were prepared by coprecipitation as catalysts to activate CaSO3 for metronidazole (MNZ) degradation. This is the first report on layered double hydroxides activating sulfite for the degradation of organic pollutants. Meanwhile, to address the issue of self-quenching reactions readily occurring in conventional sulfite advanced oxidation systems and resulting in low oxidant efficiency, CaSO3 with slightly soluble in water was used instead of commonly used Na2SO3, to improve the limitations of traditional systems. The results showed that in the CoCu-LDHs/CaSO3 system, the degradation rate of MNZ reached 98.7% within 5 min, representing a 23.0% increase compared to the CoCu-LDHs/Na2SO3 system. Owing to the excellent catalytic performance exhibited by CoCu-LDHs, characterizations including XRD, FTIR, SEM, TEM, BET and XPS were carried out to investigate this further. The results confirmed the successful synthesis of CoCu-LDH, and the activation mechanism study revealed that Co and Cu were considered to the main elements in activating CaSO3, demonstrating good synergistic effects. In addition, the oxygen vacancies on the catalyst surface also played a positive role in generating radicals and promoting electron transfer. Subsequently, the effects of Co/Cu ratio, catalyst dosage, oxidant concentration, pollutant concentration, pH and coexisting substances on MNZ degradation were investigated. Additionally, based on the LC-MS analysis of degradation products and toxicity tests, MNZ was transformed into different intermediates with low toxicity through four pathways, eventually mineralizing into inorganic small molecules. After six cycles, the MNZ degradation rate still reached 82.1%, exhibiting excellent stability and recyclability. In general, this study provides new ideas for activating sulfite, while providing theoretical support for subsequent research on sulfite advanced oxidation system.