Publication details

Mxene-decorated spinel oxides as innovative activators of peroxymonosulfate for degradation of caffeine in WWTP effluents: Insights into mechanisms

Authors

ATRI Shalu ZAŽÍMAL František SANKARAN Sridhar Gowri DYRCIKOVA Zuzana CAPLOVICOVA Maria ROCH Tomas DVORANOVA Dana HOMOLA Tomáš PLESCH Gustav BRIGANTE Marcello MONFORT Olivier

Year of publication 2024
Type Article in Periodical
Magazine / Source Chemical Engineering Journal
MU Faculty or unit

Faculty of Science

Citation
web https://www.sciencedirect.com/science/article/pii/S1385894724093057
Doi http://dx.doi.org/10.1016/j.cej.2024.157814
Keywords MXene; Ferrite; Composites; Catalyst; Persulfate; Wastewater
Description In the frame of the environmental issues related to the efficiency of wastewaters treatment, the generation of advanced oxidation processes (AOPs) by 2D materials appears one of the most promising solutions. In this study, a novel catalytic system for peroxymonosulfate activation (PMS) was designed based on MXene (Ti3C2Tx) decorated with spinel oxides Co3O4, Fe3O4 and CoFe2O4 catalysts. Their efficiency in caffeine (CAF) degradation via PMS activation was assessed. The insertion of spinel oxides inside the multilayer structure of MXene along with their uniform surface decoration was demonstrated by SEM and TEM analyses and it also avoided the aggregation of the magnetic particles, thus increasing their efficiency. Among the different catalysts, the MXene/CoFe2O4 (MXCF) stood out as the most effective, mainly due to the Fe and Co redox cycles. The complete degradation of CAF was achieved in the dark within 10?min at natural pH using 0.2?g/L of MXCF and 0.5?mM of PMS. The novelty of current study lies in the efficient activation of PMS by, for the first time, MXCF in the dark along with mechanistic elucidation of PMS activation. The important role of Co3+/Co2+ and Fe3+/Fe2+ redox cycles alongside surface bound functional groups were highlighted. Radical scavenging and EPR experiments confirmed •OH and 1O2 as the main ROS involved in the CAF degradation. The CAF degradation pathways pointed to hydroxylation and imidazole ring opening mechanisms and MXCF catalyst also exhibited high efficiency in the degradation of sulfamethoxazole and phenol via PMS activation. To further highlight the relevance of the obtained results, treatment of tertiary effluents of wastewaters treatment plant (WWTP) in Bratislava contaminated by CAF exhibited a complete pollutant degradation after 3?h by supplying 0.2?g/L of catalyst and 2?mM PMS in the dark.
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