Activation of peroxymonosulfate for ciprofloxacin degradation by a novel oxygen-deficient CoTiO3/TiO2NTs/Ti composite catalytic membrane:Electron transfer pathway and underlying mechanism

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The technique of activating peroxymonosulfate (PMS) by enriching oxygen vacancies (Vo) in heterogeneous catalysts has gained extensive attentions in the removal of emerging contaminants, e.g., antibiotics from wastewater. In this study, a Vo-CoTiO3/TiO2NTs/Ti (Vo-CTNs) catalytic membrane with rich oxygen vacancies was prepared and employed for the activation of PMS in degrading ciprofloxacin (CIP) in a continuous flow reactor. The averaged degradation efficiency of CIP in the Vo-CTNs/PMS system could reach 97.3 %, significantly higher than that in the CoTiO3/TiO2NTs/Ti (CTNs) system (91.1 %). Quenching experiments and electron paramagnetic resonance analysis collectively confirmed the presence of •OH, SO4•−, O2•− and 1O2 during the CIP degradation process. The results of the electrochemical experiments demonstrated that in the presence of oxygen vacancies, the mutual conversion between Co2+ and Co3+ was facilitated, resulting in a lower transfer resistance. At an initial CIP concentration of 10 mg/L and a membrane flux of 600 LMH, the degradation efficiency and mineralization rate of CIP could reach 95.2 % and 51.1 % after 12 h of operation, respectively. Meanwhile, limited leaching of cobalt ions (52 μg/L) from the catalytic membrane was observed during treatment. Theoretical calculations revealed that Vo engineering can modulate the surface electronic states, thereby enhancing binding energy and electron transfer for PMS activation. The degradation of CIP is mainly achieved through the ring opening reactions in the piperazine, quinolone, and cyclopropyl groups attacked by reactive oxygen species. In this work, we built cobalt-based composite nanomaterials to promote effective electron transfer and minimize leaching of cobalt ions, and providing a new method for activating PMS in a continuous flow system by enriching the oxygen vacancies in the catalytic membrane. This method has potentials to be applied in treating wastewater containing antibiotics such as CIP.