Unraveling the Origin of Enhanced Activity of the Nb₂O₅/H₂O₂ System in the Elimination of Ciprofloxacin: Insights into the Role of Reactive Oxygen Species in Interface Processes

The overlooked role of reactive oxygen species (ROS), formed and stabilized on the surface of Nb₂O₅ after H₂O₂ treatment, was investigated in the adsorption and degradation of ciprofloxacin (CIP), a model antibiotic. The contribution of ROS to the elimination of CIP was assessed by using different niobia-based materials in which ROS were formed in situ or ex situ. The formation of ROS was confirmed by electron paramagnetic resonance (EPR) and Raman spectroscopy. The modification of the niobia surface charge by ROS was monitored with zeta potential measurements. The kinetics of CIP removal was followed by UV-vis spectroscopy, while identification of CIP degradation products and evaluation of their cytotoxicity were obtained with liquid chromatography-mass spectrometry (LC-MS) and microbiological studies, respectively. Superoxo and peroxo species were found to significantly improve the efficiency of CIP adsorption on Nb₂O₅ by modifying its surface charge. At the same time, it was found that improved removal of CIP in the dark and in the presence of H₂O₂ was mainly determined by the adsorption process. The enhanced adsorption was confirmed by infrared spectroscopy (IR), total organic carbon measurements (TOC), and elemental analysis. Efficient chemical degradation of adsorbed CIP was observed upon exposure of the Nb₂O₅/H₂O₂ system to UV light. Therefore, niobia is a promising inorganic adsorbent that exhibits enhanced sorption capacity toward CIP in the presence of H₂O₂ under dark conditions and can be easily regenerated in an environmentally benign way by irradiation with UV light.