ABSTRACT
Peroxymonosulfate (PMS) driven by halloysite nanotubes (HNTs) modified with nanomanganese cobaltate (MnCo2O4) generates reactive oxygen species (ROS) that offer high degradation efficiency and mineralization rates for many typical antibiotic pollutants, such as ornidazole (ONZ). The experimental results show that halloysite nanotubes (HNTs) modified with nanomanganese cobaltate (MnCo2O4@HNTs denoted as MCO@HNTs) can degrade ONZ completely over a wide pH range (6.08-11.00) with little influence of the pH value. MCO@HNTs + PMS exhibited higher catalytic activity and lower Co- and Mn-ion leaching rates. It also showed a strong anti-interference effect on natural lake water and anions. Additionally, PMS can be quickly activated and consumed in natural lakes to avoid secondary pollution. The roasting of MCO@HNTs showed good catalytic activity and stability after degrading ONZ. The combination of ion quenching and electron paramagnetic resonance (EPR) analysis illustrated that the MCO@HNTs + PMS system had a strong oxidation capacity, and the produced singlet oxygen (1O2) was the main ROS for ONZ degradation. The degradation pathway of ONZ via the MCO@HNTs + PMS system was proposed based on the types of intermediates determined via liquid chromatography-mass spectrometry (LC-MS). This comprehensive study shows the preparation of a simple, environmentally friendly, and cheap PMS activation catalyst that has practical application value in the treatment of antibiotic wastewater and provides a focus on actual water testing with residual amount of PMS.
Subject(s)
Nanotubes , Ornidazole , Clay , Reactive Oxygen Species , Peroxides/chemistry , Anti-Bacterial Agents , WaterABSTRACT
Persulfate-based advanced oxidation processes (AOPs) cannot easily achieve the efficient degradation of persistent organic pollutants (POPs) with high stability. In this study, a simple in situ precipitation method was used to prepare an amorphous Co@TiO2 heterojunction catalyst. The deposition of Co oxide on TiO2, which is relatively nontoxic, efficiently activated peroxymonosulfate (PMS) to degrade sulfamethazine (SMT) and reduce the leaching of Co ions (0.915%). A catalytic system prepared using 0.3 g L-1 Co@TiO2 and 0.5 g L-1 PMS could degrade SMT within 30 min with a degradation rate of 95.8%. Co@TiO2 could activate PMS over a wide pH range (5.00-9.00) to efficiently degrade other antibiotics and dyes. Radical-capture experiments and electron paramagnetic resonance analysis suggested that SMT degradation occurs through a combination of the free radical and non-radical pathways, in which singlet 1O2 played a major role. Owing to the novelty of the proposed composite materials, the degradation path of SMT, which was determined through liquid chromatography-mass spectrometry, differed from that reported previously. This study provides not only an advanced and renewable catalyst for SMT degradation but also a feasible strategy for designing materials for AOPs.
