Green synthesis of manganese–cobalt–tungsten composite oxides for degradation of doxycycline via efficient activation of peroxymonosulfate

The advanced oxidation process of peroxymonosulfate activated by solid catalyst is one of the main technologies to solve the pollution of antibiotics in water environment.In this work, a series of composites (MCW) containing Mn, Co, and W were synthesized using green ball milling, which does not produce the three wastes (waste gas, waste water and industrial residue). It shows a unique and high catalytic activity for peroxymonosulfate-based degradation of doxycycline (DC) under the pH condition between 4 and 9, and it can be reused five times. MCW composites remove DC using singlet oxygen and superoxide free radicals, as well as a large number of oxygen vacancies for electron storage. The formation rate of free radicals is determined by the conversion rates of Mn3+/Mn2+ and Co3+/Co2+. In addition, there are three ways to degrade DC to form 18 kinds of intermediates, and the toxicity of all the intermediates were predicted by ECOSAR program. The highly active catalysts obtained using a green synthetic route for the activation of peroxymonosulfate show a great potential for decontamination of antibiotics wastewater. [Display omitted] •MnO/CoO/WO3 composites were prepared by a green ball-milling method.•Ball-milling effectively increased the oxygen vacancy content of the composites.•The repeated use of the composites still maintains a high catalytic activity.•The degradation mechanism and pathway of doxycycline were deciphered.•A cost-effective and green way to degrade antibiotics from water is provided.