Microplastics (MPs) are distributed in a wide range of aquatic and terrestrial ecosystems throughout the planet. They are known to adsorb hazardous substances and can transfer them across the trophic web. To eliminate MPs pollution in an environmentally friendly process, we propose using a photocatalytic process that can easily be implemented in wastewater treatment plants (WWTPs). As photocatalysis involves the formation of reactive species such as holes (h+), electrons (e−), hydroxyl (OH●), and superoxide ion (O2●−) radicals, it is imperative to determine the role of those species in the degradation process to design an effective photocatalytic system. However, for MPs, this information is limited in the literature. Therefore, we present such reactive species’ role in the degradation of high-density polyethylene (HDPE) MPs using C,N-TiO2. Tert-butanol, isopropyl alcohol (IPA), Tiron, and Cu(NO3)2 were confirmed as adequate OH●, h+, O2●− and e− scavengers. These results revealed for the first time that the formation of free OH● through the pathways involving the photogenerated e− plays an essential role in the MPs’ degradation. Furthermore, the degradation behaviors observed when h+ and O2●− were removed from the reaction system suggest that these species can also perform the initiating step of degradation.
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