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Emerging contaminants (ECs) represent a wide range of compounds, whose complete elimination from wastewaters by conventional methods is not always guaranteed, posing human and environmental risks. Advanced oxidation processes (AOPs), based on the generation of highly oxidizing species, lead to the degradation of these ECs. In this context, TiO2 and ZnO are the most widely used inorganic photocatalysts, mainly due to their low cost and wide availability. The addition of small amounts of nanoclusters may imply enhanced light absorption and an attenuation effect on the recombination rate of electron/hole pairs, resulting in improved photocatalytic activity. In this work, we propose the use of silver nanoclusters deposited on ZnO nanoparticles (ZnO–Ag), with a view to evaluating their catalytic activity under both ultraviolet A (UVA) and visible light, in order to reduce energetic requirements in prospective applications on a larger scale. The catalysts were produced and then characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD) and inductively coupled plasma-optical emission spectrometry (ICP-OES). As proof of concept of the capacity of photocatalysts doped with nanoclusters, experiments were carried out to remove the azo dye Orange II (OII). The results demonstrated the high photocatalytic efficiency achieved thanks to the incorporation of nanoclusters, especially evident in the experiments performed under white light.

This study provides an overview of the environmental impacts associated with the production of different magnetic nanoparticles (NPs) based on magnetite (Fe3O4), with a potential use as heterogeneous Fenton or photo-Fenton catalysts in wastewater treatment applications. The tendency of Fe3O4 NPs to form aggregates in water makes necessary their decoration with stabilizing agents, in order to increase their catalytic activity. Different stabilizing agents were considered in this study: poly(acrylic acid) (PAA), polyethylenimine (PEI) and silica (SiO2), as well as the immobilization of the magnetite-based catalysts in a mesoporous silica matrix, SBA-15. In the case of photo-Fenton catalysts, combinations of magnetite NPs with semiconductors were evaluated, so that magnetic recovery of the nanomaterials is possible, thus allowing a safe discharge free of NPs. The results of this study suggest that magnetic nanoparticles coated with PEI or PAA were the most suitable option for their applications in heterogeneous Fenton processes, while ZnO-Fe3O4 NPs provided an interesting approach in photo-Fenton. This work showed the importance of identifying the relevance of nanoparticle production strategy in the environmental impacts associated with their use.

Today, the presence of recalcitrant pollutants in wastewater, such as pharmaceuticals or other organic compounds, is one of the main obstacles to the widespread implementation of water reuse. In this context, the development of innovative processes for their removal becomes necessary to guarantee effluent quality. This work presents the potentiality of magnetic nanoparticles immobilized on SBA-15 mesoporous silica as Fenton and photo-Fenton catalysts under visible light irradiation. The influence of the characteristics of the compounds and nanoparticles on the removal yield was investigated. Once the key aspects of the reaction mechanism were analyzed, to evaluate the feasibility of this process, an azo dye (Orange II) and an antibiotic (sulfamethoxazole) were selected as main target compounds. The concentration of Orange II decreased below the detection limit after two hours of reaction, with mineralization values of 60%. In addition, repeated sequential experiments revealed the recoverability and stability of the nanoparticles in a small-scale reactor. The benchmarking of the obtained results showed a significant improvement of the process using visible light in terms of kinetic performance, comparing the results to the Fenton process conducted at dark. Reusability, yield and easy separation of the catalyst are its main advantages for the industrial application of this process.

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