Catalysts for visible-light-driven oxidative cleaning processes and antibacterial applications (also in the dark) were developed. In order to extend the photoactivity of titanium dioxide into the visible region, nitrogen-doped TiO₂ catalysts with hollow and non-hollow structures were synthesized by co-precipitation (NT-A) and sol–gel (NT-U) methods, respectively. To increase their photocatalytic and antibacterial efficiencies, various amounts of silver were successfully loaded on the surfaces of these catalysts by using a facile photo-deposition technique. Their physical and chemical properties were evaluated by using scanning electron microscopy (SEM), transmission electron microscopy–energy dispersive X-ray spectroscopy (TEM–EDS), Brunauer–Emmett–Teller (BET) surface area, X-ray diffraction (XRD), and diffuse reflectance spectra (DRS). The photocatalytic performances of the synthesized catalysts were examined in coumarin and 1,4-hydroquinone solutions. The results showed that the hollow structure of NT-A played an important role in obtaining high specific surface area and appreciable photoactivity. In addition, Ag-loading on the surface of non-hollow structured NT-U could double the photocatalytic performance with an optimum Ag concentration of 10⁻⁶ mol g⁻¹, while a slight but monotonous decrease was caused in this respect for the hollow surface of NTA upon increasing Ag concentration. Comparing the catalysts with different structures regarding the photocatalytic performance, silverized non-hollow NT-U proved competitive with the hollow NT-A catalyst without Ag-loading for efficient visible-light-driven photocatalytic oxidative degradations. The former one, due to the silver nanoparticles on the catalyst surface, displayed an appreciable antibacterial activity, which was comparable to that of a reference material practically applied for disinfection in polymer coatings.

The synthesis and structural characterization of synthetic zinc oxide and halloysite-based zinc oxide nanocomposites (with 2–28 m/m% ZnO content) are presented. The chemical precipitation of zinc hydroxide precursors and its subsequent drying at 80 °C yielded dominantly zinc oxide (zincite). Thermal treatment at 350 °C completely transformed the remaining precursor to ZnO without causing structural dehydroxylation of the halloysite support. The procedure yielded zinc oxide nanoparticles with 10–22 nm average size having quasi-spherical scale-like morphology. The specific surface area of the synthetic zinc oxide was found to be low (13 m²/g), which was significantly enhanced after nanocomposite preparation (27–47 m²/g). The photocatalytic activity of the prepared nanocomposites was probed by the degradation of a phenolic compound (4-nitrophenol) upon UV irradiation in liquid phase. Compared to their individual constituents, an increased activity of the nanocomposites was observed, while the SSA-normalized photocatalytic activity revealed a synergic effect in nanocomposites above 9 m/m% ZnO content. The nanocomposites were found to be stable at pH = 5.6, with a minor and major mobilization of zinc ions at pH = 12.4 and pH = 1.9, respectively. The toxicity of leachates in different pH environments by Vibrio fischeri bioluminescence indicated low toxicity for ZnO nanoparticles and insignificant toxicity for the nanocomposites. The enhanced photocatalytic activity together with the lower toxicity of the halloysite-ZnO nanocomposites highlight their application potential in water treatment.

Titanium-dioxide-based semiconductors proved to be appropriate for photocatalytic application to efficiently degrade emerging organic pollutants such as various herbicides, pesticides, and pharmaceuticals in waters of environmental importance. The characterization of various TiO₂ catalysts, both bare and modified (Ag- and/or N-doped), by mechanochemical treatment was carried out in this work, regarding their structure, morphology, and photocatalytic activity. For the latter investigations, carbamazepine, an antidepressant, proved to be applicable and versatile. The photocatalytic behavior of the catalysts was studied under both UV and visible light. Besides the decomposition efficiency, monitoring the intermediates provided information on the degradation mechanisms. Mechanochemical treatment significantly increased the particle size (from 30 nm to 10 μm), causing a considerable (0.14 eV) decrease in the band gap. Depending on the irradiation wavelength and the catalyst, the activity orders differed, indicating that, in the mineralization processes of carbamazepine, the importance of the different oxidizing radicals considerably deviated, e.g., Ag-TiO₂ < DP25-TiO₂ < ground-DP25-TiO₂ < N-TiO₂ ≈ N-Ag-TiO₂ for O₂^•− and N-TiO₂ ≈ Ag-TiO₂ < N-Ag-TiO₂ < ground-DP25-TiO₂ ≈ DP25-TiO₂ for HO^• generation under UV irradiation. Toxicity studies have shown that the resulting intermediates are more toxic than the starting drug molecule, so full mineralization is required. This could be realized by a synergistic combination of heterogeneous photocatalysis and ozonation.