A long-term exposition of antibiotics represents a serious problem for the environment, especially for human health. Heterogeneous photocatalysis opens a green way for their removal. Here, we correlated the structural-textural properties of TiO₂ photocatalysts with their photocatalytic performance in ampicillin abatement. The tested nanoparticles included anatase and rutile and their defined mixtures. The nominal size range varied from 5 to 800 nm, Aeroxide P25 serving as an industrial benchmark reference. The degradation mechanism of photocatalytic ampicillin abatement was studied by employing both experimental (UPLC/MS/MS, hydroxyl radical scavenger) and theoretical (quantum calculations) approaches. Photocatalytic activity increased with the increasing particle size, generally, anatase being more active than rutile. Interestingly, in the dark, the ampicillin concentration decreased as well, especially in the presence of very small nanoparticles. Even if the photolysis of ampicillin was negligible, a very high degree of mineralization of antibiotic was achieved photocatalytically using the smallest nanoparticles of both allotropes and their mixtures. Furthermore, for anatase samples, the reaction rate constant increases with increasing crystallite size, while the degree of mineralization decreases. Importantly, the suggested degradation pathway mechanism determined by DFT modeling was in very good agreement with experimentally detected reaction products.

In this study, we describe synthesis and characterization of a floating photocatalyst for water treatment consisting of a light substrate coated by SiO₂/TiO₂ composite. Three supports of natural origin were used: natural cork, expanded clay (Liapor), and volcanic porous glass (Sorbix). The photoactivity of the coated supports was tested in a laboratory photoreactor, with Liapor being the most photoactive support with good mechanical stability. The corresponding rate constant for the degradation of a model pollutant, 4-chlorophenol, was 7.8 × 10⁻⁵ s⁻¹. Detail characterization of the coated Liapor was obtained by XRF, SEM/EDX, and UV-Vis diffuse reflectance spectroscopy, and surface area measurements. Outdoor experiments were carried out with calcined Liapor and oxalic acid or methylene blue under sunlight on pilot reactors in the Czech Republic and Vietnam. We demonstrated satisfactory photocatalytic activity, long-term stability, and reusability of the new floating photocatalyst. The photoefficiency to mineralize oxalic acid in water under sunlight was estimated as 6.7% under the applied conditions.