Martynas Lelis

In the current study, a bi-layered magnetic photocatalyst powder consisting of a Ni layer on one side and carbon-doped TiO₂ or ZnO photocatalyst layers on the other side was synthesized by magnetron sputtering technique. SEM, XRD, and XPS analysis of powders revealed that the photocatalytic TiO₂ layer had a mixed anatase-rutile structure, was doped by carbon to approximately 3 at. % and had a fraction of Ti(III) oxide. Meanwhile, the ZnO layer was crystalized in a wurtzite structure and had a considerable number of intrinsic defects, which are useful for visible light photocatalysis. The activity of magnetic photocatalyst powder was tested by photocatalytic bleaching of dyes, as well as performing photocatalytic inactivation of Salmonella bacteria under UV and visible light irradiation. It was observed, that C-TiO₂+Ni magnetic photocatalyst had relatively high and stable activity under both light sources (for five consecutive cycles dye degradation reached approximately 95%), but ZnO+Ni was generally lacking in activity and stability (over five cycles under UV and visible light, dye degradation fell from approximately 60% to 55% and from 90% to 70%, respectively). Photocatalytic treatment of bacteria also provided mixed results. On one hand, in all tests bacteria were not inactivated completely. However, on the other hand, their susceptibility to antibiotics increased significantly.

In the current study, a non-conventional application of the magnetron sputtering technique was proposed. A four-step synthesis procedure allowed us to produce a magnetic photocatalyst powder consisting of bi-layered particles with carbon-doped TiO₂ on one side, and metallic Ni on the other side. XRD, SEM and EDS methods were used for sample characterization. It was determined, that after the sputtering process optimization, the bandgap of carbon-doped TiO₂ was reduced to approximately 3.1 eV and its light adsorption increased over the whole visible light spectrum. The repetitive Rhodamine B solution bleaching with magnetic photocatalyst powder and visible light showed interesting evolvement of photocatalyst efficiency. After the first cycle, Rhodamine B concentration was reduced by just 35%. However, after the second cycle, the reduction had already reached nearly 50%. Photocatalytic bleaching efficiency continued to improve rapidly until higher than 95% of Rhodamine B concentration reduction was achieved (at tenth cycle). For the next ten cycles, photocatalytic bleaching efficiency remained relatively stable. The initial gain in efficiency was attributed to the magnetic photocatalyst particle size reduction from an initial diameter of 100–150 µm to 5 µm. Naturally, the 20–30 times size reduction resulted in a remarkably increased active surface area, which was a key factor for the increased performance.

For decades, partially oxidized hydrides were commonly considered as undesirably contaminated phases and were avoided by scientists. Nevertheless, more recently, it was realized that in some hydrides and oxides, partial substitution of dissimilar H⁻ and O²⁻ anions allows one to obtain unique optical and electrical properties that might have appealing applications in commercial products. It was determined that specific properties of so called oxyhydride materials strongly depend on the used synthesis methods; therefore, there is a great interest in exploring various variants of oxyhydride formation. In the current study, TiH_xO_y films were deposited by a reactive magnetron sputtering process in Ar-O₂-H₂ gas mixtures. Color, transparency and crystal phase composition of the films coherently reacted to the Ar:O₂:H₂ gas ratio. Namely, the rise in partial hydrogen pressure promoted the formation of anatase phase TiO₂ structure and darkening of the films. Interestingly, this had only minimal impact on the band gap values, but had a relatively strong negative effect on the photocatalytic activity of the films. The unaccustomed results stressed the difference between the partially reduced TiO₂ with a significant amount of oxygen vacancies and synthesized TiH_xO_y films where some O²⁻ ions are implicitly substituted by H⁻ ions.

Semiconductor materials used as photocatalysts are considered among the most effective ways to treat biologically polluted water. Certainly, efficiency depends on the selection of photocatalyst and its substrate, as well as the possibility of its application in a broader spectrum of light. In this study, a reactive magnetron sputtering technique was applied for the immobilisation of ZnO photocatalyst on the surface of HDPE beads, which were selected as the buoyant substrates for enhanced photocatalytic performance and easier recovery from the treated water. Moreover, the study compared the effect on the inactivation of the microorganism between ZnO-coated HDPE beads without Ni and with Ni underlayer. Crystal structure, surface morphology, and chemical bonds of as-deposited ZnO films were investigated by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy, respectively. Visible-light-induced photocatalytic treatment was performed on the Gram-negative and Gram-positive bacteria and bacteriophages PRD1, T4, and their mixture. Higher bacteria inactivation efficiency was obtained using the ZnO photocatalyst with Ni underlayer for the treatment of S. Typhimurium and M. Luteus mixtures. As for infectivity of bacteriophages, T4 alone and in the mixture with PRD1 were more affected by the produced photocatalyst, compared with PRD1.

ZnO is one of the most important industrial metal oxide semiconductors. However, in order to fully realise its potential, the electronic structure of ZnO has to be modified to better fit the needs of specific fields. Recent studies demonstrated that reactive magnetron sputtering under Zn-rich conditions promotes the formation of intrinsic ZnO defects and allows the deposition of metallic Zn phase-rich ZnO films. In photocatalytic efficiency tests these films were superior to traditional ZnO oxide, therefore, the purposeful formation of intrinsic ZnO defects, namely Zn interstitials and oxygen vacancies, can be considered as advantageous self-doping. Considering that such self-doped ZnO remains a semiconductor, the natural question is if it is possible to further improve its properties by adding extrinsic dopants. Accordingly, in the current study, the metallic Zn phase-rich ZnO oxide film formation process (reactive magnetron sputtering) was supplemented by simultaneous sputtering of copper or carbon. Effects of the selected dopants on the structure of self-doped ZnO were investigated by X-ray diffractometer, scanning electron microscope, X-ray photoelectron spectroscope and photoluminescence techniques. Meanwhile, its effect on photocatalytic activity was estimated by visible light activated bleaching of Methylene Blue. It was observed that both dopants modify the microstructure of the films, but only carbon has a positive effect on photocatalytic efficiency.

The beneficial photocatalytic properties of UV light activated TiO₂ powder are well-known and have been demonstrated with various pollutants and pathogens. However, traditionally observed photocatalytic activity of visible light activated pristine TiO₂ is insignificant but there are a few studies which have reported that under some specific conditions commercially available TiO₂ powder could at least partially disinfect microorganisms even under visible light. To better understand this phenomenon, in the current study we focused on bacteria response to the treatment by visible light and P25 TiO₂ powder. More specifically, we analyzed the relationship between the bacteria viability, outer membrane permeability, metabolism, and its capacity to generate intracellular reactive oxygen species. During the study we assayed the viability of treated bacteria by the spread plate technique and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) reduction method. Changes in bacterial outer membrane permeability were determined by measuring the fluorescence of N-phenyl-1-naphthylamine (NPN). To detect intracellular reactive oxygen species formation, the fluorescence of dichlorodihydrofluorescein diacetate (DCFH-DA) was assayed. Results of our study indicated that TiO₂ and wide spectrum visible light irradiation damaged the integrity of the outer membrane and caused oxidative stress in the metabolizing bacteria. When favorable conditions were created, these effects added up and unexpectedly high bacterial inactivation was achieved.

This study presents the thermal and chemical resistance of plasma-sprayed Al₂O₃ and Al₂O₃ doped with 13 wt.% of TiO₂ coatings and their suitability for the fire grate of straw pellet furnaces. Coatings were deposited on steel substrates using direct current atmospheric pressure plasma spraying. The surface structure, elemental, and phase composition of formed coatings were analyzed before and after the thermal treatment, imitating natural application conditions. For the experiment, the annealing temperature was 500 °C for twenty-five cycles (80 min each). It was found that the steel substrate oxidized after five thermal cycles, and the formation of iron oxides was observed. The elemental composition of the Al₂O₃ and Al₂O₃-13 wt.% TiO₂ coatings remained unchanged even after 25 cycles of heat treatment. The X-ray diffraction (XRD) results revealed that the alpha-Al₂O₃ to gamma-Al₂O₃ phase ratio in the Al₂O₃-TiO₂ coating was reduced by only 8.7% after 25 cycles.

Photocatalysis application is considered as one of the most highly promising techniques for the reduction in wastewater pollution. However, the majority of highly efficient photocatalyst materials are obtained as fine powders, and this causes a lot of photocatalyst handling and reusability issues. The concept of the floating catalyst proposes the immobilization of a photocatalytic (nano)material on relatively large floating substrates and is considered as an encouraging way to overcome some of the most challenging photocatalysis issues. The purpose of this study is to examine floating photocatalyst application for Salmonella typhimurium bacteria inactivation in polluted water. More specifically, high-density polyethylene (HDPE) beads were used as a photocatalyst support for the immobilization of carbon-doped TiO₂ films forming floating photocatalyst structures. Carbon-doped TiO₂ films in both amorphous and anatase forms were deposited on HDPE beads using the low-temperature magnetron sputtering technique. Bacteria inactivation, together with cycling experiments, revealed promising results by decomposing more than 95% of Salmonella typhimurium bacteria in five consecutive treatment cycles. Additionally, a thorough analysis of the deposited carbon-doped TiO₂ film was performed including morphology, elemental composition and mapping, structure, and depth profiling. The results demonstrate that the proposed method is a suitable technique for the formation of high-quality photocatalytic active films on thermal-sensitive substrates.