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Five different (commercial and self-synthesized) titania samples were mixed with NaBH4 and then heated to obtain black titania samples. The change in synthesis conditions resulted in the preparation of nine different photocatalysts, most of which were black in color. The photocatalysts were characterized by various methods, including X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), photoacoustic and reverse-double beam photoacoustic spectroscopy (PAS/RDB-PAS). The photocatalytic activity was tested for oxidative decomposition of acetic acid, methanol dehydrogenation, phenol degradation and bacteria inactivation (Escherichia coli) under different conditions, i.e., irradiation with UV, vis, and NIR, and in the dark. It was found that the properties of the obtained samples depended on the features of the original titania materials. A shift in XRD peaks was observed only in the case of the commercial titania samples, indicating self-doping, whereas faceted anatase samples (self-synthesized) showed high resistance towards bulk modification. Independent of the type and degree of modification, all modified samples exhibited much worse activity under UV irradiation than original titania photocatalysts both under aerobic and anaerobic conditions. It is proposed that the strong reduction conditions during the samples' preparation resulted in the partial destruction of the titania surface, as evidenced by both microscopic observation and crystallographic data (an increase in amorphous content), and thus the formation of deep electron traps (bulk defects as oxygen vacancies) increasing the charge carriers' recombination. Under vis irradiation, a slight increase in photocatalytic performance (phenol degradation) was obtained for only four samples, while two samples also exhibited slight activity under NIR. In the case of bacteria inactivation, some modified samples exhibited

Commercial titania photocatalyst-P25 was chosen for an antifungal property examination due to it exhibiting one of the highest photocatalytic activities among titania photocatalysts. Titania P25 was homogenized first (HomoP25) and then annealed at different temperatures. Additionally, HomoP25 was modified with 0.5 wt% or 2.0 wt% of platinum by a photodeposition method. The obtained samples were characterized by diffuse-reflectance spectroscopy (DRS), X-ray photoabsorption spectroscopy (XPS), X-ray diffraction (XRD) and Raman spectroscopy. Moreover, photocatalytic activity was tested for methanol dehydrogenation under UV/vis irradiation. The spore-destroying effect of photocatalysts was investigated against two mold fungal species, i.e., Aspergillus fumigatus and Aspergillus niger. Both the mycelium growth and API ZYM (estimation of enzymatic activity) tests were applied for the assessment of antifungal effect. It was found that annealing caused a change of surface properties of the titania samples, i.e., an increase in the noncrystalline part, a growth of particles and enhanced oxygen adsorption on its surface, which resulted in an increase in both the hydrogen evolution rate and the antifungal effect. Titania samples annealed at 300-500 degrees C were highly active during 60-min UV/vis irradiation, inhibiting the germination of both fungal spores, whereas titania modification with platinum (0.5 and 2.0 wt%) had negligible effect, despite being highly active for hydrogen evolution. The control experiments revealed the lack of titania activity in the dark, as well as high resistance of fungi for applied UV/vis irradiation in the absence of photocatalysts. Moreover, the complete inhibition of 19 hydrolases, secreted by both tested fungi, was noted under UV/vis irradiation on the annealed P25 sample. It is proposed that titania photocatalysts of large particle sizes (>150 nm) and enriched surface with oxygen might efficiently destroy fungal structures under mild irr

Preparation of TiO2 using the hydrothermal treatment in NH4OH solution and subsequent thermal heating at 500–700 °C in Ar was performed in order to introduce some titania surface defects. The highest amount of oxygen vacancies and Ti3+ surface defects were observed for a sample heat-treated at 500 °C. The presence of these surface defects enhanced photocatalytic properties of titania towards the deactivation of two bacteria species, E. coli and S. epidermidis, under artificial solar lamp irradiation. Further modification of TiO2 was targeted towards the doping of Cu species. Cu doping was realized through the impregnation of the titania surface by Cu species supplied from various copper salts in an aqueous solution and the subsequent heating at 500 °C in Ar. The following precursors were used as a source of Cu: CuSO4, CuNO3 or Cu(CH3COO)2. Cu doping was performed for raw TiO2 after a hydrothermal process with and without NH4OH addition. The obtained results indicate that Cu species were deposited on the titania surface defects in the case of reduced TiO2, but on the TiO2 without NH4OH modification, Cu species were attached through the titania adsorbed hydroxyl groups. Cu doping on TiO2 increased the absorption of light in the visible range. Rapid inactivation of E. coli within 30 min was obtained for the ammonia-reduced TiO2 heated at 500 °C and TiO2 doped with Cu from CuSO4 solution. Photocatalytic deactivation of S. epidermidis was greatly enhanced through Cu doping on TiO2. Impregnation of TiO2 with CuSO4 was the most effective for inactivation of both E. coli and S. epidermidis.

Graphene, graphene oxide, reduced graphene oxide and their composites with various compounds/materials have high potential for substantial impact as cheap photocatalysts, which is essential to meet the demands of global activity, offering the advantage of utilizing “green” solar energy. Accordingly, graphene-based materials might help to reduce reliance on fossil fuel supplies and facile remediation routes to achieve clean environment and pure water. This review presents recent developments of graphene-based semiconductor photocatalysts, including novel composites with faceted particles, photonic crystals, and nanotubes/nanowires, where the enhancement of activity mechanism is associated with a synergistic effect resulting from the presence of graphene structure. Moreover, antimicrobial potential (highly needed these days), and facile recovery/reuse of photocatalysts by magnetic field have been addresses as very important issue for future commercialization. It is believed that graphene materials should be available soon in the market, especially because of constantly decreasing prices of graphene, vis response, excellent charge transfer ability, and thus high and broad photocatalytic activity against both organic pollutants and microorganisms.

Seven commercial titania (titanium(IV) oxide; TiO2) powders with different structural properties and crystalline compositions (anatase/rutile) were modified with copper by two variants of a photodeposition method, i.e., methanol dehydrogenation and water oxidation. The samples were characterized by diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Although zero-valent copper was deposited on the surface of titania, oxidized forms of copper, post-formed in ambient conditions, were also detected in dried samples. All samples could absorb visible light (vis), due to localized surface plasmon resonance (LSPR) of zero-valent copper and by other copper species, including Cu2O, CuO and CuxO (x:1-2). The photocatalytic activities of samples were investigated under both ultraviolet (UV) and visible light irradiation (>450 nm) for oxidative decomposition of acetic acid. It was found that titania modification with copper significantly enhanced the photocatalytic activity, especially for anatase samples. The prolonged irradiation (from 1 to 5 h) during samples' preparation resulted in aggregation of copper deposits, thus being detrimental for vis activity. It is proposed that oxidized forms of copper are more active under vis irradiation than plasmonic one. Antimicrobial properties against bacteria (Escherichia coli) and fungi (Aspergillus niger) under vis irradiation and in the dark confirmed that Cu/TiO2 exhibits a high antibacterial effect, mainly due to the intrinsic activity of copper species.

Cosmetics and other daily care products contain titanium(IV) oxide (titania). Since multiple risk factors can increase the chance of developing cancer, an evaluation of titania safety has become a matter of concern in recent times. However, it should be pointed out that titania as an efficient photocatalyst has been also applied for inactivation of various pathogens, environmental purification and energy conversion, which might result in significant improvement of human life. Therefore, it is worth considering titania not only as a possible cancer initiator, but also as an efficient solution against cancer cells. Accordingly, in this study, the effect of commercial titania photocatalyst P25 (Degussa/Evonik) on breast adenocarcinoma MCF7 cells (ATCC (R) HTB-22 (TM), breast adenocarcinoma cell line from human) has been investigated. The cells were treated with titania at doses of 10, 30, and 50 mu g/mL under UVA/vis irradiation and in the dark. The significant morphological alterations in living cells were observed for larger doses of titania, such as changes in the shape and the size of cells, the deviation from the normal structure, and an increase in cells' mortality. Moreover, the effect was significantly higher under irradiation than in the dark confirming strong photocatalytic activity of titania P25. In contrast, the lowest dose of titania (10 mu g/mL) did not exhibit a significant impact on MCF7 cells, similarly to the nontreated cells. Accordingly, it has been proposed that locally applied titania might be considered for a cancer therapy after necessary in vivo tests to estimate any possibilities of side effects.

Titanium and its compounds are broadly used in both industrial and domestic products, including jet engines, missiles, prostheses, implants, pigments, cosmetics, food, and photocatalysts for environmental purification and solar energy conversion. Although titanium/titania-containing materials are usually safe for human, animals and environment, increasing concerns on their negative impacts have been postulated. Accordingly, this review covers current knowledge on the toxicity of titania and titanium, in which the behaviour, bioavailability, mechanisms of action, and environmental impacts have been discussed in detail, considering both light and dark conditions. Consequently, the following conclusions have been drawn: (i) titania photocatalysts rarely cause health and environmental problems; (ii) despite the lack of proof, the possible carcinogenicity of titania powders to humans is considered by some authorities; (iii) titanium alloys, commonly applied as implant materials, possess a relatively low health risk; (iv) titania microparticles are less toxic than nanoparticles, independent of the means of exposure; (v) excessive accumulation of titanium in the environment cannot be ignored; (vi) titanium/titania-containing products should be clearly marked with health warning labels, especially for pregnant women and young children; (vi) a key knowledge gap is the lack of comprehensive data about the environmental content and the influence of titania/titanium on biodiversity and the ecological functioning of terrestrial and aquatic ecosystems.