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.
Titania photocatalysts have been intensively examined for both mechanism study and possible commercial applications for more than 30 years. Although various reports have already been published on titania, including comprehensive review papers, the morphology-governed activity, especially for novel nanostructures, has not been reviewed recently. Therefore, this paper presents novel, attractive, and prospective titania photocatalysts, including zero-, one-, two-, and three-dimensional titania structures. The 1D, 2D, and 3D titania structures have been mainly designed for possible applications, e.g., (i) continuous use without the necessity of particulate titania separation, (ii) efficient light harvesting (e.g., inverse opals), (iii) enhanced activity (fast charge carriers' separation, e.g., 1D nanoplates and 2D nanotubes). It should be pointed out that these structures might be also useful for mechanism investigation, e.g., (i) 3D titania aerogels with gold either incorporated inside the 3D network or supported in the porosity, and (ii) titania mesocrystals with gold deposited either on basal or lateral surfaces, for the clarification of plasmonic photocatalysis. Moreover, 0D nanostructures of special composition and morphology, e.g., magnetic(core)-titania(shell), mixed-phase titania (anatase/rutile/brookite), and faceted titania NPs have been presented, due to their exceptional properties, including easy separation in the magnetic field, high activity, and mechanism clarification, respectively. Although anatase has been usually thought as the most active phase of titania, the co-existence of other crystalline phases accelerates the photocatalytic activity significantly, and thus mixed-phase titania (e.g., famous P25) exhibits high photocatalytic activity for both oxidation and reduction reactions. It is believed that this review might be useful for the architecture design of novel nanomaterials for broad and diverse applications, including environmental purification, energy conversion, synthesis and preparation of "intelligent" surfaces with self-cleaning, antifogging, and antiseptic properties.
Titania (titanium(IV) oxide) is highly active, stable, cheap and abundant photocatalyst, and thus commonly applied in various environmental applications. However, two main shortcomings of titania, i.e., charge carriers’ recombination and...
Ag2O/TiO2 heterojunctions were prepared by a simple method, i.e., the grinding of argentous oxide with six different titania photocatalysts. The physicochemical properties of the obtained photocatalysts were characterized by diffuse-reflectance spectroscopy (DRS), X-ray powder diffraction (XRD) and scanning transmission electron microscopy (STEM) with an energy dispersive X-ray spectroscopy (EDS). The photocatalytic activity was investigated for the oxidative decomposition of acetic acid and methanol dehydrogenation under UV/vis irradiation and for the oxidative decomposition of phenol and 2-propanol under vis irradiation. Antimicrobial properties were tested for bacteria (Escherichia coli) and fungi (Candida albicans and Penicillium chrysogenum) under UV and vis irradiation and in the dark. Enhanced activity was observed under UV/vis (with synergism for fine anatase-containing samples) and vis irradiation for almost all samples. This suggests a hindered recombination of charge carriers by p-n heterojunction or Z-scheme mechanisms under UV irradiation and photo-excited electron transfer from Ag2O to TiO2 under vis irradiation. Improved antimicrobial properties were achieved, especially under vis irradiation, probably due to electrostatic attractions between the negative surface of microorganisms and the positively charged Ag2O.
The photocatalytic disinfection (PCD) properties of TiO2 have attracted attention in the research communities because the produced reactive oxygen species (ROS) allow destruction of different types of microbes, such as fungi, bacteria, viruses, algae, unicellular organisms, etc. on surfaces, in water, and in air. However, TiO2 requires UV irradiation to produce the ROS, which limits its photoactivity in indoor environments. Surface-modified TiO2 with small Ag and CuO nanoclusters in a core–shell structure exhibits antifungal properties under dark and visible conditions, possibly because of the interaction between Ag–CuO nanoclusters in the fungi membrane and their penetration, and the co-presence of Cu2+ and Ag+ ions. Therefore, a synergetic effect is obtained with co-modification of TiO2 with silver and copper, and the sample Ag@CuO/TiO2 (core–shell structure of Ag–Cu in a ratio of 1:3) exhibits the highest antifungal activity; that is, fungi growth inhibition is observed for Aspergillus melleus and Penicillium chrysogenum. Moreover, significant inhibitions of the sporulation and generation of droplets, possibly containing mycotoxins and sclerotia under dark and visible exposure, are also obtained.
Laser synthesis was used for one-step synthesis of titania/graphene composites (G-TiO 2 (C)) from a suspension of 0.04 wt% commercial reduced graphene oxide (rGO) dispersed in liquid titanium tetraisopropoxide (TTIP). Reference titania sample (TiO 2 (C)) was prepared by the same method without graphene addition. Both samples and commercial titania P25 were characterized by various methods and tested under UV/vis irradiation for oxidative decomposition of acetic acid and dehydrogenation of methanol (with and without Pt co-catalyst addition), and under vis irradiation for phenol degradation and inactivation of Escherichia coli. It was found that both samples (TiO 2 (C) and G-TiO 2 (C)) contained carbon resulting from TTIP and C 2 H 4 (used as a synthesis sensitizer), which activated titania towards vis activity. The photocatalytic activity under UV/vis irradiation was like that by P25. The highest activity of TiO 2 (C) sample for acetic acid oxidation was probably caused by its surface enrichment with hydroxyl groups. G-TiO 2 (C) was the most active for methanol dehydrogenation in the absence of platinum (ca. five times higher activity than that by TiO 2 (C) and P25), suggesting that graphene works as a co-catalyst for hydrogen evolution. High activity under both UV and vis irradiation for decomposition of organic compounds, hydrogen evolution and inactivation of bacteria suggests that laser synthesis allows preparation of cheap (carbon-modified) and efficient photocatalysts for broad environmental applications.
The photocatalytic deactivation of volatile organic compounds and mold fungi using TiO2 modified with mono‐ and bimetallic (Pt, Cu, Ag) particles is reported in this study. The mono‐ and bimetal‐modified (Pt, Cu, Ag) titanium(IV) oxide photocatalysts were prepared by chemical reduction method and characterized using XRD, XPS, DR/UV‐Vis, BET, and TEM analysis. The effect of incident light, type and content of mono‐ and bimetallic nanoparticles deposited on titanium(IV) oxide was studied. Photocatalytic activity of as‐prepared nanocomposites was examined in the gas phase using LEDs array. High photocatalytic activity of Ag/Pt‐TiO2 and Cu/Pt‐TiO2 in the reaction of toluene degradation resulted from improved efficiency of interfacial charge transfer process, which was consistent with the fluorescence quenching effect revealed by photoluminescence (PL) emission spectra. The photocatalytic deactivation of Penicillium chrysogenum, a pathogenic fungi present in the indoor environment, especially in a damp or water‐damaged building using mono‐ and bimetal‐modified (Pt, Cu, Ag) titanium(IV) oxide was evaluated for the first time. TiO2 modified with mono‐ and bimetallic NPs of Ag/Pt, Cu, and Ag deposited on TiO2 exhibited improved fungicidal activity under LEDs illumination than pure TiO2.
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.
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