Search Results (32)

Enhancing the photocatalytic efficiency of oxide materials under Vis light remains a significant challenge within the scientific community. Natural zeolite–metal oxide composites exhibit enhanced properties, especially due to the zeolite’s large active surface area, which facilitates the incorporation of metal oxide nanoparticles into its structure, thereby significantly increasing photocatalytic efficiency. The present study presents the synthesis of Na-zeolite-decorated black-TiO₂ by the impregnation method, in order to improve the structural characteristics to absorb into visible light. The experimental protocol involves two main steps: first, the synthesis of black-TiO₂ and white-TiO₂ nanocrystals using the sol-gel method, and second, the preparation of hybrid materials, consisting of Na-zeolite decorated with black-TiO₂ and white-TiO₂, through impregnation followed by thermal treatment. The morpho-structural and optical properties of the as-synthesized materials were investigated using XRD, SEM/EDX, FTIR, and DRUV-VIS analysis. The characterization results indicated that natural zeolite has a good thermal stabilization, the lamellar texture of natural zeolite and spherical form of anatase-TiO₂ materials being highlighted by SEM. In the case of Na-zeolite-decorated black-TiO₂, the adsorption edge is slightly shifted to the visible range, while Na-zeolite-decorated white-TiO₂ absorbs only in the ultraviolet region. The above results showed that these hybrid materials are adequate for application in photocatalytic processes. Full article

Lithium aluminosilicate glasses nucleated by TiO₂ are usually melted in oxidizing conditions. The reducing conditions of glass melting, which allow to obtain ions of variable valence in lower oxidation states, can influence the ability of titania to provide proper phase assemblage, structure and properties of lithium aluminosilicate glass-ceramics. The aim of this study is to reveal this influence. The model glass containing TiO₂ was melted with and without the addition of As₂O₃. Using heat treatments between 680 °C and 1300 °C, XRD, SEM and DSC data, Raman and absorption spectroscopy, transparent glass-ceramics based on nanocrystals of β-quartz solid solutions (ss) and/or γ-Al₂O₃ with spinel structure and opaque glass-ceramics based on nanocrystals of β-spodumene ss were obtained and characterized. Three-phase immiscibility develops during secondary heat treatments. Al₂TiO₅ crystallizes from aluminotitanate amorphous regions simultaneously with the appearance of β-quartz ss, while traces of anatase and then rutile appear at elevated temperatures. Phase assemblage and the sequence of phase transformations do not depend on the redox conditions of glass melting, while the rate of these transformations is significantly higher in glass melted without the addition of As₂O₃. Absorption in glass melted without the addition of As₂O₃ and the corresponding glass-ceramics originate from octahedrally coordinated Ti³⁺ ions and Ti³⁺-Ti⁴⁺ pairs in glass and nanocrystals of γ-Al₂O₃, Al₂TiO₅ and β-quartz ss. Transparent glass-ceramics with a thermal expansion coefficient of ~0.3 × 10⁻⁶ K⁻¹ were obtained from both glasses. Full article

Anatase-phase rod-shaped TiO₂ nanocrystals are prepared by the solvothermal method, the surface is metalated, and doped nanocrystals are achieved by thermal diffusion of surface metal ions. Incorporation of dopant ions into TiO₂ lattice enhances the visible light absorption of the material and in some cases can increase the rate of photocatalysis. Even though there are overflowing studies on the preparation of doped TiO₂ materials, there are no methods that enable the precise control of dopant concentration in TiO₂ nanocrystals. We have developed a method to load the surface of oleic acid stabilized anatase-phase rod-shaped TiO₂ nanocrystals (approx. 3 ± 1 nm diameter and 40 ± 10 nm long) with transition metal ions followed by ion diffusion to prepare metal-doped nanocrystals with exact control of the dopant concentration. Specifically, in this work, Cr³⁺ adsorbs TiO₂ nanorods to yield a green colloid, followed by ion diffusion at elevated temperature. After removal of any remaining surface Cr³⁺, tan-colored chromium-doped TiO₂ nanorods can be obtained. Electron microscopy and powder X-ray diffraction indicate no change in nanocrystal size and morphology throughout the process. The TiO₂ nanorods play an important role in photocatalysis owing to their excellent chemical and physical properties. Titanium dioxide is a low-cost, non-toxic, highly stable, chemically robust material. Doped TiO₂ materials have found application in photocatalysis (oxidative degradation of organic molecules, hydrogen evolution), photovoltaics, solar cells, lithium-ion batteries, supercapacitors, and sensors. TiO₂ photocatalysis is also the basis for clean energy technologies, such as dye-sensitized solar cells and photoelectrochemical cells. In photocatalysis applications, nanocrystalline TiO₂ presents advantages of a high surface area, ability to control the surface facet, and minimized bulk recombination. Full article

This investigation reports on the efficacy of a photoelectrocatalysis (PEC) system enhanced by a nitrogen-doped TiO₂ nanocrystal-modified TiO₂ nanotube array (N-TiO₂ NCs/TNTAs) anode paired with a graphene oxide/activated carbon (GO/AC) photocathode for diclofenac removal from effluent. The FE-SEM and EDX analyses validated the elemental composition of the anode—27.56% C, 30.81% N, 6.03% O, and 26.49% Ti. The XRD results confirmed the anatase phase and nitrogen integration, essential for photocatalytic activity enhancement. Quantum chemical simulations provided a comprehensive understanding of the red-shifted absorption bands in N-TiO₂, and UV-vis DRS demonstrated a red-shift in absorption to the visible spectrum, indicating improved light utilization. The PEC configuration achieved a photocurrent density of 9.8 mA/dm², significantly higher than the unmodified and solely nitrogen-doped counterparts at 4.8 mA/dm² and 6.1 mA/dm², respectively. Notably, this system reduced diclofenac concentrations by 58% within 75 min, outperforming standard photocatalytic setups. These findings underscore the potential of N-TiO₂ NCs/TNTAs-AC-GO/PTFE composite material for advanced environmental photoelectrocatalytic applications. Full article

Thin films of titanium dioxide (TiO₂) nanocrystals, widely acknowledged for their unique physical-chemical properties and functionalities, are used in disparate technological fields, including photovoltaics, sensing, environmental remediation and energy storage. In this paper, the preparation of thin films consisting of anatase-phase TiO₂ nanorods deposited using the matrix-assisted pulsed laser evaporation (MAPLE) technique and their characterization in terms of morphology, elemental composition and wettability are presented and discussed. Particular attention is paid to the effects of the laser fluence, varied over a broad range (F = 25, 50, 100 mJ/cm²), and to the role of the capping surfactants bound to the surface of the nanorod precursors. Whereas increasing fluence favored a partial removal of the surface-bound surfactants, a post-growth UV-light-driven photocatalytic treatment of the films was found to be necessary to reduce the incorporated fraction of organics to a further substantial extent. It was noteworthy that, under our experimental conditions, the distinctive surface patterns and roughness that commonly degrade the morphology of films deposited using the MAPLE technique were not observable. This previously unreported experimental evidence was rationalized on the basis of the interaction dynamics between solvent/solute droplets ejected from the laser-irradiated target and the rough surfaces of the growing film. Full article

Hydrogen is an efficient source of clean and environmentally friendly energy. However, because it is explosive at concentrations higher than 4%, safety issues are a great concern. As its applications are extended, the need for the production of reliable monitoring systems is urgent. In this work, mixed copper–titanium oxide ((CuTi)Ox) thin films with various copper concentrations (0–100 at.%), deposited by magnetron sputtering and annealed at 473 K, were investigated as a prospective hydrogen gas sensing material. Scanning electron microscopy was applied to determine the morphology of the thin films. Their structure and chemical composition were investigated by X-ray diffraction and X-ray photoelectron spectroscopy, respectively. The prepared films were nanocrystalline mixtures of metallic copper, cuprous oxide, and titanium anatase in the bulk, whereas at the surface only cupric oxide was found. In comparison to the literature, the (CuTi)Ox thin films already showed a sensor response to hydrogen at a relatively low operating temperature of 473 K without using any extra catalyst. The best sensor response and sensitivity to hydrogen gas were found in the mixed copper–titanium oxides containing similar atomic concentrations of both metals, i.e., 41/59 and 56/44 of Cu/Ti. Most probably, this effect is related to their similar morphology and to the simultaneous presence of Cu and Cu₂O crystals in these mixed oxide films. In particular, the studies of surface oxidation state revealed that it was the same for all annealed films and consisted only of CuO. However, in view of their crystalline structure, they consisted of Cu and Cu₂O nanocrystals in the thin film volume. Full article

The preparation of visible-light-driven photocatalysts has become highly appealing for environmental remediation through simple, fast and green chemical methods. The current study reports the synthesis and characterization of graphitic carbon nitride/titanium dioxide (g-C₃N₄/TiO₂) heterostructures through a fast (1 h) and simple microwave-assisted approach. Different g-C₃N₄ amounts mixed with TiO₂ (15, 30 and 45 wt. %) were investigated for the photocatalytic degradation of a recalcitrant azo dye (methyl orange (MO)) under solar simulating light. X-ray diffraction (XRD) revealed the anatase TiO₂ phase for the pure material and all heterostructures produced. Scanning electron microscopy (SEM) showed that by increasing the amount of g-C₃N₄ in the synthesis, large TiO₂ aggregates composed of irregularly shaped particles were disintegrated and resulted in smaller ones, composing a film that covered the g-C₃N₄ nanosheets. Scanning transmission electron microscopy (STEM) analyses confirmed the existence of an effective interface between a g-C₃N₄ nanosheet and a TiO₂ nanocrystal. X-ray photoelectron spectroscopy (XPS) evidenced no chemical alterations to both g-C₃N₄ and TiO₂ at the heterostructure. The visible-light absorption shift was indicated by the red shift in the absorption onset through the ultraviolet-visible (UV-VIS) absorption spectra. The 30 wt. % of g-C₃N₄/TiO₂ heterostructure showed the best photocatalytic performance, with a MO dye degradation of 85% in 4 h, corresponding to an enhanced efficiency of almost 2 and 10 times greater than that of pure TiO₂ and g-C₃N₄ nanosheets, respectively. Superoxide radical species were found to be the most active radical species in the MO photodegradation process. The creation of a type-II heterostructure is highly suggested due to the negligible participation of hydroxyl radical species in the photodegradation process. The superior photocatalytic activity was attributed to the synergy of g-C₃N₄ and TiO₂ materials. Full article

The growth of nanocrystals (NCs) from metal oxide-based substrates with exposed high-energy facets is of particular importance for many important applications, such as solar cells as photoanodes due to the high reactivity of these facets. The hydrothermal method remains a current trend for the synthesis of metal oxide nanostructures in general and titanium dioxide (TiO₂) in particular since the calcination of the resulting powder after the completion of the hydrothermal method no longer requires a high temperature. This work aims to use a rapid hydrothermal method to synthesize numerous TiO₂-NCs, namely, TiO₂ nanosheets (TiO₂-NSs), TiO₂ nanorods (TiO₂-NRs), and nanoparticles (TiO₂-NPs). In these ideas, a simple non-aqueous one-pot solvothermal method was employed to prepare TiO₂-NSs using tetrabutyl titanate Ti(OBu)₄ as a precursor and hydrofluoric acid (HF) as a morphology control agent. Ti(OBu)₄ alone was subjected to alcoholysis in ethanol, yielding only pure nanoparticles (TiO₂-NPs). Subsequently, in this work, the hazardous chemical HF was replaced by sodium fluoride (NaF) as a means of controlling morphology to produce TiO₂-NRs. The latter method was required for the growth of high purity brookite TiO₂ NRs structure, the most difficult TiO₂ polymorph to synthesize. The fabricated components are then morphologically evaluated using equipment, such as transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), electron diffraction (SAED), and X-ray diffraction (XRD). In the results, the TEM image of the developed NCs shows the presence of TiO₂-NSs with an average side length of about 20–30 nm and a thickness of 5–7 nm. In addition, the image TEM shows TiO₂-NRs with diameters between 10 and 20 nm and lengths between 80 and 100 nm, together with crystals of smaller size. The phase of the crystals is good, confirmed by XRD. The anatase structure, typical of TiO₂-NS and TiO₂-NPs, and the high-purity brookite-TiO₂-NRs structure, were evident in the produced nanocrystals, according to XRD. SAED patterns confirm that the synthesis of high quality single crystalline TiO₂-NSs and TiO₂-NRs with the exposed {001} facets are the exposed facets, which have the upper and lower dominant facets, high reactivity, high surface energy, and high surface area. TiO₂-NSs and TiO₂-NRs could be grown, corresponding to about 80% and 85% of the {001} outer surface area in the nanocrystal, respectively. Full article

In this study, the enhanced photodegradation of a high-concentration phenol red (PR) using very fine TiO₂ nanocrystals by adding a KBrO₃ electron acceptor was reported for the first time. The structural study on TiO₂ nanocrystals using HRTEM, XRD, Raman, and EDX was performed and it confirmed the anatase phase of TiO₂ nanocrystals. UV–Vis absorbance of 20 mg.L⁻¹ PR was measured and the photodegradation was extracted. The KBrO₃ concentration effects exhibited an important enhancement in the degradation of PR dye. The efficiency of PR was increased during 110 min from 75% of pure TiO₂ to 92% and 98% of TiO₂ with 1 mg and 5 mg KBrO₃, respectively. For different samples, a first-order kinetic of dye degradation is confirmed. The instantaneous amount of degraded dye increased from 150 to 180 and 197 mg/g TiO₂ with 1 mg and 5 mg KBrO₃, respectively. The mechanism of the photodegradation reaction confirms the effect of OH^- radicals on increasing the photocatalytic activities. The addition of electron acceptors KBrO₃ improved the photocatalysis rate, where it prevented e-h recombination through conduction band electron capture, which increases the concentration of hydroxyl radicals. The proposed mechanism and results were supported by photocurrent measurements and a Raman spectra analysis of the final photodegraded products. The photocurrent of TiO₂ was observed at 1.2 µA, which was significantly improved up to 13.2, and 21.3 µA with the addition of 1 mg and 5 mg of KBrO₃. The Raman spectra of the final products confirmed that ${\mathrm{SO}}_4^{2-}$ and carbons are byproducts of PR degradation. Full article

Titanium dioxide (TiO₂) nanoparticles (NPs) are widely used in industry and commercial products. Thus, their potential risks to the environment and human health must be evaluated. Doping NPs with certain ions makes it possible to mix properties or generate new ones. Thus, in order to track TiO₂ NPs in biological assays, doping with europium (Eu³⁺) ions was performed, which luminesce in red. Here, we synthesized TiO₂ and Eu³⁺-doped TiO₂ nanocrystals (NCs) in anatase phase to verify the toxicity at different concentrations in Drosophila melanogaster and track the distribution of these NCs in vivo. We verified that the incorporation of europium improved the biocompatibility in relation to the pure samples. The presence of Eu³⁺-doped TiO₂ NCs in the gut, brain, and fat body of larvae and intestinal cells of adult animals was detected. Eu³⁺-doped TiO₂ NCs caused significant larval and pupal mortality rates, in addition to leading to the formation of reactive species, especially at high concentrations. Therefore, our data demonstrated it was possible to trace the Eu³⁺-doped TiO₂ NCs, but TiO₂ and Eu³⁺-doped TiO₂ NCs in anatase phase were toxic to fruit flies at the tested concentrations, and should be used with caution to minimize health risks. Full article

In this work, brookite TiO₂ nanocrystals with co-exposed {001} and {120} facets (pH0.5-T500-TiO₂ and pH11.5-T500-TiO₂), rutile TiO₂ nanorod with exposed {110} facets and anatase TiO₂ nanocrystals with exposed {101} facets (pH3.5-T500-TiO₂) and {101}/{010} facets (pH5.5-T500-TiO₂, pH7.5-T500-TiO₂ and pH9.5-T500-TiO₂) were successfully synthesized through a one-pot solvothermal method by using titanium (V) iso-propoxide (TTIP) colloidal solution as the precursor. The crystal structure, morphology, specific surface area, surface chemical states and photoelectric properties of the pHx-T500-TiO₂ (x = 0.5, 1.5, 3.5, 5.5, 7.5, 9.5, 11.5) were characterized by powder X-ray diffraction (XRD), field scanning transmission electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption instrument, X-ray photoelectron spectroscopy (XPS), UV-Visible diffuse reflectance spectra and electrochemical impedance spectroscopy (EIS). The photocatalytic activity performance of the pHx-T500-TiO₂ samples was also investigated. The results showed that as-prepared pH3.5-T500-TiO₂ nanocrystal with exposed {101} facets exhibited the highest photocatalytic activity (95.75%) in the process of photocatalytic degradation of methyl orange (MO), which was 1.1, 1.2, 1.2, 1.3, 1.4, 1.6, 10.7, 15.1 and 27.8 fold higher than that of pH5.5-T500-TiO₂ (89.47%), P25-TiO₂ (81.16%), pH9.5-T500-TiO₂ (79.41%), pH7.5-T500-TiO₂ (73.53%), pH0.5-T500-TiO₂ (69.10%), CM-TiO₂ (61.09%), pH11.5-T500-TiO₂ (8.99%), pH1.5-T500-TiO₂ (6.33%) and the Blank (3.44%) sample, respectively. The highest photocatalytic activity of pH3.5-T500-TiO₂ could be attributed to the synergistic effects of its anatase phase structure, the smallest particle size, the largest specific surface area and exposed {101} facets. Full article

In this work, with the the H₂TiO₃ colloidal suspension and MoS₂ as the precursors, TiO₂/MoS₂ composites composed of anatase TiO₂ nanocrystals with co-exposed {101} and [111]-facets (nanorod and nanocuboid), {101} and {010} facets (nanospindle), and MoS₂ microspheres constructed by layer-by-layer self-assembly of nanosheets were hydrothermally synthesized under different pH conditions. The characterization has been performed by combining X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectra, and UV-visible absorption spectrum analyses. The photocatalytic degradation of rhodamine B (RhB) in an aqueous suspension was employed to evaluate the photocatalytic activity of the as-prepared pHx-TiO₂/MoS₂ composites. The photocatalytic degradation efficiency of pH3.5-TiO₂/MoS₂ composite was the highest (99.70%), which was 11.24, 2.98, 1.48, 1.21, 1.09, 1.03, 1.10, and 1.14 times that of Blank, MoS₂, CM-TiO₂, pH1.5-TiO₂/MoS₂, pH5.5-TiO₂/MoS₂, pH7.5-TiO₂/MoS₂, pH9.5-TiO₂/MoS₂, pH11.5-TiO₂/MoS₂, respectively. The pH3.5-TiO₂/MoS₂ composite exhibited the highest photocatalytic degradation rate, which may be attributed to the synergistic effects of its large specific surface area, suitable heterojunction structure, and favorable photogenerated charge-separation efficiency. This work is expect to provide primary insights into the photocatalytic effect of TiO₂/MoS₂ composite with co-exposed high-energy facets, and make a contribution to designing more efficient and stable photocatalysts. Full article

In the present study, glycerol was oxidized by photocatalysis to glyceraldehyde, formaldehyde, and formic acid. Copper-doped TiO₂ was synthesized by the evaporation-induced self-assembly approach and it was used as catalyst during the glycerol photo-oxidation reactions. The prepared mesoporous material exhibited high specific surface area (242 m²/g) and band gap energy reduction of 2.55 eV compared to pure titania (3.2 eV) by the synthesis method due to the presence of copper cations (Cu²⁺ identified by XPS). The catalyst showed only anatase crystalline phase with nanocrystals around 8 nm and irregular agglomerates below 100 μm. The selectivity and formation rate of the products were favored towards formaldehyde and glyceraldehyde. The variables studied were catalyst amount, reaction temperature, and initial glycerol concentration. The response surface analysis was used to evaluate the effect of the variables on the product’s concentration. The optimized conditions were 0.4 g/L catalyst, 0.1 mol/L glycerol, and temperature 313.15 K. The response values under optimal conditions were 3.23, 8.17, and 1.15 mM for glyceraldehyde, formaldehyde, and formic acid, respectively. A higher selectivity towards formaldehyde was observed when visible light was used as the radiation source. This study is useful to evaluate the best reaction conditions towards value-added products during the oxidation of glycerol by photocatalysis using Cu/TiO₂. Full article

Mesoporous monodisperse microballs of amorphous titania were prepared from solution of absolute ethanol, tetrabutyl titanate (TBOT) and potassium chloride via a sub-zero sol–gel route. The as-obtained microballs were used as the precursor in an alcohothermal (ethanol with a small amount of water) process to synthesize monodisperse mesoporous microballs built of decahedral anatase nanocrystals. FE-SEM observation and XRD analysis have confirmed that the formed decahedral anatase-rich powder retained the original spherical morphology of the precursor. Importantly, a hierarchical structure composed of faceted anatase has been achieved under “green” conditions, i.e., fluorine-free. Additionally, the hysteresis loops (BET results) have confirmed the existence of mesopores. Interestingly, faceted microballs show noticeable photocatalytic activity under UV/vis irradiation for hydrogen generation without any co-catalyst use, reaching almost forty times higher activity than that by famous commercial titania photocatalyst—P25. It has been proposed that enhanced photocatalytic performance is caused by mesoporous structure and co-existence of two kinds of facets, i.e., {001} and {101}, and thus hindered charge carriers’ recombination. Full article

A combined ALD/MLD (where ALD and MLD stand for atomic and molecular layer deposition, respectively) deposition strategy using TiCl₄, H₂O and HQ (hydroquinone) as precursors has been applied for the preparation of inorganic–organic thin films on soda-lime glasses. The alternate deposition of TiO₂ layers, by pulsing TiCl₄/H₂O (ALD), and hybrid layers, using TiCl₄/HQ (MLD), results in the formation of thin films that are precursors for porous TiO₂-coatings after removal of the HQ template by annealing. The coated-glassed show good photocatalytic activity in the degradation of NO with up to 15% reduction of NO concentration in three successive photocatalytic cycles of 5 h each. Surface Scanning Electron Microscopy (SEM) images show that the TiO₂-coating is composed of large grains that are made up of finer subgrains resulting in a porous structure with an average pore size of 3–4 nm. Transmission Electron Microscopy (TEM) images show two regions, a porous columnar structure on top and a denser region over the glass substrate. Energy Dispersive X-Ray (EDX) analysis, nanocrystal electron diffraction and Raman spectroscopy confirm the presence of the anatase phase, which, together with the porosity of the material, accounts for the observed photocatalytic activity. Full article