Morphological control and photodegradation behavior of rutile TiO2 prepared by a low-temperature process

Flower-like rutile titania nanocrystals were prepared via a simple aqueous-phase stirring for 24 h at a low temperature of 75 °C, employing only TiCl₄, HCl as the starting materials. XRD result proved the formation of rutile TiO₂. The observations from TEM and SEM showed that the products were large-scale flower-shaped structures composed of radial nanorods. Comparative experiments demonstrated that pinecone-like, needlelike rutile TiO₂ could be easily achieved by varying the volume ratio of TiCl₄ / H₂O. The growth mechanisms of TiO₂ nanostructures prepared under different conditions and their photodegradation behavior were also discussed. It was found that the flower-like structures exhibited the highest photocatalytic activity in the photodegradation of aqueous brilliant red X-3B solution.     

Influence of nitric acid-assisted hydrothermal conditions on the characteristics of TiO2 catalysts and their activity in the oxidative steam reforming of methanol

Titania (TiO₂) nanoparticles (NPs) with different morphologies (spherical, rod-shaped, and mixed) were prepared by hydrothermal treatment of different nitric acid (HNO₃)/titanium (IV) isopropoxide (TTIP) molar ratios (0.25, 0.5, 1.0, and 1.7) at different hydrothermal temperatures (90, 150, 200, and 250 °C), hydrothermal times (6, 12, and 24 h), and calcination temperatures (500, 625, and 750 °C). The crystalline structure, morphology, and surface texture of the obtained TiO₂ NPs were characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm, field emission-scanning electron microscopy, and high resolution-transmission electron microscopy analyses. Under a larger HNO₃: TTIP molar ratio, higher hydrothermal temperature, and higher hydrothermal time, the spherical mixed anatase–rutile phase TiO₂ NPs were converted to a nanorod (NR)-shaped rutile phase (TiO₂-R). The TiO₂-R NRs gave the highest methanol conversion level (65%) and hydrogen yield (45%) in the oxidative steam reforming of methanol at 400 °C.     

Dependence of crystalline phases in titania on catalytic properties during CO hydrogenation of Co/TiO2 catalysts

The present research showed dependence of crystalline phases in titania on the catalytic properties of Co/TiO₂ catalysts during CO hydrogenation. A comparative study of anatase TiO₂- and rultile-anatase coupled TiO₂-supported Co catalysts was conducted. It was found that the presence of rutile phase (19 mol%) in titania resulted in a significant increase in the catalytic activity during CO hydrogenation. It was proposed that the role of rutile phase was to increase the stability of the support. The impact of water vapor produced during reduction on the formation of cobalt species strongly interacted with the support was probably inhibited by the presence of rutile phase in titania leading to a decrease in the reducibility loss during reduction.     

Percolation threshold for electrical resistivity of Ag-nanoparticle/titania composite thin films fabricated using molecular precursor method

To find the percolation threshold for the electrical resistivity of metallic Ag-nanoparticle/titania composite thin films, Ag-NP/titania composite thin films, with different volumetric fractions of silver (0.26 ≤ φ_Ag ≤ 0.68) to titania, were fabricated on a quartz glass substrate at 600 °C using the molecular precursor method. Respective precursor solutions for Ag-nanoparticles and titania were prepared from Ag salt and a titanium complex. The resistivity of the films was of the order of 10⁻² to 10⁻⁵ Ω cm with film thicknesses in the range 100–260 nm. The percolation threshold was identified at a φ_Ag value of 0.30. The lowest electrical resistivity of 10⁻⁵ Ω cm at 25 °C was recorded for the composite with the Ag fraction, φ_Ag, of 0.55. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), and transmission electron microscopic (TEM) evaluation of the effect of the morphology and the nanostructures of the Ag nanoparticles in the composite thin films on the electrical resistivity of the film revealed that the films consist of rutile, anatase, and metallic Ag nanoparticles homogeneously distributed in the titania matrix. It could be deduced that the electrical resistivity of the thin films formed at 600 °C was unaffected by the anatase/rutile content within the thin film, whereas the shape, size, and separation distance of the Ag nanoparticles strongly influenced the electrical resistivity of the Ag-nanoparticle/titania composite thin films.     

Fabrication of titania coatings on stainless steel via laser-induced deposition of colloidal titanium oxide from sol–gel suspension

A novel processing route that exploits the application of laser energy to induce deposition of colloidal titania (TiO₂) from sol–gel suspension was developed to produce titania coatings onto stainless steel (AISI316) substrate. Various laser parameters were investigated in order to establish the feasibility and to work out the key factors and optimal conditions for effectively fabricating these coatings on the substrate. The SEM, EDS, ATR-FTIR, XRD, and contact angle measurement were employed to analyse surface morphology, phase composition, crystalline structure, and the surface properties of the deposited titania coatings. Results show that the laser energy density plays a key role in controlling the deposition process and the deposited coating's properties, whilst traverse speed is also an effective factor. Higher laser energy density delivered to the specific area leads to thicker coatings and higher crystalline phases in the deposited coatings. At lowest energy density of 4.4 J mm⁻² tested in this work, the deposited coating is mainly amorphous, although a small amount of anatase phase is detectable. More crystalline phases are formed including anatase, rutile, substoichiometric titanium oxides, ilmenite and hematite when the laser energy density is increased to 8.7–17.4 J mm⁻². Further increases in laser energy density to 21.7 J mm⁻² results in an increase in the amount of rutile phase and the disappearance of substoichiometric titanium oxide phase. The coated surfaces show an elemental composition very close to the theoretical atomic ratio of TiO₂ which is significantly different from that of the as-dried coating from the same sol. Laser irradiation over a control solution, which has the same composition as the titania sol, but without the titania precursor, was also carried out and the result showed that no change on the solution composition was detected under all laser conditions, but slight oxidation of the substrate was observed at the higher laser energy density.     

Densification, phase composition, and properties of borosilicate glass composites containing nano-alumina and titania

Five samples of glass/ceramic composites were prepared from borosilicate glasses and both nano-aluminum oxide and nano-titanium oxide. The glass composite samples contain 10, 20, 30, 40, 50 wt.% of alumina and titania mixture. The ratio of Al₂O₃:TiO₂ in the mixture was 1:1. The formation of cristobalite in the glass matrix of low firing glass/ceramic composite substrates limits the efficiency of the ceramic substrate when it is used in circuit boards. In the present study, addition of both alumina and titania to a borosilicate glass as a ceramic filler caused the diffusion of alumina and titania phases (anatase and rutile) constituents into the glass matrix and prevented the formation of a cristobalite. Addition of both the ceramics suppresses cristobalite formation more effectively than one of them used alone and results in lower dielectric constant and thermal expansion coefficients.     

On the selective growth of titania polymorphs in acidic aqueous medium

The influence of preparation conditions on the phase composition and morphology of titania was studied for the solids synthesized by hydrothermal treatment (HT) and peptizing of hydrous TiO₂ sols in acidic medium. Mutual influence of peptizing and of additive anions (SO₄²⁻, Cl⁻) on the nature of obtained polymorphs was for the first time systematically studied and coherently explained. The solids were characterized by XRD, Raman spectroscopy, and transmission electron microscopy. It was found that peptizing step preceding HT and the presence of anions play a crucial role for the selective formation of TiO₂ anatase or rutile polymorphs. Low temperature peptizing leads to acicular rutile particles, whereas HT produces highly dispersed anatase. However if the HT was preceded by peptizing step, rutile was obtained in most cases. The influence of additives strongly depends on the moment of their introduction. Sulfate and chloride species can act as phase growth controllers, or as morphology modifiers. Sulfate hindered formation of rutile and favored anatase al low temperatures, but for already formed rutile seed, sulfate acted only as a shape controller. By contrast, chloride showed a strong tendency to promote rutile growth, whatever the conditions. A qualitative model was proposed explaining the effects observed, supported by ground state DFT and semi-empirical calculations of the aqueous Ti species.     

Characterization of a calcium phosphate–TiO2 nanotube composite layer for biomedical applications

Well-ordered nanotube arrays of titania ~ 0.7 μm high and about 40 or 110 nm in diameter were prepared via electrochemical oxidation at constant voltage (10, 15, 20 or 25 V) in a mixture of 0.86 wt.% of NH₄F, glycerol and deionized water. The effect of annealing the nanotubes at 600 °C on their morphology and structure was examined using SEM and TEM techniques. These substrates are suitable supports for a calcium phosphate coating deposited by a simple immersion in Hank solution.The nucleation and growth of a calcium phosphate (Ca–P) coating deposited on TiO₂ nanotubes (NT) from Hanks' solution was investigated using SEM. XPS and FTIR surface analytical techniques were used to characterize the self-organized porous TiO₂ layers covered with calcium phosphate coatings before and after protein adsorption. Our results confirm that the nanotubular titania layer became stable after annealing at 600 °C, while its internal structure changed from amorphous to crystalline anatase, and eventually, a mixture of anatase and rutile. These thermally stabilized TiO₂ nanotubes significantly enhance apatite formation in Hanks' Balanced Salt Solution as compared to pure Ti covered with a native oxide layer. The Ca–P/TiO₂ NT/Ti surface adsorbs a higher amount of protein (bovine serum albumin, BSA) for a geometric surface area than does the Ti surface. The above difference in protein adsorption suggests a more promising initial cellular response for a Ca–P/TiO₂ NT/Ti composite than for a typical Ti implant surface.     

Self-construction of SnO2 cubes based on aggration of nanorods

The SnO₂ cubes with the rutile structure have been successfully synthesized without using any catalyst. Their morphology and microstructure were studied by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), and elected area electron diffraction (SAED). It is revealed that the SnO₂ nanocubes exhibit high crystalline quality. The size of the nanocubes ranges from 100 nm to 300 nm. The side surfaces of nanocubes are {110} planes, while their cube axes are [001] direction. The growth mechanism of SnO₂ nanocubes was discussed and we suggested vapor-solid process should dominate the growth. These SnO₂ nanostructures represent an important example of spontaneous organization.     

TEM characterization of iron-oxide-coated ceramic membranes

Commercially available porous alumina–zirconia–titania ceramic (AZTC) membranes having a titania surface coating were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), and the Brunauer–Emmett–Teller (BET) method. TEM photomicrographs showed the as-received AZTC membrane to be a multi-layered structure consisting of a porous alumina–zirconia–titania core having ultrafine pore sizes, coated by an additional layer of nanoporous titania. Electron diffraction studies revealed an amorphous surface titania layer while the underlying AZTC membrane was crystalline. The AZTC membranes were coated 20, 30, 40, 45, or 60 times with iron oxide (Fe₂O₃) nanoparticles, after which the membranes were sintered in air at 900 °C for 30 min. TEM revealed a relatively uniform nanoporous Fe₂O₃ coating on the sintered, coated membranes, where the Fe₂O₃ coating thickness increased with increasing number of layers. Electron diffraction patterns showed the Fe₂O₃ coating to be crystalline in nature. This was confirmed by the XRD results showing the structure to be α-Fe₂O₃, while the AZTC membrane was a mixture of the anatase and rutile phase of TiO₂ as well as ZrO₂ and corundum, Al₂O₃. The average pore size of the underlying AZTC membrane increased after the Fe₂O₃-coated membrane was sintered. The nanoporosity in the sintered Fe₂O₃ coating increased until 40 layers, beyond which no significant increases in the average pore size were observed. The iron-oxide-coated membrane improved catalytic properties when used in combination with ozone to treat water. The optimal benefit, in terms of water treatment efficacy, was found at 40 layers of Fe₂O₃.     

Facile synthesis of α-MnO2 nanostructures for supercapacitors

Various α-MnO₂ nanostructures have been successfully synthesized by a simple hydrothermal method based on the redox reactions between the MnO₄⁻ and H₂O in mixture containing KMnO₄ and HNO₃. The effect of varying the hydrothermal time to synthesize MnO₂ nanostructures and the forming mechanism of α-MnO₂ nanorods were investigated by using XRD, SEM and TEM. The results revealed an evolvement of morphologies ranging from brushy spherical morphology to nanorods depending upon the hydrothermal time. The surface area of the synthesized nanomaterials varied from 89 to 119 m²/g. Electrochemical properties of the products were evaluated using cyclic voltammetry and galvanostatic charge–discharge studies, and the sample obtained by hydrothermal reaction for 6 h at 120 °C showed maximum capacitance with a value of 152 F/g. In addition, long cycle life and excellent stability of the material were also demonstrated.     

Effect of TiO2 morphology on in vitro bioactivity of polycaprolactone/TiO2 nanocomposites

TiO₂ nanostructures with different morphologies (spherical, tube, leaf-like and flower-like particles) were synthesized via a facile hydrothermal process. Polycaprolactone (PCL)/10 vol.% TiO₂ nanocomposites were prepared by solvent casting methods. In vitro bioactivity of the nanocomposite films was examined by immersion in the simulated body fluid (SBF) for up to 28 days. It was found that the morphology of titania nanostructures significantly influence the in vitro bioactivity of PCL/TiO₂ nanocomposites. This observation was attributed to the amount of anatase phase and the specific surface area of the TiO₂ nanostructures, which provide high surface exposure to SBF.     

Hydrothermal synthesis and characterization of TiO2 nanostructures using LiOH as a solvent

In the present study, we performed hydrothermal method as a simple and efficient route for the synthesis of rutile TiO₂ nanostructures in various concentrations of lithium hydroxide solutions. TiO₂ nanopowders with average sizes of 15 and 23 nm were prepared using 4 M and 7 M LiOH solutions. X-ray diffraction analysis (XRD), transmission electron microscope (FEG-STEM), scanning electron microscopy (SEM), and Brunauer–Emmet–Teller (BET) analyses were used in order to characterize the obtained products and comparison of the morphology of the powders obtained in different concentrations of LiOH solvent. It was shown that alkali solution concentration has affected the crystallinity, agglomeration ratio, particle size and specific surface area of the obtained rutile phases.     

Sol-gel synthesis of alumina,titania and mixed alumina/titania in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulphonyl) amide

In this paper we report on the synthesis of alumina, titania and mixed alumina–titania in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulphonyl) amide [Py_1,4]TFSA via sol-gel methods using aluminium isopropoxide and titanium isopropoxide as precursors. Our results show that the as-synthesized alumina is mainly mesoporous boehmite with an average pore diameter of 3.8 nm. The obtained boehmite is subject to a phase transformation into γ-Al₂O₃ and δ-Al₂O₃ after calcinations at 800 and 1,000 °C, respectively. The as-synthesized TiO₂ shows amorphous behaviour and calcination at 400 °C yields anatase which undergoes a further transformation to rutile at 800 °C. The as-prepared alumina–titania powders are amorphous and transformed to rutile and α-Al₂O₃ after calcination at 1,000 °C TiO₂. The obtained alumina–titania has a higher surface area than those of alumina or titania. The surface area of the as-synthesized alumina–titania was found to exceed 486 m² g⁻¹, whereas the surface areas of the as-synthesized boehmite and titania were around 100 m² g⁻¹, respectively.     

Effect of HNO<Subscript>3</Subscript> on crystalline phase evolution in lithium silicate powders prepared by sol–gel processes

An interesting observation is reported on the dramatic effect of HNO₃ on crystalline phase evolution in the 33.3 mol% Li₂O–SiO₂ glass–ceramic (stoichiometric composition of lithium disilicate Li₂Si₂O₅, LS₂) prepared by sol–gel processes from tetraethylorthosilicate (TEOS) and lithium ethoxide precursors. Nitric acid (65%), in molar ratio HNO₃/TEOS = 0.1, was added either to the precursor sol or to 95 °C dried gel. The product, which is amorphous at temperatures below 450 °C, transforms into crystalline lithium metasilicate (Li₂SiO₃, LS) at around 550 °C (starting temperature ∼450 °C), instead of forming crystalline LS₂. Phase separation in the glassy phase may be responsible for the formation of lithium metasilicate. XRD, ²⁹Si MAS, and ⁷Li static NMR were used to follow the crystallization evolution and network structures of the materials heat-treated at various temperatures.     

The effect of HNO3 on morphology,phase transformation,and luminescence properties of LaPO4:Eu3+ phosphors

LaPO₄:Eu³⁺ powders with different morphologies were hydrothermally constructed by adjusting the amount of HNO₃ without using a catalyst, surfactant, or template. The as-prepared products were characterized by photoluminescence spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), infrared (IR) spectra, and X-ray photoelectron spectroscopy. The SEM study revealed that the amount of HNO₃ played a crucial role in the morphology of the final products. The XRD results indicated that the as-prepared samples were in the monoclinic phase when 3 mL of HNO₃ was used. The HR-TEM micrographs and SAED results demonstrated that the prepared nanorods were single and crystalline in nature with HNO₃, and that they grew preferentially along the [0 1 2] direction. The emission spectra showed that the LaPO₄:Eu³⁺ samples had the strongest emission intensity when prepared with HNO₃.     

Synthesis and characterization of ruthenium dioxide nanostructures

We report the synthesis of ruthenium dioxide (RuO₂) nanostructures by thermal evaporation of RuO₂ powder. RuO₂ nanostructures of different shapes were synthesized at various concentration, flow rate, and pressure of oxygen. At a constant pressure of 3 torr of flowing oxygen, polygonal prism-like RuO₂ nanorods with flat tips were grown at an O₂ flow rate of 100 sccm; club-shaped nanorods with obelisk tip were formed at 300 and 600 sccm, and hollow rods with square tip were formed at 1800 sccm. A mixture of O₂ and Ar at a total flow rate of 600 sccm led to the formation of short club-shaped nanorods indicating the suppression effect of Ar on the growth of nanorods. The pressure also had a significant effect on the formation of RuO₂ nanostructures, at a fixed flow rate of 600 sccm of O₂, a pressure of 3 torr resulted in the growth of club-shaped RuO₂ nanorods, while high pressures of 380 and 760 torr resulted in the formation of both linear club-shaped and pine tree-like hierarchical RuO₂ nanorods. X-ray diffraction and transmission electron microscopy analysis indicated the formation of tetragonal phase of RuO₂ with high crystallinity. A density functional calculation on RuO₂, RuO₃, and RuO₄ was performed to help to explain the experimental results.     

Terbium and ytterbium-doped titania luminescent nanofibers by means of electrospinning technique

The study of the luminescent properties of the rare-earth (RE) elements hosted in different crystalline matrixes is strongly motivated due to technological applications in optoelectronic devices and flat panel displays. In particular, it is known that nanostuctured titania (TiO₂) is a promising host material for several trivalent rare earth ions. In this paper Tb- and Yb-doped titania nanofibers have been fabricated by electrospinning technique. A full characterization, is presented, including microstructural, thermal, spectroscopic and optical investigations. All electrospun materials consisted of randomly oriented nanofibers of fairly uniform diameter of 35 and 80 nm for, respectively, Tb-doped and Yb-doped TiO₂. The incorporation of RE elements within the titania lattice resulted in a delayed anatase to rutile phase transition, accompanied by the formation Ln₂Ti₂O₇ (Ln = Tb, Yb). All samples showed luminescent properties, the relative emission spectra were dominated by the typical Tb³⁺ and Yb³⁺ emission peaks associated to the specific Ln³⁺ 4f-transitions.     

Temperature dependent growth and optical properties of SnO<Subscript>2</Subscript> nanowires and nanobelts

SnO₂ nanowires and nanobelts have been grown by the thermal evaporation of Sn powders. The growth of nanowires and nanobelts has been investigated at different temperatures (750–1000°C). The field emission scanning electron microscopic and transmission electron microscopic studies revealed the growth of nanowires and nano-belts at different growth temperatures. The growth mechanisms of the formation of the nanostructures have also been discussed. X-ray diffraction patterns showed that the nanowires and nanobelts are highly crystalline with tetragonal rutile phase. UV-visible absorption spectrum showed the bulk bandgap value (∼ 3–6 eV) of SnO₂. Photoluminescence spectra demonstrated a Stokes-shifted emission in the wavelength range 558–588 nm. The Raman and Fourier transform infrared spectra revealed the formation of stoichiometric SnO₂ at different growth temperatures.     

Preparation and characterization of nitrogen-doped titania nanotubes

Nitrogen-doped TiO₂ nanotubes were synthesized by annealing of the anodized titania nanotubes with ammonia at the temperature of 500 °C. The ordered structure of titania nanotubes maintained after the nitrogen doping process, as is evidenced by SEM observations. Detailed structural analysis revealed that the phase transformation temperature of titania nanotube from anatase to rutile is decreased after nitrogen doping. The XRD patterns of nitrogen-doped titania exhibit an increased peak intensity and a decreased FWHM in the (110) peak of rutile in comparison with those of undoped titania under the same annealing conditions, indicating that nitrogen doping may have facilitated the phase transition at the annealing temperature of 500 °C, which is in consistence with the analysis of Raman spectra as the comparison of A_1g and E_g Raman peaks of rutile in the nitrogen-doped and undoped titania.