Effect of Hg2+doping and of the annealing temperature on the nanostructural properties of TiO2 thin films obtained by sol–gel method

This work is a study of Hg²⁺-doped TiO₂ thin films deposited on silicon substrates prepared by sol–gel method and treated at temperatures ranging between 600 to 1000 °C for 2 h. The structural and optical properties of thin films have been studied using different techniques. We analyzed the vibrations of the chemical bands by Fourier transform infrared (FTIR) spectroscopy and the optical properties by UV–Visible spectrophotometry (reflection mode) and photoluminescence (PL). The X-ray diffraction and Raman spectra of TiO₂ thin films confirmed the crystallization of the structure under the form of anatase, rutile, mercury titanate (HgTiO₃) as a function of the annealing temperature. The observation by scanning electron microscopy (SEM) showed the changing morphology, with respect to nanostructures, nanosheets, nanotubes, with the annealing temperature. The diameters of nanotubes ranged from 50 nm to 400 nm. The photoluminescence and reflectance spectra indicated that these structures should enhance photocatalytic activity.     

Synthesis and studies on photochromic properties of vanadium doped TiO2 nanoparticles

Pure and (0.5–3 at%) vanadium doped TiO₂ nanoparticles have been synthesized by wet chemical method. The as synthesized materials have been characterized by using XRD, atomic force microscope (AFM), Raman, EPR and UV–vis spectroscopy techniques. From XRD studies, both pure as well as vanadium doped TiO₂ have been found to show pure anatase phase. The value of lattice constant c is smaller in doped TiO₂ as compared to undoped and has been found to decrease with increase in vanadium concentration. AFM studies show formation of spherical particles with particle size ～23 nm in all the samples. Photochromic behavior of these materials has been studied by making their films in alkyd resin. Vanadium doped TiO₂ films show reversible change in color from beige-yellow to brownish violet on exposure to UV light. The mechanism of coloration and bleaching process has been discussed.     

Phosphatization: A promising approach to enhance the performance of mesoporous TiO2 anode for lithium ion batteries

We report phosphatization is a promising method to enhance the performance of mesoporous TiO₂ anode for lithium ion batteries. The resulting phosphated mesoporous TiO₂ possessed higher reversible capacity and better cycling stability than the pure mesoporous TiO₂. When cycled at 30 mA/g between 3.0 and 1.0 V, the initial capacity of phosphate mesoporous TiO₂ was 249 mA h/g, significantly higher than that of pure mesoporous TiO₂ (204 mA h/g). After 40 cycles, the capacity retention ratio of phosphate mesoporous TiO₂ reached 83.7%, while pure mesoporous TiO₂ had merely a capacity retention ratio of 62.3%. We believe that this phosphatization process could be used to enhance the electrochemical performance of other metal oxides for lithium ion batteries.     

Micro-Raman mapping on an anatase TiO2 single crystal with a large percentage of reactive (0 0 1) facets

After it has been successfully synthesized in 2008, so far, no Raman investigations on the micro-sized anatase TiO₂ single crystal which has a large percentage of the reactive (0 0 1) facets have been conducted to the best of our knowledge. In the present work, this unique anatase TiO₂ single crystal was investigated by noninvasive and nondestructive Raman mapping technique. Raman images of both non-polarized and polarized measurements showed that the Raman features of the crystal varied with measurement position. The differences among the Raman spectra measured on different crystal facets were believed to result from the orientations and the symmetry rules. Whereas the differences among those measured at different points of the same crystal facet under the same measurement condition were supposed to indicate the defects of the crystal structure, such as oxygen vacancies, local lattice disorder etc. Furthermore, the appearance of the two second order Raman peaks of 803 and 918 cm⁻¹ as well as the blue-shift of 395 cm⁻¹ peak implies the anharmonicity of the crystal structure, which is also probably caused by the crystal defects. Our results provide useful information about the structure of this unique anatase TiO₂ material, and could be complementary to those that acquired by other characterization techniques.     

Novel synthesis of high-surface-area ordered mesoporous TiO2 with anatase framework for photocatalytic applications

Ordered mesoporous TiO₂ materials with an anatase frameworks have been synthesized by using a cationic surfactant cetyltrimethylammonium bromide (C₁₆TMABr) as a structure-directing agent and soluble peroxytitanates as Ti precursor through a self-assembly between the positive charged surfactant S⁺ and the negatively charged inorganic framework I^? (S⁺I^? type). The low-angle X-ray diffraction (XRD) pattern of the as-prepared mesoporous TiO₂ materials indicates a hexagonal mesostructure. XRD and transmission electron microscopy results and nitrogen adsorption–desorption isotherms measurements indicate that the calcined mesoporous TiO₂ possesses an anatase crystalline framework having a maximum pore size of 6.9 nm and a maximum Brunauer–Emmett–Teller specific surface area of 284 m² g^?1. This ordered mesoporous anatase TiO₂ also demonstrates a high photocatalytic activity for degradation of methylene blue under ultraviolet irradiation.     

F–B-codoping of anodized TiO2 nanotubes using chemical vapor deposition

Chemical vapor deposition (CVD) was firstly used to simultaneously codope fluorine and boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄ · 2H₂O + NH₄F electrolyte. F–B-codoping was successfully carried out by annealing the anodized TiO₂ nanotubes through CVD, as evidenced from XPS analysis. SEM images showed that the higher the annealing temperature, the greater structure damage of F–B-codoped sample. XRD results confirmed that annealing temperature had an influence on the phase structure and boron and fluorine impurities could retard anatase–rutile phase transition. F–B-codoped samples displayed remarkably strong absorption in both UV and visible range. Under visible-light irradiation, F–B-codoped samples showed the higher I_ph and catalytic activity in methyl orange photoelectrodegradation than F-doped sample and B-doped sample. This showed a convincing evidence of F–B-codoping of TiO₂ had an obvious synergistic effect on the enhancement of photocurrents and photoelectrocatalytic activity.     

Structural evolution during the reaction of Li with nano-sized rutile type TiO2 at room temperature

Rutile type TiO₂ nanoparticles (10 nm × 200 nm in size) were prepared using a precipitation method in aqueous solution. Their lithium reactivities were followed using both classical galvanostatic insertion and in situ XRD measurements, and compared to that of a bulk and commercial nano-sized (50 nm) rutile TiO₂ sample so as to stress the interlink between Li insertion electrochemical capacity and crystallite size. For the highly divided material, we obtained a reversible capacity of 0.5 Li ion per formula unit after a first reduction step during which, the material is irreversibly transformed. Such a reduction step is shown to enlist two solid solution domains followed by the formation of a rocksalt type phase LiTiO₂. Such a specific reactivity of nano-sized rutile TiO₂ is explained in terms of better lattice strains accommodation during the insertion of lithium.     

RuO2-wired high-rate nanoparticulate TiO2 (anatase): Suppression of particle growth using silica

To enhance the high-rate capability (up to 120 C, 20 A/g) of nanoparticulate TiO₂ (anatase) formed by thermal treatment of protonated TiO₂ nanotubes, we used two types of additives: RuO₂ as an electron-conductive material [Y.-G. Guo, Y.-S. Hu, W. Sigle, J. Maier, Adv. Mater. 19 (2007) 2087] and silica as a suppressant of particle growth during heat treatment. We show systematically that both additives, when used separately, improve the high-rate performance of anatase by 25–55 mA h/g at 60 C. The combined use of both additives in a total amount of merely 2.5 wt.% leads to an improvement of more than 70 mA h/g at 60 C. The underlying mechanisms for these significant effects are briefly discussed.     

Facile preparation of large aspect ratio ellipsoidal anatase TiO2 nanoparticles and their application to dye-sensitized solar cell

A simple one-step heat-treatment of peroxotitanate complex aqueous solution at around 100 °C was resulted in the formation of ellipsoidal anatase TiO₂ nanoparticles having a high aspect ratio with no branches. The length of these ellipsoidal TiO₂ falls in the range of 200–350 nm, depending on mole ratio of Ti⁴⁺/H₂O₂. Dye-sensitized solar cell based on these ellipsoidal nanocrystalline TiO₂ as photoanode was fabricated and characterized.     

Solar active nano-TiO2 for mineralization of Reactive Red 120 and Trypan Blue: 1st Nano Update

Nano-TiO₂ was synthesized by sol–gel method. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) images, transmission electron microscope (TEM), BET surface area measurement and DRS analysis. The formation of anatase phase nano-TiO₂ was confirmed by XRD measurements and its crystalline size is found to be 15.2 nm. SEM images depict the crystalline nature of prepared TiO₂. The BET surface area of prepared TiO₂ is found to be 86.5 m² g^?1 which is higher than that of commercially available TiO₂–P25. The photocatalytic activity of prepared anatase phase TiO₂ has been tested for the degradation of two azo dyes: Reactive Red 120 (RR 120) and Trypan Blue (TB) using solar light. The photocatalytic activity of nano-TiO₂ is higher than TiO₂–P25 under solar light. The mineralization of dyes has been confirmed by chemical oxygen demand (COD) measurements.     

Synthesis and characterization of high surface area TiO2/SiO2 mesostructured nanocomposite

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO₂/SiO₂ nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (～2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ～10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO₂/SiO₂ solids are promising in term of thermal stability.     

Enhanced electrochemical performance of carbon-coated TiO2 nanobarbed fibers as anode material for lithium-ion batteries

We report the electrochemical performance of carbon-coated TiO₂ nanobarbed fibers (TiO₂@C NBFs) as anode material for lithium-ion batteries. The TiO₂@C NBFs are composed of TiO₂ nanorods grown on TiO₂ nanofibers as a core, coated with a carbon shell. These nanostructures form a conductive network showing high capacity and C-rate performance due to fast lithium-ion diffusion and effective electron transfer. The TiO₂@C NBFs show a specific reversible capacity of approximately 170 mAh g^− 1 after 200 cycles at a 0.5 A g^− 1 current density, and exhibit a discharge rate capability of 4 A g^− 1 while retaining a capacity of about 70 mAh g^− 1. The uniformly coated amorphous carbon layer plays an important role to improve the electrical conductivity during the lithiation–delithiation process.     

Photocatalytic activity of nitrogen and copper doped TiO2 nanoparticles prepared by microwave-assisted sol-gel process

Cu and N-doped TiO₂ photocatalysts were synthesized from titanium (IV) isopropoxide via a microwave-assisted sol-gel method. The synthesized materials were characterized by X-ray diffraction, UV-vis diffuse reflectance, photoluminescence (PL) spectroscopy, SEM, TEM, FT-IR, Raman spectroscopy, photocurrent measurement technique, and nitrogen adsorption–desorption isotherms. Raman spectra and XRD showed an anatase phase structure. The SEM and TEM images revealed the formation of an almost spheroid mono disperse TiO₂ with particle sizes in the range of 9-17 nm. Analysis of N₂ isotherm measurements showed that all investigated TiO₂ samples have mesoporous structures with high surface areas. The optical absorption edge for the doped TiO₂ was significantly shifted to the visible light region. The photocurrent and photocatalytic activity of pure and doped TiO₂ were evaluated with the degradation of methyl orange (MO) and methylene blue (MB) solution under both UV and visible light illumination. The doped TiO₂ nanoparticles exhibit higher catalytic activity under each of visible light and UV irradiation in contrast to pure TiO₂. The photocatalytic activity and photocurrent ability of TiO₂ have been enhanced by doping of the titania in the following order: (Cu, N) - codoped TiO₂ > N-doped TiO₂ > Cu-doped TiO₂ > TiO₂. COD result for (Cu, N)-codoped TiO₂ reveals ∼92% mineralization of the MO dye on six h of visible light irradiation.     

Photoinduced hydrophilic and photocatalytic response of hydrothermally grown TiO2 nanostructured thin films

It is demonstrated that nanostructured titanium (IV) oxide (TiO₂) films can be deposited on glass substrates at 95 °C using hydrothermal growth, their properties being greatly affected by the substrate materials. Anatase TiO₂ films grown on ITO for deposition period of 50 h were observed to exhibit a very efficient, reversible light-induced transition to super-hydrophilicity, reaching a nearly zero contact angle. Enhanced photocatalytic activity (65%) was found for the rutile TiO₂ samples grown on microscope glass, possibly due to their higher roughness with respect to anatase grown on ITO. The effect of the substrate material used is discussed in terms of the TiO₂ phase and morphology control, for the best photoinduced hydrophilic and photocatalytic performance of the samples.     

Tremella-like molybdenum dioxide consisting of nanosheets as an anode material for lithium ion battery

Tremella-like structured MoO₂ consisting of nanosheets was obtained via a Fe₂O₃-assisted hydrothermal reduction of MoO₃ in ethylenediamine aqueous solution. The as-prepared product was characterized and tested with scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and capacity measurement as anode material for lithium ion batteries. This structured MoO₂ shows very high reversible capacity (>600 mA h g⁻¹), good rate capability and cycling performance, presenting potential application as anode material for lithium ion batteries with high rate capability and high capacity.     

Self-assembled Li4Ti5O12/TiO2/Li3PO4 for integrated Li–ion microbatteries

This work aims to maximize the number of active sites for energy storage per geometric area, by approaching the investigation to 3D design for microelectrode arrays. Self-organized Li₄Ti₅O₁₂/TiO₂/Li₃PO₄ composite nanoforest layer (LTL) is obtained from a layer of self organized TiO₂/Li₃PO₄ nanotubes. The electrochemical response of this thin film electrode prepared at 700 °C exhibited lithium insertion and de-insertion at 1.55 and 1.57 V respectively, which is the typical potential found for lithium titanates. The effects of lithium phosphate on lithium titanate are explored for the first time. By cycling between 2.7 and 0.75 V the LTL/LiFePO₄ full cell delivered 145 mA h g^− 1 at an average potential of 1.85 V leading to an energy density of 260 W h kg^− 1 at C/2. Raman spectroscopy revealed that the γ-Li₃PO₄/lithium titanate structure is preserved after prolonged cycling. This means that Li₃PO₄ plays an important role for enhancing the electronic conductivity and lithium ion diffusion.     

NiCo2O4 nanosheets supported on Ni foam for rechargeable nonaqueous sodium–air batteries

NiCo₂O₄ nanosheets supported on Ni foam were synthesized by a solvothermal method. A composite of NiCo₂O₄ nanosheets/Ni as a carbon-free and binder-free air cathode exhibited an initial discharge capacity of 1762 mAh g^− 1 with a low polarization of 0.96 V at 20 mA g^− 1 for sodium–air batteries. Na₂O₂ nanosheets were firstly observed as the discharged product in sodium–air battery. High electrocatalytic activity of NiCo₂O₄ nanosheets/Ni made it a promising air electrode for rechargeable sodium–air batteries.     

Structural and electrochemical investigation of Li2MgSnO4 anode for lithium batteries

Hexagonal Li₂MgSnO₄ compound was synthesized at 800 °C using Urea Assisted Combustion (UAC) method and the same has been exploited as an anode material for lithium battery applications. Structural investigations through X-ray diffraction, Fourier Transform Infra Red spectroscopy and ⁷Li NMR (Nuclear Magnetic Resonance spectroscopy) studies demonstrated the existence of hexagonal crystallite structure with a = 6.10 and c = 9.75. An average crystallite size of ∼400 nm has been calculated from PXRD pattern, which was further evidenced by SEM images. An initial discharge capacity of ∼794 mA h/g has been delivered by Li₂MgSnO₄ anode with an excellent capacity retention (85%) and an enhanced coulombic efficiency (97–99%). Further, the Li₂MgSnO₄ anode material has exhibited a steady state reversible capacity of ∼590 mA h/g even after 30 cycles, thus qualifying the same for use in futuristic lithium battery applications.     

Thermal stability of TiO2-anatase: Impact of nanoparticles morphology on kinetic phase transformation

TiO₂ is a material of great interest for many technological applications among which, as catalyst support. As this specific application requires a good thermal stability of the material, the phase transition between the two most commonly used titania polymorphs, anatase and rutile, has been extensively studied over the past decade. However not much importance has been given to the initial and final particles morphologies. In this study, anatase nanoparticles with an elongated shape were synthesized and their kinetic phase transformation was studied. The thermal treatments were conducted at temperatures ranging from 500 to 700 °C. The morphology evolution and the phase transition were characterized by X-ray diffraction and transmission electron microscopy. The phase transformation kinetics is best described by the interface nucleation models. The values of the measured kinetic parameters are significantly lower than those proposed in the literature for isotropic particles, with an activation energy of E_a = 345 kJ mol^?1. The influence of morphology and, as a consequence, the influence of exposed faces on anatase particles, are presented and discussed.     

Preparation and electrochemical lithium storage of flower-like spinel Li4Ti5O12 consisting of nanosheets

In this paper, flower-like spinel Li₄Ti₅O₁₂ consisting of nanosheets was synthesized by a hydrothermal process in glycol solution and following calcination. The as-prepared product was characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction and cyclic voltammetry. The capacity of the sample used as anode material for lithium ion battery was measured. This structured Li₄Ti₅O₁₂ exhibited a high reversible capacity and an excellent rate capability of 165.8 m Ahg⁻¹ at 8 C, indicating potential application for lithium ion batteries with high rate performance and high capacity.