Pure and (zinc or iron) doped titania powders prepared by sol-gel and used as photocatalyst

Pure and doped (zinc and iron) nanocrystalline titania powders were prepared by the sol-gel route. Doping tends to change the existing crystalline phases and their degree of crystallinity, but particle size distribution and morphology of the particles are also affected. In the pure titania system, the main crystalline phase is anatase but rutile is also present. The doped (Zn and Fe) titania crystallizes only as anatase. The undoped titania shows a bimodal distribution of particles size: fine (20-40 nm) and coarse (300-500 nm) grains. The doped TiO₂ powder also exhibits a much more uniform particle size distribution, with all grains under 40 nm.The photocatalytic efficiency of suspended powders was tested on the decolouration of Orange II aqueous solutions under visible artificial light irradiation. The maximum decolouration reached by the pure TiO₂ was 81% at a rate of 3.6 × 10⁻³ min⁻¹. Iron doping decreases the photocatalytic activity; the maximum dye degradation was only 43% at a rate of 1.3 × 10⁻³ min⁻¹. On the contrary, the performance of Zn-doped titania was better, having a decolouration rate of 17.7 × 10⁻³ min⁻¹.     

Preparation of high solids content nano-titania suspensions to obtain spray-dried nanostructured powders for atmospheric plasma spraying

Nanosized TiO₂ powder with an average primary size of ∼20 nm and surface area of ∼50 m²/g (Aeroxide^® P25, Degussa-Evonik, Germany) was used as starting material. A colloidal titania suspension from the same supplier was also used (W740X). The dispersing conditions were studied as a function of pH, dispersant content, and solids loading. Well-dispersed TiO₂ nanosuspensions with solids contents up to 30 vol.% (62 wt%) were obtained by dispersing the powder with 4 wt% PAA. Suspensions with solids contents as high as 35 vol.% were prepared by adding the TiO₂ nanoparticles to the TiO₂ colloidal suspension under optimised dispersing conditions.TiO₂ powder reconstitution was performed by spray drying both types of nanosuspensions to obtain free-flowing micrometre-sized nanostructured granules. The spray-dried nanostructured TiO₂ granules were deposited on austenitic stainless steel coupons using atmospheric plasma spraying. Coating microstructure and phase composition were characterised using scanning electron microscopy and X-ray diffraction techniques.     

Preparation, characterization and photoactivity of TiO2 obtained by a reverse microemulsion route

TiO₂ was synthesized by a reverse microemulsion route. By using different water contents in the reverse microemulsion, we obtained three different materials named R = 10, R = 20 and R = 30. The reverse microemulsion synthesis has the advantage that the kind of the crystalline titania structure obtained may be changed by simply modifying the water content in the microemulsion.The synthesized materials were characterized by nitrogen adsorption, scanning and transmission electron microscopy, and X-ray diffraction. Methylene blue (MB) was used as testing dye; we studied the pH effect and catalyst dosage in the MB photodegradation. The degradation kinetics was also studied.     

TiO2 nanotubes manufactured by anodization of Ti thin films for on-chip Li-ion 2D microbatteries

The use of self-organized TiO₂ nanotube arrays electrochemically grown onto Si is investigated for the fabrication of an alternative electrode dedicated to on-chip Li-ion 2D microbatteries. Discharge/charge curves and cycling performance are studied in lithium-anode electrochemical test cells for both amorphous and crystalline titania nanotubes. At 5 μA cm⁻² amorphous TiO₂ nanotube layers onto Si deliver a maximum areal capacity of 89 μAh cm⁻² in the first reversible discharge and 56 μAh cm⁻² over 50 cycles. We demonstrate that these nanostructured thin film electrodes showing such electrochemical performances are compatible with IC technology.     

Porous titania microspheres with uniform wall thickness and high photoactivity

Highly porous titania particles were prepared by depositing thin films of titania, using alternating reactions of TiCl₄ and hydrogen peroxide, on poly(styrene-divinylbenzene) (PS-DVB) template particles via atomic layer deposition (ALD) at 77 °C. The composition of the titania films was verified by XPS analysis and the titania films were directly observed by TEM. TGA/DSC was used to study the thermal decomposition of the polymer template. Porous titania particles with uniform wall thicknesses were successfully obtained after the template PS-DVB was removed by oxidation in air at 400 °C for 24 h. Verification of the resulting porous structure of the titania particles was done by cross-sectional SEM and nitrogen adsorption–desorption analysis. Porous titania particles were treated at different temperatures. XRD analysis was used to determine the microstructure and phase transformation of titania at elevated temperatures. The photocatalytic activity of these porous titania particles was studied by methylene blue decomposition under UV light at room temperature and was found to be comparable to that of commercial anatase titania nanoparticles (~20 nm). Depositing Na₂SO₄ on TiO₂ retarded the TiO₂ phase transformation from anatase to rutile during calcination and, thus, greatly increased the photoactivity of the porous titania particles.     

Biodiesel production from supercritical carbon dioxide extracted Jatropha oil using subcritical hydrolysis and supercritical methylation

This study investigates supercritical carbon dioxide (SC-CO₂) extraction of triglycerides from powdered Jatropha curcas kernels followed by subcritical hydrolysis and supercritical methylation of the extracted SC-CO₂ oil to obtain a 98.5% purity level of biodiesel. Effects of the reaction temperature, the reaction time and the solvent to feed ratio on free fatty acids in the hydrolyzed oil and fatty acid esters in the methylated oil via two experimental designs were also examined. Supercritical methylation of the hydrolyzed oil following subcritical hydrolysis of the SC-CO₂ extract yielded a methylation reaction conversion of 99%. The activation energy of hydrolysis and trans-esterified reactions were 68.5 and 45.2 kJ/mole, respectively. This study demonstrates that supercritical methylation preceded by subcritical hydrolysis of the SC-CO₂ oil is a feasible two-step process in producing biodiesel from powdered Jatropha kernels.     

Shock-consolidated TiO2 bulk with pure anatase phases fabricated by explosive compaction using underwater shockwave

Titanium dioxide (TiO₂) bulk with pure anatase phases was fabricated by an explosive compaction technique using an underwater shockwave. Dynamic shock pressure of 6 GPa was used to consolidate anatase TiO₂ powders. Its microstructural, crystalline structural and photocatalytic characteristics were observed and measured by various techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and photocatalytic activity measurement system. It was confirmed that the relative density of anatase TiO₂ compact is about 96% (3.73 g/cm³) of the theoretical density (3.89 g/cm³) and a strong surface bonding between particles is formed by a shock energy. In X-ray diffraction analysis, high purity anatase phases, broadened peaks due to lattice defects and decreased crystallite size were found. For the photocatalytic activities, the anatase TiO₂ compact was quite excellent compared to the commercial sintered TiO₂ bulk.     

Tailoring high-surface-area nanocrystalline TiO2 polymorphs for high-power Li ion battery electrodes

The crystallization and morphology of brookite and anatase titania (TiO₂) were controlled using the urea-mediated hydrolysis/precipitation route in the presence of the Ti³⁺ ions. Without the strong complexing agents and the non-hydrothermal conditions, simple alterations to the urea concentration led to the synthesis from brookite nanorods to anatase nanoflowers at a low temperature below 100 °C, whereas the BET specific surface area evolved from 102 to 268 m² g⁻¹, respectively. A possible formation mechanism was also proposed for these TiO₂ nanostructures. The excellent reversible capacity and rate capability were achieved for the anatase nanoflowers because of the small crystallite size and significantly large surface area.     

Synthesis of polypyrrole/Ni-doped TiO2 nanocomposites (NCs) as a protective pigment in organic coating

This study reports the synthesis of polypyrrole/Ni-doped TiO₂ nanocomposites (NCs) as a protective pigment in organic coatings. Polypyrrole/Ni-doped TiO₂ NCs were prepared by in situ chemical oxidative polymerization of pyrrole monomer in the presence of Ni-doped TiO₂ nanoparticles (NPs) with ammonium persulfate (APS) as oxidant. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) result show a core–shell structure of the pigments. The XRD results indicate that the average crystalline size of Ni-doped TiO₂ NPs is larger than TiO₂ NPs while the sizes of polypyrrole/TiO₂ NCs and polypyrrole/Ni-doped TiO₂ NCs were 93.46 ± 0.06 and 26.16 ± 0.06 nm respectively. Hence the thickness of the shell in the core–shell incorporating the Ni-doped/TiO₂ NPs was very thin and the area of synthesized PPy is increased. The electrochemical impedance spectroscopy (EIS) results show that increasing the area of synthesized polypyrrole in the presence of Ni-doped-TiO₂ NPs can increase its ability to interact with the ions liberated during the corrosion reaction of steel in the presence of NaCl.     

Improvement of performances of complex non-platinum electrode materials for hydrogen evolution

Structural and electrochemical characteristics of hypo-hyper d-electrocatalytic materials aimed for preparation of electrodes for hydrogen evolution were studied and modified in order to improve their performances. All studied materials were of general composition 10% Ni + 18% TiO₂ + C.All materials were prepared of amorphous or crystalline TiO₂, crystalline Ni or NiCo (10-20 nm) and Vulcan XC-72, by sol-gel procedure.Both, material's intrinsic catalytic activity and surface area were affected by applied modifications. As a result, the electrocatalytic activity was improved, e.g. transformation of TiO₂ into anatase form lowers the HER overpotential for 60 mV. Introduction of MWCNTs was even more effective, lowering η for 120 mV. Co addition to metallic phase lowers η for utmost 195 mV.Combined modification of TiO₂ and carbon substrate lowers η for 145 mV, while the complete modification of all three catalyst's components was the most effective with 230 mV decrease of overpotential.     

Preparation and characterisation of visible light responsive iodine doped TiO2 electrodes

Characteristics are presented of new iodine doped TiO₂ (I-TiO₂) prepared via the hydrothermal method, where titania (IV) complexes with a ligand containing an iodine atom have been used as a precursor. The structure of samples has been examined by XPS, XRD, UV-vis and FT-IR-ATR techniques. These studies confirm that the obtained powder exhibits a decrease in the bandgap energy value (E_g = 2.8 eV). The report presents electrochemical studies of I-TiO₂ films on a Pt electrode, which allow determination of the flatband potential E_fb = −0.437 V vs. SCE (in 0.5 M Na₂SO₄). Cyclic voltammetry measurements show anodic and cathodic activities under Vis and UV-vis radiation. The photocurrent enhancement due to visible light radiation reached 30% of the whole photoacitivity exhibited under UV-vis illumination.     

Reactive Hydrothermal Liquid‐Phase Densification (rHLPD) of Ceramics – A Study of the BaTiO3[TiO2] Composite System

A densification process called reactive hydrothermal liquid‐phase densification (rHLPD), based on principles of hydrothermal reaction, infiltration, reactive crystallization, and liquid‐phase sintering, is presented. rHLPD can be used to form monolithic ceramic components at low temperatures. The densification of barium titanate–titania composite monoliths was studied to demonstrate proof of concept for this densification model. Permeable, green titania (anatase) compacts were infiltrated with aqueous barium hydroxide solutions and reacted under hydrothermal conditions in the temperature range 90°C–240°C. The effects of reaction time and temperature on the conversion of titania (anatase) into barium titanate were studied. Utilizing a 72 h reaction at 240°C between l.0 M Ba(OH)₂, an anatase (TiO₂) powder compact, and a corresponding Ba/Ti ratio of 1.5, it was possible to crystallize a composite 95 wt% (88 mol%) BaTiO₃ and 5 wt% (12 mol%) TiO₂. The composite had a relative density of ~90% with a compressive strength of 172 ± 21 MPa and a flexural strength of 49 ± 4 MPa.     

Phase evolution and microwave dielectric properties of MgO-B2O3-SiO2-based glass-ceramics

The densification and crystallization behaviors of MgO-B₂O₃-SiO₂ (MBS) glass with various amounts of TiO₂ additions (0-10 wt.%) were investigated by means of thermal analysis, X-ray powder diffraction and scanning electron microscopy. A microwave dielectric characterization was performed in order to evaluate the suitability of MBS glass-ceramics as a low-permittivity dielectric substrate. The densification of the MBS glass started below 700 °C. The main crystalline phases of Mg₂B₂O₅ and MgSiO₃ appeared at 800 and 950 °C, respectively. The Mg₃TiB₂O₈ and TiB_0.024O₂ phases additionally crystallized in TiO₂-added MBS glass-ceramics at 1000 °C. The permittivity increased from 6.1 in pure MBS glass to 6.9 in MBS glass with 10 wt.% of TiO₂. The addition of TiO₂ enhanced the crystallization and consequently increased the Qxf-values of the MBS glass (11 300 GHz) up to 16 500 GHz. The improvement of the Qxf-values became the most evident at 1050 °C. Dense MBS glass-ceramics sintered at 850 ≤ T ≤ 950 °C exhibited Qxf-values of 5000-8000 GHz (at ∼12 GHz), which are comparable with the values of CaO-B₂O₃-SiO₂-based glass-ceramics.     

An approach to laminated flexible Dye sensitized solar cells

We have built TiO₂ Dye sensitized solar cells (DSSCs) that combined flexible TiO₂ photoanodes coated on ITO/PET substrates with a gel electrolyte based on PVDF-HFP-SiO₂ films. Titanium isopropoxide (TiP₄) was used as additive to TiO₂ nanoparticles for increasing power conversion efficiency in Dye sensitized solar cell electrodes prepared at low-temperature (130 °C). An efficiency η_AM1.5G = 3.55% on ITO/PET substrates is obtained at 48 mW/cm² illumination with a standard liquid electrolyte based on methoxypropionitrile. Among several solvents forming gels with PVDF-HFP-SiO₂, N-methyl (pyrrolidone) (NMP) was found to enable the most stable devices. A power conversion efficiency η_AM1.5G = 2% was obtained under 10 mW/cm² with flexible TiO₂-ITO-PET photoanodes and the PVDF-HFP-SiO₂ + NMP gel electrolyte.     

Effect of 2-propanol and water contents on the crystallization and particle size of titanium dioxide synthesized at low-temperature

Two series of titanium dioxide, TiO₂, powder were prepared at a temperature of 50 °C without any catalyst. The effects of 2-propanol and water contents on the formation of crystalline powder mixture of anatase and brookite were systematically studied. The characteristics of produced powder were determined by employing X-ray diffraction, transmission electron microscopy, nitrogen adsorption test and Fourier transform infrared spectroscopy.     

Electrochemical lithium storage of titania nanotubes modified with NiO nanoparticles

The nanotubes of mixed TiO₂(B) and anatase phases, obtained by hydrothermal synthesis and subsequent calcination, are modified with NiO nanoparticles. In the modified products, NiO nanoparticles with poor crystallinity exist inside titania tubes and are attached to the outside surface of the nanotubes according to X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray spectra (EDS) analysis. The titania nanotubes, modified with 5 wt.% NiO in which NiO nanoparticles were distributed homogenously, exhibit the optimal cycle performance and a good capability for high rate discharge. The lithium ion diffusion is mainly related to the anatase phase, while the electrochemical reaction activity is attributed to the TiO₂(B) phase. Relative to titania nanotubes, NiO-modified nanotubes have a better electrochemical reaction activity, which is beneficial for the improvement of the high rate charge-discharge capability.     

Controlled fabrication of nanosized TiO2 hollow sphere particles via acid catalytic hydrolysis/hydrothermal treatment

TiO₂ hollow spheres of controlled size were synthesized by combined acid catalytic hydrolysis and hydrothermal treatment, which involves the deposition of an inorganic coating of TiO₂ on the surface of carbon spheres prepared by a hydrothermal method and subsequent removal of the carbon spheres by calcination in air. The obtained TiO₂ hollow spheres were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and powder X-ray diffraction. The results revealed that the size and surface morphology of the TiO₂ hollow spheres can be controlled by adjusting the concentration of the aqueous solution of glucose used to produce the template carbon spheres. Increasing the concentration of the glucose solution increased the average diameter of the TiO₂ hollow spheres from 190 to 300 nm. TiO₂ hollow spheres prepared using a glucose solution with a concentration of 0.7 mol/L are uniform in size with a diameter of 220 nm and shell thickness of 28 nm. The phenol removal rate of the sample prepared by calcination at 600 °C is 1.35 times higher than that of TiO₂ made by the same method without using the carbon template.     

Preparation of high solid loading titania suspension in gelcasting using modified boiling rice extract (MBRE) as binder

Preparation of high solid loading homogeneous titania suspension using modified boiling rice extract (BRE) as consolidator (network-former)/binder for gelcasting application has been investigated. To achieve in situ consolidation forming of TiO₂ ceramic, the gel network formed by swelling and gelatinization of the modified BRE (MBRE) with 2-hydroxyethylmethacrylate was studied. The dispersion behaviour of the titania powder and rheology of the suspension under the influence of binder content, dispersant (Darvan 821A) concentration and pH of the dispersing media have been discussed. The present process of gel casting deals with 50-80 weight% solid loading of titania particles with MBRE (2-10 weight% to that of total solid loading) in presence of dispersant (ammonium salt of polyacrylic acid [(C₄H₅O₂-NH₄⁺)n]). The influence of BRE concentration and solid particle loading on rheological properties of aqueous titania suspensions has been analyzed under steady and oscillatory shear conditions. Thermogravimetry (TG) and differential thermal analysis (DTA) on gelcast green body has been evaluated and analyzed. The characterization of green and sintered body has been done with respect to density, porosity and microstructure.     

Effect of liquid reaction on the synthesis of Ti3SiC2 powder

Synthesis of Ti₃SiC₂ powder was carried out by heat treating powder mixtures of Si, TiC and coarse Ti (−150 μm) in a temperature range of 1000–1400 °C. The phase content of Ti₃SiC₂ in the synthesized powder was improved to 99% when heat treated at 1400 °C for 4 h. Ti–Si liquid reaction was found to occur above the binary eutectic temperature, and this liquid reaction is believed to have assisted the synthesis reaction of Ti₃SiC₂.     

Ni/nano-TiO2 composite electrodeposits: Textural and structural modifications

Nanocomposite coatings were obtained by electrochemical codeposition of TiO₂ nano-particles (mean diameter 21 nm) with nickel, from an additive-free Watts type bath. The electrodeposition of Ni-TiO₂ composites was carried out on a rotating disk electrode (RDE), by applying direct current. Pure Ni deposits were also produced under the same experimental conditions for comparison. The surface morphology, the crystallographic orientation of nickel matrix and the grain size of the deposits were investigated, along with the distribution and the percentage, of the embedded nano-particles in nickel matrix, as a function of pH, current density and concentration of TiO₂ nano-particles in the bath. The observed textural modifications of composite coatings are associated with specific structural modifications of Ni crystallites provoked by the adsorption-desorption phenomena occurring on the metal surface, induced by the presence of TiO₂ nano-particles. It has been observed that the presence of TiO₂ nano-particles favours the [1 0 0] texture of nickel matrix. Moreover, the codeposition of titania nano-particles with nickel was found to be favoured at low pH and low applied current values. As the titania incorporation percentage is increased, a considerable grain refinement in the nanometer region was revealed followed by an improvement of the quality of the nickel preferred orientation.