Sol-Gel Processed TiO2-Based Nano-Sized Powders for Use in Thick-Film Gas Sensors for Atmospheric Pollutant Monitoring

Sol-gel routes were used to prepare pure and 5 at% and 10 at% Ta- or Nb-dope TiO₂ nano-sized powders. The thermal decomposition behaviour of the precursors was studied using simultaneous thermogravimetric and differential thermal analysis (TG/DTA). X-ray diffraction (XRD) analysis showed that the powders heated to 400°C were crystalline in the anatase TiO₂ structure. The pure TiO₂ powder heated to 850°C showed the rutile structure. The addition of Ta and Nb inhibited the anatase-to-rutile phase transformation up to 950–1050°C. Ta was soluble in the titania lattice up to the concentration of 10 at%, while the solubility of Nb was 5 at%. Thick films were fabricated with these powders by screen printing technology and then fired for 1 h at different temperatures in the 650–1050°C range. Scanning electron microscopy (SEM) observations showed that the anatase-to-rutile phase transformation induces a grain growth of about one order of magnitude for pure TiO₂. The addition of Ta and Nb is effective to keep the TiO₂ grain size at a nanometric level even at 950°C, though grain growth was observed with increasing temperature. The gas-sensitive electrical response of the thick films were tested in laboratory, in environments with CO in dry and wet air. Conductance measurements showed a good gas response only for the nanostructured titania-based films. For field tests, the prototype sensors were placed beside a conventional station for atmospheric pollutant monitoring. The electrical response of the thick films was compared with the results of the analytical instruments. The same trend was observed for both systems, demonstrating the use of gas sensors for this aim.     

Sol-Gel Nanosized Semiconducting Titania-Based Powders for Thick-Film Gas Sensors

Pure, 5 at%, and 10 at% Ta- or Nb-doped TiO₂ nanosized powders were prepared by the sol-gel method. The powders heated to 400°C have the crystalline anatase structure. While the pure TiO₂ powder heated to 850°C has the rutile structure, the addition of Ta and Nb inhibited the anatase-to-rutile phase transformation at this temperature. Ta was soluble in the titania lattice up to the concentration of 10 at%, while the solubility of Nb was 5 at%. Thick films were fabricated with these powders by screen printing technology and then fired at 650°C and 850°C for 1 h. SEM observations showed that the anatase-to-rutile phase transformation induces a grain growth of about one order of magnitude for pure TiO₂. The addition of Ta and Nb is effective to keep the TiO₂ grain size at the nanometric level even at 850°C. Conductance measurements showed that a good gas response is observed only for the nanostructured titania-based films. The CO response of these materials is only slightly affected by humidity.     

The effect of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders

Mesoporous F⁻-doped TiO₂ powders were prepared by hydrolysis of titanium tetraisopropoxide (TTIP) in a mixed NH₄F-H₂O solution. Effects of F⁻ ion content and calcination temperatures on the phase composition and porosity of mesoporous titania were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and BET surface areas. The results showed the BET surface area (S_BET) of the pure and doped powders dried at 100°C ranged from 260 to 310 m²/g as determined by nitrogen adsorption. With increasing calcination temperatures, the S_BET values of the calcined titania powders decreased due to the increase in crystalline size. The pore size distribution was bimodal with fine intra-particle pore and larger inter-particle pore as determined by nitrogen adsorption isotherms. The peak pore diameter of intra-particle pore increases with increasing F⁻ ion content. At 700°C, all the titania powders exhibit monomodal pore size distributions due to the complete collapse of the intra-particle pores. The crystallization of anatase was obviously enhanced due to F⁻-doping at 400°C and 500°C. Moreover, with increasing F⁻ ion concent, F⁻ ions not only suppressed the formation of brookite phase at low temperature, but also prevented phase transition of anatase to rutile at high temperature.     

Phase composition and magnetic properties of niobium-iron codoped TiO2 nanoparticles synthesized in Ar/O2 radio-frequency thermal plasma

Nanoparticles of Nb⁵⁺-Fe³⁺ codoped TiO₂ with various Nb⁵⁺ concentrations (Nb/(Ti+Fe+Nb)=0-10.0 at%) and Fe³⁺ (Fe/(Ti+Fe+Nb)=0-2.0 at%) were synthesized using Ar/O₂ thermal plasma. Dopant content, chemical valence, phase identification, morphology and magnetic properties were determined using several characterization techniques, including inductively coupled plasma-optical emission spectrometer, X-ray photoelectron spectroscopy, X-ray diffraction, UV-vis diffuse reflectance spectrometer, field-emission scanning electron microscopy, transmission electron microscopy and SQUID commercial instrument. The XRD revealed that all the plasma-synthesized powders were exclusively composed of anatase as major phase and rutile. The rutile weight fraction was increased by the substitution of Fe³⁺ for Ti⁴⁺ whereas it was reduced by the Nb⁵⁺ doping. The plasma-synthesized Nb⁵⁺-Fe³⁺ codoped TiO₂ powders had intrinsic magnetic properties of strongly paramagnetic and feebly ferromagnetic at room temperature. The ferromagnetic properties gradually deteriorated as the Fe³⁺ concentration was decreased, suggesting that the ferromagnetism was predominated by the phase composition as a carrier-mediated exchange.     

Evolution of titania nanotubes-supported WOx species by in situ thermo-Raman spectroscopy, X-ray diffraction and high resolution transmission electron microscopy

Structural evolution of WO_x species on the surface of titania nanotubes was followed by in situ thermo-Raman spectroscopy. A total of 15 wt% of W atoms were loaded on the surface of a hydroxylated titania nanotubes by impregnation with ammonium metatungstate solution and then, the sample was thermally treated in a Linkam cell at different temperatures in nitrogen flow. The band characteristic of the WO bond was observed at 962 cm⁻¹ in the dried sample, which vanished between 300 and 700 °C, and reappear again after annealing at 800 °C, along with a broad band centered at 935 cm⁻¹, attributed to the v₁ vibration of WO in tetrahedral coordination. At 900 and 1000 °C, the broad band decomposed into four bands at 923, 934, 940 and 950 cm⁻¹, corresponding to the symmetric and asymmetric vibration of WO bonds in Na₂WO₄ and Na₂W₂O₇ phases as determined by X-ray diffraction and High resolution transmission electron microscopy (HRTEM). The structure of the nanotubular support was kept at temperatures below 450 °C, thereafter, it transformed into anatase being stabilized at temperatures as high as 900 °C. At 1000 °C, anatase phase partially converted into rutile. After annealing at 1000 °C, a core-shell model material was obtained, with a shell of ca. 5 nm thickness, composed of sodium tungstate nanoclusters, and a core composed mainly of rutile TiO₂ phase.     

The influence of cobalt doping on photocatalytic nano-titania: Crystal chemistry and amorphicity

Photocatalysts of nominal composition (Ti_1−xCo_x)O_2−δ with 0.001?x?0.05 were prepared via a sol-gel technique followed by air firing (200-1000 °C). The incorporation of cobalt inhibited crystal growth and slightly raised the anatase to rutile transformation temperature (∼700 °C). An amorphous component was invariably significant with the maximum content (41-53 wt%) appearing simultaneously with the removal of anatase, suggesting that rutile crystallizes via an aperiodic structure. While the introduction of cobalt shifted the apparent band gap to visible light energies this did not enhance performance as there was limited miscibility of cobalt in titania, non-catalytic secondary phases were present, and active Ti³⁺ sites were displaced by cobalt.     

Preparation and characterization of SiO2/TiO2 composite microspheres with microporous SiO2 core/mesoporous TiO2 shell

SiO₂/TiO₂ composite microspheres with microporous SiO₂ core/mesoporous TiO₂ shell structures were prepared by hydrolysis of titanium tetrabutylorthotitanate (TTBT) in the presence of microporous silica microspheres using hydroxypropyl cellulose (HPC) as a surface esterification agent and porous template, and then dried and calcined at different temperatures. The as-prepared products were characterized with differential thermal analysis and thermogravimetric (DTA/TG), scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption. The results showed that composite particles were about 1.8 μm in diameter, and had a spherical morphology and a narrow size distribution. Uniform mesoporous titania coatings on the surfaces of microporous silica microspheres could be obtained by adjusting the HPC concentration to an optimal concentration of about 3.2 mmol L⁻¹. The anatase and rutile phase in the SiO₂/TiO₂ composite microspheres began to form at 700 and 900 °C, respectively. At 700 °C, the specific surface area and pore volume of the SiO₂/TiO₂ composite microspheres were 552 and 0.652 mL g⁻¹, respectively. However, at 900 °C, the specific surface area and pore volume significantly decreased due to the phase transformation from anatase to rutile.     

Synthesis, characterization, and photocatalytic activity for hydrogen evolution of nanocrystalline mesoporous titania prepared by surfactant-assisted templating sol-gel process

Nanocrystalline mesoporous titania was synthesized via a combined sol-gel process with surfactant-assisted templating method, treated under various calcination conditions, and evaluated for its photocatalytic activity through photocatalytic hydrogen evolution from an aqueous methanol solution. In this synthetic method, applied surfactant template molecules functioned as both mesopore-forming and gelation-assisting agents. The resulting products were methodically characterized by TG-DTA, XRD, N₂ adsorption-desorption, diffuse reflectance UV-Vis spectra, SEM, and TEM analyses. The partial phase transformation from anatase to rutile occurred beyond calcination temperature of 600 °C and anatase-rutile transition kinetics was also investigated. The calcination conditions and crystalline phases existing in the products exerted significant effect on the photocatalytic hydrogen evolution activity. The activity of the synthesized titania treated under appropriate calcination conditions was considerably higher than that of commercial titania powders, Ishihara ST-01 and Degussa P-25. It is clearly seen that the introduction of mesopore into titania photocatalyst substantially improved the photocatalytic performance.     

Thermal and hydrothermal stability of flame hydrolytically synthesized SiO2/TiO2 mixed oxides

The phase stability of the two TiO₂ modifications (anatase and rutile) in fumed SiO₂/TiO₂ nano-composites (0–24.8 wt-% silica) under thermal and hydrothermal conditions was investigated by X-ray powder diffraction, transmission electron microscopy (TEM) and gas adsorption methods (BET). The results show that the phase transformation from anatase to rutile type of structure and the growth of anatase crystallites are significantly retarded by mixing small amounts of SiO₂ into TiO₂, while the specific surface area is maintained. The SiO₂/TiO₂-composites reveal a remarkable shift in the anatase to rutile transformation temperature from approx. 500 °C (pure TiO₂) to approx. 1000 °C (samples with SiO₂ contents of more than 10%). The rate of phase transformation from anatase to rutile is enhanced under hydrothermal conditions compared to conventional thermal treatment, e.g. pure titania (AEROXIDE^® TiO₂ P25) annealed under hydrothermal conditions (100 g/m³ absolute humidity, 4 h at 600 °C) had a rutile content of 85%, while the same specimens annealed in absence of humidity contained only 46% rutile. However, the difference in rate of phase transformation became less pronounced when the silica content in SiO₂/TiO₂-composites was further increased.TEM results showed that the surface of the anatase crystallites was covered with silica. This averts coalescence of anatase crystallites and keeps them under a critical size during the annealing process. When the crystal domains grew larger, a rapid conversion to rutile took place. The critical size of anatase crystallites for the phase transformation was estimated to be 15–20 nm.     

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer/anatase titanium oxide nanocomposites possessing photocatalytic activity even after calcination at 1000 °C

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R_F-(VM)_n-R_F] underwent the sol-gel reaction under alkaline conditions in the presence of anatase titanium oxide nanoparticles (an-TiO₂) in tetrahydrofuran to give the corresponding fluorinated oligomer/anatase titanium oxide nanocomposites [R_F-(VM-SiO₂)_n-R_F/an-TiO₂]. Crystalline structure of an-TiO₂ in the nanocomposites thus obtained was found to keep completely its structure without phase transformation to rutile even after calcination at 1000 °C, although crystalline structure of the original an-TiO₂ nanoparticles underwent a complete phase transformation to the rutile under similar conditions. Interestingly, R_F-(VM-SiO₂)_n-R_F/an-TiO₂ nanocomposites before and after calcination at 1000 °C exhibited the similar photocatalytic activity for the decolorization of methylene blue under UV light irradiation.     

Immobilization of yttrium over crystalline titania

A co-precipitation method was adopted for the immobilization of yttrium radioactive waste over crystalline titania. A high uptake of⁹¹Y was observed over the preformed hydrous titania. Weighable quantity of Y was coprecipitated with Ti(IV) hydroxide and a maximum of 38 wt% was found to be adsorbed. Mixed masses were calcined separately at 800 and 1000°C for 20 hours, and soxhlet leach tests at 97°C, repeated 7 times at an interval of 24 hours, showed the release of yttrium in the order of 10^–1 and 10^–2 g·m^–2·d^–1, respectively. X-ray powder diffraction analysis revealed that the yttrium was immobilized in the titania crystal lattice which suffered some structural changes with the formation of new mineral phase Y₂Ti₂O₇ which is accompanied by rutile and little quantity of anatase form of titania at 800°C, and only rutile form of titania at 1000°C.     

Kinetics study on phase transformation from titania polymorph brookite to rutile

TiO₂ is a polymorphic material of great scientific interest due to its semiconductor properties and uses in heterogeneous photocatalysis. Understanding the stability of the polymorphs is important for designing TiO₂-based photocatalysts and solar cells. Although the phase transformation of anatase→rutile has been well studied, there is only one published work on brookite→rutile to date. The brookite→rutile transformation has been studied in this work using natural material from the Magnet Cove igneous complex mechanically processed to several micrometers in size. The pure phase brookite is annealed from 800 to 900 °C without detection of the anatase polymorph. The transformation kinetics are described by both the standard first-order model, with an activation energy of E_a=411.91 kJ/mol, and the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, with an activation energy of E_a=492.13 kJ/mol. The rate parameter of the first-order model for the phase transformation is expressed as k=6.85×10¹⁴ exp(−49,451/T) s⁻¹ for the first-order model and k=4.19×10¹⁸ exp(−59,189/T) s⁻¹ using the JMAK model. The obtained activation energy is higher than that of brookite nano-crystals. Our results show that the JMAK model fits the kinetics data better than other models.     

Synthesis of anatase nanoparticles with extremely wide solid solution range and ScTiNbO6 with α-PbO2 structure

Anatase-type nanoparticles Sc_XTi_1−2XNb_XO₂ with wide solid solution range (X=0-0.35) were hydrothermally formed at 180 °C for 5 h. The lattice parameters a₀ and c₀, and the optical band gap of anatase gradually and linearly increased with the increase of the content of niobium and scandium from X=0 to 0.35. Their photocatalytic activity and adsorptivity by the measurement of the concentration of methylene blue (MB) that remained in the solution in the dark or under UV-light irradiation were evaluated. The anatase phase existed stably up to 900 °C for the samples with X=0.25-0.30 and 750 °C for that with X=0.35 during heat treatment in air. The phase with α-PbO₂ structure and the rutile phases coexisted in the samples with X=0.25-0.30 after heated at temperatures above 900-950 °C. The α-PbO₂ structure having composition ScTiNbO₆ with possibly some cation order similar to that seen in wolframite existed as almost completely single phase after heat treatment at temperatures 900-1500 °C through phase transformation from anatase-type ScTiNbO₆.     

水热法合成掺杂铁离子的小管径TiO2纳米管

碳纳米管这种一维结构的新材料的发现为物理、化学、材料科学和纳米科学开辟了全新的研究领域.近年来,非碳无机类富勒烯(Inorganic Fullerenelike,简称IF)纳米管也受到人们的广泛关注.     

Synthesis of visible-light reactive TiO2−xNy photocatalyst by mechanochemical doping

Yellowish TiO_2−xN_y was prepared by a novel mechanochemical nitrogen-doping method. The samples were prepared by a high-energy ball milling of P25 titania with different nitrogen sources such as hexamethylenetetramine, urea or ammonium carbonate, followed by calcination in air at 400 °C. The high mechanical energy accelerated the phase transformation of anatase to rutile, while the existence of the nitrogen reagents tended to block the transformation. The calcination treatment slightly increased the crystallinity of the prepared titania. The prepared powders possessed two absorption edges at around 400 and 540 nm and showed an excellent photocatalytic ability for the oxidation of nitrogen monoxide under visible light irradiation. Under the irradiation of visible light with wavelengths of >510 nm, nitrogen monoxide could be continuously removed by the nitrogen doped titania prepared from the P25 titania-hexamethylenetetramine mixture, while the powders prepared using urea and ammonium carbonate as nitrogen sources showed lower activities. This mechanochemical technique might be widely useful for doping oxides with nonmetallic elements.     

Phase-compositional control and visible light photocatalytic activity of nitrogen-doped titania via solvothermal process

Nitrogen-doped titania nanoparticles consisted of pure anatase, rutile and brookite phases were successfully prepared by a solvothermal process in TiCl₃-HMT (hexamethylenetetramine, C₆H₁₂N₄)-alcohol mixed solution. The powders were yellow or beige and showed excellent visible light absorption and photocatalytic ability for the oxidative destruction of nitrogen monoxide under irradiation of visible light of wavelength >510 nm.     

Preparation and Characteristics of Nb<Superscript>5+</Superscript>, Ta<Superscript>5+</Superscript>/TiO<Subscript>2</Subscript> Nanoscale Powders by Sol–Gel Process Using TiCl<Subscript>3</Subscript>

Nanoscale TiO₂ powders doping with niobium and tantalum were prepared using TiCl₃ as a source matter. Characterization of the materials was performed by Thermoanalys, particle size, XRD, BET, FTIR, Magnetic Susceptibility. The influence of niobium and tantalum ions on the phase transition was studied, the changes in the crystal size and microstain distributions obtained at 400C were analyzed. The results show that the substitutes of Nb^{5 +}, Ta^{5 +} for Ti⁴⁺ in the anatase structure cause distortions and improve to form rutile. When the dopant content is over certain molar percent, biphase reappears. The IR spectra and magnetic susceptibility indicate the Nb–Nb (or Ta–Ta) bonds along c-axis in rutile by two Nb^{5 +} (Ta^{5 +}) ions located in sites adjacent along the c-axis appear with the dopant content. The magnetic characteristics at rutile showed a weak paramagnetism.     

Effects of Ti Addition on Alumina/Titania Composite Aerogels Synthesized by Sol–Gel Process and Supercritical Ethanol Drying

Alumina/titania composite aerogels with different titania contents were synthesized by the sol–gel process and supercritical ethanol drying. The structures and morphologies of synthesized aerogels were analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and N₂ adsorption–desorption tests. Supercritical ethanol drying induced the crystallization of titania, which prompted the transformation of the structure from pseudoboehmite to γ‐Al₂O₃ . Reversely, alumina retarded the anatase‐to‐rutile transformation of titania. The content of titania significantly affected the structure and morphology of alumina/titania composite aerogels. A high content of titania (≥40%) resulted in the phase separation of titania particles, which grew to form the anatase phase octahedral particles with well‐developed facets. When the titania content was low, titania particles could be homogeneously dispersed in alumina particles to form spherical clusters with the poor crystallinity. Titania particles were in the anatase phase, and no rutile phase was formed until the temperature rose to 1000°C. In addition, titania addition resulted in a decrease in the specific surface area (SSA) of alumina aerogels because the SSA of titania was lower than that of alumina aerogels.     

Thermal properties of undoped, S-doped, Nb-doped, and S, Nb co-doped titania nanoparticles prepared by sol–gel method

One of the classic methods to extend the spectral response of a wide band gap titania semiconductor to visible light is impurity doping. This study has studied undoped, S-doped, Nb-doped, and S, Nb co-doped titania nanopowders prepared by sol–gel. The relationship between the doping conditions and the thermal stability, phase composition, crystallinity, morphology of particles, and the influence of dopant in similar conditions was investigated. Also the relationship between the dopant and the properties of titania nanosized powders, such as thermal stability, phase composition, crystallinity, morphology and size of particles, was investigated. Thermogravimetry coupled with differential thermogravimetry, X-ray diffraction, energy-dispersive X-ray spectroscopy, and scanning electron microscope was used for the characterization of the materials. During heating of the air dried samples, their chemical degradation took place giving rise to anatase phase.     

Characterization of brookite and a new corundum-like titania phase synthesized under hydrothermal conditions

Brookite rich samples were synthesized under hydrothermal conditions by using TiCl₃ as precursor. They also contained a new titanium oxide phase that has the same crystalline structure as Ti₂O₃, and is stable after annealing in air. Samples were characterized with X-ray powder diffraction, transmission electron microscopy and thermogravimetry. Crystalline phases were refined by using the Rietveld method, from which phase concentrations and atomic bond lengths were obtained as a function of sample annealing temperature. Samples contained brookite, anatase, rutile and the new corundum-like phase: Brookite's concentration was larger than 50 wt%, while the one of the corundum-like phase reached 20(6) wt%. The local symmetry and the atomic bond lengths of these two phases depended on the crystallite size; for both, there is a correlation between the evolution of the atomic bond lengths with temperature and their transformation into another phase. The hydrothermal conditions stabilized brookite, anatase, and the corundum-like phase at high temperature: This last phase was stable in air, even at 900°C.