Photocatalytic degradation of dodecyl-benzenesulfonate over TiO2–Cu2O under visible irradiation

A series of TiO₂–Cu₂O mixed oxides were prepared by the hydrolysis of titanium butoxide and reduction of copper acetate with hydrazine. These composite oxides were characterized by X-ray diffraction (XRD), inductively coupled plasma spectrometry (ICP), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption and UV–vis techniques. Photocatalytic degradation of dodecyl-benzenesulfonate (DBS) under visible irradiation was performed, and effects of composition of catalysts and reaction conditions were studied. It was observed that TiO₂–Cu₂O composite oxides exhibited better photocatalytic activity than Cu₂O or TiO₂ alone. Among these composite oxides, the 5%TiO₂–Cu₂O displayed the highest activity, and the degradation percentage of DBS and COD reached 97.3% and 65%, respectively. In addition, it was found that the decomposition of DBS followed the first-order kinetics and the adsorption of DBS followed the Langmuir model. Oxygen in solution played a vital role in the elimination of COD.     

Weighting the influence of TiO2 anatase/brookite ratio in TiO2–Ag porous nanocomposites on visible photocatalytic performances

Nanocomposites based on TiO₂ aerogel and Ag nanoparticles have been successfully obtained through different synthesis methods and their specific surface areas have been determined by N₂ sorption (BET method). The photocatalytic potential for salicylic acid degradation has been evaluated. It was found that under visible light irradiation, all synthesized nanocomposites exhibit higher photocatalytic activity than the commercially available Aeroxide P25. By correlating the structural parameters with the photocatalytic performances, it has been found that the Ag nanoparticles and brookite phase presence alongside the anatase play important roles on the visible photocatalysts behavior. For the Ag containing samples with mixed anatase–brookite phases, it has been observed that the visible photocatalytic performance decreases with the increase in brookite crystalline phase content. On the other hand, the addition of Ag nanoparticles results, as expected, in a clear enhancement of the visible photocatalytic activity.     

SAXS/DSC/WAXD study of TiO2 nanoparticles and the effect of γ-radiation on nanopolymer electrolyte

Nanostructured polymer electrolytes are very attractive materials for components of batteries and opto-electronic devices. (PEO)₈ZnCl₂ polymer electrolytes and nanocomposites were prepared using Poly(ethylene oxide) (PEO) γ-irradiated with a selected dose of 529 kGy and with an addition of 10% of TiO₂ nanograins. The influence of the added nanosize TiO₂ grains on the polymer electrolytes and the effect of the γ-radiation from a Co-60 source were studied by small-angle X-ray scattering (SAXS) simultaneously recorded with differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) at the synchrotron ELETTRA. Infrared (IR) and impedance spectroscopy (IS) were also performed [1]. It was shown by previously performed IS that the room temperature conductivity of the nanocomposite polymer electrolyte increased more than two times above 65 °C, relative to pure composites of PEO and salts. We observed all changes between 20 °C and 100 °C for treated and as prepared polymer electrolyte in the SAXS, DSC and WAXD spectra and especially during the phase transition to the super-ionic phase at 65 °C [2] and [3]. The SAXS/DSC measurements yielded insight into the temperature-dependent changes of the grains of the electrolyte as well as into the differences due to different heating and cooling rates. The crystal structure and the melting and crystallization temperatures of the nanosize grains were revealed by the simultaneous WAXD measurements.     

Microwave dielectric properties of BaO–TiO2–TeO2 ternary system

Besides the applications as optical functional materials, tellurium oxides also have attracted interest as microwave dielectric materials. Most TeO₂-based binary and ternary system have large negative temperature coefficient of resonant frequency (τ_f), which is not compatible for the low-temperature cofired ceramic. To compensate τ_f close to zero, two single-phase predecessors of BaTe₄O₉ and TiTe₃O₈ are synthesized in air at 530–560 and 620–680 °C, respectively. The two predecessors show exceptional dielectric properties and their τ_f are opposite. The BaO–TiO₂–TeO₂ ternary system compounds are investigated by adjusting the ratio of BaTe₄O₉ and TiTe₃O₈ and sintered at 520–580 °C to develop the microwave properties and compensate the τ_f. After sintered at 560 °C, the ceramic sample with the composition of 0.47BaTe₄O₉–0.53TiTe₃O₈ exhibits a dielectric permittivity of 28, a Q × f-value of 12,200 GHz, and a τ_f of 4.0 ppm/°C measured at 10 GHz.     

Influence of platinum nano-particles on the photocatalytic activity of sol–gel derived TiO2 films

Different 1-step or 2-step photo-platinization methods have been implemented to load sol–gel TiO₂ photocatalytic thin films with platinum nano-particles. These methods enable flexible variations in the amount of loaded particles, and they strongly influence the structure and size of these particles and the morphology of derived platinized films. The photocatalytic activity of platinized films has been studied. It is shown that optimal platinization conditions allow envisaging thin film photocatalysts with enhanced properties. Best performances are reached when the films are loaded with platinum particles for 30 or 60 min using a 1-step platinization method, which yields photocatalytic activities about 4 times greater than that of non-platinized films. Photocatalytic activity differences induced by the 1-step or 2-step photo-platinization methods are discussed in relation to the amount of loaded platinum together with structural and morphological features.     

Annealing effect on the performance of RuO2–Ta2O5/Ti electrodes for use in supercapacitors

The preparation of RuO₂–Ta₂O₅/Ti electrodes, by dip-coating, for use in supercapacitors was investigated. The stability and specific capacitance of the electrodes annealed at various temperatures was examined. The results show that highly stable electrodes with a specific capacitance of 170 F g RuO₂⁻¹ were obtained at approximately 250 °C, while electrodes with a lower capacitance (130 F g RuO₂⁻¹) were obtained at 300 °C. The annealing time needed to obtain a stable RuO₂–Ta₂O₅/Ti electrode at various temperatures correlates well with the Arrhenius’ law: with the activation energy (E) of the annealing reactions for the electrodes being estimated as 73.5 kJ mol⁻¹. SEM images of the electrodes show the coating films to have rough surface morphology with cracks 2–6 μm in width. XRD data indicate that the coating films obtained are composed of crystalline RuO₂ and amorphous tantalum oxide.     

Dielectric properties and microstructure of TiO2 modified (ZnMg)TiO3 microwave ceramics with CaO–B2O3–SiO2

The low-fired (ZnMg)TiO₃–TiO₂ (ZMT–TiO₂) microwave ceramics using low melting point CaO–B₂O₃–SiO₂ as sintering aids have been developed. The influences of Mg substituted fraction on the crystal structure and microwave properties of (Zn_1−x Mg _x )TiO₃ were investigated. The result reveals that the sufficient amount of Mg (x ≥ 0.3) could inhibit the decomposition of ZnTiO₃ effectively, and form the single-phase (ZnMg)TiO₃ at higher sintering temperatures. Due to the compensating effect of rutile TiO₂ (τ_f = 450 ppm/°C), the temperature coefficient of resonant frequency (τ_f) for (Zn_0.65Mg_0.35)TiO₃–0.15TiO₂ with biphasic structure was adjusted to near zero value. Further, CaO–B₂O₃–SiO₂ addition could reduce the sintering temperature from 1150 to 950 °C, and significantly improve the sinterability and microwave properties of ZMT–TiO₂ ceramics, which is attributed to the formation of liquid phases during the sintering process observed by SEM. The (Zn_0.65Mg_0.35)TiO₃–0.15TiO₂ dielectrics with 1 wt% CaO–B₂O₃–SiO₂ sintered at 950 °C exhibited the optimal microwave properties: ε ≈ 25, Q × f ≈ 47,000 GHz, and τ_f ≈ ± 10 ppm/°C.     

Adsorption and photocatalysis of nanocrystalline TiO2 particles prepared by sol–gel method for methylene blue degradation

Titanium dioxide (TiO₂) powders were synthesized by using TiO₂ colloidal sol prepared from titanium-tetraisopropoxide (TTIP) and used as a starting material by applying the sol–gel method. The effect of aging times and temperatures on physical and chemical properties of TiO₂ sol particles was systematically investigated. The results showed that the crystallinity and average particle size of TiO₂ can be successfully controlled by adjusting the aging time and temperature. The samples after calcination of TiO₂ powders were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and nitrogen adsorption measurements. In addition, the photocatalytic activity of synthesized TiO₂ powders was evaluated by studying the degradation of 10 ppm aqueous methylene blue dye under 32 W high pressure mercury vapor lamp with 100 mg of TiO₂ powders. The highest photocatalytic activity was observed in TiO₂ powder synthesized at 90 °C for 0 h attributed to the presence of anatase and rutile phases in an 80:20 ratio.     

Highly active sulfided CoMo catalysts supported on (ZrO2–TiO2)/Al2O3 ternary oxides

(ZrO₂–TiO₂)/Al₂O₃ ternary oxide at 20 mol% Al₂O₃ (80% ZrO₂–TiO₂, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl₂·8H₂O) and titanium (TiCl₄) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S_g = 387 m² g⁻¹, V_p = 0.74 ml g⁻¹, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO₂–TiO₂ deposition over alumina substrate resulted in decreased proportion of Mo⁶⁺ species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H₂S/H₂ at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS₂ phase (at 2.8 atoms/nm²), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO₂–TiO₂)/Al₂O₃ and the corresponding Al₂O₃-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo⁶⁺ over the oxidic impregnated precursor with (ZrO₂–TiO₂)/Al₂O₃ ternary carrier resulted, after sulfiding, in increased amount of MoS₂ phase that could be efficiently promoted by cobalt.     

TiO2光催化还原CO2研究进展

简要综述了近年来用于光催化还原CO2的Ti O2材料,包括单一Ti O2光催化材料、金属负载型Ti O2材料、半导体复合Ti O2光催化材料、有机光敏化剂修饰Ti O2光催化材料、Ti O2分子筛光催化材料及其他Ti O2光催化材料,总结了各种Ti O2材料光催化CO2的优势,并介绍了其相应的光催化反应机理。     

Synthesis of (Zn,Mg)TiO3–TiO2 composite ceramics for multilayer ceramic capacitors

(Zn_0.8Mg_0.2)TiO₃–xTiO₂ composite ceramics has been prepared via the solid-phase synthesis method. TiO₂ was employed to tone temperature coefficient of resonant frequency (τ_f) and stabilize hexagonal (Zn, Mg)TiO₃ phase. 3ZnO–B₂O₃ was effective to promote sintering. The movement of grain boundary was obvious because of the liquid phase sintering. The scanning electron microscope (SEM) photographs and energy dispersive spectrometer (EDS) patterns showed that segregation and precipitation of dissociative (Zn, Mg)TiO₃ grains occurred at grain boundary during sintering. SnO₂ was used as inhibitor to prevent the grain boundary from moving. The dielectric behaviors of specimen strongly depended on structural transition and microstructure. We found that 1.0 wt.% 3ZnO–B₂O₃ doped (Zn, Mg)TiO₃–0.25TiO₂ ceramics with 0.1 wt.% SnO₂ additive displayed excellent dielectric properties (at 1000 °C): ?_r = 27.7, Q × f = 65,490 GHz (at 6.07 GHz) and τ_f = −8.88 ppm °C⁻¹. The above-mentioned material was applied successfully to make multilayer ceramic capacitors (MLCCs), which exhibited an excellent electrical property. The self-resonance frequency (SRF) and equivalent series resistance (ESR) of capacitor decreased with capacitance increasing, and the quality factor (Q) of capacitor reduced as frequency or capacity increased.     

Synthesis and properties of glasses in the K2O–SiO2–Bi2O3–TiO2 system and bismuth titanate (Bi4Ti3O12) nano glass–ceramics thereof

Glasses were prepared by the melt-quench technique in the K₂O–SiO₂–Bi₂O₃–TiO₂ (KSBT) system and crystallized bismuth titanate, BiT (Bi₄Ti₃O₁₂) phase in it by controlled heat-treatment at various temperature and duration. Different physical, thermal, optical, and third-order susceptibility (χ³) of the glasses were evaluated and correlated with their composition. Systematic increase in refractive index (n) and χ³ with increase in BiT content is attributed to the combined effects of high polarization and ionic refraction of bismuth and titanium ions. Microstructural evaluation by FESEM shows the formation of polycrystalline spherical particles of 70–90 nm along with nano-rods of average diameter of 85–90 nm after prolonged heat treatment. A minor increase in dielectric constants (ε_r) has been observed with increase in polarizable components of BiT in the glasses, whereas a sharp increase in ε_r in glass–ceramics is found to be caused by the formation of non-centrosymmetric and ferroelectric BiT nanocrystals in the glass matrix.     

An investigation on the reaction mechanism of LiAlH4–MgH2 hydrogen storage system

The mechanism and hydrogen absorption/desorption properties of LiAlH₄ + xMgH₂ (where x = 1, 2.5, and 4) composites have been investigated. With the combination of MgH₂ and LiAlH₄ by mechanical grinding, initial decomposition temperatures of the mixtures can be reduced by about 50 °C. Mechanical grinding treatment makes MgH₂ react with LiAlH₄ to release a certain amount of hydrogen. The final resultants of the composites after thermal decomposition contain Al₁₂Mg₁₇. Intermetallic Al₁₂Mg₁₇ hydrogenated into Al₂Mg₃, MgH₂ and Al firstly, intermediate Al₂Mg₃ then transforms into MgH₂ and Al in the subsequent hydriding process. Hydrogenation of intermediate Al₂Mg₃ is supposed to occur synchronously to that of Al₁₂Mg₁₇, therefore demarcation of the two hydrogenation processes is ambiguous. Al₁₂Mg₁₇ can be totally recovered by complete dehydriding. Formation of Al₁₂Mg₁₇ alters the reaction pathway of LiAlH₄ + xMgH₂ (where x = 1, 2.5, and 4) systems and improves their thermodynamic properties. The dehydrogenation process of LiAlH₄ + xMgH₂ (x = 1, 2.5, and 4) composites contain two stages, their maximum desorption capacity reaches 7.46 wt.%.     

Glass formation and third-order optical nonlinear characteristics of bismuthate glasses within Bi2O3–GeO2–TiO2 pseudo-ternary system

Glass-forming region of Bi₂O₃–GeO₂–TiO₂ (BGT) pseudo-ternary system was determined by using melt-quench method. A series of high transparent glass samples were selected and their structural characteristics were investigated by FT-IR and Raman spectra. By employing Z-scan and optical Kerr shutter techniques with femtosecond laser pulses as excitation source, third-order optical nonlinearities (TON) of the BGT glasses as well as the TON response time were investigated at wavelength of 800 nm. The ultrafast nonlinear response and high figure of merit suggest great potentials of BGT glasses in applications of all-optical switching or related optical devices.     

Innovative one-step immobilization of TiO2 on polymer material by the sol–gel method under IL/MW conditions

An innovative one-step immobilization of titanium dioxide (TiO₂) nano-particles on organic polymer (PMMA) substrate at ambient condition is reported in this article. This immobilization can be achieved by the sol–gel method under ionic liquid/microwave heating conditions. In this method, a sol–gel reaction is conducted at specific sites of the polymer surface. These sites are the tiny cavities of the rough surface resulting from the softening and swelling effect of an alcohol, such as isopropyl alcohol, on the polymer surface under microwave irradiation. The roughness of the polymer surface is an important factor for the effective immobilization. In addition, ionic liquid can induce low temperature surface anatase crystallization of immobilized titanium dioxide in a short time. From the field emission scanning electron microscopy and energy dispersive spectroscopy observation, the TiO₂ particles could be effectively immobilized on the PMMA substrate. Raman spectra analysis data showed that the immobilized TiO₂ was anatase phase. The experimental data also shows that the immobilized TiO₂ prepared by this novel method has good immobilization stability and photocatalytic water treatment performance.     

Low-temperature sintering and microwave dielectric properties of 5Li2O–0.58Nb2O5–3.23TiO2 ceramics

The effect of B₂O₃ addition on the sintering, microstructure and the microwave dielectric properties of the 5Li₂O–0.58Nb₂O₅–3.23TiO₂ (LNT) ceramics have been investigated. It is found that the LNT ceramics could be sintered well at ∼880 °C with low-level doping of B₂O₃ (≤2 wt.%). Only Li₂TiO₃ solid solution (Li₂TiO₃ss) crystal structure could be detected for all the ceramics with various amounts of B₂O₃ addition from the X-ray diffraction (XRD) results. And interestingly, two phases with different color in SEM images are observed in B₂O₃-doped LNT ceramics. EDS results suggest that the two different phases are two Li₂TiO₃ss phases with different amount of Nb. In addition, there is no much degradation in the microwave dielectric properties with the B₂O₃ adding. In the case of 0.5 wt.% B₂O₃-doped samples sintered at 880 °C, good microwave dielectric properties of ?_r = 22, Q × f = 32,000 GHz, τ_f = 9.5 ppm °C⁻¹ are obtained.     

A heterostructured SnO2–TiO2 thin film prepared by Langmuir–Blodgett technique

SnO₂–TiO₂ heterostructure films were prepared through Langmuir–Blodgett (LB) route. LB films of octadecyl amine (ODA)–titanyl oxalate multilayer deposited on Si (100) and decomposed at 600 °C showed rutile and anatase phases of ultrathin TiO₂ film. Subsequently, multilayer LB film of ODA–stannate deposited on the pre deposited TiO₂ film after decomposition at 600 °C resulted in thin SnO₂ films on the TiO₂ thin film. The phase analysis of the SnO₂–TiO₂ film showed cassiterite phase of SnO₂ as well as the rutile/anatase mixture of TiO₂ indicating a SnO₂–TiO₂ heterostructured film. Surface morphology of the pure TiO₂ film and SnO₂–TiO₂ film were analyzed by using AFM. Electrical characterization by AC impedance analysis suggested SnO₂–TiO₂ heterostructure formation. DC current voltage measurement showed increase in photocurrent indicating visible light absorption and efficient charge separation under the sunlight type radiation.     

Fabrication of light absorbing TiO2 μ-donuts

TiO₂ µ-donuts were fabricated on glass and silicon by sol-gel technique using a mask of PMMA nanopillars created by removing PS from a spin-coated composite polymer of PS and PMMA. X-ray diffraction confirmed the anatase TiO₂ phase. X-ray photoelectron spectra showed signals from Ti 2p_3/2 at 458.8 eV and O 1s at 530.4 eV confirming presence of TiO₂. The heights and diameters of the TiO₂ µ-donuts are ~ 353 nm and ~ 2.8 µm, respectively as revealed by atomic force microscopy. UV-vis absorption spectra of TiO₂ µ-donuts showed an unusual light absorption at ~ 524 nm making its potential use in solar-cell applications.