Preparation and characterization of N–I co-doped nanocrystal anatase TiO2 with enhanced photocatalytic activity under visible-light irradiation

N–I co-doped TiO₂ nanoparticles were prepared by hydrolysis method, using ammonia and iodic acid as the doping sources and Ti(OBu)₄ as the titanium source. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and ultraviolet–visible diffuse reflection spectroscopy (UV–vis DRS). XRD spectra show that N–I–TiO₂ samples calcined at 673 K for 3 h are of anatase structure. XPS analysis of N–I–TiO₂samples indicates that some N atoms replace O atoms in TiO₂ lattice, and I exist in I⁷⁺, I⁻ and I⁵⁺ chemical states in the samples. UV–vis DRS results reveal that N–I–TiO₂ had significant optical absorption in the region of 400–600 nm. The photocatalytic activity of catalysts was evaluated by monitoring the photocatalytic degradation of methyl orange (MO). Compared with P25 and mono-doped TiO₂, N–I–TiO₂ powder shows higher photocatalytic activity under both visible-light (λ > 420 nm) and UV–vis light irradiation. Furthermore, N–I–TiO₂ also displays higher COD removal rate under UV–vis light irradiation.     

Preparation of high surface area LaTiO2N photocatalyst

Nanocrystalline LaTiO₂N with a surface area of 27.5 m²/g was synthesized by nitridation of amorphous La₂O₃/TiO₂ composite powder at 900 °C for 8 h using NH₃ as the reactant gas. X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) results revealed that the as-prepared LaTiO₂N nanocrystals had a mean diameter of about 30 nm. It was found that the absorption edge of the oxynitride is significantly red-shifted compared with that of La₂Ti₂O₇ as increasing the nitridation temperature. The UV–vis absorption spectra indicated that the synthesized oxynitrides displayed good light absorption properties not only in the ultraviolet light but also in the visible-light region.     

Structure characteristics and lithium ionic conductivity of La(0.57−2x/3)SrxLi0.3TiO3 perovskites

La_{(0.57–2x/3)}Sr _x Li_0.3TiO₃ perovskites were synthesised using a conventional solid-state reaction. Large Sr²⁺ ions partially substituting for La³⁺ ions were found to disturb the cubic perovskite structure and cause the superstructure lines to gradually decrease in the x-ray diffraction patterns and almost disappear when x = 0.12. On the contrast, there still exist superstructure diffraction spots in the electron diffraction pattern on microdomain when x = 0.12. The lithium ion conductivities of the compounds were improved in the range of 0 x 0.08, which does not obey the principle of the carrier concentration. An expansion of the unit cell and the disordering of La³⁺ (Sr²⁺), Li⁺ ions and vacancies in A sites could be a mechanism for the enhancement of the conductivity with Sr²⁺ doping.     

Electrical properties of BaSnO3 in substitution of antimony for tin and lanthanum for barium

Polycrystalline materials of BaSn_1–x Sb _x O_3– and Ba_1–y La _y SnO_3– were prepared. Substitutional solubilities of antimony for tin and lanthanum for barium, respectively, in BaSnO₃ were obtained to be x=0.18 for BaSn_1–x Sb _x O_3– and y<0.052 for Ba_1-y La _y SnO_3–. The X-ray photoemission spectroscopy measurements showed the valence of antimony and tin is mixed in our samples of BaSn_1–x Sb _x O_3–. At lower temperature, magnetic susceptibilities of BaSn_1–x Sb _x O_3– and Ba_1–y La _y SnO_3– satisfy the Curie law, indicating the existence of non-interacting localized electrons at the Sn⁴⁺ site, and forming a Sn⁴⁺+e^– state in these systems. By substitution of antimony and lanthanum in BaSnO₃, the conductive properties are semiconductor-like. To explain this conductive behaviour, three types of mechanism were taken into consideration.     

Study of La1−xMnO3−δ non-stoichiometry and defect structure using ESR and iodometry

The oxidation states of manganese in the La_1–xMnO_3– (x = 0.09–0.11) were investigated by electron spin resonance (ESR) and iodometry. The ESR analysis carried out at room temperature for the samples prepared in air revealed the presence of broad peaks at g = 2.0, considered to be relevant to Mn²⁺. It was also found that the intensity of the peak increased as lanthanum vacancy content increased. The average valence state of manganese, determined by iodometry, was approximately 3.2, and decreased by 1 as the lanthanum vacancy increased by 1. Similar trends were observed with the samples prepared at P _{o 2} = 1×10^–7. The results indicated that Mn²⁺ is stably present in the La_1–xMnO_3– having an average valence number exceeding 3.0. A series of experimental results with respect to the non-stoichiometry of La_1–xMnO_3– can be explained by assuming that Mn²⁺ is stabilized after forming a complex with a lanthanum vacancy and two oxygen vacancies.     

Rapid electroplating of photocatalytically highly active TiO2-Zn nanocomposite films on steel

Nanocomposite films consisting of TiO₂ and Zn with thickness of 10–15 m (TiO₂-Zn) have been electrodeposited on steel plates by rapid plating from a ZnSO₄-based bath (I _d > 10 A dm^–2). Upon addition of NH₄NO₃ to the bath (<0.3 g L^–1), the uptake of TiO₂ in the film significantly increased. Glow discharge optical emission spectrometry clarified that TiO₂ particles were incorporated throughout the film and the loaded amount increased near the surface. The first-order rate constant (k/h^–1) for gas-phase CH₃CHO oxidation was employed as an indicator of the photocatalytic activity. The k value for the TiO₂-Zn film prepared at I _d = 12 A dm^–2 (0.20 h^–1) was comparable to that for the sample from a ZnCl₂-based bath at I _d = 4 A dm^–2 (0.27 h^–1). X-ray diffraction measurements indicated that a TiO₂-ZnO nanocomposite layer was generated on the surface by the heat treatment in air at 673 K for 6 h. Consequently, the photocatalytic activity was further improved (k = 0.29 h^–1); this effect was explained in terms of the synergy of TiO₂ and ZnO in photocatalysis.     

Characterization of hydroxyapatite powders prepared by ultrasonic spray-pyrolysis technique

The hydroxyapatite (HAp) powder was prepared by the ultrasonic spray-pyrolysis technique; the characterization of the resulting powders was performed. Five kinds of the starting solutions with the Ca/P ratio of 1.67 were prepared by mixing Ca(NO₃)₂, (NH₄)₂HPO₄ and HNO₃; the concentrations of Ca²⁺ and PO₄ ^3– were in the ranges of 0.10 to 0.90 mol·dm^–3 and 0.06 to 0.54 mol·dm^–3, respectively. These solutions were sprayed into the heating zone to prepare the HAp powders. The heating zone was composed of two electric furnaces; the lower furnace was used for the evaporation of the solvent from the droplets (300–500°C) and the upper furnace for the pyrolysis of the precipitated metal salts (750–900°C). The easily sinterable HAp powder was prepared by spray-pyrolysing the solution with Ca²⁺ (0.50 mol·dm^–3) and PO₄ ^3– (0.30 mol·dm^–3) at the temperatures of 800°C (the upper furnaces) and 400°C (the lower furnaces). The resulting powder was composed of the spherical particles with diameters of 1 m or below. Even without the calcination and grinding operations, the relative densities of the compacts fired at 1150 and 1200°C for 5 h attained maxima 95%. The microstructure of the sintered compacts appeared to be uniform; the average grain size was 3 m. The activation energies for the grain growth of the sintered HAp compacts were 120 to 147 kJ · mol^–1 · K^–1.     

Nitrogen-containing aluminium titanate

In the Ti-Al-O-N system a phase isostructural to aluminium titanate but with expanded unit cell dimensions was observed. It was stable between 1400 and 1700 °C and has unit cell dimensions of a=0.3719 nm, b=0.9703 nm and c=0.9869 nm with a composition of Ti _1.00 ⁴⁺ Al _0.54 ³⁺ Ti _1.46 ³⁺ N _0.28 ^3– O _4.58 ^2– _0.14 Several samples were prepared by reaction sintering mixtures of TiN, Al₂O₃ and AlN powders at 1400 to 1470 °C for 4 h in a nitrogen atmosphere to maximize this phase. One specific advantage of the nitrogen-containing aluminium titanate over aluminium titanate is that the former is unchanged at 1150 °C in a nitrogen atmosphere whereas the latter decomposes. In the Al₂O₃-TiO₂ oxide system Al₂TiO₅ solid solution extends to approximately Al_0.75Ti_2.25O₅ at 1470 °C under the mildly reducing conditions of a graphite furnace. The unit cell volume increases linearly with the increasing replacement of Al³⁺ by Ti³⁺.     

Properties of Er3+-doped phosphate glasses and glass fibres and efficient infrared to visible upconversion

Some thermomechanical properties such as expansion, transition temperature and high-temperature viscosity of phosphate glasses with different P₂O₅ and BaO compositions have been measured. Absorption and fluorescence spectra of the phosphate glasses with different Er³⁺ doping have also been measured. The Er³⁺ doping concentration with respect to the maximal fluorescence intensity is 0.75 mol %. The attenuation of the fibre at a wavelength of 1.53 m is 12.8 db m^–1. Upconversion of 1.064 m NdYAG laser pulses into intense green 547 and 667 nm light in the 0.75 mol % Er³⁺-doped phosphate glass fibre has been achieved. The output power of the two fluorescence signals of green 547 nm and red 667 nm are 178 and 42 W, respectively, with an upconversion efficiency of 1.78×10^–2% and 4.2×10^–3% respectively.     

Phonon Modes in CMR Manganites at Elevated Temperatures

Phonon modes of the colossal magnetoresistance manganites La_0.7Ca_0.3MnO₃ and La_0.8Li_0.2MnO₃ have been investigated by far-infrared (100–700 cm^–1) reflectivity spectroscopy at elevated temperatures (300–800 K). The three principal optical phonons all move systematically to lower frequency as temperature increases, in accordance with a Grüneisen relationship. The La(Ca,Li)–(MnO₃) vibration (170 cm^–1) varies with cation mass as expected. The Mn–O stretching mode (580 cm^–1) has a higher frequency in the Li-doped compound than in the Ca-doped, whereas the O–Mn–O bending mode )340 cm^–1) occurs at the same frequency in each, demonstrating that the cation strongly influences the Mn–O– length but not the bond angle.     

Soft chemical synthesis and characterization of lithium nickel oxide electrode materials

Soft chemistry was used to prepare ordered nanophase Li_0.6NiO₂ electrode materials by completing the oxidation of Ni²⁺ to Ni³⁺ and/or Ni⁴⁺ species with H₂O₂ oxidant during solution reactions at 50–60 °C and evaporation at 105–150 °C rather than during sintering. Both elemental analysis and electron spectroscopy for chemical analysis (ESCA) results indicate that oxidation was completed. The deconvoluted ESCA spectra of nickel ions exhibited a semi-quantitative ratio of Ni⁴⁺Ni³⁺=6040 which presented no significant change with increase of sintering time. After sintering for up to 11 h at 700°C, ordered Li_0.61Ni_0.96O_2.0 ceramics were formed (R3m, a ₀=0.2837 nm, c ₀=1.417 nm). Distribution of the crystallite size was in the range of 80–200 nm. As sintering times were increased, the crystallite shapes exhibited a more distinct morphology, and the ordering degree of the cations was enhanced, while the conductivity was sharply enhanced up to 2.0×10^{–1 –1} cm^–1 at 30 °C. Compared to conventional ceramic and solution methods, the ordered nanophase Li_0.61 Ni_0.96O_2.0 ceramics was obtained at 700 °C with shorter sintering times ( 11 h).     

A study of the immobilization of strontium over crystalline titania

The immobilization of strontium over titania was carried out by the method of coprecipitation. From a preliminary study, an appreciable uptake (52.8%) of⁹⁰Sr was observed over preformed titania material. A weighable amount of strontium was coprecipitated with Ti(IV) hydroxide and a maximum of 34 wt% Sr was found to be adsorbed. The leachability of the mixed materials prepared by the addition of 250 and 400 mg Sr²⁺, calcined at 1000 °C, by soxhlet apparatus refluxing at 97 °C and repeated seven times at intervals of 24 h, was found to be of the order of 10^–9 and 10^–5 g cm^–2 d^–1, respectively. X-ray powder diffraction analysis revealed that strontium was immobilized in the crystalline matrix of rutile, which suffered some structural changes with the formation of new phases, SrTiO₃+Sr₂TiO₄ and SrTiO₃, respectively.     

Spin dynamics in the LTT phase of La-Sr cuprates as revealed by ESR

We present the results of the ESR study on Gd spin probes of the spin dynamics of the CuO₂ planes in the low temperature tetragonal (LTT) phase of La_2–xSr_xCuO₄ which is stabilized below 110 – 130 K by doping this compound by Eu. Instead of the Korringa like behaviour occurred in the orthorhombic (LTO) phase at higher temperatures, Gd³⁺ ESR linewidth H broadens considerably at low temperatures in the LTT phase. Maximal broadening of H is observed for the samples with suppressed superconductivity. The analysis of the data shows that the spin correlation length in the LTT phase rapidly increases at low temperatures and for non superconducting samples may exceed 100 lattice constants. Correspondingly, the frequency of the antiferromagnetic spin fluctuations decreases down to 10¹⁰ – 10¹¹sec^–1. It is argued that such extremely slow antiferromagnetic spin dynamics is a characteristic property of the magnetism in the LTT structural phase of La_2–xSr_xCu0₄.     

Synthesis of Sr- and Fe-doped LaGaO3 perovskites by the modified citrate method

Fine particle strontium and iron substituted lanthanum gallates La_1–x Sr _x Ga_1–y Fe _y O_3–, where x = 0.2, 0.4, and 0.6; y = 0.2, 0.4, 0.6, and 0.8, have been synthesized by a modified citrate method. The formation of these powders was confirmed by the X-ray powder diffraction (XRD) and the fine particle of La_0.6Sr_0.4Ga_0.2Fe_0.8O_3– was investigated by scanning electron microscopy (SEM), and particle size analysis. The single phase of La_0.8Sr_0.2Ga_0.4Fe_0.6O_3–, La_0.6Sr_0.4Ga_0.2Fe_0.8O_3–, and La_0.4Sr_0.6Ga_0.2Fe_0.8O_3– powders could be obtained both with and without calcination. The amount of the secondary phase increased when the amount of Sr in La_1–x Sr _x Fe_0.6Ga_0.4O_3– was more than 0.2 (x > 0.2) and the amount of Fe in La_0.6Sr_0.4Ga_1–y Fe _y O_3– and La_0.4Sr_0.6Ga_0.2Fe_0.8O_3– was less than 0.8 (y < 0.8). The results indicated that in the pH range of 1.36–9.27, the single phase of La_0.6Sr_0.4Ga_0.2Fe_0.8O_3– was formed without calcination and the pH had negligible effects on the structure and lattice parameter. The fine particle of these calcined powders (<4 m) was obtained with the average particle size 1.70 m at pH = 1.36 and with the average particle size between 0.56–0.60 m at pH range between 3.39–9.27, and with a lattice parameter about 3.9 Å.     

Synthesis of hydrous SnO2 and SnO2-coated TiO2 powders by the homogeneous precipitation method and their characterization

Hydrous SnO₂ and SnO₂-coated TiO₂ powders were synthesized by the homogeneous precipitation method using urea and the products were characterized by X-ray diffraction, thermogravimetry, differential thermal analysis, scanning electron microscopy and energy- dispersive X-ray microanalysis. Electrical conductivities were measured with an impedance analyser. Hydrous SnO₂ powder prepared under conditions without SO ₄ ^2– ions was a bulky product containing 75 wt% of water. The addition of SO ₄ ^2– ions to the solution changed bulky hydrous SnO₂ to a dense product; approximately spherical particles were obtained with an average particle size of 0.14 ± 0.03 m. with 13.5 wt % of absorbed water. Antimony-doped hydrous SnO₂ prepared under conditions with SO ₄ ^2– ions consisted of approximately spherical particles with an average particle size of 0.17 ± 0.04 m with 15.0 wt % of absorbed water. Hydrous SnO₂-coated TiO₂ powders with a good dispersion state and with various Sn/Ti ratios were prepared under conditions with SO ₄ ^2– ions. All the as-prepared coated powders were white, but the products doped with Sb³⁺ ions were turned to pale blue by heat treatment at 600° C for 1 h and their electrical conductivities increased by orders of about 3.0 in comparison with those of the other two.     

Thermal stabilization of aluminium titanate and properties of aluminium titanate solid solutions

Aluminium titanate has a near zero thermal expansion coefficient (=0.8×10^–6 °C^–1) in the range 20 to 1000 °C, nevertheless it decomposes below 1200 °C.The thermal stabilization of Al₂TiO₅ without altering its thermal expansion has been considered by partial substitution in the structure compound of Al³⁺ ions by Fe³⁺ ions.The solid solutions prepared by solid state reaction are in agreement with the general formula Al(1–x)₂Fe_2x TiO₅(0<x<0.2)The iron ions present in the crystal structure of Al₂TiO₅ act on its lattice parameters and bring about a catalytic effect in the formation of materials.Solid solutions show a strong thermal stability and a thermal expansion coefficient specially for the solid solution (x=0.1) which is not far from the Al₂TiO₅ value even after annealing for 300 h at 1000 °C.The mechanical properties of such materials corresponding to that solid solution present strength values lower than Al₂TiO₅ ones. After annealing, however, these are improved later due to a microcrystallization.     

The high-temperature thermal expansion of BiPbSrCaCuO superconductor and the oxide components (Bi2O3, PbO,CaO, CuO)

The thermal expansion of superconducting Bi_1.6Pb_0.4Sr₂Ca₂Cu₃Ox (BiPbSrCaCuO) and its oxide components Bi₂O₃, PbO, CaO and CuO have been studied by high-temperature dilatometric measurements (30–800°C). The thermal expansion coefficient for the BiPbSrCaCuO superconductor in the range 150–830°C is =6.4×10^–6K^–1. The temperature dependences of L/L of pressed Bi₂O₃ reveals sharp changes of length on heating (T ₁=712°C), and on cooling (T ₂=637°C and T ₃=577°C), caused by the phase transition monoclinic-cubic (T ₁) and by reverse transitions via a metastable phase (T ₂ and T ₃). By thermal expansion measurements of melted Bi₂O₃ it is shown that hysteresis in the forward and the reverse phase transitions may be partly caused by grain boundary effect in pressed Bi₂O₃. The thermal expansion of red PbO reveals a sharp decrease in L/L, on heating (T ₁=490°C), related with the phase transition of tetragonal (red, a=0.3962 nm, c=0.5025 nm)-orthorhombic (yellow, a=0.5489 nm, b=0.4756 nm, c=0.5895 nm). The possible causes of irreversibility of the phase transition in PbO are discussed. In the range 50–740°C the coefficient of thermal expansion of pressed Bi₂O₃ (_m=3.6 × 10^–6 and _c=16.6×10^–6K^–1 for monoclinic and cubic Bi₂O₃ respectively), the melted Bi₂O₃ (_m=7.6×10^–6 and _c=11.5×10^–6K^–1), PbO (_t=9.4×10⁶ and _or=3.3×10^–6K^–1 for tetragonal and orthorhombic PbO respectively), CaO (=6.1×10^–6K^–1) and CuO (=4.3×10^–6K^–1) are presented.     

Effect of Oxygen-Deficiency of CuO2 Plane on the Structure, Magnetism, and Transport Properties

Polycrystalline samples La_{2 – x} Sr _x CuO_{4 –} (0.06 x 1.0) and the corresponding vacuum annealed samples were investigated systematically by means of XRD, infrared (IR) spectra, ESR, and resistivity. It is found that the doping of Sr and the oxygen vacancies in CuO₂ planes show different effects on the lattice parameters a and c, and the changes of a and c of La_{2 – x} Sr _x CuO_{4 –} samples (x 0.2) rest with the cooperation of the two factors. The two high frequency IR vibration modes at 500 and 689 cm^–1, which are referred to the vibrations of apical oxygen and planar oxygen, are analyzed in detail. The disappearance of the mode at 689 cm^–1 is interpreted in terms of the screened effect of charge carriers in CuO₂ planes. ESR results indicate that oxygen deficiency of CuO₂ layers not only decreases carrier concentration, but also destroys the antiferromagnetic spin correlation or spin fluctuation and results in localized Cu²⁺ spins. The effect of localized Cu²⁺ spins (or spin scattering) on the superconductivity and transport properties is discussed in the text.     

Characterization of (Pb,La) TiO3 thin films prepared by the sol-gel method

Pb_(1–1.5x)La_xTiO₃ thin films were synthesized by the sol-gel spin-coating technique. The films became crystallized when the spin-coated films were annealed at 600 °C and at higher temperature, and became amorphous when annealed at 550 °C. The breakdown voltage, V _B, was recorded at around 30 V for 600–650 °C annealed films and varied only slightly with the composition. The V _B value of the amorphous films was observed to be higher than that of the crystalline films. The ferroelectric properties of both the amorphous and crystalline films were found to be similar. The dielectric constant, charge storage density and optical index of refraction of the films were _r =5–20, Q _c=0.12–0.54 C cm^–2 and n=1.6–2.3, respectively. They all increased moderately with La³⁺ content in the films. One possible reason why the ferroelectric properties are not modified as the amorphous films crystallize, may be that the octahedra are equilateral, whether the films are amorphous or crystalline. Additionally, a possible cause which lowers the breakdown voltage in crystalline film, is the formation of lead vacancies due to lead loss. The electrical properties of films coated on bare silicon become significantly lowered due to interdiffusion between films and substrate. The diffusion of Si⁴⁺ ions into-the films can be prevented by coating SrTiO₃ on the silicon substrate as a buffer layer. The charge storage capacity consequently becomes substantially enhanced.