Ligand-assisted hydrothermal synthesis of ZnWO4 rods and their photocatalytic activities

ZnWO₄ rods were prepared using a ligand-assisted hydrothermal method with ZnCl₂ and Na₂WO₄ in the presence of various amines as ligands for zinc ions. The choice of ligand was found to play an important role in the formation of ZnWO₄ rods. The aspect ratio of the ZnWO₄ rods increased with increasing ligand strength. XRD and HRTEM confirmed that the ZnWO₄ rods grow along the [1 0 0] direction. The photochemical activities of the ZnWO₄ rods for the decomposition of Rhodamine 6G were examined. The photocatalytic activity was found to depend on the aspect ratio of the ZnWO₄ rods.     

Synthesis, characterization and photocatalytic properties of nanosized Bi2WO6, PbWO4 and ZnWO4 catalysts

Nanosized Bi₂WO₆, PbWO₄ and ZnWO₄ photocatalysts were synthesized by a mild hydrothermal crystallization process. The physical and photophysical properties of the catalysts were characterized by X-ray diffractometry, Brunauer-Emmet-Teller surface area and porosity measurements, transmission electron microscopy, Raman spectra, and diffused reflectance spectroscopy. The rhodamine-B photodegradation in aqueous medium was employed as a probe reaction to test the photoactivities of the as-prepared samples under four irradiation wavelengths. Bi₂WO₆ not only presented the photocatalytic activity in the wide spectral scope, including UV and visible light but also exhibited the strong photosensitized capability to transform RhB under visible light irradiation (λ > 490 nm). ZnWO₄ only displayed relatively high photoactivity under UV irradiation. However, PbWO₄ showed poor photoactivity under any light irradiation. On the basis of the calculated density functional theory (DFT), the photocatalytic mechanisms were discussed.     

Growth and characterization of non-linear optical crystal Cd3Zn3B4O12

Cd₃Zn₃B₄O₁₂ polycrystals were synthesized by solid-state and wet chemical reaction methods. Cd₃Zn₃B₄O₁₂ single crystals with millimeter grade were grown from the self-flux B₂O₃ (Cd:Zn:B = 1:1:1.5); and larger crystals were obtained from the PbO-0.85PbF₂ fluxes easily. As-grown crystals were characterized by differential scanning calorimetry and thermogravimetric, X-ray diffraction, infrared and Raman spectral analysis, respectively. The non-linear optical coefficient of the Cd₃Zn₃B₄O₁₂ crystal is 2.6 times as large as that of KH₂PO₄ crystal. Chemical etching shows that this crystal is very stable in neutral solution and not hygroscopic in air at room temperature.     

Crystal growth and spectral properties of pure and Co-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

Fabrication and photocatalysis of mesoporous ZnWO4 with PAMAM as a template

Mesoporous ZnWO₄ was prepared with the template of PAMAM. The as-formed samples were characterized by X-ray diffraction (XRD), nitrogen absorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy (DRS). It is found that the size of pore is in the range of 5-22 nm and that the porosity of ZnWO₄ is composed of aggregated ZnWO₄ nanoparticles. The photocatalytic activities towards degradation of rhodamine B (RhB) and malachite green (MG) under UV light has been investigated. The formation mechanism of mesoporous structures is proposed.     

沉淀法制备CaSO4:Eu和CaSO4:Dy荧光体及发光性能的研究

采用传统的液相沉淀法制备了CaSO4:Eu和CaSO4:Dy粉体,研究并对比了产品的光致发光性能.光谱测试表明,CaSO4:Eu呈近紫外窄带发射.Dy3 掺杂碱土金属硫酸盐因基质不同,发射带有所不同,以CaSO4为基质,Dy3 占据高对称的格位,具有反演对称中心,发射光谱以蓝光发射为主.     

Growth and spectral properties of Cr:KAl(MoO4)2 crystal

The Cr³⁺:KAl(MoO₄)₂ single crystal was grown by top seeding solution growth method (TSSG). Based on the absorption and emission spectra, the crystal field strength Dq, the Racah parameters B and C, the effective phonon energy ?ω and the Huang-Rhys factor S were calculated: Dq = 1494.8 cm^− 1, B = 585.5 cm^− 1 and C = 3049 cm^− 1, ?ω = 373.8 cm^− 1 and the Huang-Rhys factor S = 3.74, respectively. The value Dq/B = 2.55 indicates that Cr³⁺ ion occupies the strong crystal field site in KAl(MoO₄)₂ crystal. A comparison of crystal field parameters for Cr³⁺:KAl(MoO₄)₂ with other Cr³⁺-doped crystals was presented. The results of spectral measurement show that Cr³⁺:KAl(MoO₄)₂ may be a potential candidate for broadband laser applications.     

Characterizations and properties of Eu-doped ZnWO4 prepared via a facile self-propagating combustion method

ZnWO₄ and Eu³⁺-doped ZnWO₄ were prepared for the first time via a facile self-propagating combustion method. The structure, morphology and luminescence of the as-prepared ZnWO₄ and Eu³⁺-doped ZnWO₄ were characterized. The photoluminescent property of Eu³⁺-doped ZnWO₄ complexes indicated an energy transfer from WO₄²⁻ groups to Eu³⁺ and suggested an effective doping of Eu³⁺ into the lattice of ZnWO₄. The photocatalytic activity of ZnWO₄ and Eu³⁺-doped ZnWO₄ was investigated by the photodegradation of rhodamine B (RhB). Eu³⁺-doped ZnWO₄ showed enhanced photocatalytic activity in the photodegradation of RhB.     

Growth and spectral properties of Er:NaGd(WO4)2 crystal

A high optical quality Er³⁺-doped NaGd(WO₄)₂ single crystal with dimensions of ∅18 × 50 mm³ has been grown using the Czochralski method. The structure of the grown crystal was proved by X-ray powder diffraction. The accurate concentration of Er³⁺ ion in the crystal was measured. The absorption spectra, fluorescence spectra and fluorescence lifetime of the crystal were measured at room temperature. Green up-conversion luminescence has been observed when the crystal is excited at 965 nm.     

Optical properties of Nd:NaLa (WO4)2 single crystal

Nd³⁺-doped NaLa(WO₄)₂ single crystal with a dimension of 20 mm × 40 mm and a good optical quality was grown by Czochralski method. The polarized absorption spectra and emission spectra were measured at room temperature. The absorption cross-section and emission cross-section were presented. The Judd–Ofelt theory, extended to anisotropic system, has been applied to evaluate the intensity parameters Ω_t (t = 2, 4, 6), radiative transition rates A, radiative lifetimes τ_R and fluorescent branching ratios β. The calculated radiative lifetime was compared with the experiment data for the ⁴F_3/2 emitting level. All spectral features are strongly affected by an inhomogeneous broadening connected with the ‘disordered crystal’ character of the title compound.     

Growth and optical properties of Er,Yb:YAl3(BO3)4 crystal

Single crystal of erbium, ytterbium-codoped yttrium aluminum tetraborate Er,Yb:YAl₃(BO₃)₄(Er,Yb:YAB) has been grown by the flux method. The absorption spectrum in the visible and NIR regions of Er,Yb:YAl₃(BO₃)₄ crystal are measured at room temperature and fluorescence spectrum of Er,Yb:YAl₃(BO₃)₄ crystal are also measured at room temperature, excited by 976 nm laser. Not only the strong NIR emission peaks located at 1548 nm was observed, but also the visible up-conversion luminescence has been found. The specific heat of the Er/Yb:YAB crystal at room temperature is 0.81 J/g °C.     

CuBi2O4 single crystal nanorods prepared by hydrothermal method: Growth mechanism and optical properties

The synthesis of copper bismuth oxide (CuBi₂O₄) nanorods with single crystal structure by hydrothermal method is first reported here. The prepared CuBi₂O₄ nanorods are characterized by X-ray diffractometer, scanning electron microscopy, transmission electron microscopy (TEM) and high resolution TEM. It is found that the concentration of reagent cupric acetate has strong effect on the purity and microstructure of the prepared samples. The growth process is investigated in detail. It is proposed that the nanorods are evolved from spherical particles with oriented attachment mechanism followed by dissolution-splitting process. The optical properties of the samples are detected by UV-vis spectrometer and photoluminescence spectrometer and exhibit strong dependence on surface defect states and microstructure feature, which is mainly determined by preparation conditions.     

Template-free synthesis of ZnWO4 powders via hydrothermal process in a wide pH range

ZnWO₄ powders with different morphologies were fabricated through a template-free hydrothermal method at 180 °C for 8 h in a wide pH range. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible and luminescence spectrophotometers were applied to study the effects of pH values on crystallinity, morphology, optical and luminescence properties. The XRD results showed that the WO₃ + ZnWO₄, ZnWO₄, and ZnO phases could form after hydrothermal processing at 180 °C for 8 h with the pH values of 1, 3-11, and 13, respectively. The SEM and TEM observation revealed that the morphological transformation of ZnWO₄ powders occurred with an increase in pH values as follows: star anise-, peony-, and desert rose-like microstructures and soya bean- and rod-like nanostructures. The highest luminescence intensity was found to be in sample consisting of star anise-like crystallites among all the samples due to the presence of larger particles with high crystallinity resulted from the favorable pH under the current hydrothermal conditions.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Growth of Yb-doped Y2O3 single crystal rods by the micro-pulling-down method

The rare-earth sesquioxides (RE₂O₃, RE = Lu, Y and Sc) are very promising host crystals for advanced laser diode (LD)-pumped Yb³⁺-doped solid-state lasers due to unusual combination, almost unique of favourable structural, thermal and spectroscopic properties which are described. In spite of these favourable properties, the bulk single crystal growth technology for the rare-earth sesquioxides has not been established yet. The extremely high melting temperature at around 2400 °C has prevented it. However, we shall show that yttrium oxide crystals (Yb_xY_1−x)₂O₃, x = 0.0, 0.005, 0.05, 0.08 and 0.15 of cylindrical shape as laser rods with 4.2 mm in diameter and 15-20 mm in length have been grown from rhenium crucibles by the micro-pulling-down method. The crystal quality characterisation of undoped Y₂O₃ crystal was determined using X-ray rocking curve (XRC) analysis. Yb were homogeneously distributed in Y₂O₃ host crystal.     

Preparation of SrAl2O4: Eu, Dy nanometer phosphors by detonation method

SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer phosphors were synthesized by detonation method. The particle morphology and optical properties of detonation soot that was heated at different temperatures (600–1100 °C) had been studied systematically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results indicated SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer powders in monoclinic system (a = 8.442, b = 8.822, c = 5.160, β = 93.415) can be synthesized by detonation method, when detonation soot was heated at 600–800 °C. The particle size of SrAl₂O₄: Eu²⁺, Dy³⁺ is 35 ± 15 nm. Compared with the solid-state reaction and sol-gel method, synthesis temperature of the detonation method is lower about 500 and 200 °C respectively. After being excited under UN lights, detonation soot and that heated at 600–1100 °C can emit a green light.     

SrAl2O4:Eu2+,Dy3+光致发光搪瓷涂层的制备

稀土Eu^2 激活的铝酸盐发光材料是近年来新发展起来的新型长余辉光致发光材料，由于其发光亮度和发光余辉比传统的硫化物高许多，且无毒，无放射性，因而引起广泛关注，采用高温固相反应法制备了SrAl2O4:Eu^2 ,Dy^3 发光材料，并利用SrAl2O4:Eu^2 ,Dy^3 发光材料，参考普通搪瓷的制备工艺，制得了性能稳定的光致发光搪瓷涂层，余辉时间长达12h以上，这种发光搪瓷涂层可用于制造广告牌，交通标牌和建筑物标识牌等，在许多领域有应用前景。     

Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.     

Dy3+掺杂Bi4Si3O12晶体生长及其热释光特性

采用坩埚下降法生长了Dy³⁺掺杂浓度分别为0.1mol%、0.2mol%、0.3mol%、2mol%、3mol%和4mol%的Bi₄Si₃O₁₂(BSO)晶体。发现高浓度(2mol%以上)掺杂能够显著改变BSO晶体的析晶行为, 晶体表面析出物完全消失, 顶部呈现光滑结晶面; 低浓度(低于0.3mol%)掺杂能够显著提高晶体的光输出, 最高可达纯BSO的145%。晶体热释光谱测试结果表明: 少量Dy³⁺掺杂虽然热释光峰略有增强, 但有利于晶体光产额的提高; 高浓度掺杂则容易引起晶格畸变, 甚至产生新的缺陷, 降低晶体的光产额。     

MOVPE growth of AlxIn1−xP using tertiarybutylphosphine in pure N2 ambient

We have investigated metalorganic vapor phase epitaxy (MOVPE) growth of Al_xIn_1−xP alloy using tertiarybutylphosphine (TBP) as the phosphorus source in pure N₂ ambient. The effect of the substrate temperature on the aluminum composition of Al_xIn_1−xP epilayers during the MOVPE growth has been studied. When the source flow rates were kept unchanged, the aluminum composition of the Al_xIn_1−xP epilayer increased monotonically when the substrate temperature, T_g, was raised from 580 °C to 660 °C during the growth. It became saturated when T_g reached 660 °C and above. The crystalline quality of the grown Al_xIn_1−xP epilayers has been investigated by X-ray diffraction and photoluminescence measurements. A linear relationship between the aluminum composition of the Al_xIn_1−xP epilayer and TMAl/(TMAl + TMIn) source flow ratio has been obtained when grown at the optimized growth temperature of T_g = 630 °C. It has also been observed that the aluminum incorporation coefficient of Al_xIn_1−xP epilayers decreased when the V/III source flow ratio was increased during the MOVPE growth.