Al-pillared clays supported rare earths and palladium catalysts for deep oxidation of low concentration of benzene

Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H₂-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d_0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m²/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C.     

用于白光LED的高亮度蓝白色荧光粉Ca2SiO3Cl2：Eu2+的发光性质

采用固相法在较低温度下合成了Eu²⁺激活的Ca₂SiO₃Cl₂高亮度蓝白色发光材料,并对其发光性质进行了研究。其发射光谱由两个谱带组成,峰值分别位于420,498nm处,归结为Ca₂SiO₃Cl₂晶体中占据两种不同Ca²⁺格位的Eu²⁺离子的5d→4f跃迁发射。改变Eu²⁺浓度,可以使样品的发光在蓝白色和绿白色之间变化。当Eu²⁺浓度为0.005mol^-1时,样品呈现很亮的蓝白色发光。两个发射峰的激发光谱均分布在250~410nm的波长范围内,峰值分别位于333,369nm处。Ca₂SiO₃Cl₂:Eu²⁺可被InGaN管芯产生的近紫外辐射有效激发,是一种性能良好的白光LED用单一基质蓝白色荧光粉。     

溶胶-凝胶法制备小颗粒(Y,Gd)BO_3∶Eu及其表征

用溶胶 凝胶方法制备了平均粒径为 1～ 2 μm的小颗粒、高发射效率的 (Y ,Gd)BO3 ∶Eu红色发射荧光体。用XRD、SEM、粒度分析和PL光谱对荧光体作了表征和研究。常规固相反应合成 (Y ,Gd)BO3 ∶Eu需在 1 2 0 0℃以上才能形成均一的固溶体。而溶胶 凝胶法制取稀土正硼酸盐 80 0℃灼烧已可形成均一的单相 (Y ,Gd)BO3 ∶Eu,在 1 1 0 0℃可得到发光亮度最高的荧光体。它的亮度是常规固相反应于 1 2 0 0℃制得的荧光体的 1 2 0 %。采用溶胶 凝胶法制取 (Y ,Gd)BO3 ∶Eu荧光体 ,可在相当宽的实验条件范围内得到小粒径、窄分布和高亮度的荧光体 ,且有良好的颗粒形貌。     

Visualization of rigorous sum rules for Franck–Condon factors: spectroscopic applications to Xe2

A fully quantum mechanical approach to the calculation and normalization of the Franck–Condon factors for diatomic species is described. The treatment is based on the fundamental demand of completeness of the energy eigenfunctions, which results in the rigorous sum rule for the Franck–Condon overlap integrals. The importance of this general rule has been discussed and thoroughly illustrated in the case of diatomic xenon molecules. Exactly solvable reference potentials for this system have been constructed and a complete basis of the actual energy eigenstates (including both bound and scattering states) has been created. Several direct spectroscopic applications to xenon excimers are presented, and their good agreement with relevant experimental data demonstrated. In particular, a kinetic model is proposed to explain the observed oscillatory structures in the fluorescence spectra of Xe₂^* [Chem. Phys. Lett. 117 (1985) 301] related to their classical left turning points. The same model gives a uniform explanation to the well-known first and second emission continua of rare gases.     

Solid phase extraction for analysis of biogenic carbonates by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS): an investigation of rare earth element signatures in otolith microchemistry

Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 °C. Lower temperatures (i.e. 2600 °C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 μg in the injection volume (70 μl) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 °C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO₃ in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences.     

稀土配合物Eu(asprin)_3phen发光特性的研究

将稀土配合物Eu(asprin)_3phen掺杂到导电聚合物PVK中,制成结构分别为ITO/PVK:RE配合物/LiF/AI(1),ITO/PVK:RE配合物/PBD/LiF/AI(2)的电致发光(EL)器件。发现二者的电致发光谱存在着较大的差别:在器件(1)中,来自Eu~(3 )的位于594nm(~5D_0→~7F_1)和614nm(~5D_0→~7F_2)处的发光强度大致相当,而在器件(2)中,EL主要来自Eu~(3 )位于614nm的发光,594nm处的发光很弱,与薄膜状态下的光致发光谱(PL)一致。并针对此现象进行了初步讨论。     

绿色荧光粉YAGG∶Tb,Gd用于FED的尝试

FED器件的发展迫切需要具有化学和热稳定性 ,高亮度 ,长寿命的新型荧光材料。本文合成了Gd3 +离子共掺杂的YAGG∶Tb获得了YAGG∶Tb ,Gd ,并将其用于 0～ 30 0 0V低压范围 ,对其在不同电压和电流密度下的发光特性进行了测试。结果表明 ,该种材料特性优于ZnO∶Zn并且不存在电压与电流饱和     

Magnetic behaviour of TbMnFe

Neutron diffraction and M?ssbauer measurements have been carried out on the cubic Laves phase intermetallic TbMnFe. The magnetic moment on the transition metal atom is found to be low, 0.2μ _B, at room temperature. This moment is temperature independent down to 10 K. Magnetic moment on the rare earth atom varies from 2.5μ _B at 296 K to 7.27μ _B at 10 K. M?ssbauer spectra recorded at 298 K and 78 K have magnetic character but there is a large distribution of hyperfine field values. Both these features arise due to magnetic frustration created in the sample due to the competing ferro and antiferromagnetic interactions between the transition metal atoms.     

Estimating tail probabilities of heavy tailed distributions with asymptotically zero relative error

Efficient estimation of tail probabilities involving heavy tailed random variables is amongst the most challenging problems in Monte-Carlo simulation. In the last few years, applied probabilists have achieved considerable success in developing efficient algorithms for some such simple but fundamental tail probabilities. Usually, unbiased importance sampling estimators of such tail probabilities are developed and it is proved that these estimators are asymptotically efficient or even possess the desirable bounded relative error property. In this paper, as an illustration, we consider a simple tail probability involving geometric sums of heavy tailed random variables. This is useful in estimating the probability of large delays in M/G/1 queues. In this setting we develop an unbiased estimator whose relative error decreases to zero asymptotically. The key idea is to decompose the probability of interest into a known dominant component and an unknown small component. Simulation then focuses on estimating the latter ‘residual’ probability. Here we show that the existing conditioning methods or importance sampling methods are not effective in estimating the residual probability while an appropriate combination of the two estimates it with bounded relative error. As a further illustration of the proposed ideas, we apply them to develop an estimator for the probability of large delays in stochastic activity networks that has an asymptotically zero relative error.      

Search for cosmic γ-ray bursts in the (1÷50) GeV energy range

Summary A search for cosmic gamma-ray bursts in the GeV energy range has been performed by means of the EAS-TOP Extensive Air Shower array at Campo Imperatore (Gran Sasso Laboratories) during the period March–December 1990. In 2566.5 hours of measurement the obtained upper limit to the rate of bursts of amplitude >2% of the cosmic-ray intensity and time duration τ=1 s, isR≤7.9y⁻¹ (90% c.l.). Assuming for γ-rays a differential energy spectrumS(E ₀ )≈E ₀ ^−2.5 , the corresponding upper limit to the energy flux of γ-rays with energy >5 GeV in bursts of duration τ≤1 s is Φ<8.3·10⁻⁵erg cm⁻².