金属配合物和一氧化碳的反应

一氧化碳是发展可持续化学经济的重要原料。人们希望能够将一氧化碳催化转变成高附加值化学品,从而减少石油等化石资源对人类的束缚。研究均相金属配合物与一氧化碳的反应能够使人们了解一氧化碳转变及利用机理,并开发新催化剂高效地利用一氧化碳资源。本文从金属配合物与一氧化碳反应的活性点出发,分别讨论不同类型的金属配合物与一氧化碳的反应,以求让人们在分子水平上了解一氧化碳的基本反应原理;并总结了该领域存在的难点问题,展望了未来,希望更多的科研工作者投入其中,从而实现利用一氧化碳合成出各种各样的化学品和材料。     

Effect of varying lanthanide local coordination sphere on luminescence properties illustrated by selected inorganic and organic rare earth complexes synthesized in sol-gel host glasses

Inorganic and organic ligands were carefully selected to illustrate the effect of modifications in the local field environment around the rare earth lanthanide (III) on its emission properties. In this article two strategies were employed to enhance emission of lanthanides encapsulated in sol-gel glass. (i) Changing the symmetry around the lanthanide, which was diagnosed by changing the local environment around the lanthanide using different inorganic counter ions (acetate, nitrate and chloride) these ligands differ in their affinity toward the lanthanide first coordination sphere. The ligand that penetrates the lanthanide more results in more asymmetric environment and thus results in higher emission. The aim of this part was to demonstrate the change of symmetry on emission in the absence of energy transfer. Our results indicate that the acetate ion has the highest affinity toward the first coordination sphere followed by the nitrate while the chloride showed the lowest affinity. Penetration by the ligands ofthe lanthanide also results in removing OH quenchers surrounding the lanthanide and this further explains the boost in emission. (ii) A bulky organic ligand that forms a complex with the lanthanide is used. The organic ligand separates the lanthanide ion from inner O-H oscillators. In this case the chelating organic chromophore with suitable photophysical properties was employed to sensitize the lanthanide and thus energy transfer occurs via the antenna effect. The organic ligand absorbs UV light, then energy is transferred to the lanthanide and finally the lanthanide emits in the visible region. The first coordination environment surrounding europium was controlled by the ligand selection and the outer sphere was modified by doping the synthesized complexes in an optically transparent sol-gel glass host. The glass network carefully prepared by sol-gel process is effective in preventing free oxygen and water from attacking lanthanide -complexes without loss of luminescence. Emission spectroscopy measurements of the doped silica specimens confirmed the variation of Eu (III) emission depending on the first coordination sphere surrounding the europium ion. The encapsulation of the europium complexes was performed for two reasons: (i) to improve the stability of red phosphor with efficient and high color-purity characteristics under ultraviolet excitation and (ii) this work provides a framework for preparing transparent composite glasses that are robust hosts to study the fundamental interactions between nano-materials and light.     

Yb effect on the spectroscopic properties of Er-Yb codoped SnO2 thin films

We have investigated the optical properties of sol-gel thin films of tin dioxide (SnO₂) codoped with Er³⁺-Yb³⁺ as a function of Yb³⁺ concentration. The Judd-Ofelt model has been applied to absorption intensities of Er³⁺ (4f¹¹) transitions to establish the so-called Judd-Ofelt intensity parameters: Ω₂, Ω₄, Ω₆. Various spectroscopic parameters were obtained to evaluate their dependence and the potential of the samples as a laser material in the eye-safe laser wavelength (1.53 μm) as a function of Yb³⁺ concentration. An amelioration of the quality factor Ω₄/Ω₆ was found with Yb content. Both the IR photoluminescence (PL) intensity and the up-conversion emission, from Er³⁺ ion in SnO₂, were found to increase with Yb concentration. We show that the Yb³⁺ ion acts as sensitizer for Er³⁺ ion and contributes largely to the improvement of the spectroscopic properties of SnO₂:Er. The mechanism of up-conversion emission is discussed and a model is proposed. The results showed that sol-gel SnO₂ is promising gain media for developing the solid-state 1.5 μm optical amplifiers and tunable up-conversion lasers.     

Sc2O3:Ce nanocrystals: Fluorescence and its dependence on the surrounding gas pressure

The fluorescence spectra of nanocrystalline powder samples of Sc₂O₃:Ce³⁺ prepared by the sol-gel process were studied. The strong shift of the fluorescence spectra with the excitation wavelength was observed. The effect of the surrounding gaseous medium on 4f⁰5d¹→4f¹ fluorescence of Ce³⁺ ions in nanoparticles, discovered earlier in YAG:Ce³⁺, was also observed and studied in Sc₂O₃:Ce³⁺. The fluorescence intensity and the excitation power dependence of fluorescence dramatically depend on the pressure of the gaseous media.     

地球章动原因的分析与计算

介绍地球章动的特点,从理论上分析地球章动的主要原因,计算章动常数并给出了地球章动示意图的画法.所计算的章动常数与观测值相差仅2/10 000.     

稀土氟化物纳/微米材料的水热合成、形成机理和发光性质

研究了稀土氟化物纳/微米材料的设计合成、形貌控制、形成机制以及发光性质.发展了一种简单、整体、没有模板、环境友好的水热方法合成系列稀土氟化物,即用有机添加剂柠檬酸钠(Na3C6H5O7·2H2O)作为配位剂和形貌控制剂,通过改变氟源(NaF,NH4F或NaBF4)和最初溶液的pH值,得到了具有不同成分、晶体结构、尺寸和...     

新型双β-二酮、邻菲罗啉和铕(Ⅲ)三元配合物的合成与发光

合成了一个新型双β-二酮有机配体1,3-双[3-(2-噻吩基)-3-氧代丙酰基]苯、邻菲罗啉和铕的三元配合物,并应用红外光谱、紫外-可见光谱、元素分析和热重-差热分析等对配合物进行了组成确定和结构表征.荧光分析结果表明,配合物612 nm处的发射光谱为中心离子Eu3+的特征红光,属5D0→7F2跃迁带,峰形尖锐,单色性...     

Structure and properties of soda lime silicate glass doped with rare earth

Soda-lime-silicate glasses doped with different rare-earth oxides (La₂O₃, CeO₂, Nd₂O₃, Gd₂O₃ and Y₂O₃) of 1 mol% content were prepared with the traditional melting-quenching methods. In order to reveal the effects of rare-earth elements on the behavior of soda-lime-silicate glass, the structure of soda-lime-silicate glasses doped with different rare-earth oxides were determined with Fourier transform infrared spectrometer using the KBr method, and viscosity of glass melts were measured by the rotating crucible viscometer, the melting temperature of the studied glasses were derived on the basis of Arrhenius Equation, moreover the density, bending strength and molar volume were measured and calculated. The effect of rare-earth dopants on the structure of soda-lime-silicate was analyzed by a shift of peak position and variation in the full-width at half-maximum. The effect of doping rare-earth oxides into glass on the viscosity, density and bending strength was interpreted by changing in structure of soda-lime-silicate glasses doped with rare-earth oxides.     

High coercive Nd-Fe-B magnets fabricated via two-step sintering

The fabrication of Nd₁₁Dy₄Fe_76.5TM_2.5B₆ (TM=Co, Cu, Al, and Nb: at%) sintered magnets via a two-step sintering process was demonstrated. A densification of greater than 99% was achieved using the two-step sintering of the Nd-Fe-B powder. This process produced a sample with an average grain size of 6.2 μm in the Nd₂Fe₁₄B phase, resulting in an enhancement of the coercivity compared to that of the isothermally sintered sample. The suppression of grain growth was considered to be affected by the relatively low temperature during the two-step sintering and by the presence of a B-rich phase at the triple junction. Consequently, the two-step sintering process led to suppression of grain growth and a uniform grain size distribution, which resulted in improved magnetic properties, in particular in the intrinsic coercivity.     

发光二极管用SrWO4:Eu3+红光荧光粉激发谱强度的调控

采用化学共沉淀法制备了Eu³⁺掺杂摩尔分数不同、煅烧温度不同的SrWO₄:Eu³⁺系列发光粉体, 所制备的粉体均具有Eu³⁺特征的强室温红光荧光发射. 通过调节煅烧温度和掺杂摩尔分数来调控近紫外和蓝光吸收强度, 进而调控用395 nm的近紫外光和465 nm的蓝光激发样品所得红光发光强度. 研究结果表明, 所制备的SrWO₄:Eu³⁺红光荧光粉可以被紫外和蓝光发光二极管有效激 关键词： 稀土掺杂 4:Eu³⁺')" href="#">SrWO₄:Eu³⁺ 光致发光 白光发光二极管