铕在硼磷酸钡玻璃中的空气下还原及其发光性质

通过高温熔融法在空气条件下制备了Eu₂O₃掺杂的BaO-B₂O₃-P₂O₅玻璃,发射光谱中400～550 nm的宽峰为Eu²⁺的5d→4f跃迁,即在非还原气氛条件下实现了Eu³⁺→Eu²⁺的转变。首先,Eu³⁺离子不等价取代玻璃基质中的Ba²⁺导致Eu²⁺的产生。同时,固体核磁共振谱数据表明当玻璃中的B主要以[BO₄]的形式存在时,利于玻璃中的Eu以Eu²⁺价态存在。与ZnO-B₂O₃-P₂O₅∶Eu²⁺玻璃中Eu²⁺的发光相比,BaO-B₂O₃-P₂O₅玻璃中O^2-所形成的Eu的配位场强于ZnO-B₂O₃-P₂O₅玻璃中O^2-所形成的Eu配位场。Eu在BaO-B₂O₃-P₂O₅玻璃中产生的晶体场分裂能大,故d→f跃迁产生的光发射波长较长。     

Eu3+在La2O2S中的长余辉发光

The new Eu³⁺ doped lanthanum oxysulfide phosphors,which have the orange-red long afterg low emission,were synthesized by solid-state reaction method.The synthesized phosphors were characterized by X-ray diffraction.The excitation and emission spectra,afterglow spectra and afterglow decay curves were examined.XRD confirmed the phosphor as pure phase La₂O₂S.The phosphors showed typical transitions ⁵D_J(J=0,1) → ⁷J_J(J=0,1,2,3,4)of Eu³⁺.The photoluminescence spectra and afterglow spectra presented the regular alteration with various Eu³⁺ concentration, due to cross relaxation between energy levels of Eu³⁺. In addition, we studied the effects of activator concentration and dopants species on the afterglow property. The data showed afterglow result was the best with 2 % Eu³⁺ and doped with Mg²⁺ and Zr⁴⁺. A prominent phosphorescence can be seen in this phosphor after illuminated with UV light.     

Theory and application of cyclic voltammetry at a hemispherical microelectrode for a quasi-reversible reaction

The theory of cyclic voltammetry for a quasi-reversible reaction at a hemispherical microelectrode has been deduced. From the results calculated according to the theory, the heterogeneous rate constant and charge transfer coefficient can be measured with the cyclic voltammetric data obtained at an intermediate scan rate on a hemispherical microelectrode. To verify the theory, the kinetic constant for reduction of benzoquinone in acetonitrile has been determined. The result is coincident with that measured by a fast scan rate at a platinum microdisk electrode. The kinetic constant and charge transfer coefficient for reduction of 2,3,5,6-tetrachlorobenzoquinone have also been determined with the method described in this paper.     

CaWO4中Eu3+的长余辉发光

Eu³⁺ activated CaWO₄ was prepared by high temperature solid state reaction technique. Red afterglow was observed for in the CaWO₄∶Eu after exciting with 254 nm light due to Eu³⁺ transition from ⁵D₀ to ⁷F_J (J=0, 1, 2, 3,4). By the calculation of the thermoluminescence spectrum of CaWO₄∶Eu, we conclude that there were two types of trap centers: V_Ca″ was formed by substitution of Ca²⁺ by Eu³⁺ and complex traps were produced because of substitution of W⁶⁺ by Eu³⁺.     

BaY2F8∶Ce, Eu中Ce3+→Eu2+的能量传递和Ce3+→Eu3+的电子转移

采用高温固相反应法制备了BaY     

Li2O-Ln2O3-SiO2:Eu3+,Bi3+体系的结构

采用ｓｏｌ－ｇｅｌ法合成了系列发光体Ｌｉ２Ｏ－Ｌｎ２Ｏ３－ＳｉＯ２：Ｅｕ＾３＾＋，Ｂｉ＾３＾＋，并确定了发光体的物相结构。当Ｌｎ＾３＾＋＝Ｙ＾３＾＋和Ｌｎ＾３＾＋＝Ｌａ＾３＾＋时，紫外光激发下Ｅｕ＾３＾＋的发射分别以红光和橙光为主，只存在一种Ｅｕ＾３＾＋发光中心；Ｌｎ＾３＾＋＝Ｇｄ＾３＾＋时，至少存在两种Ｅｕ＾３＾＋发光中心和两种Ｂｉ＾３＾＋发光中心（共掺杂Ｅｕ＾３＾＋，Ｂｉ＾３＾＋的吸收和发射所     

功能性三价铕离子的金属有机骨架选择性荧光识别芘

成功设计并通过水热法合成了一种具有功能性三维结构的镧系金属有机骨架 Eu-4L,其配体为二苯胺四羧酸衍生物(H₄L)。Eu-4L 的骨架中含有 3D 空腔,且其比表面积较高。Eu-4L 不仅热稳定性较高,且在 pH 为 3~11 的范围内稳定性良好。Eu-4L可以作为荧光探针选择性识别稠环芳烃芘,其检测限为5 μmol·L^-1,具有较高的灵敏度,且具备可循环重复利用的特性。Eu-4L荧光识别芘的作用机理为稳态荧光识别机理。此外,对Eu-4L的荧光识别选择性、竞争能力也进行了详细地讨论。     

Solubility and Ionic Processes in the Cu X 2? MX ?H2O ( X ?=Cl?, Br?; M +=Li+, Na+, K+, NH4+, Cs+) Systems

Summary.  Solubility isotherms in the CuBr₂−MBr−H₂O (M ⁺ = Li⁺, Na⁺, Cs⁺) systems at 298.15 K were measured. The results together with other available literature data for copper chloride and bromide systems were treated by hydration analysis, and comparative discussion of ionic processes taking place in the respective saturated solutions was performed. Corresponding author. E-mail: jitka@prfdec.natur.cuni.cz Received August 6, 2002; accepted (revised) November 29, 2002 Published online April 3, 2003     

Determination of trace amounts of Eu3+ and Yb3+ ions at Nafion-coated thin mercury film electrodes

The use of Nafion-coated thin mercury film electrodes (NCTMFE) for determining trace amounts of Eu³⁺ and Yb³⁺ ions was examined. Ion-exchange preconcentration of submicromolar levels of the two rare earths was achieved efficiently at a rotating NCTMFE, while the use of “classical” Nafion-coated glassy carbon electrodes is restricted to the determination of Eu³⁺ alone. Differential-pulse voltammetry was used to quantify the accumulated ions. The influence of variables such as rotation rate, preconcentration time and scan parameters was assessed. A preconcentration -voltammetry-regeneration scheme suitable for multiple analysis with the same modified electrode was developed. Calibration graphs with a linearity range extending up to 2 μM and detection limits of 0.03 and 0.08 μM for Eu³⁺ and Yb³⁺, respectively, were obtained. For Yb³⁺, the detection limit can be lowered to 0.02 μM by electrocatalytic amplification of the signals achieved by operating in the presence of ammonium nitrate as supporting electrolyte. However, in this instance a more restricted linearity range is observed. The effect of competing incorporation caused by the presence in solution of an excess of La³⁺ is also discussed, together with the competition between Eu³⁺ and Yb³⁺ when one of the two is present in large excess over the other.     

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k _s) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (τ_L) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH₃CN, indicating that k _s varies inversely with τ_L; k _s is proportional to D of DMFc. Both D and k _s of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k _s of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte. Received: 5 February 1998 / Accepted: 23 July 1998     

Eu+2 fluorescence in BaCl2

The Ba_1?xEu_xCl₂ system was studied over wide ranges of x, particularly regarding the fluorescent emission of Eu²⁺. In addition to the commonly observed 5d → 4f band emission sharp line, f → f transitions were observed. Single crystals of Eu²⁺ containing BaCl₂ were grown via the Czochralski technique and many of the optical properties, such as transmission, fluorescence, and excitation, were measured. X-ray and thermal parameters for the Ba_1?xEu_xCl₂ system are also reported.     

淋巴细胞膜上Na+/Ca2+交换操纵的Eu3+内流的荧光法研究

利用Fura-2荧光浓度指示剂法、通过检测360nm激发荧光强度的变化,研究了Eu³⁺能否利用人外周血淋巴细胞膜上的Na⁺/Ca²⁺交换进入细胞。结果表明:用ouabain预处理细胞无Na⁺介质中测试,当加入Eu³⁺时,360nm荧光强度发生猝灭,且随着胞外加入的Eu³⁺浓度的增大而猝灭增强。表明在实验条件下Eu³⁺可以进入细胞。电压依赖性Ca     

有序介孔Al2O3∶RE3+的制备及Gd3+对Eu3+的能量传递

以P123为表面活性剂,异丙醇铝为铝源,用简易溶胶-凝胶法,获得了单掺和双掺Gd3+,Eu3+的介孔氧化铝组装体。用广角X-射线衍射仪(WAXD)进行了物相分析;小角X-射线衍射仪(SAXD)、比表面仪进行了孔结构分析和形貌表征;研究了组装体的发光性能并发现Gd3+对Eu3+有能量传递作用,并分析了能量传递过程。     

共掺Tm~(3+)离子对CaAlSiN_3∶Eu~(2+)红色荧光粉发光性能的影响

通过高温固相法,合成了Eu~(2+)单掺和Eu~(2+)、Tm~(3+)共掺CaAlSiN_3荧光粉。结合荧光光谱、余辉发射光谱和余辉衰减曲线及热释发光等测试手段对其进行了表征分析。结果表明,CaAlSiN_3∶Eu~(2+)具有主峰位于630 nm的明显的红色长余辉发光;共掺杂Tm~(3+)离子的引入,产生了654和800 nm的荧光和余辉,同时,Tm~(3+)的共掺,使CaAlSiN_3∶0.1%Eu~(2+),Tm~(3+)样品位于89.0℃热释光峰位消失,表明Tm~(3+)共掺杂改变了CaAlSiN_3∶Eu~(2+)荧光粉中的陷阱能级及其分布,从而减弱了CaAlSiN_3∶Eu~(2+)的630 nm红色可见光部分余辉发光性能。     

CaSb2O6:Bi3+,Eu3+荧光粉的制备和发光性质

采用共沉淀法及1 200 ℃后续煅烧4 h,成功制备了CaSb₂O₆:Bi³⁺,Eu³⁺荧光粉,并对其结构及发光性能进行了研究。所制备荧光粉颗粒为六边形类圆饼状,平均尺寸在100~600 nm之间。对CaSb₂O₆:Bi³⁺,Eu³⁺发光的机理分析表明,Bi³⁺对Eu³⁺的发光存在高效的敏化与能量传递。当Bi³⁺和Eu³⁺的掺杂浓度分别为0.5%和8%,Eu³⁺位于580 nm(⁵D₀→⁷F₀ )处的荧光发射显著增强,Bi³⁺,Eu³⁺共掺样品的荧光强度是CaSb₂O₆:Eu³⁺的10倍左右。调节Bi³⁺/Eu³⁺离子掺杂比,色坐标呈现了从蓝、白光到红光的变化,表明该荧光粉可分别作为蓝或红色荧光粉使用,甚至可实现从蓝、白光到红光的自由调控,这为白光LED荧光粉的发展提供了参考。     

Eu3+或Tb3+掺杂的KY2F7纳米球的制备与表征

利用简单的室温液相反应制备了KY₂F₇及镧系离子掺杂的KY₂F₇∶Eu³⁺和KY₂F₇∶Tb³⁺的纳米球，并利用XRD，TEM，SEM，XRF和荧光光谱对所制备的材料进行了表征。研究表明Eu³⁺或Tb³⁺离子已成功地掺杂在KY₂F₇纳米球中。掺杂     

Electronic excitation energy transfer between Tb3+ and Eu3+ in DMSO

Excitation of Tb³⁺ and Eu³⁺ in DMSO with 487 mμ, which corresponds to the ⁷F₆ → ⁵D₄ transition of Tb³⁺, is accompanied by a reduction in the fluorescence efficiency of Tb³⁺ as [Eu³⁺] increases and by the appearance of a weak emission from Eu³⁺. An average rate constant for both the fluorescence quenching of Tb³⁺ and the energy transfer from Tb³⁺ to Eu³⁺ with subsequent emission from the latter, was found to be (2.2 ± 0.4) × 10³ M^?1 sec^?1.     

Eu3+、Ga3+共掺杂SiO2基质材料的制备及其发光性质

通过溶胶-凝胶方法制备了稀土离子Eu³⁺和Ga³⁺共掺杂的SiO₂材料;利用IR、XRD等研究了材料的结构,结果表明材料属于非晶态,800 ℃退火后样品的主要结构仍为SiO₂的网状结构。400 ℃退火的样品在393 nm激发下发射光谱显示了Eu³⁺的特征发射光谱,产生3条明显谱带,分别是576 nm(⁵D₀-⁷F     

Eu3+在Ba2TiSi2O8中的发光

The barium titano-silicate phosphors doped with Eu³⁺ were synthesized by high temperature solid state reaction. The structures of as-synthesized samples were characterized by powder XRD. The maximum peaks of emission spectra of Ba₂TiSi₂O₈ and Ba₂TiSi₂O₈∶Eu³⁺ were respectively located at 450 and 618 nm, coming from the transitions of charge-transfer bands of Ti⁴⁺-O^2- and forced electric-dipole transition ⁵D₀-⁷F₂ of Eu³⁺. The luminous mechanisms of Ba₂TiSi₂O₈ and Ba₂TiSi₂O₈∶Eu³⁺ were suggested. The effects of concentration of Eu³⁺ on the luminous performance of Ba₂TiSi₂O₈∶Eu³⁺ were also studied and the results showed that the optimum concentration of Eu³⁺ was 0.12 mol per mole of matrix.     

Si-N共掺对CaAl2O4:Eu2+和CaAl2O4:Eu2+,Sm3+荧光粉荧光和余辉性能的优化

采用高温固相反应法制备了不同浓度Si-N共掺的CaAl2O4:Eu2+蓝色荧光粉,发现只需2%(摩尔分数)的Si-N共掺就可以明显提高荧光粉的荧光性能。研究还发现在CaAl2O4:Eu2+,Sm3+中掺入Si-N后,荧光粉的荧光强度和余辉性能都有提高。通过荧光粉的光谱图,发现共掺没有改变荧光粉中发光中心Eu离子的价态,而电子顺磁共振(EPR)谱则表明,Si-N共掺对Eu离子周围的配位环境产生了较大的影响。这说明掺杂的Si-N倾向于取代Eu2+附近的Al-O,并且由于Si-N键相对于Al-O键具有较短的键长,使发光中心周围晶体骨架的刚性得到了增强,从而减少了晶格热震动导致的非辐射跃迁能量损失,提高荧光粉的发光性能。同时,热释光谱表明,掺杂的Si-N会在发光离子周围产生新的缺陷能级,从而提高荧光粉的余辉性能。