KMgF_3∶Eu和KMgF_3∶Eu-Ce单晶体中Eu~(2+)与Ce~(3+)的格位取代和能量传递

在 77K测定了两个晶体的高分辨发射光谱 ,讨论了单掺杂 Eu2 + 和双掺杂 Eu2 + 及 Ce3+ 的 KMg F3中的格位取代问题 .在 KMg F3∶ Eu-Ce中观察到了 Eu2 + 的 6P5/ 2 能级到 Ce3+ 的 4 f 5 d能级间的间接能量传递 ,讨论了能量传递机理

KMgF_3∶Eu,X(X=Ce,Cr,Gd,Cu)体系中Eu~(2+)振动光谱和共掺离子的格位取代

测定了一系列单掺杂 Eu2 +和双掺杂 Eu,X( X=Ce,Cr,Gd,Cu)的 KMg F3晶体在 30 0 K和 77K的高分辨发射光谱以及伴随的振动光谱 ,据此研究了 Eu2 + 在这些体系中的振动跃迁特征 ,并指认了每一振动峰所对应的正则振动模式 .首次发现了在共掺杂体系中 Eu2 +振动频率与其它掺杂离子格位取代间的相关性

掺Eu~(3+)、Tb~(3+)或Ce~(3+)的InBO_3的合成与光谱

采用固相反应法合成了InBO_3:Re(Re=Eu,Tb,Ce),研究了InBO_3基质中稀土离子的光谱特性,观察到电荷迁移带位于255 nm附近,Eu~(3+)离子在InBO_3 中产生极强的~5D_0→~7F_1 的跃迁表明Eu~(3+)离子在该基质中占据对称性格位。Tb~(3+)的4f-5d 允许跃迁位于240 nm附近,而4f-5d 禁戒跃迁位于267 nm附近,Tb~(3+)离子呈现出极强的~5D_4→~7F_5 发射。Ce~(3+)离子在InBO_3 中不发光。

KZnF_3中Ce~(3+)→Eu~(2+)的能量传递

研究了KZnF3中Ce3+和Eu2+的光谱特性，在共掺Ce3+和Eu2+的体系中，观察到了Ce3+对Eu2+的能量传递过程．计算了能量传递的鼻子效率，探讨了能量传递机理．研究发现，Ce3+的存在有利于Eu2+的f-f跃迁线状发射.

Crystal growth and TG-DTA properties of K(2)Ln(NO3)(5).2H(2)O (Ln = La, Ce, Pr, Nd, Sm)

Single crystals of KLnN(Ln=La, Ce, Pr, Nd, Sm) can be grown in water solution with pH approximate to 1 similar to 2 at about 40 degrees C. Crystals of KLnN (Ln=La, Ce, Pr, Nd) are orthorhombic with space group Fdd2. KPrN crystal was grwon and its crystal structure was determined for the first time. The KPrN crystal parameters obtained by the direct method are as follows: a=21.411(3) Angstrom, b=11.2210(10)Angstrom, c=12.208(2) Angstrom, Z=6, R=0.0240. The TG-DTA curves of KLnN(Ln=La,Ce, Pr, Nd, Sm) demonstrate that the processes of dehydration, melt, irreversible phase transition and decomposition of NO3- take place in sequence with the temperature increasing(except KCN). There are three steps in the decomposition of NO3- in KLnN(Ln=La, Nd, Sm) while two steps in KLnN (Ln=Ce, Pr). K(2)Ln(NO3)(5). 2H(2)O are formed at about 225 degrees C by the reaction of the starting materials of KNO3 and Ln(NO3)(3). nH(2)O.

Recovery of Ce(IV) and Th(IV) from rare earths(III) with Cyanex 923

Solvent extraction of Ce(IV), Th(IV) with Cyanex 923 in n-hexane from sulphuric acid medium was studied with the dependence of the extraction on acidity and temperature being investigated. The Ce(IV) and Th(IV) extraction mechanism was proposed by slope analysis and the IR spectra of purified Cyanex 923 saturated with Ce(IV) were employed to determine the composition of the Ce(IV) complex. The equilibrium constant and thermodynamic functions of Th(IV) extraction were calculated and the characteristics of the stripping of Ce(IV), Th(IV) from the loaded organic phase were studied. (C) 1998 Elsevier Science B.V. All rights reserved.

High efficient extraction of M@C-2n (M = La, Ce) by a high pressure and high temperature method

A high pressure and high temperature method was used to efficiently extract on a large scale metallofullerenes M@C-2n (M=La,Ce) in a closed vessel under argon gas protection. With pyridine as the HPHT solvent, about 60-80% M@C-2n and 30-55% M@C-82 can be enriched, M@C-82 is dissolved selectively; With toluene as the HPHT solvent, M@C-2n can also be efficiently extracted, especially M@C-74, which is a new member of M@C-2n soluble species. (C) 1998 Elsevier Science Ltd. All rights reserved.

Separation of Ce(IV) and RE(III) with hollow fiber membrane-based extraction

Separation of Ce(IV) and RE(III) was investigated by hollow fiber membrane-based extraction with contercurrent recirculating operation. The mass transfer coefficients of Ce(IV) and RE(III) and the effective factors to them were tested. The results show the mass transfer coefficient of Ce(IV) is larger than that of RE(III), and their mass transfer mechanism is different. The mass transfer of Ce(IV) was controlled by the resistance in water critical layer due to its more rapid interfacial reaction rate and larger distribution coefficient, which was different from RE(III) mass transfer with a slow interfacial reaction rate and small distribution coefficient. Ce(IV) was separated from the mixed solution of Ce(IV) and RE(III) by means of the difference of their mass transfer rates.

LiMAlF_6(M=Ca,Sr)基质中Ce~3+、Eu~3+、Tb~3+的光谱研究

合成了Ce3+、Eu3+、Tb3+激活的LiMAlF6(M=Ca,Sr)磷光体，研究了它们的光谱特性．观察到稀土离子在LiCaAlF6和LiSrAlF6中的光谱十分相似．这与它们所处的晶场环境相同有关．发现Ce3+在此基质中有较弱的330nm发射，这一Ce3+的发光中心可用于作为材料质量的评价.

Al_2O_3-B_2O_3-Ce_2O_3体系中Ce~(3+)的光谱特性与基质的相关性

在Al2 O3_B2 O3_Ce2 O3体系中 ,于 12 0 0～ 140 0℃的温度范围内 ,合成了一系列不同配比 (Al/B比从 4 5～ 2变化 )磷光体 .研究了它们的结构和光谱特性之间的相关性 .发现随着基质配比Al/B从 4 5～ 2的变化 ,基质结构发生明显的变化 .这种变化导致光谱特性的巨大变化 ,表明铈离子晶场环境的变化 ,随着配比的变化 ,激发与发射峰向短波方向移动 .在合适的配比下 ,可以获得新型的稀土发光材料

K_2Ln(NO_3)_5·2H_2O(Ln=La,Ce,Pr,Nd,Sm)的晶体生长和热重-差热分析研究

本文生长出了K2Ln（NO3）5.2H2O（Ln=La；Ce；Pr；Nd；Sm）的单晶，并对其进行了晶体结构及差热-热重分析研究．结果表明，K2Ln（NO3）5.2H2O（Ln=La；Ce；Pr；Nd）的晶体属正交晶系，Fdd2空间群．首次生长出KPrN单晶并用直接法解出其晶体结构．解得KPrN的晶胞参数为：a=11．2210（10）,b=21．411（3），c=12．208（2）,Z=6；R=0．0240．对KLnN加热，则依次出现脱水、熔化、不可逆相变和NO的分解过程（K2Ce（NO3）5·2H2O除外）K2Ln（NO3）5·2H2O（Ln＝La；Nd；Sm）的NO分三步分解，K2Ln（NO3）5·2H。O（Ln=Ce；Pr）的NO分两步分解·KNO3和Ln（NO3）3·nH2O的混合物在225℃左右生成K2Ln（NO3）5

Synthesis, extraction and electronic structure of Ce@C-2n

In view of the growing interest in endohedral lanthanide fullerenes, Ce, as a typical +4 oxidation state lanthanide element, has been systematically studied. The synthesis, extraction and electronic structure of Ce@C-2n are investigated. Soot containing Ce@C-2n was synthesized in high yield by carbonizing CeO2-containing graphite rods and are back-burning the CeC2-enriched cathode deposit in a DC are plasma apparatus. Ce@C-2n, dominated by Ce@C-82, can be efficiently extracted from the insoluble part of the soot after toluene Soxhlet extraction by pyridine at high temperature and high pressure in a closed vessel. About 60% Ce@C-2n (2n = 82,80,78,76) and 35% Ce@C-82 can be enriched in the pyridine extract. This fact is identified by desorption electron impact mass spectrometry (DEI MS). The electronic structure of Ce@C-2n is analyzed by using X-ray photoemission spectroscopy (XPS) of pyridine-free film. It is suggested that the encapsulated Ce atom is in a charge state close to +3 and was effectively protected from reaction with water and oxygen by the enclosing fullerene cage. Unlike theoretical expectation, the electronic state of Ce@C-82 is formally described as Ce+3@C-82(3-). (C) 1997 Elsevier Science Ltd.

Studies on extracting solutions of endohedral rare-earth metallofullerenes by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Thirteen extracting solutions of rare-earth metallofullerenes containing La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb respectively have been investigated by means of matrix-assisted laser desorption/ionization time-of-night, mass spectrometry. The influences of the positive-ion/negative-ion mode, laser intensity, matrix and mass discrimination to the analytical results are studied, based on which the optimal analytical conditions have been determined. The results show that the extracting solutions contain large quantities of rare-earth metallofullerenes brs;des empty fullerenes, On the basis of comparing their relative intensities, the different structure stabilities and solubilities of metallofullerenes with different rare-earth metals encapsulated into the fullerene cages, as well as some possible reasons to those differences, are discussed.

Synthesis and luminescence characteristics of LiMgAlF6:Ln(3+) (Ln = Ce, Eu, Tb)

By solid state reaction, LiMgAlF6 and LiMgAlF6:Ln(3+) are synthetized with the ratio 120/100/110 of LiF/MgF2/AlF3, at 1008 K, in high-purity Ar stream. Their crystal structure which belongs to hexagonal system are determined by X-Ray-Diffraction (XRD). Luminescence characteristics of Ce3+, Eu3+, Tb3+ and sensitization of Ce3+ to Tb3+ in LiMgAlF6 are studied. It is shown that the sensitization of Ce3+ to Tb3+ is efficient and a bright green emission is observed.