LUMINESCENCE AND ENERGY-TRANSFER OF RARE-EARTH-METAL IONS IN MG2Y8(SIO4)(6)O-2

The photoluminescence of Ce3+, Tb3+ and Sm3+, and energy transfer from Ce3+ to Tb3+, Dy3+ and Sm3+ in Mg2Y8(SiOd(4))(6)O-2 are reported and discussed. The Ce3+ ion shows blue luminescence under UV excitation, and occupies simultaneously the 4f site and 6h site in the host lattice. The optimum concentrations for the D-5(3) and D-5(4) emissions of Tb3+ and the (4)G(5/2) emission of Sm3+ are determined to be 0.04, 0.20 and 0.10 mol in every mol of Mg2Y8(SiO4)(6)O-2, respectively. The critical distances responsible for the cross-relaxation between the D-5(3)-D-5(4) and F-7(6)-F-7(0) transitions of Tb3+ and between the (4)G(5/2)-F-4(9/2) and H-6(5/2)-F-4(9/2) transitions of Sm3+ are estimated to be 1.43 and 1.06 nm, respectively. Both Tb3+ and Dy3+ can be sensitized by Ce3+, but Ce3+ and Sm3+ quench each other.

PREPARATION, CRYSTAL-STRUCTURE, AND VIBRATIONAL-SPECTRA OF PEROVSKITE-TYPE MIXED OXIDES LAM(Y)M'(1-Y)O(3) (M,M'=MN, FE, CO)

Three series of samples LaMnyCo1-yO3+/-lambda, LaFeyMn1-yO3+/-lambda, and LaFeyCo1-yO3+/-lambda (y = 0.0 to 1.0) with Perovskite structure were prepared by an explosion method different from the generally used ceramic techniques. The variation of crystal

LUMINESCENCE AND ENERGY MIGRATION IN THE OXYAPATITE CA2GD8(SIO4)6O2 DOPED WITH SEVERAL RARE-EARTH AND MERCURY-LIKE IONS

Energy transfer phenomena have been observed by activating the oxyapatite host-lattice Ca2Gd8(SiO4)6O2 with Eu3+, Tb3+, Dy3+, Sm3+. This is based on the energy migration in the Gd3+ sublattice and trapping by the activators. The trapping efficiency for G

超微LaMO_3（M＝Fe，Cr，Mn，Co）的导电性与粒度的关系

用Ｓｏｌ－Ｇｅｌ法合成了ＬａＭＯ＿３（Ｍ＝Ｆｅ，Ｃｒ，Ｍｎ，Ｃｏ）超微粉末．Ｘ射线衍射分析表明，不同焙烧温度下所合成的化合物均为单相．ＳＥＭ分析表明，粒子呈球形，室温电阻率测量表明，电阻率随粒度的变化呈两种类型：ＬａＦｅＯ＿３，ＬａＣｒＯ＿３随粒度的增大，电阻率增加；而ＬａＭｎＯ＿３，ＬａＣｏＯ＿３随粒度的增大，电阻率减小．

不同热化学还原LiNbO_3：Ti或Mn晶体杂质电荷态和点缺陷

采用光学吸收和电子顺磁共振（ＥＳＲ）技术表征不同热化学还原ＬＩＮｂＯ３：Ｔｉ，Ｍｌｉ（ＬＮ：Ｔｉ，Ｍｎ）和纯的Ｌｉ／Ｎｂ＝０．９４５一致熔化ＬｉＮｂＯ３（ＬＮ）晶体的热力学还原习性．将ＬＮ：Ｔｉ（厚度为１ｍｍ）样品放在Ｌｉ２ＣＯ３中、６００℃、保温７ｈ，产生６９０ｕｒｎ（～１．８ｅＶ，Ｔ＝６７％）和峰值靠近７８５ｎｍ（Ｔ＝７１％）的７７０￣８１０ｎｍ光学吸收带，它们分别对应于Ｔｉ（３＋）的２Ｔ→２Ｅ跃迁以及室温稳定Ｆ＋心滞有一个电子的氧空位）．经真空１．２Ｐａ，８００℃２ｈ还原后，存在峰值为６７５ｎｍ（Ｔ＝５２％）的４８０～７８０ｎｍ平滑吸收带，它们是Ｔｉ（３＋）、Ｆ心和Ｆ＋心重叠吸收，但是，在Ａｒ气氛下、９００℃、８ｈ处理后，仅能看到峰值在６７５ｎｍ（Ｔ＝５２％）的６００～７８０ｎｍＴｉ（３＋）的弱吸收．来自未处理ＬＮ：Ｔｉ晶体的室温和Ｘ带的ＥＳＲ＄观察到ｇ＝４．３４８，共振磁场０．１５２ＴＨ（ｐ－ｐ）＝０．０１６３Ｔ微波吸收峰，以及四组精细结构Ｂ线（每一ｆｓ线是由６条超精细结构ｈｆｓ组成），ｇ值从３．４６０～１．６７９吸收，它们分别归为于晶体杂质Ｆｅ（３＋）和Ｍｎ（２＋）离子．真空还原后，Ｆｅ（３＋）的

LUMINESCENCE AND ENERGY-TRANSFER IN GDP5O14-EU3+,SM3+ SINGLE-CRYSTALS

In this paper we report on the luminescence and energy transfer in GdP4O14:Eu3+,Sm3+ (GdPP:Eu,Sm) in single crystals grown by the hydrothermal method. The room temperature excitation, emission, absorption and IR spectra of the crystals have been measured and analysed. The energy transfer from Gd3+ and Sm3+ to Eu3+ ions in GPP:Eu,Sm crystals is also discussed.

LUMINESCENCE OF BI(3+) AND THE ENERGY-TRANSFER FROM BI(3+) TO R(3+) (R=EU,DY,SM,TB) IN ALKALINE-EARTH BORATES

At room temperature, the Bi3+ ion shows broad band characters of its luminescence in Ca2B2O5, M3B2O6 ( M=Ca,Sr ) and SrB4O7. The maxima of the Bi3+ S-1(0)-->P-3(1) absorption bands are located in the range of 240-300nm, but the energy variation of the corresponding P-3(1)-->S-1(0) emissions is very large. The maxima of these emission bands change from 350nm in Ca3B2O6;Bi3+ to 586nm in SrB4O7:Bi3+. The Stokes shift of the Bi3+ luminescence increases from 6118 cm-1, in Ca2B2O5:Bi3+, to 24439 cm-1, in SrB4O7:Bi3+. The emission intensity of the Bi3+ luminescence increases with the decreasing Stokes shift. It has been found that in Ca2B2O5, the Bi3+ ion could transfer its excitation energy to the R3+ ions ( R=Eu, Dy, Sm, Tb ) , but in, Ca3B2O6 and Sr3B2O6, only Bi3+-->Eu3+ was observed. No energy transfer from Bi3+ to R3+ was detected in SrB4O7.

甲烷氧化偶联La-Mn-Li系复合氧化物催化剂的研究

用XRD、IR、XPS和SEM等方法研究了混合氧化物LiLa_(1-x)Mn_xO_2的结构和它们对甲烷氧化偶联的催化性能。结果表明,随着MnO_2的变化,可形成一系列复合氧化物,其中三元复合氧化物La_2Mn_(1-y)Li_yO_4是甲烷氧化偶联的活性相,由于Li~+部分取代Mn~(2+)形成Li~+-O~--Mn(2+)缺陷簇,增加了活性氧种的浓度和再生速度是这种氧化物具有较高甲烷偶联活性的主要原因。脉冲实验证明,CH_4脱氢生成CH_3·偶联生成C_2H_6,进一步氧化脱氢生成C_2H_4都可在催化剂表面完成,而CO和CO_2是在气相反应中生成的。在780℃C_2收率可达23.9%。

溶胶—凝胶法制备LaMO_3超微粉末(M=Cr、Mn、Fe、Co、Ni)

使用溶胶—凝胶法低温合成多组分氧化物玻璃的详细工艺已有报导。我们亦成功地用该法制备出了钕玻璃薄膜和钕玻璃纤维。本文报道利用此法低温合成LaCrO_3、LaMnO_3、LaFeO_3、LaCoO_3、LaNiO_3超微粉末的研究结果。

[n-C_9H_(19)NH_3]_2MCl_4(M=Cu、Mn、Zn、Co)层结构配合物固-固相变的热分析和红外光谱研究

本文用差示扫描量热(DSC)、热重(TG)和红外光谱法研究了标题配合物(简记为C_9M)的热稳定性和固—固相变.讨论了中心金属离子对热稳定性和相变的影响.发现其热稳定性依C_9Co>C_9Mn>C_9Zn>C_9Cu降低.固—固相变数目、相变温度和相变的有序—无序效应主要取决于中心金属离子的种类。Zn组配合物总相变的无序效应比Cu组高,在高温相为完全无序相。C_9Zn配合物低温相变(285K)主要来源于链间相互作用和堆积态的有序—无序变化.高温相为“链熔化”态.

A NOVEL METAL THIAMINE COMPLEX WITH A CYCLIC DIMER FORMED BY METAL-BRIDGED 2 THIAMINE LIGANDS - CRYSTAL-STRUCTURE OF [MN(THIAMINE)CL2(H2O)]2[THIAMINE]2CL4.2H2O

The crystal structure of [Mn(thiamine)Cl2(H2O)]2[thiamine]2Cl4.2H2O has been determined by X-ray diffraction methods. The compound contains a cyclic dimer of a complex cation with two thiamine ligands bridged by two Mn(II) ions across a crystallographic center of symmetry. Each Mn(II) is coordinated by two chloride atoms, a water molecule, a N(1') atom of the pyrimidine from a thiamine and an O(53) atom of the hydroxyethyl side chain from another thiamine. There are two free-base thiamine molecules related by a center of symmetry in the unit cell, which form a base-pair through the hydrogen bonds. Both the independent thiamine molecules in the asymmetric unit assume the common F conformation with phi-T = 10.0(9) and 3.6(10) and phi-P = 85.6(7) and 79.6(7), respectively. The compound provides a possible model for a metal-bridged enzyme-coenzyme complex in thiamine catalysis. Crystallographic data: triclinic, space group P1BAR, a = 12.441(4), b = 13.572(4), c = 11.267(3) angstrom, alpha = 103.15(2), beta 89.03(3), gamma = 115.64(2)-degrees, Z = 1, D(calc) = 1.524 g cm-3, and R = 0.050 for 3019 observed reflections with I > 3-sigma(I).

INVESTIGATION ON THE LUMINESCENCE PROPERTIES OF DY3+ AND EU3+ IN M3LN2(BO3)4 (M=CA, SR, BA, LN= LA, GD, Y)

In this paper, the luminescence properties of Dy3+ and Eu3+ in M3Ln2 (BO3)4 (M = Ca,Sr,Ba; Ln = La, Gd, Y) were systematically studied. The hypersensitive transitions of Dy3+ and Eu3+ were investigated in relation to the host compositions; the relationship between the energy of Eu3+ charge-transfer band and M2+ ion was discussed, and the concentration quenching of Dy3+ luminescence was reported.

INVESTIGATION ON THE LUMINESCENCE PROPERTIES OF DY-3+ AND EU-3+ IN ALKALINE-EARTH BORATES

In this paper, the yellow-to-blue intensity ratio of Dy3+ (Y/B) and the red-to-orange intensity ratio of Eu3+ (R/O) were studied in relation to the compositions and structures of alkaline-earth borates. The dependence of the energy of the Eu3+ charge-transfer band (CTB) and of the emission intensity of Dy3+ on the alkaline-earth ions and the boron content of the hosts is discussed.