Me_2CeO_4(M=Ca,Sr,Ba)的结构与发光特性

1998年Science上报导了一种新的一维结构发光体—Sr_2CeO_4,引起人们的关注。美国已制备出满足场发射显示器(FED)用 Sr_2CeO_4蓝色荧光粉,而且确信其用于场发射显示器具有很大的潜力。本文中合成了M_2CeO_4(M=Ca,Sr, Ba),讨论了其发光与结构的相关性。Me_2CeO_4(M=Ca,Sr, Ba)均采

Perovskite-like mixed oxides La2-x(Sr,Th)(x)CuO4+/-lambda

Two groups of mixed oxides La2-xThxCuO4+/-lambda (0.0 less than or equal to x less than or equal to 0.4) and La2-xSrxCuO4+/-lambda (0.0 less than or equal to x less than or equal to 1.0) were prepared. Their crystal structures were studied with XRD and IR spectra, etc. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) was measured through chemical analyses. Catalysis of the abovementioned mixed oxides was investigated in phenol hydroxylation, good results were obtained for some mixed oxides, and found that the catalysis of these mixed oxides have close relation with their defect structure and composition. A radical substitution mechanism was also proposed for this catalytic reaction.

Synthesis and properties of optically active aromatic polyimides derived from optically pure 1,1'-bi-2-naphthol

A series of new optically active aromatic polyimides containing axially dissymmetric 1,1'-binaphthalene-2,2-diyl units were prepared from optically pure (R)-(+)-or (S)-(-)-2,2'-bis(3,4-dicarboxyphenoxy)-1,1'-binaphthalene dianhydrides and various aromatic diamines via a conventional two-step procedure that included ring-opening polycondensation and chemical cyclodehydration. The optically pure isomer of dianhydride was prepared by a nucleophilic substitution of optically pure (R)-(+)or (S)-(-)1,1'-bi-2-naphthol with 4-nitrophthalonitrile in aprotic polar solvent and subsequent hydrolysis of the resultant tetranitrile derivatives, followed by the dehydration of the corresponding tetracarboxylic acids to obtain the dianhydrides. These polymers were readily soluble in common organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., and have glass transition temperatures of 251-296 degrees C, and 5% weight loss occurs not lower than 480 degrees C. The specific rotations of the optically active polyimides ranged from +196 degrees to +263 degrees, and the optical stability and chiroptical properties of them were also studied. (C) 1997 John Wiley & Sons, Inc.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

Luminescence properties of Ce3+ in KMF3(M=Mg, Ca, Sr, Ba) hosts with perovskite structure

KMF3(M = Mg, Ca, Sr, Ba) compounds were synthesized by solid state reaction under argon atmosphere. Their structures were determined by X-ray diffraction. It belongs to cubic system with perovskite structure. The excitation and emission spectra of KMF3:Ce3+ were measured. According to the characteristics of spectral structures, the occupation site of Ce3+ is discussed.

The synthesis of a 1,1'-bi-2-naphthol-based bis(ether anhydride) and aromatic polyimides derived therefrom

2,2'-Bis(3,4-dicarboxyphenoxy)-1,1'-binaphthyl dianhydride was used as a new monomer with various aromatic diamines to obtain polyimides by the usual two-step method. The bis(ether anhydride) was prepared by a nucleophilic substitution of I,1'-bi-2-naphthol with N-phenyl-4-chlorophthalimide, N-methyl-4-nitrophthalimide or 4-nitrophthalonitrile in aprotic polar solvent, and subsequent hydrolysis of the resulting bis(ether imide)s or bis(ether dinitrile), and then dehydration of the corresponding tetracarboxylic acid to afford the dianhydride. Most of the obtained polyimides were soluble in chloroform, pyridine, DMF, etc. The polyimide prepared from p-phenylene diamine was partial crystalline, whereas the others showed amorphous patterns in a WAXD study. These polymers have glass transition temperatures between 255-294 degrees C and 5% weight loss temperatures in the range of 502-541 degrees C in nitrogen and 473-537 degrees C in air. (C) 1997 Elsevier Science Ltd.

复合氧化物La_(2-x)(Sr,Th)_xCuO_(4±λ)——一种新型的苯酚羟化催化剂

二酚(邻苯二酚,对苯二酚)是重要的化工原料,二酚生产一直是人们所关注的课题,70年代以前主要采用的一些污染严重的生产过程正被逐渐淘汰。目前,利用过氧化氢和苯酚为原料联产邻苯二酚和对苯二酚,在化工生产中占有重要的地位。常见的催化剂有等。但这些催化剂也具有明显的不足之处,前两者具有均相催化反应本身难以克服的缺点,后者虽具有多相催化过程的优点,但由于此类催化剂难以制取,而且此类催化剂主要反应孔道的孔径较小(<0.9 nm),反应物和生成物难以在孔道中扩散,使得反应速度较慢。当前国际上还正在积极寻找新的催化体系以达到高效无污染生产二酚的目的。

离子型晶体的点电荷电量的确定和晶体的化学键性质MX(M=Mg,Ca,Sr,Ba,X=O,S,Se,Te;不含MgTe)

离子型晶体的点电荷电量的确定和晶体的化学键性质ＭＸ（Ｍ＝Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ｘ＝Ｏ，Ｓ，Ｓｅ，Ｔｅ；不含ＭｇＴｅ）孟庆波武志坚张思远（中国科学院长春应用化学研究所稀土无机材料实验室，长春１３００２２）ＮｅｔＣｈａｒｇｅａｎｄＣｈｅｍｉｃａｌＢｏｎ...

Eu~(3+)在YAG中的发光性能及Eu~(3+)、Bi~(3+)间的能量传递

ＹＡＧ作为一种新型的功能材料已引起了人们极大的兴趣，我们采用溶胶、凝胶法合成了ＹＡＧ：Ｅｕ和ＹＡＧ：Ｅｕ，Ｂｉ，研究了Ｅｕ３＋在ＹＡＧ中的发光及Ｅｕ３＋，Ｂｉ３＋间的能量传递。１实验部分将纯度９９．９９％Ｙ２Ｏ３，Ｅｕ２Ｏ３和Ｂｉ２Ｏ３分别溶于ＧＲ级ＨＮＯ３中，配制成一定浓度的溶液，然后以Ｙ（ＮＯ３）３，Ｅｕ（ＮＯ３），Ｂｉ（ＮＯ３）３和Ａｌ（ＮＯ３）３为初始原料，按（Ｙ１－ｘＥｕｘ）３ＡＬ５Ｏ１２和（Ｙ１－ｘ－ｙＥｕｘＢｉｙ）３Ａｌ５Ｏ１２化学式量配比，充分混匀后加入柠檬酸，缓慢蒸干，在４００℃灼烧２ｈ

Roles of oxygen vacancy and lower valence metallic ion in direct decomposition of NO over La-2-x(Sr,Th)(x)CuO4+/-lambda

Two systems of La2-xSrxCuO4+/-lambda and La2-xThxCuO4+/-lambda, mixed oxides with K2NiF4 structure were synthesized. The compositions and structures of the catalysts were characterized by means of XRD, XPS, chemical analysis and so on. The catalytic behavior for the direct decomposition of NO has been investigated. The results show that the catalytic activity is closely related to the oxygen vacancy and lower valence metallic ion in the direct decomposition of NO. The presence of oxygen vacancy is necessary for mixed oxide to have steady activity in NO decomposition.

MMgF_4(M=Ca,Sr,Ba)体系中Eu和Tb的电荷迁移

于不同气流中,合成了MMgF_4:xEU,yTb复合氟化物燐光体.该体系中Eu~(3+)和Eu~(2+)共存.Tb的存在影响Eu的价态存在形式.ESR测试表明,随Tb的掺入浓度增加,Eu~(2+)的浓度呈规律性变化.随Eu的掺入,样品的XPS谱中出现了四价铽的Tb_3d(5/2)特征伴峰.认为Eu~(3+)和Tb~(3+)之间存在电荷迁移平衡.即Eu~(3+)+Tb~(3+)(?)Eu~(2+)+Tb~(4+).通过半定量手段研究了SrMgF_4中这一平衡的平衡常数.

Ce~（3＋）在钙钛矿型KMF_3（M＝Mg、Ca、Sr、Ba）基质中的发光特性

采用高温固相反应法，在Ａｒ气氛中合成了ＫＭＦ３（Ｍ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）基质化合物和掺杂Ｃｅ３＋的磷光体。经Ｘ射线衍射分析确定，ＫＭｇＦ３和ＫＣａＦ３属于立方晶系、钙钛矿型结构，ＫＳｒＦ３和ＫＢａＦ３具有类似的结构。测定了ＫＭＦ３∶Ｃｅ３＋的发光光谱，观察到与其结构对应的分为二种不同的光谱结构，讨论了Ｃｅ３＋的取代格位

多组分氧化物Ag－Bi－V－Mo－O催化作用的光电子能谱研究

多组分氧化物Ａｇ－Ｂｉ－Ｖ－Ｍｏ－Ｏ催化作用的光电子能谱研究宋伟，李静，窦伯生（中国科学院长春应用化学研究所长春１３００２２）关键词　钼钒酸铋，助剂Ａｇ，ＸＰＳ，Ａｒ~＋刻蚀，氧化还原对于烃类选择氧化反应中复合氧化物的催化作用，普遍认为是Ｒｅｄｏｘ机...

丙烷氧化反应中多组分氧化物Bi－V－Mo－O催化作用的红外光谱研究

丙烷氧化反应中多组分氧化物Ｂｉ－Ｖ－Ｍｏ－Ｏ催化作用的红外光谱研究李静，宋伟，窦伯生（中国科学院长春应用化学研究所长春１３００２２）关键词钼钒酸铋，丙烷，选择氧化，催化作用机理，红外光谱迄今对于含有钼、铋复合氧化物催化剂的活性中心和作用机理存在不同看...