The role of redox property of La2-x(Sr,Th)(x)CuO4 +/-lambda playing in the reaction of NO decomposition and NO reduction by CO

Two systems of mixed oxides, La2-xSrxCuO4 +/- lambda (0.0 less than or equal to x less than or equal to 1.0) and La(2-x)Tn(x)CuO(4 +/-) (lambda) (0.0 less than or equal to x less than or equal to 0.4), with K2NiF4 structure were prepared. The average valence of Cu ions and oxygen nonstoichiometry (lambda) were determined by means of chemical analysis. Meanwhile, the adsorption and activation of nitrogen monoxide (NO) and the mixture of NO + CO over the mixed oxide catalysts were studied by means of mass spectrometry temperature-programmed desorption (MS-TPD). The catalytic behaviors in the reactions of direct decomposition of NO and its reduction by CO were investigated, and were discussed in relation with average valence of Cu ions, A and the activation and adsorption of reactant molecules. It has been proposed that both reactions proceed by the redox mechanism, in which the oxygen vacancies and the lower-valent Cu ions play important roles in the individual step of the redox cycle. Oxygen vacancy is more significant for NO decomposition than for NO + CO reaction. For the NO + CO reaction, the stronger implication of the lower-valent Cu ions or oxygen vacancy depends on reaction temperature and the catalytic systems (Sr- or Th-substituted). (C) 2000 Elsevier Science B.V. All rights reserved.

Eu~(2+):MAl_2O_4(M=Ba~(2+),Sr~(2+))的发光与晶体化学键相关性的研究

本文应用复杂晶体化学键理论对Eu~(2+):MAl_2O_4(M=Ba~(2+),Sr~(2+))晶体的化学键参数进行了计算,讨论了晶体中Eu~(2+)的发光性与其所取代离子格位的化学键性质间的关系。

M_2B_5O_9Cl:Eu(M=Ca,Sr,Ba)的真空紫外光谱特性的研究

采用高温固相反应法合成了M_2B_5O_9Cl:Eu(M=Ca,Sr,Ba)中荧光体,测量了荧光体的真空紫外激发光谱,研究了M_2B_5O_9Cl:Eu(M=Ca,Sr,Ba)的真空紫外光谱特性,观察到基质吸收带位于120～200 nm区域,Eu~(2+)离子的5d能级劈裂随着M~(2+)的半径的增加而减小,同时也观察到基质与稀土离子之间存在的能量传递。

Evaluation of bond covalency and bond valence in Sr-doped perovskite-type compounds

Formulas for decomposing of complex crystals to a sum of binary crystals are described and applied to the study of bond covalency in La1-xSrxFeO3 (0.0 less than or equal to x less than or equal to 0.9) and Ca1-xSrxMnO3 (0.0 less than or equal to x less than or equal to 0.5). The bond valence is treated by bond-valence sums scheme. The results indicate that, for both compounds, with the increasing doping level, the bond covalency and bond valence show the same trend, namely, larger bond covalency corresponds to higher bond valence. For La1-xSrxFeO3, with the increase of doping level, the bond covalency of La-O, Ca-O decreases in the orthorhombic (0.0 less than or equal to x less than or equal to 0.2) and rhombohedral (0.4 less than or equal to x less than or equal to 0.7) systems, then increases slightly for the cubic (0.8 less than or equal to x less than or equal to 0.9) system, but that of Fe-O increases for all crystal systems. A sharp decrease in bond covalency was observed where the crystal changes from orthorhombic to rhombohedral, while a smooth trend was seen for the rhombohedral-to-cubic transition. On the other hand, for orthorhombic Ca1-xSrxMnO3, the bond covalency of Ca-O, Sr-O, and Mn-O (4-coordinate site) decreases with the increasing doping level, that of Mn-O (2-coordinate site) increases.

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.

甲烷与二氧化碳重整制取合成气反应的研究ⅢSr(La)NiAl11O19积炭动力学

用热重（ＴＧＡ）方法，研究了ＬａＮｉＡｌ１１Ｏ１９和ＳｒＮｉＡｌ１１Ｏ１９催化剂上甲烷与二氧化碳重整反应的积炭动力学．实验结果表明，甲烷裂解是ＣＨ４＋ＣＯ２反应中主要的积炭反应；甲烷与二氧化碳重整反应的积炭速率随反应温度升高而增大，但其衰减速度也较快；ＣＨ４＋ＣＯ２反应的积炭速率相对甲烷分压的反应级数是１，相对二氧化碳分压的反应级数是－０．５；在ＳｒＮｉＡｌ１１Ｏ１９中掺入Ｌａ３＋离子，提高了催化剂上甲烷裂解反应的活化能，降低了ＣＯ２消炭反应的活化能，从而提高了催化剂的抗积炭能力.

La_(2-x)(Sr,Th)_xCuO_(4±λ)系催化剂的表征及对CO+NO反应催化性能的研究

合成了x值不同的La2 -xSrxCuO4±λ( 0 .0≤x≤ 0 .1 )和La2 -xThxCuO4±λ( 0 .0≤x≤ 0 .4)两系列K2 NiF4型复合氧化物催化剂 ,用XRD和IR研究了催化剂的晶体结构 .利用化学分析和XPS等方法测定了该系列含Cu氧化物中Cu离子的平均价态、非化学计量氧 (λ)和催化剂的表面和体相组成 .通过控制B位Cu离子的价态和氧化物的非化学计量氧在一定范围内有规律的变化 ,考察对NO +CO反应的催化性能 ;利用MS TPD法研究了该系列氧化物对NO和CO +NO等小分子的吸附和活化性能 ,在此基础上探讨了含Cu的A2 BO4型复合氧化物对NO +CO反应中的催化作用本质 .发现在低温反应条件下 ,NO分子的活化是控制步骤 ,催化剂的活性与低价离子及其含量有关 .在较高反应温度下 ,NO的吸附为控制步骤 ,催化活性与氧空位有关

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.

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.

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...

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.

Comparative study on the doping effect of 3d elements in Bi(1.5)Pb(0.2)Sr(2)Ca(2)Cu(2.8)M(0.2)O(y) (M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni, or Zn)

With XRD, R-T, and ac chi measurements a comparative study on the doping effects of 3d elements in Bi(1.5)Pb(0.2)Sr(2)Ca(2)Cu(2.8)M(0.2)O(y) (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, or Zn) has been carried out. The effects of the former five members are significantly different, both on phase formed and on T-c, from the latter four. It seems that the effect on phase stabilization correlates with the valency of the doped cation. In connection with the instability of the 2223 phase, the correlation has been discussed.