Effect of strontium substitution on the activity of La2-xSrxNiO4 (x=0.0-1.2) in NO decomposition

The aim of this work is to study the effect of Sr substitution on the redox properties and catalytic activity of La2-xSrxNiO4 (x = 0.0-1.2) for NO decomposition. Results suggest that the x = 0.6 sample shows the highest activity. The characterization (TPD, TPR, etc.) of samples indicates that the x = 0.6 sample possesses suitable abilities in both oxidation and reduction, which facilitates the proceeding of oxygen desorption and NO adsorption. At temperature below 700 degrees C, the oxygen desorption is difficult, and is the rate-determining step of NO decomposition. With the increase of reaction temperature (T > 700 degrees C), the oxygen desorption is favorable and, the active adsorption of NO on the active site (NO + V-o + Ni2+ -> NO--Ni3+) turns out to be the rate-determining step. The existence of oxygen vacancy is the prerequisite condition for NO decomposition, but its quantity does not relate much to the activity.

Relationship between the structure and catalytic activity of La2-xSrxNiO4-lambda(0<=x<=1) mixed oxides for NH3 oxidation

A series of samples having the composition of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) were prepared and used as catalysts for NH3 oxidation. It was found that the La and oxygen vacancies exist in the La2-xSrxNiO4-lambda(0 less than or equal to x less than or equal to 1). The unit cell volume decreases with the increase of x. For bath c and a parameters there appeared a turning point at x = 0.5. Doping with a lower valence cation Sr2+ in the case of La2NiO4 resulted in an increase of Ni3+, consequently the formation of oxygen vacancies, the increase of reducing ability and the increase of catalytic activity. In the oxygen TPD of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) appeared three peaks, the alpha' peak at about 400K was attributed to the surplus oxygen desorption, the a peak at 700K which approaches to a maxium at x = 0.6 was attributed to the oxygen adsorbed at oxygen vacancies. The beta peak at about 1000K which depends closely on the x and favors the catalytic activity was attributed to the reduction of Ni3+. The catalytic activity of La-2-x SrxNiO4 mixed oxides in the NH3 oxidation in general could be attributed to the extent of the redox reaction: 2Ni(2+) + O-2 + V-0(..) reversible arrow 2Ni(3+) + 20(-) where V-0(..) representes the oxygen vacancies and O- the oxygen species adsorbed at the vacancies.

THE EFFECT ON PHYSICAL-PROPERTIES OF THE SUBSTITUTION OF CA OR BA FOR SR IN NDSRNIO4

A new solid solution series, NdSr(1-x)M(x)NiO(4) (M = Ca: 0.0 less than or equal to x less than or equal to 1.0; M = Ba: 0.0 less than or equal to x less than or equal to 0.6), was synthesized by solid state reaction, and the structures, magnetic and electrical properties and optical spectra of this series have been studied. All the samples crystalized in tetragonal systems, with the exception of NdCaNiO4, which crystallized in the orthohombic system. IR spectra of NdSr1-xCaxNiO4 indicated that the lengths of two Ni-O bonds decrease with increasing Ca content. The electrical conduction changed from metallic-type to semiconductive-type when x greater than or equal to 0.4 (M = Ca, Ba), and the room temperature resistivities of NdSr1-xCaxNiO4 increased with the increase of Ca content. Magnetic susceptibility measurements revealed that Ni+3 ions in all the samplies were in low-spin state over the temperature range 77-300 K.

Influence of Fe3+ on perovskite oxides: La2/3Ca1/3Mn1-xFexO3

The structure and magnetoresistance properties in sintered samples of La-2/3 Ca-1/3 Mn1-x FexO3 (0 less than or equal to x less than or equal to 0.84) are studied by using Mossbauer spectroscopy, XRD and magnetic measurement. There are antiferromagnetic interactions between Fe and its nearest neighbors (Fe, Mn) when 0 less than or equal to x less than or equal to 0.67, which are important factors influencing the double-exchange between Mn3+ and Mn4+, Curie temperature, magnetic moment and GMR. It is suggested that the Mn3+(Fe3+)/Mn4+ system also consists of magnetic clusters with different sizes.

Synthesis, characterization and electrical properties of solid state electrolyte materials La2-xCaxMo1.7W0.3O9-delta (0 <= x <= 0.2)

The new compounds La2-xCaxMo1.7W0.3O9-delta (0 <= x <= 0.2) in which La3+ substituted with Ca2+ were synthesized by dry-chemistry techniques based on the oxygen Ionic conductor La2Mo1.7W0.3O9. The new series were characterized by X-ray Diffraction (XRD), Raman and X-ray Photoelectron Spectroscopy (XPS) and the electrical conductivity of samples were investigated by AC impedance spectroscopy. The lattice parameters were reduced due to the smaller atomic radius of the Ca2+ compared with that of the La3+. Furthermore, Additional oxygen vacancies were introduced into La2Mo1.7W0.3O9 lattice by substitution, and then the oxygen ionic conductivity was increased. At 550 degrees C, the conductivity increased 89.9%, that is, from 0.79 x 10(-4) S center dot cm(-1) (x=0) to 1.5 X 10(-4)S center dot cm(-1) (x=0.16, 0.2).

Effect of valence of copper in La2-xThxCuO4 on NO decomposition reaction

NO decomposition reaction was investigated over La2-xThxCuO4, in which the valence of copper was controlled by Th substitution and was characterized by XPS measurement. A close correlation between the valence of copper and the activity was observed. The activity increased with the decrease of the average oxidation number of copper, and increased with the increase of Cu+ content, suggesting that the transition metal with low valence (Cu+) is active for the reaction in the present cases.

Synthesis, structure and ionic conductivity of La2/3-xLi3xMoO4

A series of compounds, La2/3 - xLi3xMoO4, were first prepared. Their structures are tetragonal scheelites with the cationic defects. The cell parameters a, c and values of c/a decrease with the increasing of the substitution amount (3x) of lithium ion. Cationic vacancies are getting more as Li+ concentration is lower. The diffusion of lithium ion is predominant. The concentration of charge carriers increases with increasing the substitution amount (3x) of lithium ion, meanwhile, the concentration of cationic vacancies decreases. The conductivity approaches the best when the substitution amount (3x) of lithium ion is about 0.3. The conductivity of La0.567Li0.3MoO4 is 6.5 x 10(-6) S . cm(-1) at room temperature.

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.

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.

Preparation, physico-chemical behavior and catalytic property for ammonia oxidation of perovskite like mixed oxides La2-xSrxCuO4-lambda

A series of Sr2+ doped perovskite like oxides La2-xSrxCuO4-lambda (x = 0 similar to 1) were prepared, the structure, lattice parameters, content of Cu3+, oxygen vacancies created by Sr2+ substitution and composition of these complex oxides were studied by XRD and iodic titration method. The redox ability,active oxygen species and surface image were evaluated and analyzed with TPD, TG, XPS and SEM measurements. The catalytic activity for ammonia oxidation over these oxides was tested, and the relationship among the catalytic properties, structure, nonstoichiometric oxygen,redox ability and surface behavior were correlated and some information on the mechanism of ammonia oxidation was obtained.

Superconductor mixed oxides La2-xSrxCuO4+/-lambda for catalytic hydroxylation of phenol in the liquid-solid phase

Superconductor mixed oxides are often used as catalysts at high temperature in gas-solid phase oxidations and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of La2-xSrxCuO4+/-lambda (x = 0, 0.1, 0.7, 1) mixed oxides in phenol hydroxylation at lower temperatures are studied, and we find that the value of x has a significant effect on catalytic activity: the lower its value, the higher the catalytic activity; a mechanism is proposed to explain the experimental phenomena.

SYNTHESIS, CHARACTERIZATION AND CATALYTIC BEHAVIOR OF LA2-XSRXCOO4+/-LAMBDA (X=0-2) IN COMPLETE OXIDATION

A series of mixed oxides La2-xSrxCoO4+/-lambda (x=0-2) with varying x values was synthesized. The crystal structure of this series of mixed oxides was studied by using XRD. The result showed that when x=0.25-1.5 the mixed oxides possessing K2NiF4 structure are formed. The valences of the transition metal Co and the relation between +/-lambda content and x value by using chemical analysis method have been measured, too. The redox property of this series of mixed oxides and different kinds of oxygen species were studied by IR, TPD, TPR, XPS and SEM methods. The catalytic activity in the complete oxidation of CO and CH4 was investigated and the relationships between the activity, composition and structure of the mixed oxides have been elucidated.

La2Zr2O7的增韧及陶瓷纤维的制备

La2Zr2O7是一种近年来才提出的新型热障涂层材料，该材料熔点高，在熔点以下不发生相变，热导率低，抗烧结及没有氧传输发生，这些特点使得它作为一种高温下应用的热障涂层材料越来越引起人们的重视。但是，由于该材料的热膨胀系数和断裂韧性比较低，它的实际应用受到了限制。 在本论文中，使用高压烧结的方法获得了致密化的纳米La2Zr2O7块体材料，并对其断裂韧性和热膨胀系数进行了研究。得到的La2Zr2O7纳米材料的断裂韧性和热膨胀系数分别为1.98MPam1/2和9.6×10-6K-1 (200-1000℃)，这些数值明显高于非纳米的La2Zr2O7陶瓷(断裂韧性和热膨胀系数分别为1.40 MPam1/2 和 9.1×10-6 K-1，该结果表明纳米化是一种提高材料断裂韧性和热膨胀系数的有效方法。在La2Zr2O7纳米粉末中加入8YSZ纳米颗粒，高压烧结后使其颗粒充分生长，在得到的复相化合物中观察到形成了类似棒状晶体的自增韧相，使得复合材料的断裂韧性(1.88 MPam1/2)比La2Zr2O7有所提高，甚至超过了同样条件下制备的8YSZ样品的断裂韧性。 La2Zr2O7的断裂韧性也可以通过在基体中添加BaTiO3铁电材料得到明显的提高。当添加BaTiO3的体积含量达到10vol％时，4.5GPa，1450℃高压烧结10min得到的复合材料断裂韧性达1.98 MPam1/2，明显高于同条件下烧结的La2Zr2O7 (1.60MPam1/2)。应力诱导下BaTiO3的电畴转向是主要的增韧原因。随着BaTiO3颗粒添加的体积含量增加，复相化合物的热膨胀系数也明显提高。当掺杂20vol％BaTiO3时，得到的复合材料平均热膨胀系数达到10.2×10-6K-1 (150~1200℃)。 我们通过在4.5GPa, 1650℃高压烧结5min的方法还获得了掺杂YAG纳米颗粒的La2Zr2O7纳米复相陶瓷。在室温下测量了材料的维氏硬度，并通过压痕裂纹长度计算出了材料的断裂韧性。随着YAG纳米颗粒体积含量的增加，纳米复相陶瓷的断裂韧性和维氏硬度都依次增加，当添加20vol％的YAG纳米颗粒时达到最大，分别为1.93 MPam1/2和11.45GPa。断裂韧性增加的机理可归结为以下三点：一是YAG纳米颗粒的添加提高了La2Zr2O7基体的晶界强度，二是基体晶粒尺寸变化的影响，三是YAG纳米颗粒对裂纹的偏转和钉扎作用。添加微米YAG颗粒的复相化合物因为和纳米复相陶瓷具有不同的增韧机制，因此断裂韧性的变化趋势也不相同，在掺入10vol％的YAG微米颗粒时，复合材料的断裂韧性最大，而后降低，当掺入YAG微米粒子的体积含量达到20vol％时，断裂韧性甚至低于La2Zr2O7。 从20世纪90年代开始，电纺作为一种合成纤维的办法越来越吸引人们的注意。其合成的纤维长度长，直径均匀，并且组成范围很广。最初，电纺只是被用来合成一些有机聚合物的纤维，最近，很多研究组开始致力于使用电纺的方法合成复合纤维或者陶瓷纤维。 在本论文中，我们使用电纺的方法获得了La2Zr2O7纳米纤维和SiC单晶纳米线。1000℃煅烧得到的La2Zr2O7纳米纤维具有烧绿石结构，直径在200~500nm之间。同样的温度煅烧时得到的La2Zr2O7纳米纤维的比表面积要明显高于粉末样品的，表明纤维的抗烧结性能比粉末的高。得到的SiC纳米线直径在50~100nm之间，表面有一约5nm厚的无定形的SiO2薄层。 使用电纺的方法，恰当的控制煅烧条件，我们获得了La2Ce2O7， La2(Zr0.745Ce0.386)2O7.524和8YSZ中空纤维。这种中空结构减小了粒子之间的接触面积，提高了材料的抗烧结性能。在扫描电镜分析的基础上，我们总结了这些中空纤维的形成过程。