La0.6Sr0.4MnO3纳米薄膜的制备及其光催化活性

在室温下,采用溶胶-凝胶法和浸渍提拉技术在载玻片基底上制备出了钙钛矿型La0.6Sr0.4MnO3薄膜;采用TG/DTA技术分析了金属羧酸盐凝胶的热分解历程;通过XRD进行了物相分析,并计算了其晶粒尺寸;利用AFM观察了薄膜的形貌特征.实验结果表明,La0.6Sr0.4MnO3薄膜在570 ℃形成,为三方晶系,其平均晶粒度为10.8 am.采用制备出的La0.6Sr0.4MnO3薄膜对多种水溶性染料进行了光催化降解实验,研究发现,该纳米薄膜有较好的光催化效果,在9 h内对酸性红A、酸性橙Ⅱ、弱酸性黄C-3GN、直接绿BE、弱酸性蓝C-RL的脱色率分别达到95.56%,89.70%,97.56%,98.40%和81.16%.     

Magnetocaloric properties of La0.6Ca0.4MnO3

A theoretic work on magnetocaloric properties of the polycrystalline La_0.6Ca_0.4MnO₃ system near a second-order phase transition from a ferromagnetic to a paramagnetic state is presented. The value of the magnetocaloric effect has been determined from the calculation of magnetization as a function of temperature under different external magnetic field shifts. The magnetic entropy change ?S _M reaches a peak of about 3 J kg^?1 K^?1 at 266 K upon 1.60 KA/m applied field variation. The ?S _M distribution is much more uniform than that of gadolinium, which is desirable for an Ericson-cycle magnetic refrigerator, which is beneficial for the household application of active magnetic refrigerant materials.     

Ag/La0.6Sr0.4MnO3 Catalysts for Complete Oxidation of Alcohol Fueled Car Exhausts

Alcohol fuel has been suggested as an alternative for car operation to reduce gasoline consumption^[1]. However, being different from that of gasoline car, alcohol-fueled car exhaust principally contains unburned alcohol and formaldehyde/acetaldehyde^[2]. These volatile C₁/C₂ organics may have an undesirable impact on air quality. Most of the existing catalysts for complete oxidation of alcohol are precious metal catalysts supported by γ-Al₂O₃^[2,3].     

Influence of heat treatment on the magnetic and magnetocaloric properties in Nd0.6Sr0.4MnO3 compound

In the present investigation, the effect of annealing temperature on the structural, electrical transport and the magnetocaloric effect of Nd_0.6Sr_0.4MnO₃ manganites have been studied. Rietveld refinement of XRD data reveals that all samples are single phase with a space group (Pnma). Heat treatment enhances the grain size and decreases the porosity. All samples suffer Curie transition from ferromagnetic to paramagnetic. Magnetocaloric parameters have been determined by the analysis of isothermal M (H) curves around Curie temperature (ΔH = 2 T) for samples. Heat treatment enhances magnetic entropy, which reaches a maximum at T_an = 900 °C. In addition, the rate cooling power records highest value at T_an = 700 °C.     

Electrochemical characteristics of La0.6Sr0.4CoO3-δ, Pr0.6Sr0.4CoO3-δ and Gd0.6Sr0.4CoO3-δ on Ce0.85Sm0.15O1.925 electrolyte

Cyclic voltammetry, chronoamperometry and electro-chemical impedance have been used for the analysis of the following medium temperature half-cells: Ce_0.85Sm_0.15O_1.925| La_0.6Sr_0.4CoO_3-δ, Ce_0.85Sm_0.15O_1.925| Pr_0.6Sr_0.4CoO_3-δ and Ce_0.85Sm_0.15O_1.925| Gd_0.6Sr_0.4CoO_3-δ. The influence of the atomic mass of the A–site cation in the perovskite cathode on the oxygen reduction kinetics has been discussed. The total polarisation resistance, obtained from the Z′′, Z′-plots, increases with the rise of atomic mass of the cation in the A-site position. Two different time constants have been obtained for the oxygen electroreduction process, and the replacement of La³⁺ by Gd³⁺ in the cathode material decreases somewhat the surface catalytic activity, but the noticeably higher low-frequency series resistance, i.e. mainly diffusion-like mass transfer resistance, values have been obtained. However, the mainly diffusion-limited process at T≤773 K for Gd_0.6Sr_0.4CoO_3-δ and the kinetically mixed process (diffusion + charge transfer) for Pr_0.6Sr_0.4CoO_3-δ and La_0.6Sr_0.4CoO_3-δ have been established. At higher temperature (T≥993 K) and more negative potentials, the O₂ reduction process is limited mainly by the heterogeneous charge transfer step. Presented at the fourth Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005.     

低浓度甲烷甲醇深度氧化Ag/La0.6Sr0.4MnO3催化剂

用柠檬酸溶胶－凝胶法制备钙钛矿型Ｌａ０．６Ｓｒ０．４ＭｎＯ３氧化物,并用Ａｇ对其进行修饰,制得Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３系列催化剂。结果表明,６％Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３催化剂上甲烷或甲醇氧化转化９５％时的反应温度Ｔ９５可低至７３５Ｋ（对ＣＨ４）或４２１Ｋ（对ＣＨ３ＯＨ）;适量Ａｇ的负载修饰并不改变催化剂基质氧化物Ｌａ０．６Ｓｒ０．４ＭｎＯ３的纳米级钙钛矿型结构;Ａｇ的掺杂诱使催     

Ag/La0.6Sr0.4MnO3基催化剂上CH3OH和CO的完全氧化

合成了Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３、Ａｇ／Ｌａ０．６Ｓｒ０．４ＭｎＯ３／γ－ＡＩ２Ｏ３两毓催化剂,发现钙钛矿型Ｌａ０．６Ｓｒ０．４ＭｎＯ３对低浓度ＣＨ３ＯＨ或ＣＯ的完全氧化显示出相当高的催化活性,适量Ａｇ对钙钛矿型Ｌａ０．６Ｓ５０．４ＭｎＯ３基质的修使其对ＣＨ３ＯＨ或ＣＯ完全氧化催化活性获明显提高;在６％Ａｇ／２０％Ｌａ０．６Ｓｒ０．４ＭｎＯ３／γ－ＡＩ２Ｏ３催化剂 ,ＣＨ３ＯＨ完全氧化的Ｔ     

Oxygen nonstoichiometry and ionic transport properties of La0.4Sr0.6CoO3-delta

Homogeneous samples of La0.4Sr0.6CoO3-delta were obtained by the glycine nitrate process. The oxygen nonstoichiometry was determined from oxygen exchange measurements as a function of oxygen partial pressure (10(-4) bar < PO2 < 10(-2) bar) and temperature (300 degrees C < T< 900 degrees C). The chemical diffusion coefficient D was obtained from oxygen exchange measurements applying a stepwise variation of the oxygen partial pressure of the ambient atmosphere of a disk-shaped sample. The amount of oxygen absorbed or desorbed by the perovskite was analyzed as a function of time. Chemical diffusion data were evaluated using simplified and exact fitting procedures taking into account the surface exchange coefficient. Alternatively, galvanostatic polarization measurements were performed in a PO2-range between 10(-4) and 10(-2) bar to yield D and the ionic conductivity sigma(i) from the long time solution of the diffusion equation. Values for D from polarization measurements at T= 775 degrees C and from oxygen exchange measurements at T= 725 degrees C are in good agreement with each other. D and sigma(1) increase with increasing PO2 (10(-4) to 10(-2) bar). The ionic conductivity shows a maximum at 3-delta approximately 2.82 and decreases with decreasing oxygen content indicating the possible formation of vacancy ordered structures.     

锰掺杂Ba0.6Sr0．4TiO3-MgTiO3复相陶瓷的制备和介电性能

以分析纯的Ba(NO3)2、Sr(NO3)2、草酸和钛酸丁酯为原料,采用草酸盐共沉淀法制备了钛酸锶钡(Ba0.6Sr0.4tiO3,BST)纳米粉体.XRD和SEM分析结果表明,该方法制备出立方相的Ba0.6Sr0.4TiO3粉体,平均粒径小于100 nm,具有较高的烧结活性.用传统固相法制备了锰掺杂钛酸锶钡.钛酸镁(Ba0.6Sr0.4TiO3-MgTiO3,BST-MT)复相陶瓷,系统研究了掺杂0.1%-2.0%(x,摩尔分数,下同)锰对钛酸锶钡-钛酸镁复相陶瓷微观形貌和介电性能的影响机理.结果表明,当锰的掺杂量小于1.5%时,Mn作为受主掺杂取代占据钙钛矿ABO3的B位,因此导致居里点略微向高温偏移和相变扩散的发生,锰的掺杂导致晶格畸变,促进了晶粒生长,使晶界相比例下降,因此介电损耗随着锰掺杂量的增大而减小;当锰的掺杂量为1.5%时,介电损耗达到最小值,继续增大掺杂量,介电常数下降,介电损耗上升.     

稀土掺杂Ba0.6Sr0.4TiO3薄膜的介电及发光性能

以钛酸锶钡和稀土氧化物粉末靶为靶材, 用离子束溅射法在MgO(100)和Si(100)基片上组合制备了不同掺杂浓度的Ba0.6Sr0.4TiO3:Re(BST:Re)薄膜样品阵列. 沉积得到的多层无定形薄膜经低温扩散、高温晶化, 形成BST:Re多晶薄膜. 以扫描近场微波显微镜测定BST:Re/MgO(Re=Er, Eu, Pr/Al)样品的介电常数, 研究掺杂种类及掺杂浓度对BST薄膜介电常数的影响. 结果表明, 稀土离子的适量掺杂使BST薄膜介电常数有所提高, 其中, Er3+和Eu3+的最佳掺杂浓度分别为4.5%及5.7%(原子分数) 左右时, 介电常数值达到最高. 而共掺杂Pr3+和Al3+的样品则在n(AL):n(Pr)为4-8之间介电性能最佳. 另外, 测量了BST:Re/Si(Re=Er, Eu)样品的光致发光谱, 发现Er3+和Eu3+在BST薄膜样品中的发光猝灭浓度分别为4.20%和8.95%(原子分数).     

钙钛矿型锰酸盐(Sm_(0.4)Ca_(0.6)MnO_3)的水热合成及其电性能

以Sm(NO3)3,Ca(NO3)2,KMn O4和Mn Cl2为原料,用水热法合成了混合价态的钙钛矿型锰酸盐Sm0.4Ca0.6Mn O3(1),其结构和性能经SEM,元素分析,TGA,XRD,XPS,I-V曲线和变温电阻表征。结果表明:1为黑色立方晶体,正交晶系,空间群Pnma;1的晶胞参数a=5.336(6),b=5.341(7),c=7.491(6),V=213.56(3)3;1的热稳定性较好,有半导体特性和负磁电阻效应。     

La0.6Sr0.4Co1-yFeyO3钙钛矿复合氧化物的GNP法合成与导电性能

采用甘氨酸-硝酸盐(GNP)法合成出La_0.6Sr_0.4Co_1-yFe_yO₃(y=0～1.0)体系复合氧化物,对合成产物的结构、烧结性能和导电性进行了表征.研究结果表明,不同n(Co)/n(Fe)比的合成粉料中形成菱形六面体钙钛矿结构,合成粉料的颗粒细小均匀.在室温～900℃范围内,La_0.6Sr_0.4CoO₃(y=0)的电导率随温度的升高而单调降低,其它n(Co)/n(Fe)比的样品电导率随着温度升高到600℃附近时达到最大值.在低温段,La_0.6Sr_0.4Co_1-yFe_yO₃体系的导电行为符合小极化子导电机制,导电活化能随n(Co)/n(Fe)比的降低而增大.与常规固相合成法相比,甘氨酸-硝酸盐法制备的La_0.6Sr_0.4Co_1-yFe_yO₃具有更高的烧结活性和电导率.     

Improvement in stability of La0.4Ba0.6CoO3 cathode by combination with La0.6Sr0.4Co0.2Fe0.8O3 for intermediate temperature-solid oxide fuel cells

Improvement in long-term stability and cathodic activity of La_0.4Ba_0.6CoO₃ (BLC) was studied by mixing with La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF). LSCF exhibits good long-term stability; however, surface activity is not high like Co-based perovskite. On the other hand, the cathodic activity of BLC is high; however, long-term stability was not so good and large degradation at initial period is observed. Combination of the two oxides shows small overpotential as well as improved long-term stability. Effects of BLC/LSCF ratio on stability and overpotential were studied and it was found that BLC–LSCF (7:3) showed the most stable and small cathodic overpotential among the examined compositions. Although the power density was still slightly decreased over 24 h at 0.5 V terminal voltage, the maximum powder density of the cell using BLC–LSCF composite oxides for cathode shows 2.5 times larger than that of the cell using LSCF cathode and 1.06 times larger than that of BLC. Degradation rate is smaller than 4 % from 5 to 24 h on this BLC–LSCF cathode at current density as high as 682 mA/cm² after 24 h operation.     

中温燃料电池阴极材料la0.6sr0.4fe0.8co0.2o3的合成与性能

固体氧化物燃料电池;阴极材料;溶胶-凝胶法     

La0.6Sr0.4Co0.8Fe0.2O3钙钛矿复合氧化物的柠檬酸盐法合成与导电性能

采用柠檬酸盐法合成出La0.6Sr0.4Co0.8Fe0.2O3钙钛矿复合氧化物超细粉料,考查了各种影响溶胶与凝胶的形成以及合成粉料晶体结构与颗粒形态的因素,并确定了最佳的合成条件。研究了烧成温度对La0.6Sr0.4Co0.8Fe0.2O3电导率的影响,发现1200℃是最合适的烧成温度。研究结果表明,在室温～900℃范围内,样品的电导率在600℃附近出现峰值(～103S·cm-1),在低温段样品的导电行为符合小极化子导电机制,不同烧成温度的样品的导电活化能基本一致(5.31～5.79kJ·mol-1)。与常规固相合成法相比,柠檬酸盐法合成的La0.6Sr0.4Co0.8Fe0.2O3具有更高的烧结活性和电导率。     

Relationship between spontaneous generation of voltage and structural features in a single crystal of Pr0.6Ca0.4MnO3

Spontaneous generation of electrical voltage U was found for the perovskite-like single crystal of Pr_0.6Ca_0.4MnO₃, wherein the charge and orbital orderings occur at T _CO = 240 K and the antiferromagnetic one occurs at the Neel point T _N = 174 K. With decreasing the temperature, the U value increases first slowly (in the temperature range of 300 K-T _CO) and then more rapidly (T _CO-T _N). Starting from T _N, U increases exponentially and, at 85 K, reaches the value of 115 mV (in the ab plane) and 6.5 mV (along the c axis). The magnetic field has a different effect on the U value in different temperature ranges: in the temperature range of 85–130 K, it decreases U and, in the range of 130–240 K, increases U. The spontaneous voltage is thought to be caused by the existence of ferromagnetic and charge-orbital-ordered clusters of different topology in the sample. The latter clusters have own features and their structure are described by the non-centrosymmetric space group P2₁ nm.     

Decomposition of High Concentration Hydrogen Peroxide over Alumina-Supported Lao.6Sr0.4MnO3 Perovskite Catalyst

In recent years there has been ever-increasing interest in space propellants that are more environmentally benign,less toxic and easier and safer to handle than conventional ones     

XPS study of Ba_(0.6)K_(0.4)BiO_3

Single crystal Ba_(0.6)K_(0.4)BiO_3 was studied by using XPS.The results show that there isno evidence for the presence of Bi~(5+) in single crystal of Ba_(0.6)K_(0.4)BiO_3;instead,there is evidence forthe presence of mixed valent Bi~(3+) and Bi~((3+)-δ).Moreover,the O1s XPS results suggest the presenceof mixed valent O~(2-) and O~(1-),and the valence band spectrum suggests the high degree of covalencyfor Bi—O bonds.     

纳米La0.6Sr0.4Co0.2Fe0.8O3-δ阴极粉体的溶液燃烧法合成与性能表征

采用硝酸盐-甘氨酸溶液燃烧法合成了La0.6Sr0.4Co0.2Fe0.8O3-?啄(LSCF)前驱粉体, 通过XRD、BET、FESEM及激光粒度仪等手段对粉体进行表征. 结果表明, 所合成的LSCF粉体为纯钙钛矿结构, 具有高达22.9 m2·g-1的比表面积, 粒度均匀, 平均颗粒尺寸为175 nm. 非等温烧结实验表明该粉体具有良好的低温烧结活性. 在阳极NiO-YSZ(氧化钇稳定氧化锆)负载的电解质YSZ上, 于800 ℃烧结制备LSCF阴极组成的单元电池Ni-YSZ/YSZ/LSCF, 在700 ℃下以H2作燃料时具有良好的电池性能, 最大功率密度为0.97 W·cm-2, 在0.7 V时的功率密度约达到0.83 W·cm-2. 这种无中间缓冲层的低温制备LSCF阴极方法, 简化了电池结构及其制备过程, 同时提高了电池的性能.