室温固态反应制备纳米Ba1－xSrxTiO3固溶体及其结构与介电性能研究

采用室温固态反应合成了一系列Ba_1－xSr_xTiO₃固溶体纳米粉末(0≤x≤1.0). 经XRD物相分析和d-间距-组成图证明, 产品为立方晶系的完全互溶取代固溶体. TEM形貌观察, 粒子基本为球形, 平均粒径40 nm. 该方法具有产率高, 无需溶剂, 对环境无污染等优点. 通过制陶实验, 分别测定了该系列固溶体的室温介电常数、介电损失以及介电常数随温度的变化. 结果发现, 采用室温固态反应在BaTiO₃中掺入适量锶, 由于掺杂离子均匀进入母体晶格, 引起居里点降低, 室温介电常数达11000以上, 介电损耗由BaTiO₃纯相的0.03 (3%)降为0.008 (0.8%). 纳米粉体的烧结温度为1180 ℃, 比传统微米级粉体的烧结温度降低100～150 ℃.     

Ce1－xNdxO2－δ固溶体的电子顺磁共振谱和阻抗谱的研究

利用溶胶-凝胶方法在800 ℃焙烧10 h后, 合成了固溶体Ce_1－xNd_xO_2－δ (x＝0.05～0.55), X射线衍射(XRD)测试表明固溶体已经形成立方萤石结构; 电子顺磁共振谱(EPR)研究表明在固溶体Ce_1－xNd_xO_2－δ中随着掺杂量x的增大, Ce^3＋离子含量减少, 说明掺杂Nd^3＋离子可以抑制Ce^4＋的还原; 交流阻抗谱的测量表明固溶体Ce_0.9Nd_0.1O_2－d 具有离子导电特性, 600和700 ℃时的电导率分别为4.25×10^－3和1.12×10^－2 S•cm^－1, 活化能为0.68 eV.     

La1-xCaxFeO3-δ系阴极材料的GNP法合成及电性能研究

采用甘氨酸-硝酸盐(GNP)法合成了LaFeO₃及La_1-xCa_xFeO_3-δ(x=0.1～0.5)系列粉体，用TG-DTA、XRD、TEM、SEM等对产物形成过程及微结构进行了表征。结果表明，所合成的系列样品均形成钙钛矿结构的单相固溶体。在x≤20mol%的Ca含量范围内，产物为正交钙钛矿结构；当x>30mol%时，转变为立方钙钛矿相。相同条件下产物的衍射峰强度、晶胞体积及晶粒尺寸都随Ca含量的增大而减小。采用直流四端子法测量了烧结体在中温(450～800 ℃)区的电导率。掺杂使样品导电能力显著增强，电导率随Ca²⁺掺入量的增大先增大后减小，La_0.6Ca_0.4FeO_3-δ样品的电导率最高。在低温段，各样品的导电行为符合小极化子导电机制，导电活化能为13.67～22.70 kJ·mol^-1。     

柠檬酸溶胶-凝胶法制备的Ce1-xZrxO2: 结构及其氧移动性

采用 XRF、XRD、Raman、XPS、H₂-TPR 以及与氩离子刻蚀相结合的XPS等表征技术对柠檬酸溶胶-凝胶法制备的Ce_1-xZr_xO₂ (0≤x≤1)样品的结构及其氧移动性进行了研究. 结果表明, Ce_1-xZr_xO₂ 样品的晶型结构对其中氧的移动性有明显影响. 当x≤0.15 时, Ce_1-xZr_xO₂ 以立方CeO₂相 Ce-Zr-O 固溶体存在, 随着Zr含量的逐渐增加, CeO₂晶胞体积减小、氧空位浓度增加, 氧移动性逐渐增强; 当x＞0.15时, 形成四方ZrO₂相和立方CeO₂相Ce-Zr-O固溶体的混合物, 随着Zr含量的逐渐增加, 四方ZrO₂相的含量增加、氧空位浓度减小, 氧移动性逐渐减弱. 因此, Ce_0.852Zr_0.152O₂样品具有最高的氧移动性.     

Ba1-1.5yLayZrxTi1-xO3固溶体的合成、结构与介电特性

用软化学合成方法在100℃以下制备了一系列Ba_1-1.5yLa_yZr_xTi_1-xO₃(0<x<0.3, 0≤y≤0.08)固溶体纳米粉末。XRD物相分析及晶间距-组成图表明，产品为完全互溶取代固溶体。用TEM观察可知其粒子为均匀球形，平均粒径为60纳米。通过制陶实验，对该系列固溶体的介电特性分别进行了测试。结果表明：采用化学掺杂方法在BaTiO₃中掺入适量锆、镧后，样品的室温介电常数可提高到30，000以上，并呈现出规律性。     

(Zn，M)TiO3(M=Co，Ni，Co0.5Ni0.5)固溶体的溶胶-凝胶法合成

通过改进的溶胶-凝胶工艺在低温(800 ℃)下合成了基于钛酸锌(ZnTiO₃)体系的(Zn_1-xCo_x)TiO₃、(Zn_1-xNi_x)TiO₃和[Zn_1-x(Co_0.5Ni_0.5)_x]TiO₃陶瓷固溶体。采用X射线衍射分析(XRD)和差示扫描量热法(DSC)等测量技术对产物进行了物相和热稳定性分析。XRD结果表明，获得单一六方相(Zn_1-xCo_x)TiO₃、(Zn_1-xNi_x)TiO₃和[Zn_1-x(Co_0.5Ni_0.5)_x]TiO₃时各自的固溶稳定区间为0.5 ≤ x ≤ 1.0, 0.9 ≤ x ≤ 1.0和0.8 ≤ x ≤ 1.0。与此同时，热分析结果证实，伴随钛酸锌基陶瓷体系掺杂钴量的增加，其六方相的热稳定性提高，且效果比掺杂镍更加显著。     

Li[Ni1/3Mn1/3Co1/3]O2掺杂Mo研究

采用高温固相合成法制备了Li[Ni_(1－x)/3Mn_(1－x)/3Co_(1－x)/3Mo_x]O₂ (x＝0, 0.005, 0.01, 0.02). 对它们进行了XRD, SEM, 循环伏安及充放电容量测试, 结果发现, 掺杂x＝0.01 Mo的样品具有较高的嵌锂容量和良好的循环稳定性, 在20 mA/g放电电流密度和2.3～4.6 V的电压范围内具有211.6 mAh/g的首次放电比容量, 循环50周后放电比容量仍能达到185.9 mAh/g, 容量损失为12.1%.     

钙钛矿型LaxSr1－xNi1－yCoyO3光电催化活性研究

用甘氨酸-硝酸盐燃烧合成法, 制备La_xSr_1－xNi_1－yCo_yO₃复合氧化物的陶瓷粉末, 对钙钛矿氧化物进行了XRD结构分析. 在通氧或不通氧下测试氧还原和氧析出的循环伏安曲线. 结果表明: 该氧电极具有双功能催化特性, 但不完全可逆. 利用汞灯作为激发光源, 进行几种水溶性染料和五种混合染料光解实验, 利用紫外-可见、红外以及人工神经网络光度法研究La_xSr_1－xNi_1－yCo_yO₃的催化性能. 结果表明: La_xSr_1－xNi_1－yCo_yO₃ (x＝0.7, 0.9, 1; y＝0.3, 0.75)复合氧化物都具有较强光催化特性; La_xSr_1－xNi_1－yCo_yO₃的光催化活性高于La_xSr_1－xNiO₃, 这与B位离子(Ni^2—, Co^2－)的电子构型有关; Co^2＋的加入可使La_xSr_1－xNiO₃的光催化活性有所提高.     

Ba0.4Sr0.6Co1-xFexO3-δ系阴极材料的制备和表征

采用甘氨酸-硝酸盐(GNP)法合成了中温固体氧化物燃料电池阴极材料Ba_0.4Sr_0.6Co_1-xFe_xO_3-δ(x=0.0～0.8)系列粉体。利用XRD和SEM对材料的结构和微观形貌进行分析,用直流四端子法测量了烧结陶瓷体在中温(450～800 ℃)范围内的电导率。结果表明,制备的样品为单一钙钛矿相,随着Fe含量增加,XRD衍射峰值向高角度方向稍有偏移。电导率随着温度及Fe含量的变化出现极大值,在x＜0.2时,Ba_0.4Sr_0.6Co_1-xFe_xO_3-δ系列烧结体在中温(450～800 ℃)区的电导率,随Fe掺入量的增大而增大,x=0.2样品的电导率最高,800 ℃时达244.7 S·cm^-1,远超过文献报道值,进一步增大Fe含量导电性能变差。     

BaCe0.8-xNbxGd0.2O3-δ(0≤x≤0.45)的制备及性能研究

采用高温固相反应法制备了质子导体BaCe_0.8-xNb_xGd_0.2O_3-δ(0≤x≤0.45)。结合XRD、SEM、EIS等技术对其物相、微观形貌、稳定性及电导率进行了研究。结果表明,在1 600 ℃烧结5 h制备的质子导体BaCe_0.8-xNb_xGd_0.2O_3-δ(0≤x≤0.45)均能保持主相为斜方晶的钙钛矿结构。Nb的加入可明显提高烧结样品的致密性及在CO₂和水蒸气气氛下的稳定性。在湿润H₂/Ar(0.4%,V/V)气氛中800 ℃下,x=0.1样品的电导率为5.73 mS·cm^-1,电导活化能为0.35 eV,与x=0的样品相当。     

Phase formation and physicochemical properties of perovskite complex oxides based on bismuth ferrite

The effect of the cationic composition on the formation of perovskite solid solutions based on bismuth ferrite(Bi_{1 − x/3}□ _x/3)[Fe_{1 − x} Ti _x ]O₃ with x = 0.00–0.48, Δx = 0.03, has been studied. The homogeneity range of the perovskite phase under the conditions of the solid-phase synthesis of solid solutions has been determined, and the effect of the cationic composition on the physicochemical properties of solid solutions has been studied.     

氮掺杂碳纳米管修饰电极的电化学行为

制备了氮掺杂改性的碳纳米管, 并用循环伏安法(CV)测定了多巴胺(DA)和抗坏血酸(AA)在不同氮含量的碳纳米管修饰电极上的电化学行为. 结果表明, 氮掺杂碳纳米管修饰电极对AA和DA有不同的电催化行为, 其中高氮含量修饰电极对AA的催化作用强, 而低氮含量修饰电极对DA的催化作用强. 微分脉冲伏安法(DPV)的结果显示, DA的氧化峰电流与其浓度在5.0×10^－6～2.0×10^－4 mol/L范围内呈良好的线性关系, 检出限达1.64×10^－6 mol/L (S/N＝3); AA氧化峰电流与其浓度在3.0×10^－5～1.0×10^－2 mol/L范围内呈良好的线性关系, 检出限达3.26×10^－6 mol/L (S/N＝3). 该修饰电极在AA大量存在(AA浓度为DA浓度两万倍)时可选择性地实现多巴胺的测定而不造成干扰.     

原位制备钛酸锶钡/铌酸锶钡复相陶瓷的研究

0引言驰豫型铁电陶瓷是近年来广泛研究和迅速发展的一种新型功能陶瓷[1]。通过把具有不同相变温度的驰豫型铁电体层层叠加,可以获得具有稳定的介电常数鄄温度关系的复合材料[2]。钛酸锶钡Ba1-xSrxTiO3和铌酸锶钡SrxBa1-xNb2O6都是重要的驰豫型铁电体,并且其居里温度均随Ba/Sr比     

Calorimetric search for the discontinuity in Fe<Subscript>0.96</Subscript>S-Ni<Subscript>0.96</Subscript>S solid solutions

Heat capacity of unstable quenched solid solutions (Fe_1−xNi_x)_0.96S was measured by DSC (enthalpy method and scanning heating). According to optic microscopy and X-ray powder diffraction, the samples are homogeneous phase of NiAs type with unit cell parameters changing regularly with composition. Heat capacity changes with composition irregularly due to the difference in magnetic properties of the end members: C _p/1.96R=4.1 for Fe-rich samples and 3.3 for Ni-rich ones. There is no exact limit between two types of magnetic ordering. Instead, samples with intermediate composition (0.7<x<0.8) show large fluctuations in C _p due to the inconsistency of alternative (FeS and NiS) types of magnetic ordering.     

Physicochemical and Catalytic Properties of La1 – xCaxFeO3 – 0.5x Perovskites Prepared Using Mechanochemical Activation

The phase composition of La_{1 – x} Ca _x FeO_{3 – 0.5x} perovskites synthesized from preactivated oxides was studied by powder X-ray diffraction analysis and differential dissolution. The system does not form a continuous series of homogeneous solid solutions. No intermediate samples from this series are monophasic. It was found that the synthesis under nonequilibrium conditions (mechanical activation + calcination at 900° for 4 h) resulted in nonequilibrium microheterogeneous solid solutions with degrees of calcium substitution for lanthanum of no higher than 0.5. A longer calcination (for 16 h) or an increase in the calcination temperature of solutions up to 1100 ° decreased the calcium content of the samples down to x 0.2 because of the formation of a brownmillerite phase. The catalytic activity of the test samples in the oxidation of CO changed nonmonotonically with x, and it was maximum at x = 0.5–0.6, which correlates with the maximum density of interphase boundaries in these samples.     

Thiourea complexes in synthesis of Cd1 ? xZnxS solid solutions

Solid solutions of the CdS-ZnS system deposited as polycrystalline films by aerosol pyrolysis from aqueous solutions of cadmium and zinc thiourea complexes have been studied. The phase composition and solid-phase solubility are dictated by the nature of initial complexes. From solutions of [M(thio)₂(CH₃COO)₂] complexes, sphalerite sulfides are precipitated, which form a continuous solid solution s-Cd_1−x Zn _x S, whereas the use of the [M(thio)₂Cl₂] precursor leads to crystallization of the wurtzite w-Cd_1−x Zn _x S solid solution based on CdS (the homogeneity range 0–20 mol % ZnS) and the s-Cd_1−x Zn _x S solid solution based on zinc sulfide (50–100 mol % ZnS). The structure of the solid phase in the sulfide system is attributed to the specific features of the stereochemistry of complex precursors.     

Solid Solubility,Raman Spectra and Electrical Property of the Solid Solutions Ce1‐xNdxO2‐δ by Sol‐gel Route

Ce_1‐xNd_xO_2‐δ (x = 0.05–0.55) solid solutions prepared by sol‐gel route were crystallized in a cubic fluorite structure. The solid limit was determined to be as high as x = 0.45. Raman spectra of the solid solutions with lower composition exhibited only one band, which was assigned to F_2g mode. Increasing composition produced broad and asymmetric F_2g mode with an appearance of low frequency tail. The new broad peak observed at higher frequency side of the F_2g mode associated with the oxygen vacancy in the lattice. The impedance spectra of the solid solutions showed definitely ionic conduction, and Ce_0.80Nd_0.20O_2‐δ solid solution possessed a maximum conductivity. At 500 °C, the conductivity and activation energy were 2.65 × 10^?3S/cm and 0.82 eV, respectively.