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1.
(Zn1-xMnx)C2O4·2H2O在空气中的热分解动力学研究   总被引:1,自引:0,他引:1  
用热分析(TG-DTG/DTA)、X射线衍射(XRD)技术和透射电镜(TEM)研究了固态物质Zn1-xMnxC2O4•2H2O在空气中热分解的过程。热分析结果表明,Zn1-xMnxC2O4•2H2O在空气中分两步分解,其失重率与理论计算失重率相吻合。 XRD和TEM结果表明,Zn1-xMnxC2O4•2H2O分解的最终产物为Zn1-xMnxO,其颗粒大小约为10-13 nm。在非等温条件下对Zn1-xMnxC2O4•2H2O的热分解动力学进行了分析。用Friedman法和Flynn-Wall-Ozawa(FWO)法求取了分解过程的活化能E,并用多元线性回归给出了可能的机理函数。Zn1-xMnxC2O4•2H2O两步热分解的活化能分别为155.7513 kJ/mol 和215.9397 kJ/mol。  相似文献   

2.
本文采用离子交换法分别制备了双复合锂锰氧化物Li0.60[MgxMn1-x]O2(0.05 ≤ x ≤ 0.15)和三复合锂锰氧化物Li0.60[MgxCoyMn1-x-y]O2(x=0.05,0.05 ≤   相似文献   

3.
基于尖晶石晶体结构信息,本文采用热力学三亚晶格模型,将材料热力学计算和第一性原理计算相结合,研究了ZnxMn1-x Fe2O4和NixMn1-xFe2O4立方相中的Zn2+、Ni2+、Mn2+以及Fe3+在8a和16d亚晶格上的占位有序化行为。结果表明:在锰铁氧体中,室温下Mn2+完全占据在8a亚晶格上,Fe3+完全占据在16d亚晶格上,属于正尖晶石结构;随着热处理温度升高,在1 273 K达到热处理平衡时的占位构型为(Fe0.093+Mn0.912+)[Fe1.913+Mn0.092+]O4,在热处理温度升至1 473 K时,达到热处理平衡时的占位构型为(Fe0.113+ Mn0.892+)[Fe1.893+Mn0.112+]O4,均与实验结果符合较好。在锌铁氧体中,室温下Zn2+完全占据在8a亚晶格上,Fe3+完全占据在16d亚晶格上,属于正尖晶石结构;在热处理温度较高时,Zn2+和Fe3+发生部分置换,符合实验结果。在镍铁氧体中,半数的Fe3+在室温下占据在8a亚晶格上,Ni2+与剩下另一半的Fe3+共同占据在16d亚晶格上,仅在热处理温度较高的时候发生微弱变化,亦与已有的实验结果吻合。在此基础上,本文进一步通过热力学预测建立了立方相尖晶石结构的ZnxMn1-xFe2O4、NixMn1-xFe2O4复合体系中阳离子占位行为与热处理温度对占位的影响。  相似文献   

4.
嵌入化合物LixMn2O4的水热浸渍合成研究   总被引:6,自引:0,他引:6  
本文用水热浸渍二步法合成了尖晶石型LixMn2O4微粉,并对其采用XRD,SEM, ICP, XPS和IR等进行测试。结果表明产物为单相立方晶体,粒子尺寸范围0.15-0.5 μm, LixMn2O4中X为0.96,其中锰为Mn3+和Mn4+混合价态存在。该液相合成LixMn2O4材料的方法尚未见报道。  相似文献   

5.
>为获得综合性能更好的锂离子二次电池正极材料, 分析了Co掺杂对LixNiO2电化学性能的影响. 采用密度泛函DFT理论对LixNiO2和LixNi0.5Co0.5O2的平均放电电压和态密度进行了计算. 同时, 用共沉淀法制备了LixNiO2和LixNi0.5Co0.5O2锂离子二次电池正极材料, 并对其进行了XRD结构分析和恒流充放电测试. 实验和计算结果表明: 随锂离子嵌入正极(电池放电), 电池的电压逐渐降低, 材料的态密度峰向低能量方向移动; 与LixNiO2相比, LixNi0.5Co0.5O2的电压平台相对较高(当0.25≤x≤0.5), 而且在Li嵌/脱时, LixNi0.5Co0.5O2的结构变化相对较小; Co离子的掺入, 减小了NiO6八面体的畸变度, 使材料的电化学稳定性得以提高. 在钴掺杂镍酸锂体系中, NiO6和CoO6具有相互的稳定作用.  相似文献   

6.
顾大明  谢颖  史鹏飞  付宏刚 《化学学报》2006,64(12):1223-1227
>为获得综合性能更好的锂离子二次电池正极材料, 分析了Co掺杂对LixNiO2电化学性能的影响. 采用密度泛函DFT理论对LixNiO2和LixNi0.5Co0.5O2的平均放电电压和态密度进行了计算. 同时, 用共沉淀法制备了LixNiO2和LixNi0.5Co0.5O2锂离子二次电池正极材料, 并对其进行了XRD结构分析和恒流充放电测试. 实验和计算结果表明: 随锂离子嵌入正极(电池放电), 电池的电压逐渐降低, 材料的态密度峰向低能量方向移动; 与LixNiO2相比, LixNi0.5Co0.5O2的电压平台相对较高(当0.25≤x≤0.5), 而且在Li嵌/脱时, LixNi0.5Co0.5O2的结构变化相对较小; Co离子的掺入, 减小了NiO6八面体的畸变度, 使材料的电化学稳定性得以提高. 在钴掺杂镍酸锂体系中, NiO6和CoO6具有相互的稳定作用.  相似文献   

7.
Ca2-xSrxZn4Ti15O36∶Pr red long decay phosphor was synthesized by high temperature solid state reaction. Photoluminescence property and crystalline and unit cell parameters of the orthorhombic were investigated by fluorescence spectrophotometer and by powder X-ray diffraction, respectively. The emission intensity at 618 nm changes sharply when the concentration of Sr2+ (x) is less than 0.1 and the emission intensity reaches the maximum when x is equal to 0.007. There is an obviously broad excitation band at 270 nm when x is equal to 0.003 and it disappears gradually when x is over 0.01. The unit cell a parameter of Ca2-xSrxZn4Ti15O36∶Pr decreases while c parameter increases with the increases of the concentration of the doped Sr2+. When x is over 0.1 the value of the unit cell parameters a and c become stable. TL peaks of Ca2Zn4Ti15O36∶Pr, Ca1.993Sr0.007Zn4Ti15O36∶0.002Pr3+, 0.002Na+, are located at 62 ℃, 88 ℃, respectively, which indicates that there are deeper traps in Ca1.993Sr0.007Zn4Ti15O36∶0.002Pr3+, 0.002Na+.  相似文献   

8.
(Zn,M)TiO3(M=Co,Ni,Co0.5Ni0.5)固溶体的溶胶-凝胶法合成   总被引:1,自引:0,他引:1  
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(Zn1-xCox)TiO3、(Zn1-xNix)TiO3和[Zn1-x(Co0.5Ni0.5)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(Zn1-xCox)TiO3、(Zn1-xNix)TiO3和[Zn1-x(Co0.5Ni0.5)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。  相似文献   

9.
采用高温固相法在空气中合成了Ba1.97-yZn1-xMgxSi2O7:0.03Eu,yCe3+系列荧光粉。分别采用X-射线衍射和荧光光谱对所合成荧光粉的物相和发光性质进行了表征。在紫外光330~360 nm激发下,固溶体荧光粉Ba1.97-yZn1-xMgxSi2O7:0.03Eu的发射光谱在350~725 nm范围内呈现多谱峰发射,360和500 nm处有强的宽带发射属于Eu2+离子的4f65d1-4f7跃迁,590~725 nm红光区窄带谱源于Eu3+5D0-7FJ (J=1,2,3,4)跃迁,这表明,在空气气氛中,部分Eu3+在Ba1.97-yZn1-xMgxSi2O7基质中被还原成了Eu2+;当x=0.1时,荧光粉Ba1.97Zn0.9Mg0.1Si2O7:0.03Eu的绿色发光最强,表明Eu3+被还原成Eu2+离子的程度最大。当共掺入Ce3+离子后,形成Ba1.97-yZn0.9Mg0.1Si2O7:0.03Eu,yCe3+荧光粉体系,其发光随着Ce3+离子浓度的增大由蓝绿区经白光区到达橙红区;发现名义组成为Ba1.96Zn0.9Mg0.1Si2O7:0.01Ce3+,0.03Eu的荧光粉的色坐标为(0.323,0.311),接近理想白光,是一种有潜在应用价值的白光荧光粉。讨论了稀土离子在Ba2Zn0.9Mg0.1Si2O7基质中的能量传递与发光机理。  相似文献   

10.
方钧  石富城  包蕙质  千坤  姜志全  黄伟新 《催化学报》2013,34(11):2075-2083
利用X射线衍射、N2吸附等温线、X射线光电子能谱、X射线吸收谱、H2-程序升温还原、甲基橙选择化学吸附和等电点测定等方法研究了共沉淀方法制备的一系列CexTi1-xO2复合氧化物的结构. 成功发展了甲基橙选择化学吸附和等电点方法研究CexTi1-xO2复合氧化物的最外层表面结构, 并定义了“等价CeO2表面覆盖度”来描述CexTi1-xO2复合氧化物的最外层表面结构. CexTi1-xO2复合氧化物 (x ≥ 0.7)形成立方萤石相固溶体, Ce0.3Ti0.7O2表现出纯的单斜相, 而其它复合氧化物表现出混合相. CexTi1-xO2复合氧化物最外层表面结构的演变行为不同于其体相结构.Ce0.7Ti0.3O2立方萤石相固溶体最外层表面已经部分形成了单斜相Ce0.3Ti0.7O2, 随Ce含量的降低, 单斜相Ce0.3Ti0.7O2从最外层表面向体相生长. CexTi1-xO2复合氧化物立方萤石相固溶体和单斜相Ce0.3Ti0.7O2分别在相对较低和较高的温度表现出好的还原性能. 上述结果提供了全面和深层次的CexTi1-xO2复合氧化物结构信息.  相似文献   

11.
MMe5(dmpe) (M = Nb or Ta, dmpe = Me2PCH2CH2PMe2) reacts with H2 (500 atm) and dmpe in THF at 60°C to give MH5(dmpe)2? NbH5(dmpe)2 readily reacts with two mol of CO or ethylene (L) to give NbHL2(dmpe)2. The exchange of the hydride ligand with the ethylene protons in NbH(C2H4)2(dmpe)2 is not rapid on the 1H NMR time scale (60 MHz) at 95°C.  相似文献   

12.
New Compounds in the System CaO/SiO2/CaCl2/H2O The hydrothermal formation of novel calcium silicate hydrates of compositions 5 CaO · 2 SiO2 · CaCl2 · 4 H2O, 5 CaO · 2 SiO2 · CaCl2 · 2 H2O and 4 CaO · 2 SiO2 · CaCl2 · H2O from Ca3SiO5 and mixtures of CaO and SiO2, respectively, in presence of calciumchloride at 200°–350 °C is described. From molybdate-reaction, 29Si MAS NMR, DTA and TG measurements it is concluded that these compounds are based on disilicate anions and are to be interpreted as calcium hydroxide disilicate chlorides.  相似文献   

13.
一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…  相似文献   

14.
Glasses with the compositions 50.9 SiO2 · 20.8 Al2O3 · (20.8 ? x) MgO· × ZnO · 3.7 TiO2 · 3.7 ZrO2 with x = 0, 2.3, 4.6 and 9.3 were annealed at temperatures in the range from 850 to 1100 °C. Depending on temperature, high- or low-quartz solid solutions, magnesium aluminosilicate, mullit and spinel precipitated. These glass–ceramics exhibit excellent mechanical properties and are potential candidates for applications in micromechanics or as hard disc substrate.The larger the ZnO concentration, the lower is the glass transition temperature. Also microhardnesses and Young’s moduli increased with increasing ZnO concentration. The nucleation temperature was of minor importance. To achieve good mechanical properties, the initially formed high-quartz phase must transform to the corresponding low-quartz phase. This occurs if the quartz phase contains only minor MgO or ZnO concentrations, which can be achieved by increasing the annealing times or temperature. Then MgO, ZnO and Al2O3 occur as separate spinel or gahnite phase.  相似文献   

15.
Reactions of [Cp2Ti(btmsa)] (btmsa = bis(trimethylsilyl)acetylene) with R4Sb2 (R = Me, Me3Si) give [Cp2TiSbMe2]2 (1) or [Cp2TiSb(SiMe3)2]2 (2) respectively. [Cp2TiCl]2·2Mes4Sb2 (3) is serendipitously formed from [Cp2Ti(btmsa)] and Mes2SbH containing NH4Cl traces.  相似文献   

16.
An experimental study on the conversion of NO in the NO/N2, NO/O2/N2, NO/C2H4/N2 and NO/C2H4/O2/N2 systems has been carried out using dielectric barrier discharge (DBD) plasmas at atmospheric pressure. In the NO/N2 system, NO decomposition to N2 and O2 is the dominating reaction; NO conversion to NO2 is less significant. O2 produced from NO decomposition was detected by an on-line mass spectrometer. With the increase of NO initial concentration, the concentration of O2 produced decreases at 298 K, but slightly increases at 523 K. In the NO/O2/N2 system, NO is mainly oxidized to NO2, but NO conversion becomes very low at 523 K and over 1.6% of O2. In the NO/C2H4/N2 system, NO is reduced to N2 with about the same NO conversion as that in the NO/N2 system but without NO2 formation. In the NO/C2H4/O2/N2 system, the oxidation of NO to NO2 is dramatically promoted. At 523 K, with the increase of the energy density, NO conversion increases rapidly first, and then almost stabilizes at 93–91% of NO conversion with 61–55% of NO2 selectivity in the energy density range of 317–550 J L−1. It finally decreases gradually at high energy density. A negligible amount of N2O is formed in the above four systems. Of the four systems studied, NO conversion and NO2 selectivity of the NO/C2H4/O2/N2 system are the highest, and NO/O2/C2H4/N2 system has the lowest electrical energy consumption per NO molecule converted.  相似文献   

17.
phase diagrams of KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E 1: 622°C, 8.5 mol % KBO2, 56.5 mol % KCl, and 35 mol % K2CO3; E 2: 710°C, 23 mol % KBO2, 43 mol % K2CO3, and 34 mol % K2MoO4; E 3: 710°C, 23 mol % KBO2, 43 mol % K2CO3, and 34 mol % K2WO4. The specific heats of melting of the eutectics were determined.  相似文献   

18.
In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.  相似文献   

19.
The lithium-ion-conducting inorganic solid electrolytes in the oxide systems Li2O-SiO2-P2O5 and Li2O-TiO2-SiO2-P2O5 were prepared by the solid-state reaction, and the electrolyte pellet made by cold-pressing method had diameter of 13 mm and was about 1 mm thick. Phase identification and surface morphology of the products were carried out by X-ray diffraction and scanning electron microscopy. Ionic conductivity of the pellets was investigated through ac impedance. The results show that the adding of other cations can improve the ionic conductivity of the solid electrolyte, and the sintering temperature and duration can influence the ionic conductivity. The maximum ionic conductivity in the samples is 9.9 × 10−4 S/cm in the Li2O-TiO2-SiO2-P2O5 system. Original Russian Text ? W. Li, M. Wang, Z.H. Li, X.F. Shang, H. Wang, Y.W. Wang, Y.B. Xu, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 11, pp. 1341–1345.  相似文献   

20.
本文利用一种具有H_2O_2催化活性的Cu-MOF[Cu_3(BTC)_2(H_2O)_3,简称HKUST-1],构建了以邻苯二胺(OPD)为颜色指示分子的比色传感体系,实现了对H_2O_2和多巴胺(DA)的快速灵敏检测。HKUST-1起到催化H_2O_2氧化OPD的作用,反应体系能够呈现出显著的颜色变化。在优化条件下,415nm处的吸收峰强度与H_2O_2浓度呈双线性关系,线性范围分别为10~50 mmol/L和50~100 mmol/L,相对标准偏差分别为0.9947和0.9995,最低检出限为1.29mmol/L。由于DA能抑制H_2O_2氧化OPD,因此比色传感体系还可以用于快速检测DA,线性范围分别为0.25~5μmol/L和2.5~25μmol/L,相对标准偏差分别为0.9783和0.9705,最低检出限为0.262μmol/L。该项工作拓展了Cu-MOFs材料在生物分子催化和生物传感方面的应用。  相似文献   

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