The conditions of formation and physicochemical properties of Nd1 ? xBaxMn1 ? yFeyO3 phases

The homogeneity regions of Nd_{1 − x} Ba _x MnO₃ (0.0 ≤ x ≤ 0.25) and NdMn_{1 − y} Fe _y O₃ (0.0 ≤ y ≤ 1.0) orthorhombic solid solutions in air at 1373 K were determined. The region of the existence of Nd_{1 − x} Ba _x Mn_{1 − y} Fe _y O₃ orthorhombic solid solutions in air at 1373 K was studied. A fragment of the phase diagram of the NdMnO₃-BaMnO₃-BaFeO_2.5-NdFeO₃ quasi-quaternary complex oxide system in air at 1373 K was suggested. The mechanothermal properties of Nd_0.75Ba_0.25MnO₃, Nd_0.8Ba_0.2Mn_0.9Fe_0.1O₃, Nd_0.8Ba_0.2Mn_0.7Fe_0.3O₃, and Nd_0.8Ba_0.2Mn_0.5Fe_0.5O₃ doped neodymium manganates were studied.     

Acid-base properties of the surfaces of CdxHg1–xTe solid solutions

The acid-base properties of actual CdTe and CdHgTe surfaces were investigated by means of non-aqueous conductometric titration for pHpzc determination, mechanochemistry, and UV spectroscopy. It was shown that the alkaline nature of their surface was due to the dissociative adsorption of atmospheric water flowing on the coordination-saturated surface atoms of cadmium with vacancy defects. The adsorbed water was involved in the formation of tellurium oxide TeO₂ and H₂TeO₃ tellurous acid in the dispersion of CdTe and CdHgTe.     

The enthalpies of formation of Sm1 + xBa2 ? xCu3Oy substitution solid solutions

The enthalpies of reactions of Sm_{1 + x} Ba_{2 − x} Cu₃O _y substitution solid solutions (x = 0, 0.1, 0.2, 0.3, 0.7, and 0.8) with 1.07 N HCl were measured at 298.15 K in a hermetic isothermic-shell swinging calorimeter. The results and the literature data were used to calculate the standard enthalpies of their formation from simple substances and binary oxides (Δ_f H _298.15^o and Δ_ox H _298.15^o). The dependence of the enthalpy of formation on the degree of samarium substitution for barium was obtained.     

The enthalpies of formation of substitution solid solutions Pr1 + xBa2 ?xCu3Oy

The enthalpies of reactions of substitution solid solutions Pr_{1 + x} Ba_{2 − x}Cu₃O _y , where x = 0, 0.2, 0.4, 0.6, and 0.9, with 1.07 N HCl were measured at 298.15 K in a hermetic swinging isothermic-shell calorimeter. The results and the literature data were used to calculate the standard enthalpies of formation of solid solutions from the elements and oxides. The dependence of the enthalpy of solid solution formation on the degree of praseodymium substitution for barium (x) was revealed.     

Synthesis and X-ray diffraction study of complex oxides of the Zn2 ? x(ZraSnb)1 ? xFe2xO4 composition

A multicomponent system of complex refractory oxides of the composition Zn_{2 − x} (Zr _a Sn _b )_{1 − x} Fe_2x O₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 4: 1; x = 0−1.0; Δx = 0.05) was studied by X-ray diffraction. The samples were prepared from oxides of appropriate metals by low-temperature plasma synthesis (hydrogen-oxygen flame). Two phases with wide homogeneity ranges were identified: α phase crystallized in the crystal system of inverse cubic spinel and β phase with the structure of tetragonal spinel. The phase boundaries were found. Structural data are presented for about 100 solid solutions.     

Catalytic activity of V-substituted Cs2Te0.2H0.6 + xPMo12 ? xVxOn heteropoly compounds in selective oxidation of isobutane

A series of Cs₂Te_0.2H_{0.6 + x} PMo_{12 − x} V _x O _n (x = 0–3) heteropoly compounds has been prepared and tested in the partial oxidation of isobutane. Catalytic tests show that at 350°C very high selectivity to methacrylic acid (60.1%) can be achieved at isobutane conversion of 12.2% over a Cs_2.0Te_0.2H_1.6PMo₁₁VO _n catalyst with only one molybdenum atom per unit cell substituted by vanadium. The presence of Te⁴⁺ in the heteropoly compounds appears to interfere with the dehydrqgenation step and favor the formation of methacrolein and methacrylic acid.     

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.     

Quantum-chemical study of chlorophosphoranes: II. Structure of molecules of (Cl2)aP(ClnX3?n)e series, and mutual influence of axial and equatorial substituents

The quantum-chemical calculations of the (C₆H₅)₂PCl₃ molecule were performed by the methods RHF/6-31G(d) and MP2/6-31G(d) with complete and partial optimization of its geometry. The results of calculations were used for evaluating the NQR frequencies of ³⁵Cl and the parameters of asymmetry of the of electric field gradient on the ³⁵Cl nuclei of this molecule. According to the results of calculations with the partial optimization of geometry and to the experimental data of ³⁵Cl NQR the bond lengths were found of central atom P in the solid state of this compound. The mutual influence of its axial and equatorial bonds was studied. It is shown that in chlorophosphoranes the ³⁵Cl NQR frequencies of the axial and equatorial chlorine atoms decrease with the decrease in the bond lengths of phosphorus atom.     

LixZryOz三元化合物的制备及表征

采用高温固相法制备了4种高纯度晶相组成的LixZryOz三元化合物,研究了焙烧温度、时间、反应物的种类和初始反应物物质的量比对产物组成的影响,进一步用XRD、SEM及BET分析方法对产物的晶相结构、表面形貌及比表面积进行了表征.实验结果表明,Li2CO3与ZrO2在适当条件下可以合成得到单斜相Li3ZrO3;以LiOH替代Li2CO3,在适当条件下可以分别合成得到四方相Li2ZrO3和三斜/单斜相Li6Zr2O7;进一步以Zr(NO3)4·5H2O代替Zr02,可将单斜相Li6Zr2O7的制备时间由96 h缩短至24 h.SEM照片显示产物硬团聚明显,粒径分布在1～10μm间,BET分析表明样品比表面积处于1.0～9.0 m2·g-1间分布,反应过程中锂的过量以及长时间高温焙烧是引起产物粒径长大和产生硬团聚的主要原因.     

LixNi0.8-yCo0.2ZnyOp的合成及电化学性能研究

A series of single-phase Li_xNi_0.8-yCo_0.2Zn_yO_p(0.96 ≤x≤ 1.10， 0 ≤y≤ 0.05， 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method， in which LiOH·H₂O， Zn-doped spherical Ni(OH)₂ and Co₂O₃ were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD， SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine， narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity， but also a better cycling stability characterization than the un-doped one. The Li_1.06Ni_0.75Co_0.22Zn_0.03O_2.03 material has an initial reversible capacity as high as 160.5mAh·g^-1; and a first discharge efficiency 89.2%， and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles.     

Effects of combined substitution of Dy and Mo or Si on the crystal structures and magnetic properties of Nd1?yDyyFe11?xTiMx (M = Mo, Si) compounds

A series of Nd_1−y Dy _y Fe_11−x TiM_x (M = Mo, Si) alloys have been prepared by arc melting and studied by X-ray diffraction and neutron diffraction. All samples are found to crystallize in the ThMn₁₂-type structure. The lattice parameters a and c and unit cell volume V of Nd_0.5Dy_0.5Fe_11−x TiMo _x alloys increase linearly with increasing content of Mo (x), while the lattice parameters a and c and unit cell volume V of Nd_0.5Dy_0.5Fe_11−x TiSi _x alloys decrease linearly with increasing content of Si(x). In Nd _y Dy_1−y Fe_11−x TiM _x (M = Mo, Si) compounds, Ti and Mo atoms preferentially occupy the 8i sites and Si atoms preferentially occupy the 8j and 8f sites. Magnetic measurements show that the substitution of Fe by either Mo or Si leads to a decrease in the Curie temperature. Supported by the National Natural Science Foundation of China (Grant No. 20775088) and the Foundation of State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (Grant No. KF2008-06)     

Oxygen nonstoichiometry and the thermodynamic properties of manganites Ca1 ? x ? ySrxLayMnO3 ? δ

The content of oxygen in Ca_{0.6 − y} Sr_0.4La _y MnO_{3 − δ}, where y = 0 and 0.05, was determined by coulometric titration over the temperature range 650–950°C at oxygen partial pressure in the gas phase varied from 10⁻⁴ to 1 atm. The results were used to calculate the partial molar enthalpy, Δ$ \bar H $ \bar H _O(δ), and entropy, Δ$ \bar S $ \bar S _O(δ), of oxygen in manganites. Changes in the Δ$ \bar H $ \bar H _O(δ) and Δ$ \bar S $ \bar S _O(δ) dependences caused by the introduction of lanthanum are evidence of the formation of local clusters of the double perovskite type in the Ca_0.6Sr_0.4MnO_{3 − δ} matrix.     

多元掺杂尖晶石型Li1.02MxMn2-xQyO4-y正极材料的电化学特性

The effect of doping on the electrochemical performance was studied for spinel type Li_1.02M_xMn_2-xQ_yO_4-y used as cathode material in lithium-ion battery. TG/DTA curves of the precursor(the raw materials) doped with different elements were studied. The spinel materials Li_1.02Mn₂O₄, Li_1.02Co_0.02Cr_0.01La_0.01Mn_1.96F_0.02O_3.98, Li_1.02Co_0.02Cr_0.01 La_0.01Mn_1.96Cl_0.02O_3.98, Li_1.02Co_0.02La_1.02Mn_1.97Cl_0.02O_3.98, Li_1.02Co_0.02Cr_0.01Mn_1.97O₄, were prepared by solid-state reaction method after the pretreatment of conversion under low temperature and uniform mixing. X-ray diffraction patterns showed that all the samples had perfect spinel structure. SEM indicated that the particles of the samples had uniform size and were distributed evenly. The results of the charge/discharge curves showed that Li_1.02Co_0.02Cr_0.01La_0.01Mn_1.96F_0.02O_3.98 had better performance than other materials according to the inhibition of decline of reversible capacity of spinel Li_1.02M_xMn_2-xQ_yO_4-y. Therefore, cycle performance had been improved so obviously that 93.9% of the initial capacity were preserved after 100 cycles. Furthermore, electrochemical impedance tests were carried out with the spinel Li_1.02Co_0.02Cr_0.01La_0.01Mn_1.96F_0.02O_3.98 as working electrode, Lithium as counter electrode and reference electrode. Results showed that this material possessed good charge/discharge reversible capability and had the lowest impedance in 3.95～4.25 V range (on the stage of charge / discharge).     

Conductivity of La1 ? xSrxSc1 ? yMgyO3 ? α (x = y = 0.01–0.20) in reducing atmosphere

The ion and proton transfer numbers were measured by emf method in La_{1 − x} Sr _x Sc_{1 − y} Mg _y O_{3 − α} (x = y = 0.01–0.20) system in reducing hydrogen-containing atmosphere in the range of temperatures from 630 to 920°C and pH₂O from 0.61 to 2.65 kPa. Total ionic, proton, and oxygen conductivities of this system was measured as well. The electroconductivity measurements were carried out vs. pO₂ (from air to 10⁻¹⁴ Pa).     

凝胶自燃法合成LaxSr1-x CoyFe1-y O3-α纳米粉体

用凝胶自燃法制备了La_xSr_1-x Co_yFe_1-y O_3-α纳米粉体，研究了粉体的元素组成和掺杂性能，表征了粉体的晶相结构，测试了其粒度和形貌。结果表明应用凝胶自燃工艺合成的La_xSr_1-x Co_yFe_1-y O_3-α粉体材料粒子大小非常均匀，元素掺杂性能好，晶相单一，不需经高温热处理便能直接形成钙钛矿型结构。     

纳米钙钛矿LaxSr1-xFe1-yCoyO3复合氧化物的制备和表征

用甘氨酸-硝酸盐燃烧合成法，制备La_xSr_1-xFe_1-yCo_yO₃复合氧化物的陶瓷粉末，对该钙钛矿型氧化物进行了XRD、IR、紫外漫反射光谱及循环伏安曲线分析。结果表明：该复合氧化物粉体平均晶粒为15.3～29.8 nm,为立方和正交晶系。该氧电极具有双功能催化特性，但不完全可逆。对水溶液染料进行光解实验，利用紫外-可见、人工神经网络光度法研究La_xSr_1-xFe_1-yCo_yO₃的催化性能。结果表明：CO²⁺的加入可使La_xSr_1-xFeO₃的光催化活性有所提高，B位离子(Fe³⁺，CO²⁺)改变与加入，使La_xSr_1-xFe_1-yCo_yO₃(x=0.7，0.3；y=0.3，0.9，1)光催化活性高于La_xSr_1-xFeO₃。同时，对5种染料进行紫外光解，在0.75 h，脱色率大于91%，并为动力学一级反应。     

橙红色荧光粉Ca1-x-ySmxBiySiO3的制备及其发光性能

以Sm³⁺作为激活剂,Bi³⁺作为辅助激活剂,采用水热法合成Ca_1-x-ySm_xBi_ySiO₃前驱体,然后在1 100 ℃焙烧得到系列橙红色荧光粉.用X-射线衍射仪、扫描电镜和荧光分光光度计和傅里叶变换红外光谱等手段对样品的组成、结构和形貌及其发光性质进行分析和表征.分析结果表明：产物都为三斜晶系结构的Ca_1-x-ySm_xBi_ySiO₃和四方结构的方石英SiO₂共熔体.在405 nm近紫外光激发下,产物的发射光谱由3个峰组成,发射峰值位于566、606和650 nm处,分别归属于Sm³⁺的⁴G_5/2→⁶H_J/2(J=5,7,9)跃迁.产物的激发光谱在405 nm有很强的发射带,与近紫外LED芯片匹配.随着Sm³⁺掺量的增加,样品发光强度先增强后减弱,当Sm³⁺的物质的量分数为3%时发光强度达到最大,浓度猝灭机理为电偶极-电偶极相互作用.当Bi³⁺的物质的量分数在0.3%~1.5%时,对产物Ca_0.97Sm_0.03SiO₃的荧光强度起敏化作用.Sm³⁺和Bi³⁺的最佳物质的量分数分别为3%和0.5%.     

直接Z型Zn2SnO4-xNx/ZnO1-yNy异质结光催化剂的制备及机理

采用微波溶剂热法成功制备直接Z型Zn_2SnO_(4-x)N_x/ZnO_(1-y)N_y核壳结构异质结光催化剂。2种物质不同的功函数改变了其表面电荷密度,并在界面处形成内建电场,导致其从传统的Ⅰ型镶嵌异质结转变为Ⅱ型异质结,再转变为Z型异质结构。N杂质原子替代O原子进入Zn_2SnO_4和ZnO的晶格,在两者的价带(VB)顶部形成双杂质能级。核壳结构的Z型异质结光催化剂对罗丹明B的降解速率为纯相Zn_2SnO_(4-x)N_x的1.40～1.43倍,同时具有良好的循环稳定性,且可以降解亚甲基蓝、甲基橙、水杨酸等污染物。Z型异质结的形成使其光生电子-空穴对具有较强的氧化还原能力,而双杂质能级的存在可以拓宽其光响应范围并提高载流子的分离效率。因此,Zn_2SnO_(4-x)N_x/ZnO_(1-y)N_y异质结光催化剂高的光催化活性归因于Z型异质结和双杂质能级的协同作用。     

Determination of diffusion coefficient of lithium in LiMyMn2 ? yO4 spinels using potentiostatic intermittent titration technique

The potentiostatic intermittent titration technique is used to study lithium transport in the LiM _yMn_{2 − y} O₄ compounds with a spinel structure intended for application as cathodic materials in lithiumion and lithium-polymer batteries. The materials are synthesized using the sol-gel method and the melt-impregnation method. Kinetic and diffusion characteristics of the Li _x Mn₂O₄ and Li _x Mn_1.95Cr_0.05O₄ compounds are determined at 25°C as dependent on lithium content 0 < x < 1. The diffusion coefficient of lithium varies significantly in the range of 10⁻¹⁰ to 10⁻¹³ cm²/s under variation of the electrode composition; the surface resistance depends weakly on the concentration of lithium and is 200–500 Ohm cm².     

Determination of diffusion coefficient of lithium in LiMyMn2 ? yO4 spinels using galvanostatic intermittent titration technique

The galvanostatic intermittent titration technique is used to study lithium transport in the LiM _y Mn_{2 − y} O₄ compounds with a spinel structure intended for application as cathodic materials in lithium-ion and lithium-polymer batteries. Equilibrium intercalation isotherms of the Li _x Mn₂O₄ and Li _x Mn_1.95Cr_0.05O₄ compounds and also their diffusion characteristics are determined at 25°C as dependent on lithium content x, 0 < x < 1. The diffusion coefficient of lithium varies in a complex way in the range of 10⁻¹⁰ to 10⁻¹² cm²/s under variation of the electrode composition.