层状钙钛矿型Sm2-2xSr1+2x-2yCa2yMn2O7(x=0.2，0.3，0.4，0.5；y=0，0.2，0.3)的溶胶凝胶合成及电性能研究

Layered perovskite manganites with a nominal chemsitry of Sm_2-2xSr_1+2x-2_yCa_2yMn₂O₇(x=0.2, 0.3, 0.4, 0.5; y=0, 0.2, 0.3) were prepared using sol-gel method. The crystal structures of these compounds were studied by X-ray diffraction (XRD) and FTIR absorption spectra. The absorption peaks become weaker and move a little to higher frequency with increasing of Sm/Sr concentration. As the Sm doping increases to x=0.2 and x=0.3, the absorption peaks show a cubic structure character, reflecting that the samples suffer from a transition from tetragonal structure to cubic structure. This coincides with the X-ray diffraction results. The high temperature electrical properties were studied by conventional four-probe method. Although all samples exhibit the semiconductive behavior, lnρ-1 000/T curves are not linear and they obey the small polaron hopping mechanism. Moreover, the resistivity decreases with x reducing. This is due to that Sm doping increases the Jahn-Teller ion Mn³⁺/Mn⁴⁺ ratio, and decreases the e_g bandwidth.     

掺镍型层状LixNiyMn1-yO2正极材料的合成与电性能研究

A kind of cathode material of layered Li_xNi_yMn_1-yO₂ characterized with the O2 type has been synthesized by a simple method. Its precursor Na_xNi_yMn_1-yO₂ has been prepared from manganese dioxide， nickel hydroxide and sodium carbonate at high temperature in air and quickly cooled in cold water， then it has been exchanged by the melted LiNO₃ at 300～400℃ in air. The effects of calcine-temperature for the precursors and its compositions (the content of Na and Ni) on the electrochemical properties of the material Li_xNi_yMn_1-yO₂ have been investingated by XRD and electrochemical tests. The results show that the sample Li_0.7Ni_0.3Mn_0.7O₂， has the best electrochemical properties which shows only one charge-discharge potential stage of 2.8～3.0V and has a high specific capacity over 180mAh·g^-1 cycled between 2.0～4.20V. A significant structure transformation to the spinal-type phase has not been found in the charge-discharge cycling and the discharge specific capacity around 165mAh·g^-1 has re-mained after the 20th cyclings for the material.     

LiNi1-xMxVO4的红外光谱和拉曼光谱研究

The vanadates of LiNi_1-xM_xVO₄(M=Fe,Co,Ni) containing VO₄ tetrahedrons were synthesized by soft chemical method through a new mild liquid route. The samples sintered at 450℃ for 3h and at 650℃ for 3h are named for LT-LiNiVO₄ and for MT-LiNi_1-xM_xVO₄ respectively. All of the products were measured by X-ray diffraction, IR and Raman spectra respectively. In comparison with IR spectra of V₂O₅ and NiO, the LT-LiNiVO₄ has a strong and broad IR absorption band of VO₄ tetrahedrons located at 600～850cm^-1 with three small splitting peaks corresponding to the asymmetry stretching vibrations of V-O bonds. The results of IR and Raman spectra for MT-LiNi_1-xM_xVO₄ show that the cations of Ni²⁺, Co²⁺, Fe²⁺ have the influences on the frequency shifts of the V-O vibrations.     

CexPr1-xO2-δ复合氧化物的XRD和Raman表征

A series of Ce_xPr_1-xO_2-δ mixed oxides were synthesized by sol-gel method and characterized by Raman and XRD techniques. When x value was changed from 1.0 to 0.5, only a cubic phase CeO₂ was observed. The samples were very well crystallized on decreasing x from 0.50 to 0.99. For Ce_xPr_1-xO_2-δ samples 465 cm^-1 and 1 150 cm^-1 Raman peaks are attributed to the Raman active F_2g mode of CeO₂. The broad peak at about 570 cm^-1 in the region of 0.3 ≤x≤ 0.99 can be linked to lattice defects resulting in oxygen vacancies. The new band at about 195 cm^-1 may be attributed to the asymmetric vibration caused by the formation of oxygen vacancies. Calcination temperatures had great effect on the peak intensity for CeO₂ but less effect on Ce_0.8Pr_0.2O_2-δ in Raman spectra. It might be due to the transformation of the colors for the mixed oxides, the insertion of Pr atom into the ceria lattice could enhance the sintering resistance and thermal stability of the mixed oxides.     

Ca2-3xLa8+2x□x(SiO4)6O2的合成及其导电性能的研究

The silicate oxyapatites Ca_2-3xLa_8+2x□_x(SiO₄)₆O₂(x=0, 0.17, 0.33, 0.50, 0.67) was synthesized via a sol-gel method at low temperature. The apatite phases have been characterised by X-ray diffraction (XRD), conducting properties was studied by electrical chemistry impedance spectroscopy (EIS). The conductivity of La_9.33□_0.67(SiO₄)₆O₂ is 1.58×10^-3 S·cm^-1 at 700 ℃, it is higher about 4 270 times than that of Ca₂La₈(SiO₄)₆O₂, the activation energy is decreasing from 1.37 eV to 0.84 eV. With cation vacancies increasing,the conducting mechanism is gradually translation from a direct linear pathway free oxygen ion conduction to a curve pathway interstitial oxygen ion conduction. The electrical conductivities is almost independent of the oxygen partial pressure, this suggests that the oxyapatites exhibited almost pure O^2- ion conduction over a wide range of oxygen partial pressure.     

纳米尖晶石LixMn2O4的制备与电化学性能表征

Nano-spinel Li_xMn₂O₄(0.6 ≤x≤ 1.0) was synthesized by two steps of coprecipitation and calcination. The influences of calcination temperature, time and Li/Mn ratio on the crystal structure and the particle size of Li_xMn₂O₄ were investigated. It was shown that the higher the calcination temperature, the more complete the crystal structure, and the larger the particle size. Moreover, the influence of calcination time on the crystal structure was insignificant when it was more than 3h at 700℃. With the increase of x in Li_xMn₂O₄ in the range of 0.6～1.0, the d111 and lattice parameter a increased first and then decreased. The electrochemical properties of nano-spinel LiMn₂O₄ using as cathode material of lithium-ion battery were studied. The low discharge capacity might be due to the irreversible capacity loss brought by the large surface area and lattice vacancies of the nano-spinel.     

SrTi1-xMgxO3-δ钙钛矿型氧化物催化剂甲烷氧化偶联反应性能的研究

The structure and catalytic properties of SrTi_1-xMg_xO_3-δ perovskite-type catalysts for oxidative coupling of methane (OCM) have been studied by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Temperature-programmed desorption (O₂-TPD) methods. It has been shown that doping Mg²⁺ cations to the B site of SrTi_1-xMg_xO_3-δ perovskite-type catalysts results in the formation of oxygen vacancies in the lattices of oxide cata-lysts. With increasing the amount of Mg²⁺ doped in the B site of SrTi_1-xMg_xO_3-δ, methane conversion and C₂ selectivity first increase and then decrease remarkably. The SrTi_1-xMg_xO_3-δ catalyst with x=0.1 has the highest methane conversion and C₂ yield. It is suggested that the oxygen vacancies produced by Mg²⁺ cations doping are the sites responsible for oxygen activation, and the adsorbed oxygen species on the surface of SrTi_1-xMg_xO_3-δ catalysts are the main active species for OCM reaction. However, the over high content of the adsorbed oxygen species on the surface results in the complete oxidation of methane. Introducing water steam into feedstock can improve the catalytic properties of SrTi_1-xMg_xO_3-δ perovskite-type catalysts for OCM reaction at lower temperature. The SrTi_0.9Mg_0.1O_3-δ catalyst has the methane conversion of 28.0 % with C₂ hydrocarbons selectivity of 36.8 % under reaction temperature of 550 ℃.     

锂离子电池正极材料LiNi1-xCoxO2的合成及电化学性能研究

LiNi_1-xCo_xO₂ cathode materials for lithium ion batteries were synthesized by the co-precipitation and solid-state reaction methods with LiOH·H₂O, Ni(NO₃)₂·6H₂O and Co(NO₃)₂·6H₂O as raw materials. The materials were characterized by XRD, SEM and electrochemical tests. The results showed that synthesized cathode materials were with layered structure similar to α-NaFeO₂ and uniform morphology and nearly normal grain size distribution and better electrochemical performance when x was 0.18. The first charge and discharge capacity of the cathode material was 224.3 mAh·g^-1 and 194.2 mAh·g^-1, respectively. 88.5% of the first discharge capacity remained at the 20th cycle.     

Cu1-xAgxI(x=0.5～0.6)纳米微粒的制备与表征

In the presence of PVPK30,Cu_1-xAg_xI nanoparticles were prepared by ion exchange reaction.The product was characterized by FT-IR,XRD,TEM,EDS and SPS,respectively.It was found that the value of x is ap-proximately 0.5～0.6and the average diameter of the nanoparticles is 10～20nm.The product shows surface photovoltage property of semiconductor and the existence of Cu⁺ greatly enhances the separation efficiency of photoinduced electron-hole pairs.Meanwhile,SPS of Cu_1-xAg_xI nanoparticles with different X (Ag/I)value had been investigated. The results show that when X is 0.5～0.576, the SPS intensity of Cu_1-xAg_xI nanoparticles is highest.     

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.     

Ni_xCu_(1-x)Fe_2O_4的H_2/CO_2氧化还原反应性能

完全还原的NixCu1-xFe2O4(x=0.25,0.5,0.75)可用来分解CO2。采用共沉淀法制备了NixCu1-xFe2O4(x=0.25,0.5,0.75)系列铁酸盐的纳米微粒,利用H2-TG数据分析NixCu1-xFe2O4(x=0.25,0.5,0.75)中Cu2+的还原反应动力学数据,得出表观活化能Ea并不是单纯随着Ni2+或Cu2+含量的变化而变化,当x=0.25时反应活化能具有最大值。通过CO2-TG比较不同样品经H2完全还原后分解CO2的活性,得出Ni0.5Cu0.5Fe2O4具有最低的起始反应温度和最大的分解活性,并采用XRDRietveld拟合方法对Ni0.5Cu0.5Fe2O4的完全还原产物和分解CO2产物进行物相分析。     

The regular features of chlorine formation in the systems NaCl-MexOy-O2 and Ca(Zn)Cl2-MexOy-O2

The reaction of sodium, calcium, and zinc chlorides with atmospheric oxygen in the presence of transition metal oxides and antimony oxide at temperatures exceeding the melting temperatures of chlorides was studied. The content of chorine, product of oxidation of chloride ions in molten NaCl and CaCl₂, was determined as a function of the polarization force of cations of transition metal oxides.     

Electronic structure of magnetic semiconductors Cd1 ? xMnxGeAs2 and Cu1 ? xMnxGaTe2

The band structures of pure semiconductors CdGeAs₂ and CuGaTe₂, as well as magnetic semiconductors Cd_{1 − x} Mn _x GeAs₂ and Cu_{1 − x} Mn _x GaTe₂ (x = 0.0625), have been calculated by the density functional theory method. In both compounds, the Mn3d orbitals form a narrow band near the Fermi level. In the case of Cd_{1 − x} Mn _x GeAs₂, the Mn3d orbitals are slightly involved in chemical bonding. In the case of Cu_{1 − x} Mn _x GaTe₂, the same orbitals are considerably involved in chemical bonding. The relationship of these results with the properties of the compounds and ferromagnetism models is discussed. Original Russian Text ? S.V. Murashov, V.G. Yarzhemsky, V.I. Nefedov, E.N. Murav’ev, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 8, pp. 1327–1331.     

Ce0.5-xZr0.5-xBa2xO2负载TiO2光催化降解气相苯

在密闭不锈钢反应器内研究了Ce0.5-xZr0.5-xBa2xO2负载锐钛型TiO2光催化降解气相苯的性能.确定了该系列光催化剂的最佳Ba含量,并应用X射线衍射、紫外-可见漫反射光谱以及X射线光电子能谱对催化剂进行了表征.结果表明,TiO2在载体表面均匀分散.在210~400 nm范围内,TiO2/Ce0.5-xZr0.5-xBa2xO2比TiO2吸收更多的紫外光.TiO2/Ce0.5-xZr0.5-x-Ba2xO2包含Ti和O两种元素,TiO2/Ce0.5-xZr0.5-xBa2xO2的Ti 2p结合能向低能端偏移.Ce0.5-xZr0.5-xBa2xO2表面负载TiO2能有效提高催化剂的光催化活性.Ce0.5-xZr0.5-xBa2xO2的作用是转移电子和使催化剂在紫外区的吸收增强.     

六方类钙钛矿体系La2-xNdxCa2MnO7的结构和相关系

利用柠檬酸盐前驱物法制备了La_2-xNd_xCa₂MnO₇系列样品，并利用Rietveld方法对结构进行了精修。结果表明：体系中存在两个单相区(x ≤ 1.0，x ≥ 1.5)和一个两相区(1.0< x< 1.5)。体系这种结构变化可以用稀土离子半径变化说明。     

Solid Potassium-Conducting Electrolytes in the System K2 ? 2xAl2 ? xPxO4

New high-conductance potassium-cation solid electrolytes based on potassium aluminate are synthesized by means of partial substitution of five-charged phosphorus cations for three-charged aluminum cations and investigated. The maximum conductivity in the system K_{2 − 2x} Al_{2 − x} P _x O₄ is found to equal 5 × 10⁻³ S cm⁻¹ at 200°C and ∼1 S cm⁻¹ at 700°C, which is one of the best values for potassium solid electrolytes. The principal factors responsible for the high conductance are the stabilization of a high-temperature form of potassium aluminate and the formation of additional vacancies in the potassium sublattice, which occurs during the substitution process Al³⁺ → P⁵⁺ + 2V _K ^′ . __________ Translated from Elektrokhimiya, Vol. 41, No. 12, 2005, pp. 1501–1504. Original Russian Text Copyright ? 2005 by Burmakin, Shekhtman.     

新型固体氧化物燃料电池阴极材料Ca2-xSrxFe2O5的电化学性能研究

采用固相法合成了固体氧化物燃料电池(SOFC)阴极材料2-xSrxFe2O5(x=0.00,0.05,0.10,0.15,0.20),利用XRD和SEM对其结构和微观形貌进行了表征.结果表明该阴极材料与固体电解质Sm0.8Ce0.2O1.9(SDC)在1000℃烧结时不发生化学反应,且烧结4 h后,二者之间可形成良好的接触界面.利用交流阻抗谱技术对阴极材料的电化学性能进行研究,结果显示,阴极上的反应过程主要为电荷的迁移反应,其中Ca1.95Sr0.05Fe2O5电极在空气中700℃下具有最小的极化电阻为0.95Ω·cm2.当测试温度为700℃时,阴极电流密度为74mA·cm-2时,阴极过电位为100mV.     

SiO2负载氮掺杂TiO2可见光响应光催化剂的制备及性能

以四氯化钛为钛源,尿素为氮源,采用液相水解-沉淀法制得SiO2负载N掺杂TiO2可见光响应TiO2-xNy/SiO2光催化剂(TSN)。以苯酚为模型物,考察了TSN在可见光区、紫外光区及太阳光下的光催化活性,以及催化剂的使用寿命、分离性能。采用XPS、FTIR、UV-Vis DRS、XRD、TEM和低温氮物理吸附等对催化剂的结构进行表征。结果表明,N以阴离子形式进入TiO2体相并置换晶格中的O,适量N掺杂的TSN在紫外光区、可见光区及太阳光下均表现出较高的活性。SiO2与TiO2界面间有Ti-O-Si键形成,结合牢固。N掺杂在TiO2表面生成Ti-O-N键,形成新的能级结构,使催化剂的吸收红移至450~500 nm,诱发TiO2可见光催化活性。SiO2负载可减小TiO2颗粒平均尺寸,增加催化剂比表面积;同时SiO2负载还可改善催化剂的分离性能,提高催化剂使用寿命。     

纳米复合材料Ag/MxOy-TiO2(MxOy=ZnO、Al2O3和Fe2O3)的制备及其微波辅助光催化降解甲基橙

采用溶胶-凝胶-程序升温溶剂热一步法,利用表面活性剂EO₂₀PO₇₀EO₂₀(P123)作为模板剂,分别制备了三元纳米复合材料Ag/ZnO-TiO₂、Ag/Al₂O₃-TiO₂和Ag/Fe₂O₃-TiO₂。通过XRD、氮气吸附-脱附测定、TEM以及扫描电子显微镜配合X-射线能量色散谱仪(SEM-EDS)等对合成的3种催化剂进行了对比表征分析。结果表明,复合材料Ag/M_xO_y-TiO₂中Ag以单质形式存在并较好地分布在M_xO_y-TiO₂表面上。所合成产物颗粒尺寸较小(约10 nm左右),形貌较好。其中,Ag/ZnO-TiO₂的比表面积与Ag/Al₂O₃-TiO₂十分相近,略大于Ag/Fe₂O₃-TiO₂。光催化活性研究中,以甲基橙为模型分子且辅以微波场作用。结果显示,上述三元复合材料的活性均明显高于未掺杂银的二元复合材料,其中Ag/ZnO-TiO₂的光催化活性最好,在90 min内对甲基橙的降解率高达86%。     

A quantum chemical study of self-association of HAlBu 2i and ClAlBu 2i

The self-association of di-iso-butylaluminum hydride and di-iso-butylaluminum chloride is studied at the level of density functional theory and second order M?ller-Plesset perturbation theory. Thermodynamic parameters of the monomeric, dimeric, trimeric, and tetrameric forms of HAlBu₂ ⁱ and ClAlBu₂ ⁱ in a range of 203 K to 373 K are calculated. The energy of solvation is taken into account by the COSMO polarized continuum model. Based on the obtained results the equilibrium concentrations of the associated forms of organoaluminum compounds (OACs) are calculated, which agree with the experimental data. So, at room temperature the dimeric or trimeric forms of OACs are dominant in the gas phase and non-polar solvents; the tetrameric form is present, while the concentration of the monomeric form is negligibly low and decreases with decreasing temperature or diluting.