无机溶胶-凝胶法制备B型和M型VO2粉体

以V2P5为原料,采用无机溶胶-凝胶法制备出V2O5粉体,在H2气氛下热处理得到了VO2(B)粉体,再在Ar气氛下热处理VO2(B)粉体,制备出了VO2(M)粉体.采用X射线衍射(XRD)、红外吸收光谱(IR)、差热分析(DTA)等方法对样品进行了成分和结构分析,结果表明,当热处理温度为500℃、H2浓度50%时,得到VO2(B)粉体;然后,在Ar气氛下分别经过550、600、650、700℃处理1h后,VO2由B型向M型转变,700℃处理成功制备出了VO2(M)粉体.     

Synthesis and study of compounds of the general formula MITh2(VO4)3 (MI = Li, Na, Ag, K, Rb, Cs, Tl)

Double vanadates of thorium and univalent metals with r(M^I) < 1.6 Å were prepared by high-temperature solid-phase reactions. Representatives of this series with larger M^I atoms were prepared by the solgel method. The compounds crystallize in three structural types: zircon for Li and Na derivatives, scheelite for AgTh₂(VO₄)₃, and potassium thorium vanadate for the compounds containing K, Rb, Cs, and Tl. Thus, two morphotropic transitions are observed in the series of the compounds studied. The bands in the IR spectra were assigned, and the effect of the site symmetry of the VO₄ tetrahedra on the number of absorption bands was revealed. The incongruent melting points of the compounds were determined by differential scanning calorimetry.     

Solid-state reactions in V x O y (NH4VO3)-P2O5 and V x O y (NH4VO3)-(NH4)2HPO4 closed systems

Solid-state reactions in V _x O _y (NH₄VO₃)-P₂O₅ and V _x O _y (NH₄VO₃)-(NH₄)₂HPO₄ closed systems can be used to synthesize vanadyl hydrogen phosphate at 300°C and a variety of ammonium vanadium phosphates at lower and higher temperatures.     

Thermal and luminescent properties of M2Zn(VO3)4 (M = Rb, Cs)

We have developed processes for the synthesis of the Rb₂Zn(VO₃)₄ and Cs₂Zn(VO₃)₄ tetrametavanadates. Rb₂Zn(VO₃)₄ has been prepared by solid-state reaction (350°C) between presynthesized RbVO₃ and ZnV₂O₆ powders, and Cs₂Zn(VO₃)₄ has been prepared by the Pechini method (sol-gel process). Both metavanadates crystallize in monoclinic symmetry (sp. gr. P2₁/m). Thermochemical characterization results demonstrate that the vanadates undergo complex transformations during heating to 450°C and subsequent cooling. As a result, the materials are in a nonequilibrium state at room temperature and consist of both the parent double metavanadates and their peritectic decomposition products. We believe that the formation of the structure of the M₂Zn(VO₃)₄ compounds from their melts is a kinetically hindered process. These compounds are structurally stable only at temperatures below 369 (Rb₂Zn(VO₃)₄) or 420°C (Cs₂Zn(VO₃)₄). We have measured for the first time the diffuse reflectance and photoluminescence excitation spectra of the two tetrametavanadates in their emission range and their photoluminescence spectra at various excitation wavelengths and determined their chromaticity coordinates. Their X-ray luminescence and scintillation decay characteristics have been determined for the first time under pulsed electron beam excitation. The electron excitation dissipation processes in the cesium and rubidium compounds are shown to be similar. We discuss the origin of the emission bands in the mixed vanadates and their potential application areas.     

Porous yolk-shell structured Na3(VO)2(PO4)2F microspheres with enhanced Na-ion storage properties

Na3(VO)2(PO4)2F(NVPOF)has been considered as one potential candidate for sodium-ion batteries because of its high operating voltage and theoretical capacity.However,the poor intrinsic electronic conductivity significantly restricts its widespread application.In response to this drawback,we adopt the optimization strategy of tuning the morphology and structure to boost the electrical conductiv-ity and mitigate the capacity fading.In this paper,NVPOF microspheres with unique porous yolk-shell structure were fabricated via a facile one-step solvothermal method for the first time.By monitoring the morphological evolution with time-dependent experiments,the self-sacrifice and Ostwald ripening mechanism from rough spheres to yolk-shell structure was revealed.Benefited from the favorable inter-woven nanosheets shell,inner cavity and porous core structure,the resulting NVPOF electrode exhibits superior rate capability of 63 mA h g-1 at 20 C as well as outstanding long-cycling performance with the capacity retention up to 92.1％over 1000 cycles at 5 C.     

钒酸锰负极材料的制备及其性能

本研究通过流变相反应-热解法制备了碳包覆钒酸锰锂离子电池负极材料,通过XRD、TEM和电化学测试对材料进行了表征.所制备的材料微观组织呈不规则的短圆柱形和球形,其直径分布在30～50 nm之间,短圆柱形颗粒长度在200 nm左右.在充放电电压为3.0 V到0.02 V范围内,当充放电电流为0.1 A/g时,钒酸锰负极材料首次可逆充电容量为876 mAh/g,经过100次充放电循环后,可逆充电容量为843 mAh/g;以2.0 A/g的大电流充放电时,可逆充电容量仍然保持在334 mAh/g左右,表现出较优秀的大电流充放电能力.     

聚(苯胺-邻六氟羟基苯胺)共聚物的合成及其性能表征

采用过硫酸铵作为引发剂,通过化学氧化聚合法制备了一系列可溶性的聚(苯胺-邻六氟羟基苯胺)(PAH)的共聚物。利用傅里叶红外光谱(FTIR)、核磁共振氟谱(19F-NMR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、紫外光谱(UV)和场发射扫描电子显微镜(FESEM)等对共聚物的化学结构和形貌等进行了表征和分析。结果表明,邻六氟羟基苯胺(HAFIP)成功导入了共聚物主链中,共聚物的数均分子量Mn介于6.51×10~4与9.04×10~4之间。HAFIP的存在抑制了共聚物的醌式结构n→π*跃迁,随着共聚物中邻六氟羟基苯胺(HAFIP)摩尔分数的增大,共聚物形貌逐渐由纳米纤维向纳米颗粒变换。与聚苯胺难于溶解于一般有机溶剂不同的是,当邻六氟羟基苯胺(HAFIP)的摩尔分数超过0.5时,共聚物可以完全溶解于四氢呋喃、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺等有机溶剂中,表明HAFIP的导入,可以大幅改善聚苯胺的溶解性能,从而扩展聚苯胺的应用范围。     

Combustion Synthesis of Glass (B2O3-Al2O3-MgO)-Ceramic (TiB2) Composites

The combustion synthesis, or self-propagating high temperature synthesis (SHS), technique has been used to produce glass ceramic composites that have a glass matrix based on B₂O₃-MgO-Al₂O₃and a crystalline ceramic phase of TiB₂. Conditions for producing glassy materials by the SHS technique are discussed and the thermodynamics of these combustion reactions are analyzed. The combustion characteristics, i.e., ignition energy, combustion temperature, and wave velocity have been determined. Green density of the pellets had a significant effect on the combustion characteristics. Green pellets with low density were used to reduce heat loss, thus enabling the synthesis of those compositions having low adiabatic temperatures. The glass-forming region of these SHS glasses was found to be in relatively good agreement with that of samples produced by the traditional furnace-melting method.     

Electrochemical synthesis and physicochemical study of lanthanum(III) acetylacetonate complexes

Anodic dissolution of lanthanum metal in the presence of acetylacetone in ethanol, acetonitrile, and water was studied. Adducts of lanthanum tris--diketonates [La(EtOH)_0.5(AA)₃], [La(HAA)(AA)₃], and La(AA)₃(H₂O)₄, respectively, were isolated from these solutions. Electrochemical oxidation of lanthanum in the course of electrolysis is accompanied by its chemical dissolution. The compositions of the compounds obtained were confirmed by IR spectroscopy, mass spectrometry, thermal gravimetric analysis, isothermal heating, and elemental analysis for metal.Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 510–512.Original Russian Text Copyright © 2004 by Kostyuk, Dik, Tereshko, Trebnikov.     

Hydrothermal synthesis of W and Mo co-doped VO2(B) nanobelts

W and Mo co-doped VO₂(B) nanobelts which used formic acid as reduction acid, NH₄VO₃ as vanadium source, (NH₄)₆W₇O₂₄?·?6H₂O and (NH₄)₆Mo₇O₂₄?·?4H₂O as doped sources were synthesised by the hydrothermal method. The samples were characterised by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). TEM and HRTEM images showed the samples had a length of 1?µm and a width of 100?nm. XRD, FTIR and XPS spectra revealed that Mo⁶⁺ and W⁶⁺ incorporated into the VO₂(B) lattice and formed solid-solution phases with VO₂(B).     

二氧化钒超薄纳米片的制备及其光学性能研究

采用V2O5作为钒源,以乙二醇(EG))为还原剂,在190℃的条件下,通过简单的水热途径制备出了VO2 (B)超薄纳米片晶.并利用X射线衍射(XRD)、扫描电镜(SEM)、荧光分光光度计(PL)对样品的结构、形貌及荧光性能进行表征.研究结果表明:以乙二醇(EG)为还原剂制备出的晶体为纳米VO2 (B),长180～350...     

Facile synthesis,phase transition,optical switching and oxidation resistance properties of belt-like VO2(A) and VO2(M) with a rectangular cross section

Belt-like VO₂(A) with a rectangular cross section (VA-RCS) was successfully synthesized using V₂O₅, H₂C₂O₄·2H₂O and H₂O as the starting materials by a facile hydrothermal approach. Some synthetic parameters, such as, the reaction time, reaction temperature and concentration of H₂C₂O₄·2H₂O, were systematically investigated to control the fabrication of belt-like VA-RCS. The formation mechanism of belt-like VA-RCS was proposed. Subsequently, belt-like VO₂(M) with a rectangular cross section (VM-RCS) was prepared by the irreversible transformation of VA-RCS at 700 °C for 2 h under the inert atmosphere. The phase transition temperature (T_c) of VA-RCS and VM-RCS was evaluated by DSC test. The optical switching properties of VA-RCS and VM-RCS were studied by the variable-temperature infrared spectra, and it was found that the as-obtained VA-RCS and VM-RCS could be used as the optical switching materials. Furthermore, the oxidation resistance properties of VA-RCS and VM-RCS were investigated by TGA, indicating that they have good thermal stability and oxidation resistance below 400 °C in air.     

Synthesis and characterization of Dy(OH)3 and Dy2O3 nanotubes

Dy(OH)3 nanotubes with high aspect ratios of up to about 50 were synthesized in the presence of poly(ethylene glycol) via a hydrothermal method. Poly(ethylene glycol), as a nonionic surfactant, plays an important role in the formation of morphologies. Subsequent thermal treatment of Dy(OH)3 nanotube precursors at 450 degrees C for 6 h led to Dy2O3 nanotubes, during which the precursor tubular morphology was maintained. Selected-area electron diffraction and high-resolution transmission electron microscopy reveal the single-crystal nature of the Dy(OH)3 and Dy2O3 nanotubes. The morphologies and crystalline structure of the as-obtained products were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, respectively. By this method, we can obtain a mass of products.     

Synthesis and physicochemical properties of titanium(IV)- and cobalt(II)-Based photocatalytic oxide composites

We have studied the phase transitions, morphology, and photocatalytic activity of composites based on titanium(IV) and cobalt(II) oxides at Co doping levels from 0.5 to 60 wt % and heat-treatment temperatures from 80 to 1150°C. The highest photocatalytic activity under illumination in the spectral range λ ≥ 670 nm is offered by mesoporous X-ray amorphous and multiphase (X-ray amorphous phase, anatase, rutile, and CoTiO₃) nanomaterials containing 5–20 wt % Co, whereas two-phase materials (rutile + CoTiO₃) have the lowest photocatalytic activity.