离子浮选法从钨酸盐溶液中分离钨钼

利用作者试验室合成的捕收剂采用离子浮选法进行了钨钼分离．对于（ＮＨ４）２ＷＯ４溶液和Ｎａ２ＷＯ４溶液体系，每克钼捕收剂用量为６７６ｇ的条件下，对于含钼量为０４～１２ｇ／Ｌ的料液，其除钼率可达到９４％～９９％．     

Characterization of polyether‐poly(methyl methacrylate)‐lithium perchlorate blend electrolytes

Solid polymer electrolyte (SPE) systems based on interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices, with lithium perchlorate as guest salt, were prepared. These electrolytes were presented as free‐standing films, and their thermal and electrochemical properties were characterized by conductivity and electrochemical stability measurements. The properties of the interpenetrating blends of poly(ethylene oxide‐co‐propylene oxide) and poly(methyl methacrylate) host matrices as the electrolyte component of a solid‐state electrochromic device are reported and the results obtained suggest that this electrolyte provides an encouraging performance in this application. The most conducting electrolyte composition of this SPE system is the formulation designated as SPE2‐0PC (5.01 × 10^?4 S cm^?1 at about 57°C). The lowest decomposition temperature was registered with the SPE6‐15PC composition (233°C). The average transmittance in the visible region of the spectrum was above 41% for all the samples analyzed. After coloration the device assembled with 71 wt% PC presented an average transmittance of 15.71% and an optical density at 550 nm of 0.61. Copyright © 2010 John Wiley & Sons, Ltd.     

Barium Sodium Niobate Powders and Thin Films: Preparation and Ferroelectric Behavior

Powders and thin films of barium sodium niobate, Ba₄Na₂Nb₁₀O₃₀, of filled tungsten bronze type ferroelectric were processed by a sol-gel route using barium metal, niobium ethoxide and sodium methoxide as precursors. Polycrystalline powder resulted after heat treating the gel powder at or above 650°C. Thin films of Ba₄Na₂Nb₁₀O₃₀ showed no preferred orientation on Si(100), Pt/Si(100) and sapphire substrates. Hysteresis measurements at 1 kHz for the thin films annealed at 750°C, obtained using a prehydrolyzed precursor solution, and gave remanent polarization of 17.34 µC/cm² and coercive field of 62.5 kV/cm. Microstructural investigation of surface morphology of these films revealed grains about 0.3 µm in size. Prehydrolysis of the precursor solution was found to be necessary to achieve dense films with ferroelectric properties.     

The preparation of nanophase tungsten carbide powder with zeolite-X catalysts

The reduction–carburization of tungsten trioxide (WO₃) under carbon monoxide flow was studied in the temperature range of 300–750 °C. The reduction–carburization of WO₃ was improved by mechanically mixing with zeolite-HX, -NaX and -KX. The interaction between cation in zeolite-X and oxygen in WO₃ affected the improvement of the reduction–carburization of WO₃ to WC. Moreover, the improved reduction–carburization of WO₃ could lead to the decrease of reaction temperature. Because the particle size of WC is in contact with a reaction temperature, the nanophase WC can be prepared at low temperature. In particular, the particle size of WC was controlled by reaction temperature. The particle sizes of produced WC at 550, 650 and 700 °C were 25, 50 and 100 nm respectively.     

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2− (M=Mo,W)

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO₂(N₃)₂ (M=Mo, W), were prepared through fluoride–azide exchange reactions between MO₂F₂ and Me₃SiN₃ in SO₂ solution. In acetonitrile solution, the fluoride–azide exchange resulted in the isolation of the adducts MO₂(N₃)₂⋅2 CH₃CN. The subsequent reaction of MO₂(N₃)₂ with 2,2′‐bipyridine (bipy) gave the bipyridine adducts (bipy)MO₂(N₃)₂. The hydrolysis of (bipy)MoO₂(N₃)₂ resulted in the formation and isolation of [(bipy)MoO₂N₃]₂O. The tetraazido anions [MO₂(N₃)₄]²⁻ were obtained by the reaction of MO₂(N₃)₂ with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO₂(N₃)₂, (bipy)WO₂(N₃)₂, [PPh₄]₂[MoO₂(N₃)₄], [PPh₄]₂[WO₂(N₃)₄], and [(bipy)MoO₂N₃]₂O by their X‐ray crystal structures.     

微波消解-磷钼蓝分光光度法测定钨矿石中的磷含量

针对钨矿石中的微量元素磷,采用混合酸快速微波消解结合磷钼蓝分光光度法进行测定。经选择优化样品的微波消解和实验测定条件,结果表明:HCl+HNO3+HF的混合酸微波消解后的样品,在硫酸介质中,有钼酸铵存在时,用抗坏血酸将磷还原成磷钼蓝络合物,在825nm处比色测定。方法的加标回收率为98.9%~101.6%,结果准确可靠。硅在熔样过程中挥发除去不会干扰测定,砷会干扰实验,可在酸介质中加入碘化钾,使砷还原至低价而不干扰磷的测定。     

Small‐Sized Tungsten Nitride Particles Strongly Anchored on Carbon Nanotubes and their Use as Supports for Pt for Methanol Electro‐oxidation

The anchoring of small‐sized WN (tungsten nitride) nanoparticles (NPs) with good dispersion on carbon nanotubes (CNTs) offers an effective means of obtaining promising materials for use in electrocatalysis. Herein, an effective method based on grinding treatment followed by a nitridation process is proposed to realize this goal. In the synthesis, a solution containing H₄[SiO₄(W₃O₉)₄] (SiW₁₂) and CNTs modified with polyethylenimine (PEI‐CNTs) was ground to dryness. Small‐sized WN NPs were anchored onto the CNTs with good dispersion after calcination under NH₃. Under hydrothermal assembly conditions (absence of grinding), WN particles of larger size and with inferior dispersion were obtained, demonstrating the important role of the grinding process. The benefit of the small‐sized WN has been demonstrated by using WN/CNTs as a support for Pt to catalyze the methanol electro‐oxidation reaction. The mass activity of Pt‐WN/CNTs‐G‐70 (where G denotes the grinding treatment, and 70 is the loading amount (%) of WN in the WN/CNTs) was evaluated as about 817 mA mg^?1_Pt, better that those of commercial Pt/C (340 mA mg^?1_Pt) and Pt/CNTs (162 mA mg^?1_Pt). The Pt‐WN/CNTs‐G also displayed good CO tolerance. In contrast, Pt‐WN/CNTs prepared without the grinding process displayed an activity of 344 mA mg^?1_Pt, verifying the key role of grinding treatment in the preparation of WN/CNTs with good co‐catalytic effect.