Preparation and properties of homogeneous V2O5-SiO2 xerogel composite based on interpenetrating polymer network

In this paper, we report the conducting and electrochemical properties of a homogeneous V₂O₅-SiO₂ xerogel composite obtained from the simultaneous polymerization in both inorganic components (Si-O and V-O based polymers) forming an interpenetrating polymer network, where a mutual “solubility” due to cross-links and entanglements was observed. The presence of V₂O₅ inside the silica matrix has a strong effect on electrical conductivity; measurements showed room temperature conductivity almost 1000 times higher than what is found in the literature. In addition, the electrochemical behavior is quite similar to that found in V₂O₅ xerogel. Moreover, the effects of thermal treatment on the conducting and electrochemical properties were investigated. It was found that both properties were improved with no significant effect on V₂O₅ xerogel layered structure.     

Vapour and plasma ignition thresholds for visible pulsed-laser ablation of metallic targets

The coupling of visible nanosecond laser pulses to metallic targets irradiated in vacuum is studied. The expressions of the vapour and plasma ignition times are obtained. Two cases for vapour breakdown in the plasma ignition process are considered. The first case is that 40 generations of new electrons are born in vapour generation time before plasma formation as assumed in the literature. The second case is that 10 generations of new electrons are born in vapour generation time. Molybdenum (Mo), niobium (Nb) and aluminium (Al) targets are considered for illustrations of our results. The expression of the plasma ignition time for the Al target is substantially different from that reported in the literature. The vapour and plasma ignition threshold laser intensities are calculated and compared with those reported in the literature. Reasons for disagreement are discussed. The plasma ignition threshold estimated in the second case is noted to be in good agreement with the reported experimental result.     

Synthesis of aromatic poly(thioether ketone)

Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc.     

Crystallization and second harmonic generation in thermally poled niobium borophosphate glasses

Crystallization of glasses with compositions (1−x)(0.95 NaPO₃+0.05 Na₂B₄O₇)+xNb₂O₅, x=0.4, 0.43, 0.45, 0.48 was investigated by differential scanning calorimetry and X-ray powder diffraction. Crystallization of two phases was observed in the glasses with x=0.43-0.48. First phase is a sodium niobate with the structure of tetragonal tungsten bronze () and second phase is Na₄Nb₈P₄O₃₂ (). The crystallization of sodium niobate is correlated with increasing of nonlinear optical efficiency reported for thermally poled glasses with x>0.4. The results of Raman spectroscopy show the formation of three-dimensional (3D) niobium oxide framework in the glasses with increase of niobium concentration. This framework is supposed to have tetragonal tungsten bronze structure and to be responsible for nonlinear optical properties of the glass. Second harmonic generation signals of as prepared and crystallized glass after thermal poling are compared. The nucleation and crystallization do not improve the NLO properties of the glasses under study.     

CO2氧化丙烷脱氢MoO3-V2O5/SiO2催化剂研究

采用表面改性和等体积浸渍法制备了MoO3-V2O5／SiO2复合氧化物，采用TPR、IR、TPD和微反技术表征了催化剂对CO2和C3H8的吸附性能和CO2部分氧化丙烷脱氢的反应性能．结果表明：随MoO3加入量的增加，V=O还原温度降低，晶格氧更易活化．CO2和丙烷的活化温度降低，丙烷转化率增高，丙烯选择性下降．V=O中晶格氧的活化是CO2氧化丙烷制丙烯反应的关键．     

Aromatic hydrocarbons, carbocyclic ligands spanning several oxidation states in both Main Group and transition elements. Recent advances with early transition d elements

In this paper some synthetic procedures to obtain (η⁶-arene)metal derivatives are reviewed. The metal-atom-arene-vapor co-condensation technique is the most appropriate to generate complexes of polycyclic aromatic hydrocarbons or heterocycles. As far as the aluminium halide-mediated synthesis is concerned, two classes of reaction are observed. When AlX₃ is used with a metal halide in the presence of an aromatic hydrocarbon in the absence of any reducing agent, AlX₃ can function as a dehalogenating agent, to give ionic compounds of general formula [M(η⁶-arene)n](AlX₄)_m, or it can add across the M---X bond with formation of M(μ-X)_nAlX_4−n systems. In both cases the metal displays its typical oxidation state. However, the use of AlX₃ in combination with aluminium (the Fischer-Hafner reducing system) affords ionic or covalent low-oxidation-state metal(η⁶-arene) complexes. Attention is focused on our most recent results concerning the synthesis, properties and reactivity of η⁶-arene derivatives of Group 4 and 5 elements, showing, inter alia, the first example of a tetraarylborate anion behaving as a 12-electron donor to one metal atom and low-valent η⁶-arene compounds as useful reagents in the inorganic and coordination chemistry of the corresponding metal in nonaqueous systems.     

水相锌二次电池正极材料V2O5/C的电化学性能研究

采用溶胶－凝胶法合成了一种V₂O₅/C复合材料.扫描电镜（SEM）和红外光谱（FTIR）分析表明,这是一种外层V₂O₅胶体包覆内层乙炔分子的多孔复合材料.以V₂O₅/C作正极,锌片为负极,Zn(ClO₄)₂溶液为电解质组成水相锌二次电池,采用循环伏安（CV）和电化学阻抗谱（EIS）等方法研究发现:V₂O₅:C质量比为1:1时电极具有最好的电化学性能,电池开路电压达1.64 V; Zn^2＋能分别在1.01 V和1.26 V处分步嵌入V₂O₅/C结构中A、B两种位置,其嵌入电流密度峰值最高可达70 mA•g^－1,并且具有较好的循环充放电性能;在一定放电深度下,V₂O₅/C电极反应速率受Zn^2＋的扩散过程控制.     

Optimizing Cs-exchange in titanosilicate with the mineral pharmacosiderite topology: framework substitution of Nb and Ge

Titanosilicates with complete or partial substitution of Ge or Nb in the framework and having the mineral pharmacosiderite topology were hydrothermally prepared and their ion-exchange properties towards Cs were studied for Ti/Ge/Si, Ti/Si, Nb/Ti/Si and pure Ge phases. The basis for the differences in the ion exchange properties measured as distribution coefficients (K_d) for these materials are detailed via structural characterization using the Rietveld refinement technique on the X-ray powder diffraction data. The differences in affinity towards Cs⁺ result either from the degree of hydration of the exchanger resulting in different coordination environments or the position of cesium ion in the eight-ring channel.     

Structural materials: metal-silicon-Boron. The Nb-rich corner of the Nb-Si-B system

Phase equilibria in the Nb-Nb₅Si₃-NbB region were studied in the melting (crystallization) range by means of light microscopy, XRD, SEM and EMPA on alloys after arc-melting and annealing at 1800°C and at subsolidus temperatures. Phase transition and melting temperatures were determined by DTA and pyrometric Pirani-Alterthum technique resulting in a solidus projection and two isopleths, Nb₇₇Si₂₃-Nb₇₇B₂₃ and Nb₉₉Si₁-Nb₅Si₂B. The T₂-phase Nb₅Si_3−xB_x (0?x?2, Cr₅B₃-type) was found to form equilibria with (Nb), NbB, Nb₃Si, and with the T₁-phase (Mn₅Si₃ derivative type). The T₂-phase melts incongruently (Nb₅Si_1.8B_1.2 at 2245°C) and forms a quasibinary eutectic with the niobium solid solution on a minimum tie-line at ∼1880°C.     

Preparation and crystal structure of Nb6.74 Ta5.26S4 – a new compound in the ternary system Ta?Nb?S

Nb_6.74Ta_5.26S₄ has been prepared by high temperature techniques. The crystal structure has been determined from single crystal X-ray diffraction data (R/R_w = 0.0588/0.0655). The compound crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 959.11 (26) pm, b = 336.37 (10) pm, and c = 3282.51 (74) pm. The orthorhombic cell contains four formula units. Its structure is similar to that of Nb-rich sulfides, rather than to that of Ta-rich sulfides. The metal coordinations are capped distorted cubic prisms and pentagonal prisms while the coordinations of sulfur are capped trigonal prisms.