Microwave Activation of Processes in Mesopores: The Thiourea Electrooxidation at Mesoporous Platinum

In situ microwave activation is applied to the electrochemical oxidation of thiourea at low surface area (polished polycrystalline) and at high surface area (electrodeposited mesoporous platinum coated) platinum microelectrodes. The one electron oxidation of thiourea to formamidine disulfide is monitored as a function of the different activation parameters. In the absence of microwaves (ambient temperature, low mass transport) increasing the surface area (roughness) increases the thiourea oxidation response predominantly due to adsorption effects. In the presence of high microwave intensities, high mass transport and thermal effects further increase the oxidation current at mesoporous platinum. The most effective thickness of the mesoporous platinum film for the thiourea oxidation process is estimated as 3 μm independent of electrode diameter, temperature, or mass transport effects.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

In situ observations of domain wall motion in Mn–Zn and Ni–Zn ferrites by Lorentz microscopy and electron holography

Domain wall motion in Mn–Zn and Ni–Zn ferrites with applied magnetic fields is investigated by in situ observations with Lorentz microscopy and electron holography. It is found that both Mn–Zn and Ni–Zn ferrites have a mean grain size of approximately 10 μm and several pores with sizes ranging from 0.2 to 1.1 μm. In situ observations by Lorentz microscopy with an applied magnetic field reveals that in Mn–Zn ferrite, the domain walls move easily across the grain boundary, while in Ni–Zn ferrite, the domain walls move along the grain boundary but are pinned at the grain boundary and pores. From in situ observations of Ni–Zn ferrite by electron holography, it is clarified that domain wall pinning at the grain boundary retards a sensitive increase in magnetic flux parallel to the applied field direction, which is considered to result in high hysteresis loss.     

Vibrational EELS and DFT study of propionic acid and pyruvic acid on Ni(1 0 0): Effects of keto group substitution on room-temperature adsorption and thermal chemistry

The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K.     

Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

保偏光纤偏振器

利用保偏光纤的弯曲损耗特性绕制而成的光纤偏振器已有过报道。但文献[1]中报道的偏振器尺寸太大(φ=100mm),不利于光纤陀螺的小型化。本文介绍一种采用“熊猫”型光纤制成的偏振器,其尺寸较小(φ=30mm),消光比可达到33dB。     

Frequency domain measurements on Na2B4O7−V2O5 semiconducting glass

Summary Dielectric measurements on Na₂B₄O₇(99.5%)−V₂O₅(0.5%) glass system, in the frequency range 10⁻³ to 10⁴ Hz and temperature range 300 to 500 K, have been carried out. The normalized plots of complex capacitance have shown a single mechanism responsible for conduction for both volume and surface measurements with their close values of activation energies (0.67±0.03) eV and (0.64±0.03) eV, respectively. The low-frequency dispersion (LFD) behaviour has been observed to be perturbed by the presence of more than one competing process. The impedance plots have shown a parallel combination of a capacitor (C) and a resistor (R), with some contribution of a dispersive element due to charge accumulation in the vicinity of the electrodes. The values ofR andC were found to be of the same order of magnitude, for both surface and volume measurements. The observedR has shown a decrease with an increase in temperature due to an increase in mobility of Na⁺ ions, whereasC remains practicaly constant. The complex capacitance surface behaviour is dominated by volume, due to hygroscopy of this glass system.     

High-Throughput Screening of Ten Microcystins and Nodularins, Cyanobacterial Peptide Hepatotoxins, by Reversed-Phase Liquid Chromatography-Electrospray Ionisation Mass Spectrometry

Liquid chromatography-electrospray ionisation mass spectrometry was evaluated in the high-throughput analysis of microcystins and nodularins, cyanobacterial peptide hepatotoxins. Extracts originating from cyanobacterial strains and field material were separated on a 30 mm × 4 mm I.D. Merck Purospher STAR RP-18e column using a rapid gradient of aqueous formic acid and acetonitrile, ionised by electrospray technique and analysed on a Micromass Quattro II triple-quadrupole mass spectrometer operated in the selected ion recording (SIR) mode. The total analysis time per sample was 2.8 min corresponding to 514 samples a day. The system showed good robustness during a series of 320 repetitive injections of a field sample containing three major microcystins.     

对期望理论的两个重要推进——损失厌恶系数λ及参考点研究

行为金融学是近20年来最为重要的新兴金融理论,期望理论更是其中的亮点,其运用领域之广超乎人们的想象,所以对它的完善改进具有非常重要的意义。本文对期望理论中的损失厌恶系数和参考点问题进行了深入研究,并且得出了创新性的结果:损失厌恶系数不是常数而是动态变量;得出了内生且纳入更多投资者行为特征的参考点。这些结果是对期望理论的重要改善和推进,对其在大量金融领域和涉及到财富偏好的问题的解决中都大有裨益。     

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本文研究了独立随机变量之和的绝对矩的几个性质, 其中包括$\ep|X+Y|-\ep|X-Y|$的表达式, 这里$X$和$Y$是相互独立的随机变量.