Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

基于图像相关分析的砂土模型试验变形场量测

高分辨率数码相机的出现为砂土模型试验变形场非接触量测法的研究开发提供了一条简便经济而且实用的途径,在模型试验观测面上,不再需要布置嵌入式量测标志点或描画网格,直接用数码相机在试验各阶段拍摄照片,然后对照片序列进行图像相关分析,即可得出模型试验的变形场分布。利用图像匹配技术追踪模型上点的位移,借用FEM常用的等参单元的概念进行图像校准和应变计算,采用双线性插值技术可以实现微小变形量测,并提出同时用平移和旋转搜索方法,以适应砂土模型的变形特点。精度检验试验结果表明,一个像素以下的平移量测标准方差达到0.19个像素,数值试验表明,15°旋转刚体变形量测,非旋转搜索和旋转搜索的标准方差分别为0.49和0.08个像素。最后给出一个在砂土地基承载力离心机模型试验中的应用实例,分析结果包含砂土模型位移场、最大剪应变场和体积应变场的分布图。结果表明这一方法使得砂土模型局部化变形、剪切带和渐进破坏过程的量化分析成为可能。     

数字电影JPEG 2000码流从无损压缩到有损压缩的高效转码

本文讲述了利用JPEG 2000位平面编码优势实现图像码流由无损压缩向有损压缩高效转码的方法.现行转码方法要求先将JPEG 2000无损码流解码,然后将其重新编码形成有损码流,浪费了大量计算能力和时间.为减少此种浪费,建议从无损码流的解码开始就减少码流通过数量.此外通过独特的速率控制,使通常与削减码流相伴的质量下降减少了.实验结果证明此种方法不仅使计算的复杂程度明显降低,而且主观评价的图像质量十分接近全部无损解码的效果.     

A bona fide two-dimensional percolation model: an insight into the optimum photoactivator concentration in La2/3-xEuxTa2O7 nanosheets

La–Eu solid solution nanosheets La_2/3−xEu_xTa₂O₇ have been synthesized, and their photoluminescence properties have been investigated. La_2/3−xEu_xTa₂O₇ nanosheets were prepared from layered perovskite compounds Li₂La_2/3−xEu_xTa₂O₇ as the precursors by soft chemical exfoliation reactions. Both the precursors and the exfoliated nanosheets exhibit a decrease in intralayer lattice parameters as the Eu contents increase. However, there is a discontinuity in this trend between the nominal Eu content ranges x≤ 0.3 and x ≥ 0.4. This discontinuity is attributed to the difference in degree of TaO₆ octahedra tilting for the La- and Eu-rich phases. La_2/3−xEu_xTa₂O₇ nanosheets exhibit red emission, characteristic of the f–f transitions in Eu³⁺ photoactivators. The photoluminescence emission can be obtained from both host and direct photoactivator excitation. However, photoluminescence emission through host excitation is much more dominant than that through direct photoactivator excitation, and this behavior is consistent with that of all the other rare-earth photoactivated nanosheets reported previously. The absolute photoluminescence quantum efficiency of the La_2/3−xEu_xTa₂O₇ nanosheets increases as the experimentally determined Eu contents increase up to x=0.45 and decrease above it. This result is in good agreement with the optimum photoactivator concentration expected from the percolation theory. These solid solution La_2/3−xEu_xTa₂O₇ nanosheets are excellent models for validating the theory of optimum photoactivator concentration in the truly two-dimensional photoactivator matrix.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

Cold storage characteristics of mobile HTS magnet

A cold storage system specialized in mobile high-temperature superconducting (HTS) magnets (e.g. for magnetically levitated (maglev) vehicles) has been proposed. In this system, a cooling source is detachable and a HTS coil is capable of maintaining superconducting state with its heat capacity. This system allows a considerably lightweight HTS magnet.An apparatus was constructed to evaluate the possibility of using cold storage systems in maglev vehicles. The thermal characteristic of this apparatus was based on a magnet for previous maglev test vehicles [1]. The operational temperature range of the magnet was assumed from 20 K to 50 K. Some experiments indicated that heat conduction by residual gas was not negligible. Especially over 30 K, gas conduction took a large part of heat input. This phenomenon is attributable to reduction of cryopumping effect. However, activated carbon in the apparatus compensates cryopumping effect. A unique heat capacitor was also used to enhance the cold storage effect. Water ice was chosen as a heat capacitor because water ice has a higher heat capacity than metallic materials at cryogenic temperatures. A small amount of water ice also prolonged cryogenic temperature condition. These results indicate 1 day of cold storage is probable in a magnet for maglev vehicles.     

Elution of copper from vermiculite with environmentally benign reagents

For the purpose of remediation of soils polluted by heavy metals, the use of some strong synthetic chelating agents such as ethylenediaminetetraacetic acid (EDTA) has been proposed. However, EDTA would not be considered as the preferential choice for the remediation of soil polluted with heavy metals like copper because of its nonbiodegradability and permanent residence in the natural environment. In the present work, some novel environmentally benign chelating agents, glucosamine hydrochloride, chito-oligosaccharide and -asparaginic-N,N-diacetic acid (ASDA) were screened to find alternatives to EDTA by investigating the elution of copper from vermiculite with these reagents and comparing their effectiveness with EDTA. The effects of suspension contact time, reagent concentration and equilibrium pH of the solution on the removal of copper were examined. A stoichiometric amount of EDTA can quantitatively remove copper in both acidic and neutral conditions. Chito-oligosaccharide was a slightly less-effective reagent under acidic conditions compared to EDTA, and an amount well in excess of stoichiometry is required to achieve the maximum removal of copper from vermiculite. Glucosamine hydrochloride shows a relatively weak ability for the liberation of copper. The elution behavior of ASDA was equivalent to EDTA in acidic and neutral media. It was concluded that ASDA is the best substitute for EDTA because of its similar high complexing ability and superior biodegradability.     

Electric dichroism studies of the bonding of Co(III) chelate with synthetic polyelectrolytes

The interactions of bis-2-(2-pyridylazo)-1-naphthol Co(III), [Co(III) (αPAN)₂⁺], with five kinds of synthetic polyelectrolytes have been studied by spectrophotometric and transient electric dichroism measurements. The polyelectrolytes were: poly(styrene sulphonic acid) (PSS); poly(acrylic acid) (PAA); poly(l-glutamic acid) (PLG); $\text{poly}\text{(N}{}^{\mathrm{<mtext>e</mtext>}}\text{,N}{}^{\mathrm{<mtext>e</mtext>}}\text{-}\text{dicarboxylmethyl-}\text{l}\text{-lysine}$ (PDCML); and poly(l-lysine) (PLL). The equilibrium constant of the reaction:

with P = polyelectrolyte residue was determined spectrophotometrically: K₁ is > 10⁷ M^?1 (PSS); (1.4 ± 0.2) × 10⁴ M^?1 (PAA); (4.0 ± 0.4) × 10³ M^?1 (PLG); (1.4 ± 0.2) × 10⁶ M^?1 (PDCML); and < 10² M^?1 (PLL) at pH 6–8. From transient electric dichroism, the angle (ψ) between the αPAN plane and the polymer axis was determined to be 65° (PSS); 52° (PAA); 55° (PLG); and 52° (PDCML). The large K₁ and ψ values for PSS are ascribed to the hydrophobic interaction between the aromatic αPAN ring and the styrene sulphonate residues of PSS. Using stopped-flow electric dichroism measurements, rapid transfer of a bound Co(III) chelate from the PDCML to PSS chains was shown to occur.     

Stereoselective Hydrolysis of Amino Acid Esters Catalyzed by β-Cyclodextrin-L(or D)-histidine Compounds

The catalytic activity of β-cyclodextrin-L(or D)-histidine compounds, β-CD-D-His(e) ( 2a ), β-CD-L-His(e) ( 2b ), and β-CD-D-D-His(a) ( 2c ), for the stereoselective hydrolysis of N-acyl-amino acid esters ( 3a-f ) was examined at 25° C (pH 7.90). The ability of 2a-c to bind the ester substrate into the cyclodextrin cavity and to attack the bound substrate by the nucleophilic imidazolyl group of the histidine moiety resulted in extremely high activity for those catalysts. However, the stereoselection of the enantiomeric esters during the inclusion of the substrate by 2a-c was found to be opposite, in terms of chiral specificity, to that during the esterolysis of 2a-c in the molecular cavity: that is, the stereoselective activity of 2a-c is very small. The catalytic activities of 2a-c are also influenced by the structural differences in 3a-f , which result in the different modes of substrate inclusion by the catalyst through hydrophobic forces.