High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

13C n.m.r. study of raw materials for carbon black

¹³C n.m.r. spectroscopy has been applied to investigate a number of coal tar and petroleum-derived carbon black feedstocks. Application of the J-modulated spin echo technique is especially rewarding, as this method renders the quaternary carbons directly detectable. Thus the quality of carbon black feedstocks can additionally be gauged on the basis of the contents of quaternary carbons, which is a direct indication of the carbon yield in the carbon black production process.     

Analysis of epoxidized natural rubber. A comparative study of d.s.c., n.m.r., elemental analysis and direct titration methods

A comparative analysis of epoxidized natural rubber samples by ¹H and ¹³C n.m.r., titrimetric, elemental and d.s.c. techniques has been made. Whereas the titrimetric method is only applicable at low epoxy contents (< 15 mol%) both n.m.r. methods give reasonable precision over the compositional range of 20–75 mol%. Elemental analysis appears less reliable. D.s.c. analysis through measurement of T_g provides the highest precision of measurement but requires independent calibration by one or more of the primary methods. The epoxy content may also be related to the polymer density.     

The influence of an intermediate MoO3 layer on the solid state reaction of cobalt oxide withγ-Al2O3

In view of the importance for Co_xO_y,-MoO₃/-Al₂O₃ hydrodesulphurization (HDS) catalysts, the reactivity of cobalt oxide layers towards cobalt aluminate formation was investigated on both MoO₃-covered and bare -Al₂O₃ substrates. Co₃O₄/MoO₃/-Al₂O₃ and Co₃O₄/-Al₂O₃ systems were prepared by vapour-deposition of MoO₃ (12 × 10¹⁵ Mo atoms/cm²) and Co (400 × 10¹⁵ Co atoms/cm²) layers onto a -Al₂O₃ substrate, followed by oxidation of the Co layer to Co₃O₄. After annealing at 800°C for 40 h, the interfacial reaction to cobalt aluminate was assessed using Rutherford backscattering spectrometry. The presence of molybdenum oxide appeared to enhance cobalt aluminate formation. The Mo atoms, which spread out over the entire cobalt-containing layer, presumably caused a high defect density, which explains the observed higher reaction rate. The amount of MoO₃ was much too low to stabilize all cobalt atoms by cobalt molybdate formation.     

The significance of defect chemistry for the rate of gas–solid reactions: three examples

Three examples are revisited in which the reaction rate could be reliably correlated with point defect chemistry highlighting the role of point defects as acid–base active centers. In the case of dehydrohalogenation of tertiary butyl chloride, AgCl becomes increasingly active as heterogeneous catalyst, if AgCl is homogeneously or heterogeneously doped. By such a procedure the silver vacancy concentration is adequately increased. The oxygen incorporation into SrTiO₃ offers an example in which the surface mechanism in terms of adsorbed species, oxygen vacancies and electronic centers has been elucidated. Appropriate surface coatings give rise to significant catalytic effects. Increasing iron (acceptor) doping not only changes the point defect chemistry but also the nature of the rate determining step. Lastly, the electrocatalytic function of Sr-doped LaMnO₃ is considered as regards oxygen reduction reaction and O²⁻ incorporation into Y-doped ZrO₂ in the context of solid oxide fuel cells. Again the defect chemistry is of prime importance for the reaction rate.     

Graft copolymerization of styrene onto casein initiated by potassium diperiodatonickelate (IV) in alkaline medium

A novel redox system, potassium diperiodatonickelate (Ni(IV))‐casein is used to initiate graft copolymerization of Styrene onto casein under different conditions in aqueous alkaline solution. Graft copolymers with both high grafting efficiency (>98%) and percentage of grafting(>300%) are obtained, which indicated that (Ni(IV))‐casein redox pair is an efficient initiator for this grafting. The effects of reaction parameters, such as monomer‐to‐casein weight ratio, initiator concentration, pH, time, and temperature, are investigated. A tentative initiation mechanism is proposed. The structures and properties of the graft copolymer are characterized by Fourier transform infrared Spectroscopy, X‐ray diffraction diagrams, and Scanning Electron Microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4247–4251, 2006     

7.63m特大型焦炉砌筑施工技术及要点

主要针对7.63m特大型焦炉砌筑施工技术,从工程实践效果分析其施工技术在质量、工期、成本等方面收到良好的经济效益和社会效益,现对7.63m特大型焦炉施工技术作简要介绍。     

掺Er^3＋镓磷酸盐玻璃的光学性质

利用熔融淬火法制备了摩尔分数为40．8Ga2O3-58．0NaPO3-1．2Er2O3掺Er^3＋镓磷酸盐玻璃,测试并研究了样品中Er^3＋的吸收光谱、1．5μm发射光谱,根据Judd-Ofelt理论计算了Er^3＋离子强度参量Ωt（t=2,4,6）及自发辐射概率、荧光分支比、自发辐射寿命．结果表明,Er3＋1．5μm发射光谱半峰全宽达到40nm．同时,利用McCumber方法计算了Er^3＋4 I13／2→^4I15／2跃迁的受激发射截面,峰值达到6．10×10^-21cm^2,测定了Er^3＋4I13／2能级荧光寿命为4．88ms,^4I13／2能级量子效率为56．3％．     

缺失数据下m相依样本的大样本性质

讨论了缺失数据在随机补充方式下均值的估计,证明了估计的相合性和渐进正态性,并给出了经验似然比统计量的渐进分布．