熔融碳酸盐燃料电池阴极材料的导电性

通过交流阻抗方法研究了熔融碳酸盐燃料电池阴极材料锂镍氧化物、锂钴氧化物和锂铁氧化物的导电性能。结果表明:锂镍氧化物电极的导电性最好,锂钴氧化物电极的导电性次之,锂铁氧化物电极的导电性最差;它们的导电性都随着温度的升高而按指数规律增加;在合成锂钴氧化物(或锂铁氧化物)的过程中,使Li2CO3轻微过量,可以提高锂钴氧化物(或锂铁氧化物)电极的导电性,而且在同一温度下,随着nLi∶nCo(或nLi∶nFe,摩尔比)值的增大,锂钴氧化物(或锂铁氧化物)电极的导电性显著增加。     

Relating catalyst structure and composition to the water–gas shift activity of Cu–Zn-based mixed-oxide catalysts

In order to investigate the effect of cerium oxide on Cu–Zn-based mixed-oxide catalysts four catalyst samples were characterized by means of XRD, in situ XANES and thermogravimetric analysis. The activity of the catalyst samples was tested for the forward water–gas shift reaction. Cerium oxide was found to increase the crystallinity of the ZnO phase indicating a segregation of the Cu and ZnO phases. The TOF of the water–gas shift reaction based on chemisorption data was found to be independent of composition and preparation conditions of the four catalyst samples. In contrast, the catalyst stability depends on composition and preparation conditions. Cerium oxide impregnated before calcination of the hydrotalcite-based Cu–Zn precursors leads to a more stable water–gas shift catalyst.     

介孔氧化铁对正辛醇乙氧基化反应的催化性能

以十二烷基磺酸钠为模板剂、乙二胺为碱性介质,将水热法合成的氧化铁/十二烷基磺酸钠复合中孔材料在550℃、空气气氛中煅烧10h,除去模板剂,得到介孔氧化铁。通过X射线衍射、氮气吸附-脱附方法对介孔氧化铁的晶体结构和表面物性进行表征。表征结果显示,煅烧后的介孔氧化铁具有典型的六方介孔的结构特征,平均孔径为5.4nm。将介孔氧化铁用于催化正辛醇乙氧基化反应,研究结果表明,升高反应温度和初始压力、增加催化剂用量,可加快环氧乙烷的反应速率,同时产物的相对分子质量分布较窄。当平均聚合度为6.5时,正辛醇聚氧乙烯醚相对分子质量分布的选择性系数达到21.1。     

Formation and electronic structure of interface

In the present work the formation of the interface between polycrystalline silver and thin films of titanium oxide was studied with photoelectron spectroscopy (XPS, UPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Titanium oxide was deposited stepwise on 100 nm thick silver films by reactive magnetron sputtering allowing to study the evolution of the interface formation process. The process involves two steps: formation of thin layer of silver oxide and subsequent growth of the TiO₂ film. For better understanding of the silver oxidation process, pure silver films were exposed to a low temperature Ar/O plasma for different time intervals providing a possibility to investigate early stages of the oxide film growth.     

Preparation and Properties of Rare Earth Modified Carbon Black/Natural Rubber Composites

The oxides Eu, Ho, Er and Dy were used to prepare the hydroxides of rare earth modified carbon black. Then natural rubber latex （NRL） was added into the reactor. The system reacted at 85 ℃ with stirring for 1 h to prepare powdered HAF-Ln（OH）3/NR composites. The effects of the kind and content of Ln on the particle size distribution of P [ NR/HAF-Ln （OH）3 ] and mechanical properties of its vulcanizate were studied respectively. It is found that rare earth can help to get the powder of the composite, the product particle with a diameter less than 0.9mm will be get when the composites containing the compound of Ho, Er and Dy with dosage of 1.0, 1.0, O. 5 percent, respectively. The adding of Ln can improve the tensile strength and tear strength of the vulcanizate effectively, what＇s more, Er and Dy can decrease the permanent set of vulcanizate significantly. The SEM studies shows that P[ NR/HAF-Dy （OH）3 ] vulcanizate shows superior mechanical properties that depend primarily on the absence of free carbon black, the fine dispersion of carbon black in the rubber matrix and better polymer-filler interaction.     

降低气体悬浮焙烧炉焙烧过程中Al_2O_3粒度破损的措施

为了降低气体悬浮焙烧炉焙烧过程中Al_2O_3粒度的破损,对气体悬浮焙烧炉焙烧过程中氧化铝粒度的影响因素进行了分析,提出了降低粒度破损的一些措施。     

Study on Oxygen Isotope Fractionation in RE Oxide Minerals

ＳｔｕｄｙｏｎＯｘｙｇｅｎＩｓｏｔｏｐｅＦｒａｃｔｉｏｎａｔｉｏｎｉｎＲＥＯｘｉｄｅＭｉｎｅｒａｌｓＦａｎｇＴａｏ（方涛），ＱｉｕＹｕｚｈｕｏ（裘愉卓）（ＩｎｓｔｉｔｕｔｅｏｆＧｅｏｃｈｅｍｉｓｔｒｙ，ＡｃａｄｅｍｉａＳｉｎｉｃａ，Ｇｕｉｙａｎｇ５...     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.