铑在不同载体材料上的分配比对低含量贵金属催化剂性能的影响

采用浸渍法制备了一系列低Pt、Rh含量的Pt-Rh型汽车尾气净化催化剂.研究了在Pt、Rh含量一定以及其他条件不变的情况下,只改变铑在不同栽体上的分配比对催化剂性能的影响,测定了催化剂对C3H8、CO、NO的起燃温度,并对催化剂样品进行了程序升温还原(H2-TPR)、程序升温脱附(O2-TPD)表征.结果表明:新鲜催化剂对C3H8、CO、NO的起燃温度相差不大,但经过1000℃、5h的水热老化后,催化剂性能发生了显著的变化,C3H8、CO、NO的起燃温度出现较大的差异,说明了铑在不同栽体上的分配比对催化剂性能有一定影响,特别是对催化剂的抗老化性能影响较大.     

Functionalization of carbon support and its influence on the electrocatalytic behaviour of Pt/C in H2 and CO electrooxidation

Chemical modification of Carbon Vulcan XC-72R for fuel cell applications has been undertaken. Treated carbons were used as carriers for the deposition of Pt nanoparticles and used as electrocatalysts. The influence of the carbon treatment, as well as that of the Pt nanoparticles generation and their deposition route has been studied. The behaviour of the electrocatalysts in the CO and hydrogen oxidation reaction (HOR) has been studied. It was observed that carbon pre-treatment lead to difference behaviour in the CO oxidation reaction compared with the performance over non treated supports. In this way, CO oxidation was controlled by the nature of the support rather than by the nature of the Pt particles alone.     

纳米载体铜基催化剂对低碳醇合成的影响

本文用沉积-沉淀法制备了新型纳米载体低碳醇合成催化剂，并与共沉淀法所制备的催化剂进行了对比，结果表明，纳米载体催化剂活性高、耐热性能好、醇收率高纳米载体对纳米载体催化剂活性大小的影响顺序为：纳米Al2O3＞纳米ZnO-ZnAl2O4＞纳米MgAl2O4＞纳米MgO.工艺参数对反应性能的影响结果表明，反应温度低，甲醇选择性高；但温度太高（＞320℃）CO2。选择性升高，且整个反应为动力学控制；压力升高可提高活性和C1-C2OH选择性，但C4OH选择性下降；结合空速对产物分布的影响，反应可能按Smith和Anderson的缩聚机理进行．     

作为城市触媒的公共文化设施及其设计

首先阐述了城市触媒的概念和内涵,然后从城市触媒的角度对公共文化设施及其设计进行了思考,分析了国内外公共文化设施的最新实例以及设计趋向和建设模式,最后指出了对当前我国公共文化设施建设的启示和指导意义.     

High temperature controlled atmosphere experiments for catalysts in a transmission electron microscope

A new transmission electron microscopy (TEM) specimen preparation procedure for high temperature experiments using a controlled atmosphere specimen holder (HTCASH) has been developed. It is designed for studying the microstructure of catalyst specimens before and after treatments in various gases. The procedure involved (1) finding a new formula for the embedding material, (2) devising a new method of making specimen supports, and (3) developing a method for removing the embedding material after the specimen has been microtomed. These techniques were then brought together to produce the ideal specimens for the HTCASH experiments. As an extra benefit, this procedure is also suitable for preparing specimens for ultrahigh resolution imaging experiments. The application of the new procedure in HTCASH experiments is illustrated through a high temperature reduction of a Co/SiO₂-923 catalyst.     

Creep forging of an aluminum bronze

Abstract

Compression tests on a commercial three-phase aluminum bronze showed significant softening above the β transformation. This was not observed in either beryllium-copper or α/β brass above their transformation temperatures. Isothermal compression tests on the aluminum bronze showed some rate sensitivity and there was no significant change in either mechanical properties or microstructure after large strains at the elevated temperature. These characteristics are typical of superplastic alloys.

Closed-die forging experiments in which a thin tapered lip was backward extruded on a cylindrical billet have shown that the material forges adequately at low pressures at temperatures above the transformation. It was concluded that creep forging of this aluminum bronze gives good die filling and surface finish.

Résumé

On a observé un adoucissement significatif d'un bronze à l'aluminium commercial (contenant trois phases) lorsque déformé en compression au-dessus de la transformation β. Le phénomène n'a pas été observe dans le cuivre au beryllium et le laiton α+β déformés au-dessus de leur temperature de transformation. Des essais de compression isotherme sur le bronze à l'aluminium ont permis d'observer une certaine sensibilité au taux de déformation; après de grandes déformations à la température élevée, les propriétés mécaniques et la microstructure n'ont pas été modifiées appréciablement. Ce comportement est typique des alliages superplastiques.

Des essais de forgeage en matrice ferme, au cours desquels une mince lèvre effilée a été extrudée, d'une manière inverse, sur une billette cylindrique, ont montré que de faibles pressions sont suffisantes pour forger le matériau adéquatement lorsqu'on opère à des températures au-dessus du point de transformation. Les auteurs ont conclu que le forgeage de fluage permet de bien remplir la cavite et d'obtenir un bon fini de surface.     

Hydrogen release from hydrolysis of borazane on Pt- and Ni-based alloy catalysts

Two types of Pt- and Ni-based alloy catalysts were synthesized and comparatively tested for hydrogen generation from aqueous borazane (ammonia- borane, _BH3NH3)${\mathrm{BH}}_3{\mathrm{NH}}_3)$ solution. The experimental results demonstrated that hydrogen release rates from some of the Pt alloys such as PtRu and PtAu are nearly 9 times higher than those from pure Pt surface, and similarly, most of the Ni alloy catalysts exhibit greatly enhanced catalytic activities than pure Ni catalyst. Particularly, hydrogen release from NiAg-catalyzed _BH3NH3${\mathrm{BH}}_3{\mathrm{NH}}_3$ hydrolysis can complete quickly at room temperature showing a stable hydrogen yield at _H2/_BH3NH3ratio=2.9${\mathrm{H}}_2/{\mathrm{BH}}_3{\mathrm{NH}}_3\mathrm{ratio}=2.9$ (molar ratio), corresponding to 8.7 wt % hydrogen release. Since the Ni alloy catalysts are less costly and highly efficient, it is feasible to use the Ni alloy catalysts for practical hydrogen generation in portable applications.     

Evolution and fractal growth of micro/nano structured wires of ruthenium synthesised by microwave irradiation of ruthenium dioxide

Ruthenium metal wires up to 3 mm long and 10-20 µm diameter, were produced in 20-30 s from anhydrous ruthenium dioxide by irradiation at 600 W in a microwave oven. The irradiation led to decomposition of ruthenium dioxide powder to ruthenium metal particles that sintered together along microwave field lines producing wires. Irradiation over 90 s produced larger features of metallic ruthenium with evidence of molten metal having been present. The evolution of wire growth proceeded in a fractal manner with self-similarity existing from the smallest to the largest wires.     

Simultaneous hydrogenation and hydroacylation of vinyl groups in polybutadiene by use of a rhodium catalyst

Vinyl groups in phenyl-terminated polybutadiene (1a) containing 99% unsaturation (27% vinyl group, 73% internal olefin), and for which the average M_n is 3400, were simultaneously hydrogenated and hydroacylated with various aromatic or heteroaromatic primary alcohols in the presence of the catalytic system RhCl₃.H₂O, PPh₃ and 2-amino-4-picoline. Sterically less hindered alcohols, such as benzyl alcohol, showed greater reactivity than sterically more hindered alcohols, such as 2-naphthylmethanol and heteroaromatic primary alcohols. Vinyl groups in phenyl-terminated polybutadiene (1b) containing 99% unsaturation (45% vinyl group, 55% internal olefin) and for which the average M_n is 1300 also showed similar reactivity toward various primary alcohols under identical reaction conditions.     

Well-dispersed perovskite-type oxidation catalysts

A novel technique for the preparation of highly dispersed rare-earth perovskite LaCoO₃ catalysts was developed. Using the conventional complexation and pyrolysis methods, an etchable component, zinc oxide (ZnO), was introduced into the precursor by adding zinc nitrate during preparation. After calcination, the independent ZnO phase was extracted by an aqueous NH₄Cl solution, resulting in well-dispersed LaCoO₃ catalysts with a surface area of over 30 m²/g. DTA-reaction tests using CO oxidation as the model reaction were performed as a quick means to illustrate the higher catalytic oxidation activities of the prepared LaCoO₃ catalysts mainly due to their high surface area.