Hydrodechlorination of 3-chloropyridine and chlorobenzene in methanol solution over alkali-modified zirconia-supported palladium catalysts

The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO₂ with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li⁺ < Na⁺ < K⁺), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other.     

Measurement of the Metal Surface Acidity/Electronegativity of Pt(110)

In previous work, it has been found that a hydrogen-covered Pt(110) surface is acidic, but quantification of the acidity has not yet been done. In this paper a spectroscopic method is developed to measure the acidity of a metal surface for the first time. The technique involves measuring the intensity of the N–H stretch from the C₅H₄XNH⁺ that forms when hydrogen coadsorbs with pyridine, 2-fluoropyridine and 3-fluoropyridine. The Bethe approximation is then used to estimate the metal surface acidity/electronegativity (MSAEL). The proton affinity/MSAEL of Pt(110) has been determined to be 907 ± 4 kJ/mol at high coverage. This is the first time the MSAEL has been measured on a metal surface. Implications for fuel cell catalysis are discussed.     

锌基合金模具的应用及探讨

本文分析了锌基合金模具制造及使用过程中容易出现热裂、翘曲、收缩的问题，并提出了解决这些问题的措施。     

Composition Range of Amorphous Mg-Ni-Y Alloys

Based on the thermodynamic point of view, a method for predication of the composition range of amorphous ter-nary alloys was proposed. The composition range of amorphous ternary alloys is determined by the comparison of the excess free energy of the amorphous alloy and the free energy of competing crystalline states. The free energy is extrapolated from the data of three binary alloys by using Toop‘s model. The method was applied to predict the composition range of amor-phous Mg-Ni-Y alloys. The theoretical results are in good agreement with the available experimental results. It indicates that the present method can be used to predict the composition range for amorphous ternary alloys.     

合成直链烷基苯环境友好固体酸催化剂的研究 Ⅲ .催化剂失活原因分析

采用固定床反应器,对催化剂的稳定性进行了初步评价。在120℃、空速相同、液固反应条件下,高苯烯比时催化剂的稳定性明显高于低苯烯比时;在苯烯比和空速相同、液固反应条件下,相对低温反应时,催化剂的稳定性明显高于高温反应。IR分析结果表明,同新鲜和反应后未失活的催化剂相比,失活后催化剂的活性组分特征衍射峰消失,出现的新的特征衍射峰可能同—CH基的振动有关。TG分析结果表明,失活后催化剂在空气流中焙烧,失重幅度比新鲜催化剂大。     

Effect of RE－Al－N on Structures and Properties of M2 Cast High Speed Steel

M 2highspeedsteel (M 2steel)isamaterialwidelyusedintoolsanddies[1,2 ] .M 2steelischarac terizedbyalongsolidificationrangeandcomplexeu tecticreactions ,whichresultsinsegregationofalloy ingelementsandformationofseveraldifferenttypesofcarbidesduringsolidification[3,4 ] .Forconventionallyprocessedhigh speedsteels ,itisinevitablethatacoarsecarbidenetworkwillbeformedduringsolidifi cation .Coarseprimarycarbidestendtoresultinun evencarbidebandsdistributionafterasubstantialamountofhotprocessing[5] .Ma…     

Metal sorption by biomass of melanin‐producing fungi grown in clay‐containing medium

The sorption of toxic metals by fungal mycelia grown in clay‐containing medium is reported in this work. Biomass of melanin‐producing microfungi of the genus Cladosporium (C cladosporioides, C resinae and C herbarum) and Aureobasidium pullulans, clay minerals and fungal mycelia grown in clay‐containing medium were compared for their equilibrium Cu and Cd uptake from pH‐buffered solutions using experimental sorption isotherms. Bentonite (Cherkassy) in the natural form was shown to be the best Cu sorbent compared with the other clays and clay minerals tested. Cu sorption isotherms fitted the Langmuir sorption model for all cases. Comparison of Cu and Cd uptake for biomass and bentonite showed a lower biomass uptake capacity but a considerably higher affinity of the biosorbent for the solute. The presence of kaolinite and palygorskite in the medium generally reduced both Cu and Cd sorption capacity and the metal‐binding ability of the fungal–clay mixtures. In contrast, addition of bentonite into the medium did not appreciably alter the Cd sorption ability but increased the sorption of Cu by A pullulans and C cladosporioides grown in this medium. A common feature for all fungi grown in the presence of bentonite was an increase in the Cu sorption capacity (Q_max) of the biomineral sorbents and a reduction in their affinity (Langmuir parameter b) compared with control biomass. A difference between predicted and experimental data obtained for biomass grown on bentonite medium was also observed. The connection between the sorption capacity of biomass grown in clay‐containing medium, mycelial morphology and the structure of fungal pellets is discussed and a mechanism for the changed sorption capacity of the combined biomineral sorbents is proposed which involves blocking or modification of binding sites on biotic and abiotic components of the ‘biomineral’ association. © 2002 Society of Chemical Industry     

Rational Synthesis of Metal Nanotubes and Nanowires from Lamellar Structures

A generic method has been developed for the synthesis of crystalline metal nanowires or nanotubes (such as bismuth nanotubes, tungsten nanowires) from lamellar structures. In a typical process, lamellar surfactant/inorganic composite precursors are first prepared by reacting cationic or anionic surfactants with inorganic species under appropriate conditions. After treating these precursors by hydrothermal pyrolysis, or other processes, crystalline metallic nanotubes or nanowires are obtained.