Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

Vapour- and liquid-side volumetric mass transfer coefficients measured in distillation column. Comparison with data calculated from absorption correlations

Volumetric mass transfer coefficients in liquid and vapour phases in distillation column were measured by the method consisting of a fitting of the concentration profile of liquid phase along the column obtained by the integration of a differential model to the experimental one. The mathematical model of distillation process includes mass and energy balances and the heat and mass transfer equations. The film model flux expressions with the convective transport contributions have been considered in the transfer equations. Vapour and liquid phases are supposed to be at their saturated temperatures along the column. Effect of changes of phase flows and physical properties of phases on the mass transfer coefficients along the column and non-ideal thermodynamic behaviour of the liquid phase have been taken into account. The concentration profiles of liquid phase are measured in the binary distillation of the ethanol-water and methanol-ethanol systems at total reflux on metal Pall Rings and Intalox saddles 25 mm in the column with diameter of 150 mm. The distillation mass transfer coefficients obtained by the fitting procedure are compared with those calculated from absorption data using Onda's, Billet's and Linek's correlations. The distillation heat transfer coefficients calculated from the model assuming saturated temperatures in both phases are compared with those calculated from the Chilton-Colburn and penetration model analogy between mass and heat transfer. The results have confirmed an agreement neither between distillation and from absorption correlations calculated mass transfer coefficients nor between analogy and from enthalpy balance calculated heat transfer coefficients. Also the concentration profiles obtained by the integration of the differential model of the distillation column using the coefficients from absorption correlation have differed from the experimental profiles considerably.     

贵金属电镀技术发展动态

以６４份参考文献综述了国内外贵金属镀覆的发展动态，简要介绍电镀、化学镀高速选择镀、脉冲电镀、激光镀等技术的应用。     

Silica-supported cobalt catalysts for the selective reduction of nitrogen monoxide with propene

Catalytic behavior of silica-supported transition metals for NO reduction with propene in the presence of oxygen was investigated. While both silica and cobalt oxides did not show any activity for the selective NO reduction, impregnated CoO/SiO₂ prepared from cobalt acetate showed good activity although the preparation conditions had significant effect on the activity. It was suggested that highly dispersed surface Co²⁺ ions on silica are responsible for the catalytic activity.     

Understanding heterogeneous catalysis on an atomic scale: a combined surface science and reactivity investigation for the dehydrogenation of ethylbenzene over iron oxide catalysts

In order to study the dehydrogenation of ethylbenzene to styrene, epitaxial iron oxide model catalyst films with Fe₃O₄(111), -Fe₂O₃(0001) and KFe _x O _y (111) stoichiometry were prepared in single crystal quality on Pt(111). They were investigated using surface science techniques before and after atmospheric pressure reaction experiments in a newly designed single crystal flow reactor. As expected from low-pressure measurements, Fe₃O₄(111) is catalytically inactive. The catalytic activity of -Fe₂O₃(0001) starts after an activation period of about 45 min. After that, the surface is essentially clean but shows a high concentration of defects. On the potassium-promoted films, however, the activation period is much longer, the activity then is higher and the surface gets covered completely with carbon and oxygen during reaction. This indicates a different reaction pathway on the promoted films with a carbon–oxygen species as catalytically active species.     

金属注射成型用水溶性粘结剂的研究

介绍了一种金属注射成型用水溶性粘结剂的制备方法，该粘结剂使用方便且安全无毒，用于金属注射成型时可用水作溶剂脱除，从而使成本大大降低。     

APPLICATION OF LINEARIZED MODELS OF MULTICOMPONENT MASS TRANSFER FOR CALCULATION OF EVAPORATION-CONDENSATION PROCESS IN TERNARY SYSTEMS

Results of calculations based on a linearized multicomponent mass transfer theory developed by Burghardt and Krupiczka are compared with experimental data of Modine for condensation-evaporation process in ternary systems. These data have been obtained for acetone-benzene-nitrogen and acetone-benzene-helium in a welted wall column. Models I and II, which take into account diffusional interactions of components in a mullicomponent mixture show good agreement with the experiments as well as with other calculation methods (Krishna-Standart and Toor-Stewart-Prober). When multicomponent mass transfer occurs in the presence of inert species, a straightforward Model II is recommended. Model I, which is more universal, requires some iterative calculations with respect to the sum of mass fluxes. According to theoretical considerations the latter model is limited to the case of low total mass flux. The results of calculations for the systems studied were reasonably good though the total mass fluxes were not small. The calculation procedure based on the presented linearized models are convergent to the proper solutions in contrast to the Krishna-Standart Model IV which in some cases can be unstable.     

Some novel polymer-supported optically active phase transfer catalysts: 2. Use in displacement,reduction, epoxidation and addition reactions

The performance of 27 novel polymer-supported chiral phase transfer catalysts in a range of phase separated reactions has been studied. The later include a number of displacement reactions, sodium borohydride reductions of prochiral ketones, the epoxidation of chalcone, the addition of nitromethane to chalcone and the addition of thiophenol to cyclohexenone. Some of the reactions were performed under liquid/liquid conditions and others using solid/liquid. No systematic difference emerged between these. In general many of the catalysts provided fast reactions and good chemical yields of products. However, in no case was any significant enantiomeric excess achieved. The latter observation is discussed in the light of the reported behaviour of analogous non-supported catalytic systems, and suggestions proposed to explain these differences.     

Evidence for non-site-isolation in ZSM-5 from ion-exchange and catalytic studies

Ion exchange of HZSM-5 samples with alkali metal cations, using metal chloride solutions, results in partially exchanged zeolites, MHZSM-5, M = Li, Na, K or Cs. The degree of exchange is found to increase with increasing ionic radius of the cations. The catalytic properties of the alkalized zeolites were evaluated using the reaction conditions under which the catalytic activity of the HZSM-5 samples in terms of n-hexane cracking is proportional to the aluminium content. From the residual catalytic activity exhibited by the Na-, K- and CsHZSM-5 samples it is concluded that each of the larger Na⁺, K⁺ and Cs⁺ ions is influencing more than one AlO ₄ ^– tetrahedron, implying that the aluminium sites in ZSM-5 are not isolated. The ion-exchange results are then interpreted in terms of non-isolated aluminium sites. The ion-exchange and catalytic properties of the zeolites as a function of aluminium content are also discussed.     

K- and Cs-FeV/Al2O3soot combustion catalysts for diesel exhaust treatment

Alkali-doped FeV oxide catalysts supported on -alumina were prepared and their catalytic activity in the combustion of diesel soot is reported. The catalysts were characterized by XRD, TPR and SEM–EDX analysis. The influence of the nature of the alkali metal (K and Cs), the temperature of treatment of the catalysts and the stability to sulfur poisoning have been investigated.

Catalysts doped with Cs were the most active and stable also after several combustion cycles and in the presence of sulfur in the stream. The activity measurements and microstructural results suggest that the combustion of soot is favored on catalysts where amorphous phases and/or mixed Fe---V---O phases, ensuring an intimate contact between iron and vanadium, are present. A reaction mechanism involving the participation of the redox couple Fe(II)–Fe(III) in the activation of the vanadium combustion sites, is proposed.