Mechanical mixtures of Me (Ni, Pd) Ce oxides and silica-supported heteropolyacids: Role and optimal concentration of each active species in n-hexane isomerization

Catalytic properties of silica-supported heteropolyacids (HPA) in a mechanical mixture with reduced Me-Ce oxides (Me = Ni, Pd) in n-hexane isomerization are studied. The role of each component of the mixed oxides (Ce and, typically, Ni and Pd) and their optimum content has been illuminated: cerium is not only beneficial for eliminating or preventing coke deposition but is also effective for maintaining the Keggin structure of the highly-organized HPA during the reaction and probably allows a better dispersion of the second metal species. Nickel and palladium, present as Ni⁰ and Pd⁰, reinforce the activation of the alkane, which is difficult to obtain by means of a direct attack by an acid, and, thus, enhance noticeably the activity of the catalyst. The best mechanical mixtures are obtained with 30–70 wt % NiCeO-HPW/SiO₂ and 50–50 wt % Pd_0.1CeO-HPW/SiO₂. These mixtures have the highest efficiency for a Ni/(Ni + W) atomic ratio of 0.66 and a Pd/(Pd + W) ratio of 0.40, respectively. Finally, the conversion of n-hexane is in the order HPW > HSiW > HBW, which seems to be consistent with the order of their acid strength as per the literature, but the isomerization selectivity appears to be slightly higher on HSiW. Published in Russian in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 24–28. The text was submitted by the authors in English.     

Palladium-catalysed three component synthesis of α,β-unsaturated amidines and imidates

Palladium-catalysed three component coupling of an alkenylbromide, isonitrile and an amine or alkoxide/phenoxide affords α,β-unsaturated-amidines and -imidates.     

Stabilized hybrid finite element methods based on the combination of saddle point principles of elasticity problems

How, in a discretized model, to utilize the duality and complementarity of two saddle point variational principles is considered in the paper. A homology family of optimality conditions, different from the conventional saddle point conditions of the domain-decomposed Hellinger-Reissner principle, is derived to enhance stability of hybrid finite element schemes. Based on this, a stabilized hybrid method is presented by associating element-interior displacement with an element-boundary one in a nonconforming manner. In addition, energy compatibility of strain-enriched displacements with respect to stress terms is introduced to circumvent Poisson-locking.

     

Beryllium (boron) clustering quest in relativistic multifragmentation (BECQUEREL Project)

A physical program of irradiation of emulsions in beams of relativistic nuclei named the BECQUEREL Project is reviewed. It is destined to study in detail the processes of relativistic fragmentation of light radioactive and stable nuclei. The expected results would make it possible to answer some topical questions concerning the cluster structure of light nuclei. Owing to the best spatial resolution, the nuclear emulsions would enable one to obtain unique and evident results. The most important irradiations will be performed in the secondary beams of He, Be, B, C, and N radioactive nuclei formed on the basis of JINR Nuclotron beams of stable nuclei. We present results on the charged state topology of relativistic fragmentation of the ¹⁰B nucleus at low energy-momentum transfers as the first step of the research.     

Synthesis and properties of the nanocomposite of zink oxide and poly(amic acid)

The composite comprised of zinc oxide quantum dots and poly(amic acid) (PAAc) was prepared and studied by X-rays diffraction, X-ray photoelectron spectroscopy, light scattering, UV absorbance and UV fluorescence. The UV absorbance of the ZnO/PAAc composite was found to be much larger than that of its components taken separately. The fluorescence of the ZnO/PAAc composite was found to be shifted to longer wavelengthes in comparison with pure ZnO. The presence of the dopant dodecylbenzenesulfonic acid was found to affect the observed fluorescence.     

effect of surface modification on the properties of hydrogen-sensitive GaAs-based Schottky diodes

The surface of hydrogen-sensitive GaAs Schottky diodes is modified by nonpolishing etching and by producing quantum wells and quantum dots in the space-charge region of the semiconductor. The sensitivity to hydrogen is found to increase by a factor of 8–37 after the etching and by two or three orders of magnitude after the introduction of quantum wells and dots. It is shown that the increased sensitivity is associated with the lowering of the barrier at the Pd/GaAs interface, the retardation of hydrogen diffusion into GaAs due to the presence of strained quantum-size layers, and an increase in the recombination current. The presence of the recombination component is supported by luminescence from the quantum wells and quantum dots, as well as from the GaAs substrate. The etch composition is shown to be a decisive factor in raising the sensitivity.     

Rapid and efficient synthesis of optically active pyrazoles under solvent-free conditions

2-Formyl glycals undergo rapid condensation with arylhydrazines under solvent-free conditions to give the corresponding optically pure 4-substituted pyrazoles in good yields with high selectivity. The stereochemistry of the products was assigned by various NMR experiments.