Regeneration studies on solid acids for batch reactor. Alkylation of isobutane with 2-butene

The regeneration of solid acid catalysts used in alkylation was studied using cal-ad. It was found that an acid site strength of −ΔH=32 kcal/mol is needed to catalyze the reaction.     

Synthesis of tungsten carbide nanocrystals and their electrochemical properties

Tungsten carbide (WC) nanocrystals have been prepared by a solvothermal method with Mg as the reductant and WO₃ and anhydrous ethanol as the precursors. The effects of time and temperature on the synthesis of WC were investigated and a probable formation mechanism was discussed. The obtained WC nanocrystals were characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and electrochemical methods. Hexagonal closepacked WC was successfully synthesized when the temperature was as low as 500°C. The content of carbon was more than that of W, indicating that the composition of the treated sample was C and WC only. The diameters of WC nanocrystals were ranged from 40 nm to 70 nm and the nanocrystals were dispersed on carbon films. The electrochemical measurements reveal that WC nanocrystals obviously promote Pt/C electrocatalytic ability for the oxygen reduction reaction. __________ Translated from Chinese Journal of Catalysis, 2008, 29(7) (in Chinese)     

AACVD of WO3 thin films from W(O)(OPri)3[O(CH2)nNMe2] (n = 2, 3)

Monomeric tungsten oxo‐aminoalkoxides W(O)(OPrⁱ)₃(L) [L = O(CH₂)_nNMe₂; n = 2 (dmae, 1) and 3 (dmap, 2 )] were synthesized by alcohol exchange with [W(O)(OPrⁱ)₄]₂ and characterized spectroscopically. 1, 2 and [W(O)(OPrⁱ)₄]₂ were used as precursors for the aerosol‐assisted chemical vapour deposition of WO₃ thin films, which were characterized by glancing angle X‐ray diffraction, SEM and transmission‐reflectance measurements. Copyright © 2008 John Wiley & Sons, Ltd.     

A comparative study on aldol‐type condensation reactions of cyclic,acyclic and substituted cyclic ketones by the W(CO)6/CCl4/UV system

Aldol‐type condensation reactions of a number of cyclic, acyclic and substituted cyclic ketones were investigated using the W(CO)₆/CCl₄/UV system. The progress of the reactions was followed by IR and GC‐MS techniques. The cyclic ketone derivatives with β‐ and γ‐substituent gave the expected condensation products. However, the α‐substituted cyclic, acyclic and unsubstituted cyclic ketones with rings larger than six did not. Formation of [W]–ketone complexes with all of the ketones used was observed by FTIR. With respect to our studies, a mechanism involving an intermediate seven‐coordinate tungsten complex has been proposed. Copyright © 2005 John Wiley & Sons, Ltd.     

Precipitates originating from tungsten crucible parts in AlN bulk crystals grown by the PVT method

In order to evaluate the possible involvement of crucible materials in the growth of AlN bulk crystals grown by physical vapor transport, we applied growth conditions with a high vertical thermal gradient and hence high supersaturation of aluminum vapor. Under these conditions, precipitates formed causing diffuse grayish substructures at the initial growth interface and in the crystal body, decorating dislocations. Electron microscopy studies revealed that the precipitates are elongated, single‐phase particles with sizes of 50–500 nm of commensurate structure, oriented along the <110> direction. Chemical analysis of the precipitates showed tungsten as well as carbon and oxygen. The lattice parameters of the precipitates are in close agreement to hexagonal tungsten hemicarbide (W₂C). The possible transport from the tungsten parts and its conversion into tungsten hemicarbide precipitates is discussed. We thus conclude that the W₂C precipitates may contribute to the decoration of dislocations, even in growth with moderate thermal gradients.     

Adsorption and dissociation of carbon trioxide on Ag(100)

Using density functional theory methods, we have studied carbon trioxide, its adsorption and dissociation on Ag(100). In the gas phase, two isomers are found, D_3h and C_2v, with the latter of 2.0 kcal mol^?1 lower in energy at the PW91PW91/6?31G(d) level. For CO₃ on Ag(100), the calculated adsorption energy is 91.2 and 89.1 kcal mol^?1 for the bi‐coord perpendicular and tri‐coord parallel structures, respectively. Upon the adsorption, 0.50 ～ 0.56 electron is transferred from silver to CO₃, indicative of significant ionic characters of the adsorbate‐surface bonding. In addition, the geometry of CO₃ is largely changed by its strong interaction with silver. For CO_3(ad) → O_(ad) + CO_2(gas), the energy barrier is calculated to be 19.8 kcal mol^?1 through the bi‐coord path. The process is endothermic with an enthalpy change of +17.3 ～ +26.7 kcal mol^?1 and the weakly chemisorbed CO₂ is identified as an intermediate on the potential energy surface. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Characterization of solid standards prepared by freeze‐drying

Solid standards prepared by freeze‐drying consistently showed a high degree of homogeneity. The freezing process, completed in fractions of a second, preserves the original homogeneous distribution of the dopants, and the subsequent sublimation step would minimize any disturbance. Compared to those prepared by conventional methods such as blending and spiking, freeze‐dried standards exhibited superior lateral distribution and better uniform depth distribution. There is, however, a concentration constraint for achieving homogeneity. At 5% doping, segregation was observed in both lateral and depth distribution. Many tungsten standards doped with 10–28 elements ranging from 10 to 200 ppm were successfully prepared and used as controls for a number of analytical techniques including glow discharge mass spectrometry (GDMS) and d.c.‐arc optical emission spectroscopy (OES). Copyright © 2009 John Wiley & Sons, Ltd.     

New high permittivity tetragonal tungsten bronze dielectrics Ba2LaMNb4O15: M=Mn, Fe

The new phases Ba₂LaMNb₄O₁₅: M=Mn, Fe were prepared by solid state reaction at 1100 °C. They have the tetragonal tungsten bronze structure, space group P4/mbm, at room temperature. The two octahedral sites show partial order of M and Nb with preferential occupancy of the smaller B(1) sites by M. Both phases have high permittivities 90±15 over the range 10-320 K. Ba₂LaFeNb₄O₁₅ is highly insulating with bulk conductivity ?10⁻⁸ ohm⁻¹ cm⁻¹ at 25 °C and tan δ?0.001 over the range 100-320 K and at 10⁵ Hz. Solid solutions between these new phases and the compositionally and structurally related relaxor ferroelectric Ba₂LaTi₂Nb₃O₁₅ show gradual loss of ferroelectric behaviour attributed to replacement of polarisable Ti⁴⁺ by a mixture of (Mn, Fe)³⁺ and Nb⁵⁺.