Selective hydrogenation of nitrobenzene to aniline in dense phase carbon dioxide over Ni/gamma-Al2O3: Significance of molecular interactions

The selective hydrogenation of nitrobenzene (NB) over Ni/gamma-Al2O3 Catalysts Was investigated using different media of dense phase CO2, ethanol, and n-hexane. In dense phase CO2, the total rate of NB hydrogenation was larger than that in organic solvents under similar reaction conditions; the selectivity to the desired product, aniline, was almost 100% over the whole conversion range of 0-100%. The phase behavior of the reactant mixture in/under dense phase CO2 was examined at reaction conditions. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions Of CO2 with the following reactant and reaction intermediates: NB, nitrosobenzene (NSB), and N-phenylhydroxylamine (PHA). Dense phase CO2 strongly interacts with NB, NSB, and PHA, modifying the reactivity of each species and contributing to positive effects on the reaction rate and the selectivity to aniline. A possible reaction pathway for the hydrogenation of NB in/under dense phase CO2 over Ni/gamma-Al2O3 is also proposed.

Cyclization of citronellal to p-menthane-3,8-diols in water and carbon dioxide

A clean process has been developed for the synthesis of p-menthane-3,8-diols from cyclization of citronellal in CO2-H2O medium without any additives. With the addition of CO2, the reaction rate could be enhanced about 6 times for the cyclization of citronellal in H2O, because CO2 dissolved into water and formed carbonic acid inducing an increase of the acidity. Although, the reaction conversion in CO2-H2O is slightly lower compared to that obtained with sulfuric acid as catalyst, CO2-H2O could replace the sulfuric acid at a relative higher reaction temperature. The reaction kinetics studies showed that the hydration of isopulegols to p-menthane-3,8-diols is a reversible reaction. The equilibrium constant and the maximum equilibrium yield obtained in CO2-H2O at a range of CO2 pressures are similar to that with sulfuric acid catalyst.

Asymmetric Michael addition of aldehydes to nitroolefins catalyzed by L-prolinamide derivatives using phenols as co-catalysts

The asymmetric Michael addition of aldehydes to nitroolefins was investigated using L-prolinamide derivatives of 2-(2'-piperidinyl)pyridine as catalyst and a variety of phenols as co-catalyst. Extensive screening toward the effect of prolinamides, phenols, and solvents on this transformation revealed that a combination of (S)-2-(2'-piperidinyl)pyridine-derived trans-4-hydroxy-L-prolinamide 2c, (S)-1,1'-bi-2-naphthol, and dichloromethane was a promising system. This system was shown to be amenable to a rich variety of aldehydes and nitroolefins and afforded the nitroaldehyde products with excellent yield, enantiomeric excess (up to 99%) and diastereoselectivity ratio (up to 99/1), even in the case of 1 mol % catalyst loading and 1.5 equiv of aldehydes.

Extended application of edge-to-edge matching model to HCP/HCP (alpha-Mg/MgZn2) system in magnesium alloys

In the present work, the edge-to-edge matching model has been introduced to predict the orientation relationships (OR) between the MgZn2 phase which has hexagonal close packed (HCP) structure and the HCP a-Mg matrix. Based on the crystal structures and lattice parameters only, the model has predicted the two most preferred ORs and they are: (1) [1 1 2 3](alpha-Mg) vertical bar vertical bar]1 1 2 3](alpha-Mg), (0 0 0 1)(alpha-Mg) 0.27 degrees from (0 0 0 1)(MgZn2), (1 0 1 1)(alpha-Mg) 26.18 degrees from (1 1 2 2)(MgZn2), (2) [1 0 1 0](alpha-Mg),vertical bar vertical bar[1 1 2 0](MgZn2), (0 0 0 1)(alpha-Mg) vertical bar vertical bar(0 0 0 1)(MgZn2), (1 0 1 1)(alpha-Mg) 3.28 degrees from ( 1 1 2 2)(MgZn2). Four experimental ORs have been reported in the alpha-Mg/MgZn2 system, and the most frequently reported one is ideally the OR (2). The other three experimental ORs are near versions of the OR (2). The habit plane of the OR (2) has been predicted and it agrees well with the experimental results.

Morphology of head-to-tail poly(3-hexylthiophene) single crystals from solution crystallization

Single crystals of head-to-tail poly(3-hexylthiophene)s have been grown through the method of isothermal solution crystallization. Electron diffraction in combination with powder X-ray diffraction revealed the crystal structure, a = 1.52 nm, b = 3.36 nm, c = 1.56 nm and alpha = beta = gamma = 90 degrees.

Extending electrochemical activity of polyaniline to alkaline media via electrostatic interaction and sol-gel route

The electroactivity of polyaniline was extended to pH = 14 alkaline media by preparation of a novel electrostatic interaction conductive hybrid from water-borne conductive polyaniline and silica network containing carboxyl groups via sol-gel process. In addition, the obtained conductive polyaniline hybrid film displayed very low conductivity threshold percolation and demonstrated excellent stability upon cycling.

Synthesis of nanowires, nanorods and nanoparticles of ZnO through modulating the ratio of water to methanol by using a mild and simple solution method

ZnO nanowires, nanorods and nanoparticles through modulating the ratio of water to methanol have been synthesized by using a mild and simple solution method. The as-prepared ZnO nanostructures have been characterized by atomic force microscopy and X-ray photoelectron spectroscopy. With the increase of the ratio of water to methanol, the morphology of ZnO nanostructures varied form denser nanowires, to sparse nanowires, to nanorods, and then to nanoparticles. The ratio of water to methanol is supposed to play an important role in the formation of ZnO nanostructures. The mechanism of formation is related to the chemical potential, which is simply proportional to their surface ratio.

Effect of different VOPO4 phase catalysts on oxidative dehydrogenation of cyclohexane to cyclohexene in acetic acid

alpha(1)-VOPO4, alpha(II)-VOPO4 and beta-VOPO4 have been investigated as catalysts for the gas phase oxidative dehydrogenation (ODH) of cyclohexane to cyclohexene with the addition of acetic acid (HOAc) in the feeds in a fixed bed reactor. Different VOPO4 phases showed different acidity and reducibility. beta-VOPO4 phase is more active than alpha(I)-VOPO4 and alpha(II)-VOPO4 in the ODH without acetic acid addition. In the presence of acetic acid, the acidity of the catalyst may play an important role in the ODH process. Due to higher acidity, alpha(I)-VOPO4 phase catalyst gives better catalytic performances than alpha(I)-VOPO4 and beta-VOPO4 for the ODH of cyclohexane by adding of acetic acid in the reactants.

Direct oxidation of benzene to phenol on manganese pyrophosphate with hydrogen peroxide

A solid catalyst manganese pyrophosphate based on non-sieves to oxidize benzene to phenol with oxidant hydrogen peroxide has shown good conversion with good selectivity in CH3CN at 65 degrees C investigating water contact angle data of three manganese salts, it is found manganese pyrophosphate has certain repulsive water character. It is further to be confirmed by benzene and phenol adsorption experiments onto catalyst surface by GC. With benzene/H2O2 ratio of 1, the benzene conversion of 13.8% with phenol selectivity of 85.0% was achieved. It is noteworthy that no any products are obtained using manganese pyrophosphate as catalyst in the oxidation of phenol in CH3CN solvent.

The reduction of Eu3+ to Eu2+ in BaMgSiO4 : Eu prepared in air and the luminescence of BaMgSiO4 : Eu2+ phosphor

The reduction of Eu3+ to Eu2+ in air has been observed in a silicate matrix for the first time in BaMgSiO4:Eu prepared by high-temperature solid-state reaction. Emission and excitation spectra were employed to detect the presence of Eu2+ ions in the compound and this reduction was explained by a charge compensation model proposed previously. In BaMgSiO4 : Eu2+, Eu2+ ions occupy three different lattice sites by substitution for Ba2+ ions. Eu2+ ions on Ba(1) and Ba(2) sites gave emissions at about 500 nm while that on Ba(3) site showed an emission band at 398 nm. All the emissions of Eu2+ ions in BaMgSiO4 : Eu2+ were not quenched at room temperature.

Liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol catalyzed by polymer resin supported palladium catalysts

Three kinds of polymer resin supported Pd catalysts were prepared by mixing PdCl2, with alkaline styrene anion exchange resins[D392 -NH2, D382, -NHCH3, D301R, -NH(CH3)(2)], strongly alkaline styrene anion exchanged resin [201 X 7DVB, -NH+ (CH3)(3)] and alkaline epoxy exchange resin (701, -NH2), and hydrogenating in liquid phase at 1.013 X 10(5) Pa. The hydrogenation of furfural was studied under the reaction conditions such as solvent, temperature. Pd content in the supported catalyst and the amount of the catalyst. The yield of hydrogenation reaction of furfural markedly increased to 100% and the selectivity to tetrahydrofurfuryl alcohol increased to over 98% by polymer (alkaline styrene anion exchange resins D392, -NH2, D382, -NHCH3) supported palladium catalysts comparing with the yield over 70% and selectivity over 97% by palladium catalyst, in 50% alcohol-50% water or pure water solution at 1.013 X 10(5) Pa. The relationship between hydrogenation and the structures of functional group in the supporting resin was examined by XPS method.

Low-temperature oxidation of methane to form formaldehyde: role of Fe and Mo on Fe-Mo/SiO2 catalysts, and their synergistic effects

The partial oxidation of methane with molecular oxygen was performed on Fe-Mo/SiO2 catalysts. Iron was loaded on the Mo/SiO2 catalyst by chemical vapor deposition of Fe-3(CO)(12). The catalyst showed good low-temperature activities at 723-823 K. Formaldehyde was a major condensable liquid product on the prepared catalyst. There were synergistic effects between iron and molybdenum in Fe-Mo/SiO2 catalysts for the production of formaldehyde from the methane partial oxidation. The activation energy of Mo/SiO2 decreased with the addition of iron and approached that of the Fe/SiO2. The concentration of isolated molybdenum species (the peak at 1148 K in TPR experiments) decreased as the ion concentration increased and had a linear relationship with the selectivity of methane to formaldehyde. The role of Fe and Mo in the Fe-Mo/SiO2 catalyst was proposed: Fe is the center for the C-H activation to generate reaction intermediates, and Mo is the one for the transformation of intermediates into formaldehyde. Those phenomena were predominant below 775 K.

Influence of a kind of polyanion to hybrid bilayer membranes

Hybrid bilayer membrane consisting of self-assembled alkanethiol and lipid monolayer on gold electrode was fabricated by the paint - freeze method. The interaction of a kind of polyanion, K7Fe3+P2W17O62H2 with such bilayer membrane was investigated by cyclic voltammetry and ac impedance. The hybrid bilayer membrane on the gold electrode showed remarkable insulating property, however, the property was lessened to some extent after interaction with the polyanion. It was found the process was in-eversible. It is presumed that the interaction between the polyanion and lipid is an interaction of K7Fe3+P2W17O62H2 with the polar head group of PC, which lessens the interaction among PC polar head groups. The resulting molecular arrangement becomes looser, even some pores are produced.

The development in oxidation of olefins to ketones catalyzed by palladium compounds

The development in the oxidation of olefins to ketones catalyzed by palladium compounds was reviewed. Some improved methods for the oxidation of olefins catalyzed by Wacker-type catalyst systems are also summarized. For this reaction, some new catalyst systems and the reaction mechanism are described. Emphasis has been given to the applications of Pd(I)/HPA(heteropoly acid), Pd(I)/FePc (iron phthalocyanine), Pd (I)/HQ (hydroquinone)/FePc, Pd (I)/HQ/HPA, Pd (I)/CuSO4/HPA catalyst systems in the oxidation of olefins to ketones; the application of Pd(I)/LCoNO2, PdCl2 (MeCN)(2)/CuCl, Pd(OAc)(2)/ pyridine, fluorous biphasic catalyst systems in the oxidation of olefins to ketones is also surveyed.

Reactivity of Pt/Al2O3 and Pt/CeO2/Al2O3 catalysts for partial oxidation of methane to syngas

The ceria modified Pt/CeO2/Al2O3 and Pt/Al2O3 catalysts were studied in the partial oxidation of methane to syngas. The SEM, XRD, TPR and TPD techniques were used for the catalyst characterization. The addition of ceria could enhance the Pt dispersion and decrease the Pt crystallise size; the activity and selectivity of catalyst for partial oxidation were improved significantly, and the methane total oxidation was suppressed sharply. The ceria effect was also discussed in a detailed way.