A periodic mesoporous organosilica (PMO) with chiral cyclohexyldiamine‐based nickel(II) complexes incorporated within the silica framework was prepared through a co‐condensation of (1R,2R)‐cyclohexyldiamine‐derived silane and Ph‐bridged silane followed by complexation of nickel(II) bromide in the presence of (1R,2R)‐N,N′‐dibenzylcyclohexyldiamine. Structural analyses by X‐ray powder diffraction, nitrogen sorption and transmission electron microscopy disclosed its orderly mesostructure while characterization by solid‐state NMR and X‐ray photoelectron spectroscopy demonstrated the well‐defined single‐site chiral bis(cyclohexyldiamine)‐based nickel(II) active centers incorporated within the PMO material. In particular, as a heterogeneous chiral catalyst, this periodic mesoporous organosilica showed high catalytic activity and excellent enantioselectivity in asymmetric Michael addition of 1,3‐dicarbonyl compounds to nitroalkenes (more than 92% conversions and up to 99% ee values). More importantly, this heterogeneous catalyst could be recovered easily and reused repeatedly nine times without obviously affecting its ee value, showing good potential for industrial applications. 相似文献
Mesoporous nanocrystalline γ‐alumina was prepared by a template‐free sol‐gel method using aluminum ethoxide as precursor. Significant parameters, such as the water/aluminum ethoxide molar ratio, the pH of the solution, and the time and temperature of aging, were optimized by the Taguchi method to obtain γ‐alumina with a high surface area and pore volume. The influences of the main parameters on the catalytic performance of the prepared catalysts were investigated via dehydration of methanol to dimethyl ether in a fixed‐bed reactor. The catalysts were characterized by X‐ray diffraction, N2 adsorption‐desorption, ammonia temperature‐programmed desorption, and scanning electron microscopy techniques. The results show that the aging temperature had a significant influence on the catalyst performance. 相似文献
A mesoporous silica (SBA‐15)‐supported pyrimidine‐substituted N‐heterocyclic carbene iridium complex was prepared and used as a catalyst for both environmentally friendly N‐alkylation of amines and β‐alkylation of secondary alcohols with primary alcohols. The structure of the supported iridium catalyst was characterized by Fourier transform infrared (FT‐IR), 13C and 29Si solid‐state nuclear magnetic resonance (NMR), small‐angle X‐ray scattering (SAXS), transmission electron microscopy (TEM), iridium K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) spectroscopic analyses which demonstrated that the coordination environment of the iridium centre and the 3‐dimensional‐hexagonal pore structure of SBA‐15 were retained after the immobilization. The catalyst was found to be highly efficient for both kinds of reaction on a wide range of substrates under mild conditions. Moreover, the supported iridium catalyst was obviously superior to the unsupported one in the N‐alkylation of aniline and β‐alkylation of 1‐phenylethanol with benzyl alcohol as substrate, which indicated that not only the iridium complex moiety but also the support material contributed to the catalytic activity of the supported iridium catalyst in these reactions. The supported iridium catalyst can be easily recycled by simple washing without chemical treatment, and exhibited excellent recycling performance without notable decrease in catalytic efficiency even after twelve test cycles for N‐alkylation of aniline with benzyl alcohol, nine cycles for N‐alkylation of different amines with different alcohols, and eight cycles for β‐alkylation of 1‐phenylethanol with benzyl alcohol, respectively. 相似文献
Electrochemical methoxylation of p‐xylene with methanol over mono‐ and multi‐metal oxide(s) modified kaolin was performed under various conditions and the conversion of p‐xylene was seen to be higher than 80 %. The oxidation states of the metal(s) after modification were found from catalyst characterization by powder X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The reaction process was monitored by UV‐Vis spectroscopy and the extent of reaction was evaluated. Investigation of the application of the products by gas chromatography/mass spectrometry (GC‐MS) could lead to an improvement of the octane number of gasoline. 相似文献
The hydrogenation of p‐nitrophenol (PNP) to p‐aminophenol (PAP) using NaBH4 as a reducing agent was studied as a test reaction for determining the catalytic activity of supported Pt catalysts. The initial reaction rate, which is accessible within less than 10 minutes via online UV‐vis spectroscopy at room temperature, ambient pressure and in water as a solvent, was used as measure for the catalytic activity. For three Pt catalysts supported on porous SiO2, porous glass and Al2O3, respectively, significant differences in the catalytic activity were observed. However, especially in case of very active catalysts, limitations of the reaction by internal or external mass transfer have to be considered. 相似文献
The influence of preparation methods on structural and catalytic properties of the Fe2O3‐Cr2O3‐CuO catalyst during the high‐temperature water‐gas shift reaction was determined. The prepared samples were characterized by X‐ray diffraction (XRD), Brunauer‐Emmett‐Teller method (BET), and temperature‐programmed reduction (TPR). The results revealed that the type of coprecipitation, i.e., simple, inverse, and differential, had a significant effect on both structural and catalytic properties. The catalyst prepared by the simple precipitation method exhibited higher activity than the catalysts generated by inverse and differential coprecipitation and the commercial catalyst. The types of precipitation agent and iron and chromium precursors were found to have a significant impact on the structural and catalytic features. 相似文献
The use of electron‐poor, fluoro‐containing arylboronic acids as general coupling partners for nickel(0)/tricyclohexylphosphine‐catalyzed cross‐coupling of aryl arenesulfonates is described. Electron‐poor fluoro‐containing arylboronic acids were found to react faster than electron‐rich/neutral arylboronic acids, with (4‐methoxyphenyl)(4‐methylbenzenesulfonato‐κO)bis(tricyclohexylphosphine)nickel. Bis(1,5‐cyclooctadiene)nickel(0)/tricyclohexylphosphine, (4‐methoxyphenyl)(4‐methylbenzenesulfonato‐κO)bis(tricyclohexylphosphine)nickel and bis(tricyclohexylphosphine)nickel(II) bromide were all found to be efficient catalysts/catalyst precursors.
Hydrogenation of p‐nitrophenol (PNP) to p‐aminophenol (PAP) using NaBH4 as a reducing agent was studied as a test reaction for determining the catalytic activity of supported Pt catalysts. The initial reaction rate, which is accessible within less than 10 min via online UV‐vis spectroscopy at room temperature, ambient pressure, and in water as solvent, was applied as measure for catalytic activity. For three Pt catalysts supported on porous SiO2, porous glass, and Al2O3, respectively, significant differences in the catalytic activity by almost one order of magnitude were observed. However, especially in the case of very active catalysts, limitations of the reaction by internal or external mass transfer have to be considered. 相似文献