Cobalt-doped mesoporous titania with a crystalline framework synthesized by surfactant templating method presented highly selective (99%) and reasonable conversion rate (49%) of catalytic oxidation of para-chlorotoluene to para-chlorobenzaldehyde in acetic acid using aqueous hydrogen peroxide as oxidant for the first time. Recycling of the catalyst indicates that the catalyst can be used a number of times without losing its activity to a greater extent. By contrast, cobalt-doped mesoporous titania without a crystalline structure and cobalt doped the commercial titania, Degussa P25 prepared by impregnation method with the similar concentration of cobalt were found inactive. The effects of catalyst concentration, reaction time, reaction temperature, and solvents on the performance of the catalyst were also investigated. 相似文献
The enthalpies of formation of simple nonmetal or metalloid oxyanions in aqueous solution are discussed. Archival values are cited and estimates are made. Trends prove evasive. 相似文献
This paper reports the results of experimental and modeling efforts to characterize partial oxidation of methane to produce synthesis gas (H2 and CO) using metal-substituted hexaaluminate catalysts in short-contact-time reactors. Hexaaluminate catalysts offer excellent high-temperature stability compared to the equivalent metal-based catalysts. The hexaaluminates are synthesized by a metal-exchange process using alumoxane precursors that enable a wide range of metal substitutions. Of all the combinations tested, RhSr-substituted hexaaluminates yielded the best performance. The catalysts are supported on alumina porous-foam structures, which are positioned within a tube furnace to control the operating temperature. Two-stage combinations of RhSr- and Ni-substituted hexaaluminates are shown to improve conversion activity and selectivity compared to a single-catalyst system. 相似文献
The oxidation of aminoethanethiol (1) was investigated in acid solutions on a glass carbon anode. It was shown that at relatively low anode potentials thiyl radicals RS· are released into the solution, but this does not lead to binding of the oxygen in the solution. Raising the anode potential leads to binding of oxygen, which is probably due to the formation of the intermediate RS+. The oxidation of 1 was studied in Ce(SO4)2+H2SO4 solution. It was shown that under certain conditions the intermediate is RS+, which subsequently converts to a product that could not be identified as any previously described product of the oxidation of thiols. Proposals are made regarding its structure and conversion pathways.B. P. Konstantinov Institute of Nuclear Physics, Russian Academy of Sciences, 188350 Leningrad. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 278–288, February, 1992. 相似文献
Electrolysis of dimethyl malonate or methyl cyanoacetate in methanol in the presence of LiCl in an undivided cell leads to formation of 1,1,2,2-cyclopropanetetracarboxylic derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1835–1836, October, 1994.This work was supported by the International Science Foundation (Grant No MHY 000). 相似文献
Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was
observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established
by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful
enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones
produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids. 相似文献
Although photooxidation has previously been shown to be successful in removing organic contaminants from water, methods combining the rapid photooxidation of the desired contaminant with easy catalyst manipulation and removal are few and far between. In the absence of an easy means of catalyst removal, the photooxidation process becomes more costly and time consuming, and photocatalysis cannot be employed as an in situ method for the remediation of aqueous organic contaminants. In this study, the photocatalyst was added to an aqueous trichloroethylene (TCE) solution in the form of TiO2-coated buoyant microspheres. The solution, placed in a flow-cell photoreactor along with the buoyant catalyst, was irradiated with a UV-filtered Xenon light source. Limited sample sizes necessitated the development of a low-cost headspace GC/MS analysis method, utilizing a standard direct-injection autosampler. This analytical technique aptly monitored reaction progress and indicated that aqueous TCE concentration decreases by nearly 90% in the first hour of irradiation. Subsequent solvent extraction GC/MS analysis indicated that the TCE is initially sorbed by the photocatalyst spheres, but as irradiation continued, TCE is removed from the catalyst spheres surfaces. During the course of irradiation, the expected TCE mineralization product hydrochloric acid appeared, as indicated by a decrease in pH and ion chromatography analysis. The microsphere-born catalyst was easily removed from the treated solution by filtration. Thus, it is possible that a method for effective, low-cost in situ photooxidation of aqueous organic contaminants will be realized in the near future. 相似文献
X-ray photoelectron spectroscopy (XPS) was adopted for the analytical characterization of composite titanium dioxide–poly(vinylidenefluoride) (TiO2–PVDF) films developed for applications in the photocatalytic degradation of pollutants.
The composites were deposited on glass substrates by casting or spin coating from TiO2–PVDF suspensions in dimethylformamide (DMF). XPS data on the TiO2–PVDF surface composition were used to optimize preparation conditions (composition of the TiO2/PVDF suspension, deposition technique) in terms of titanium dioxide surface amount and film stability.
The use of spin-coating deposition and the increase of TiO2 amount in the DMF suspensions were found to improve the titanium surface content, although high TiO2/PVDF ratios led to film instability. PVDF–TiO2 films were also used in preliminary photocatalytic degradation tests on isoproturon, a phenylurea herbicide, under solar UV irradiation; the results were compared to direct photolysis to evaluate the catalytic efficiency of immobilized TiO2 and the role played by the PVDF film during the degradation process. 相似文献
Catalytic air oxidation of the aliphatic hydrocarbons n-decane, hexanes, gasoline and diesel fuel was conducted at ambient temperature with novel iron catalysts. The concentration of n-decane in water was reduced from 1.42 g in 100 ml to 0.07 g in 100 ml in 5 h at room temperature forming carbon monoxide and water by means of intermediate aldehydes. Results of FT–IR and GC–MS analyses demonstrated formation of aldehydes and unsaturated alcohols. Carbon monoxide was detected on catalyst residues and in the vapor phase. The indicated catalytic reaction mechanisms are discussed. 相似文献