V. V. Yushchenko

SnO2/Fe2O3 nanocomposites: Ethanol-sensing performance and catalytic activity for oxidation of ethanol

SnO2/Fe2O3 nanocomposites have been prepared over the entire composition range (0–100 mol% Fe2O3) through precipitation from solution, and their ethanol-sensing performance (10–200 ppm C2H5OH) was evaluated using electrical conductivity measurements in the temperature range 150–450°C. The sensing performance of the nanocomposites is shown to strongly depend on their composition. The Fe2O3-rich (>70 mol% Fe2O3) nanocomposites offer a large C2H5OH response and low sensitivity to ambient humidity. The oxidizing and acid properties of the nanocomposites have been studied using temperature-programmed hydrogen reduction and ammonia desorption measurements, and their catalytic activity for oxidation of ethanol was assessed by gas chromatography mass spectrometry in a flow system. The results indicate that increasing the Fe2O3 content of the nanocomposites reduces the density of acid centers on their surface and enhances their activity for oxidation of ethanol.

Hydroalkylation of benzene and ethylbenzene over metal-containing zeolite catalysts

The hydroalkylation reaction of benzene and ethylbenzene over BEA zeolites with a Si/Al ratio of 9–190, MOR with Si/Al = 48, and MFI with Si/Al = 25 containing ruthenium, rhodium, platinum, or palladium was studied, as well as over the Ru/BEA zeolites with Si/Al = 42 doped with a second metal: nickel, cobalt, or rhodium. The catalytic experiments were conducted under flow conditions in the temperature range 130–190°C, a pressure of 1 MPa, a feed weight hourly space velocity of 2–64 h−1, and a stoichiometric reactant ratio. It was shown that the main reaction routes are the complete hydrogenation of benzene and ethylbenzene yielding cyclohexane and ethylcyclohexane, respectively; hydroalkylation yielding cyclohexylbenzene, para- and meta-ethylcyclohexylbenzenes, and diethylcyclohexylbenzenes; and alkylation resulting in dicyclohexylbenzenes and ethyldicyclohexylbenzenes. The ruthenium-promoted (1 wt %) zeolite BEA with Si/Al = 42 displayed the highest activity and selectivity in the benzene and ethylbenzene hydroalkylation reactions. Doping of the catalyst with cobalt and rhodium did not improve its catalytic properties, presumably, owing to the fact that the dopant metals largely occur in the cationic form according to the IR data for adsorbed CO. An admixture of nickel (0.5 wt %) to the catalyst increases the catalyst operation stability without reducing the yield of ethylcy-clohexy lbenzenes.

Conversion of dimethyl ether into C2-C4 olefins on zeolite catalysts

The effect of the nature of the metal introduced into HZSM-5 on the properties of the catalysts for the synthesis of olefins from dimethyl ether was studied. By means of the ammonia temperature-programmed desorption technique, it was shown that a decrease in the total amount of acid sites increases the selectivity for lower olefins. As the ratio of the medium to strong acid sites increases, the yield of olefins increases. The effect of the nature of gaseous additives in the feedstock on the selectivity for lower olefins was studied at T = 340°C, p = 0.1 MPa, and ν0 = 2000 h−1.

Microstructure and sensing properties of nanocrystalline indium oxide prepared using hydrothermal treatment

Nanocrystalline indium(III) oxide samples were prepared using soft chemistry. The microstructure (particle size and shape, specific surface area, pore-size distribution) and sensing properties of In2O3 were studied as functions of synthesis parameters. Indium oxide synthesis including hydrothermal treatment produces materials having high sensing sensitivity in NO2 detection.

Hydroisomerization of n-octane on platinum-containing micro-mesoporous molecular sieves

The hydroisomerization reaction of n-octane at atmospheric pressure and a temperature of 230°C on platinum-containing catalysts with a combined micro-mesoporous structure synthesized on the basis of MOR and BEA zeolites was studied. The influence of the nature of zeolite, the relative amount of micropores, the platinum content, and the Si/Al ratio on the catalytic activity was examined. The microporous materials showed a considerably higher n-octane conversion and a higher isomerization selectivity as compared to both starting zeolites and mesoporous catalysts. It was found that the BEA-based micro-mesoporous materials are more active and selective than mordenites. An increase in platinum loading from 0.2 to 0.7 wt % leads to a rise in the yield of octane isomers, and a further increase in the platinum content does not result in a substantial change in the characteristics of the processes. It was shown that a change in the Si/Al ratio has a considerable effect on the formation of polybranched C8 isomers.

Physicochemical and catalytic properties of micro-mesoporous zeolite materials

Micro-mesoporous zeolite materials differing in their content of micro- and mesopores are obtained by the recrystallization of modernite zeolite. Using physicochemical methods such as scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction analysis, small-angle X-ray scattering analysis, low-temperature adsorption of nitrogen, temperature-programmed desorption of NH3, and IR spectroscopy, it is shown that recrystallization leads first to the formation of mesopores with sizes of 20–30 Å in zeolite crystals, then to the appearance of zeolite/MCM-41 nanocomposite, and finally to the complete conversion of zeolite into mesoporous MCM-41. During this process, the concentration of strong Brønsted acid sites accessible to pyridine bases first increases then drops. The catalytic properties of the synthesized materials are studied in the reaction of alkylation of benzene by dodecene-1. It is shown that the creation of transport pores and the increase in the accessibility of acid sites due to recrystallization under soft conditions facilitate the alkylation reaction.

Structure and catalytic properties of dealuminated modified zeolites Y

The effect of treatment with a zirconyl nitrate aqueous solution on the structure; the hydroxyl-layer constitution; and the adsorptive, acid, and catalytic properties of dealuminated zeolite Y was studied. The zeolite was prepared by boiling NH4Y in an ethylenediaminetetraacetic acid disodium salt solution followed by ion exchange with ammonium chloride and calcination in a 100% steam flow at 750°C. X-ray diffraction, IR spectroscopy, and DTA data show the formation of an ultrastable form of zeolite Y. The incorporation of zirconium in zeolite led to an increase in the proportion of strong acid sites, thus raising the yield of cracking products during n-hexane conversion tested on platinum-containing catalyst samples.

Acidic and catalytic properties of dealuminated zeolite Y treated with zirconyl nitrate solution

Structure, the constitution of a surface hydroxyl layer, and the acid properties and catalytic activity in n-hexane conversion were studied for dealuminated zeolites Y modified with zirconyl nitrate to have a zirconium loading of 0.2, 0.4, and 0.8 wt %. After dealumination with ammonium hexafluorosilicate solution and exchange for NH+4, the initial zeolites were calcined at 500–550°C and washed with an acid or alkali solution. The investigation techniques used were X-ray diffraction, thermal analysis, IR spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed ammonia desorption. It was found that the introduction of zirconium increased the relative amount of strong acid sites, thus increasing the yield of n-hexane cracking products.

The physicochemical and catalytic properties of the Pt-CeO x system

The properties of the Pt-CeOx system prepared by the oxidation of the Pt2Ce intermetallic compound were studied. The sample was characterized by X-ray diffraction in situ, thermogravimetry, scanning electron microscopy (with an accessory for energy dispersion analysis), transmission electron microscopy, and temperature-programmed reduction with hydrogen. The catalytic properties of the sample were studied in the model reaction of toluene hydrogenation. The oxidation of the intermetallic compound caused the appearance of metallic platinum and cerium oxide phases and high-dispersity platinum particles encapsulated in cerium oxide. Metallic platinum on the surface of the catalyst experienced rapid deactivation in the presence of hydrogen sulfide; high-dispersity platinum particles encapsulated in cerium oxide exhibited enhanced stability toward sulfur compounds.

Catalytic oxidation of methanol on high-dispersity iron oxide in micro- and mesoporous molecular sieves

The catalytic properties of high-dispersity iron oxide deposited on micro-and mesoporous molecular sieves were studied. The deposition was performed by the in situ thermooxidative degradation of various precursors. The atomic catalytic activity of the catalysts in the oxidation of methanol was found to depend on both iron concentration and the accessibility of iron oxide particles.