Effect of gamma-irradiation on surface and catalytic properties of CuO−ZnO/Al2O3 system

A copper, zinc and aluminium mixed oxides sample having the nominal composition 0.25 CuO/0.03 ZnO/Al₂O₃ was prepared by impregnating Al(OH)₃ with copper and zinc nitrate solutions, drying at 100 °C then heating in air at 600 °C. The obtained solid was exposed to different doses of -rays (20–160 Mrad). The surface characteristics namelyS _BETV_P andr of different treated adsorbents were determined from N₂ adsorption isothems measured at –196 °C. The catalytic activity of various irradiated solids was determined by following up the kinetics of CO-oxidation by O₂ at 150–200 °C. The results showed that the doses up to 80 Mrad resulted in no significant change in theS _BET but increased slightly theV _P (20%) of the treated adsorbents. The irradiation at 160 Mrad caused an increase of 20% in theS _BET of the irradiated solid sample. The catalytic activity increased progressively by increasing the dose, a dose of 160 Mrad brought about an increase of 140% in the catalyst's activity. The apparent activation energy of the catalytic reaction decreased monotonically by increasing the absorbed dose of -rays which was attributed to a parallel induced decrease in the value of pre-exponential term of the Arrhenius equation. The observed increase in the catalytic activity due to -irradiation has been interpreted as a result of increasing the concentration of catalytically-active sites contributing in chemisorption and catalysis of CO-oxidation via a possible fragmentation of CuO crystallites.     

Effect of gamma-irradiation on surface and catalytic properties of Co3O4 doped with NiO

NiO-doped Co₃O₄ samples precalcined at 500 °C were subjected to various doses of -rays within the range 0.2-1.6 MGy. The particle size and BET-surface areas of different samples were determined using XRD and nitrogen adsorption at -196 °C. The catalytic reactions studied were conversion of ethanol and isopropanol at 250-400 °C using a micropulse technique and H₂O₂ decomposition in aqueous solution at 30-50 °C. The results revealed that the -irradiation brought a significant decrease in the particle size of Co₃O₄ phase with subsequent increase in the S_BET surface areas. The treatment brought also a progressive decrease in the total conversion of both alcohol (dehydration and dehydrogenation) falling to a minimum value (about 20% of its initial activity) at a dose of 0.8 MGy. The catalysts retain their initial activity upon exposure to a dose of 1.6 MGy. On the other hand, the catalytic activity in H₂O₂ decomposition of the investigated system decreased progressively by increasing the dose of -rays and the catalysts lost more than 90% of their initial activity upon exposure to a dose of 1.6 MGy.     

Effect of gamma-irradiation on the catalytic activity and selectivity of gamma-alumina

Methanol conversion reaction was carried out in contact with a poorly crystalline -alumina pre-irradiated with different doses of -rays. The reaction was conducted at 140–440°C using a flow technique under atmospheric pressure. The results obtained revealed that -irradiation of Al₂O₃ resulted in drastic modifications of its activity and selectivity in methanol conversion reaction. The dose of 15 Mrad was sufficient to suppress completely the formation of dimethyl ether (DME) and stimulated the formation of methane, which started at 200°C instead of 300°C in the case of the unirradiated alumina specimen. However, the rate of CH₄ formation was found to decrease as a function of the dose employed. When the dose reached 140 Mrad, DME was reproduced with a rate comparable to that measured for the unirradiated catalyst sample. These results permitted us to conclude that DME is produced on the weak acidic sites (Brönsted acidity of Al₂O₃) and is not necessarily an intermediate compound for methane formation that takes place directly from methanol on strong acidic sites (Lewis acidity). The doses of 15–75 Mrad expelled completely the Brönsted acidic sites from Al₂O₃ surface, and the doses above this limit brought about a transformation of Lewis acidic sites into Brönsted acidity that is responsible for dimethyl ether formation. This transformation occurs by the action of liberated water from the dehydration of methyl alcohol.     

Fuel Combustion Reactions and Catalysts: XXI. Synthesis and Characterization of Modified Mn–Al–O Catalysts for High-Temperature Oxidation

The phase composition of supported Mn–Al–O catalysts and their activity in the reaction of methane oxidation were studied depending on the composition of aluminum oxide supports (-Al₂O₃ with different -Al₂O₃ contents modified with individual Mg, La, and Ce oxides or Mg + La and Mg + Ce oxide mixtures) and calcination temperatures (500, 900, and 1300°C). It was found that the Mn–Al–O catalysts based on -alumina containing -Al₂O₃ and modified with Mg, La, or Ce additives are more active and thermally stable (up to 1300°C) than the samples based on pure -Al₂O₃. A conclusion was drawn that a higher degree of disorder of the structure of -Al₂O₃, compared to that of -Al₂O₃, is favorable for a deeper interaction of manganese and modifying additives with the support at the early stages of the synthesis and for the formation of Mn–Al compounds with complex composition (solid solutions and/or hexaaluminates) at 1300°C. These compounds are responsible for the stability and high activity of the catalysts in methane oxidation.     

Effect of γ-irradiation on the catalytic activity and selectivity of γ-alumina II. Conversion of isopropanol

The catalytic conversion of isopropanol was conducted over a poorly crystalline -alumina irradiated with different doses of -rays (25–150 Mrad). The catalytic reaction was carried out at 180–400°C in a flow technique under atmospheric pressure. The results showed that the dose of 25 Mrad resulted in a decrease of about 50% of the dehydration activity which suffered a further slight decrease upon irradiation at a dose of 50 Mrad. Increasing the dose in the range of 50–150 Mrad effected an increase in the dehydration activity reaching a maximum limit at 100 Mrad, then decreased abruptly by a dose of 150 Mrad. -irradiation led also to creation of some active sites contributing in dehydrogenation of isopropanol to producing acetone. These results were discussed in terms of removal of Brönsted acidity (25–50 Mrad), responsible for the dehydration reaction and to transformation of Lewis to Brönsted acidity (100 Mrad) by the action of liberated water from the dehydration reaction. The drop in dehydration activity due to irradiation at 150 Mrad might result from an efficient removal of the Brönsted acid sites created. The induced dehydrogenation activity of irradiated aluminas was attributed to creation of some electron-donor centers.     

Oscillatory variation in EMF developed due to additions of TiO2 pretreated thermally and γ-irradiated to various doses in the concentration cell made up of Ag/Ag+

Several powder samples of TiO₂ are pretreated thermally at 300, 480 and 540°C, subjected to -irradiation and after irradiation added in one of the compartment of the concentration cell made up of Ag/Ag⁺. The adsorbed oxygen species O _2ad ^– , HO _2ad ^– and O _ad ^– on TiO₂ provide negatively charged sites and develop EMF in the cell. The radiation damage, measured in terms of equilibrium EMF, received at lower doses is partially recovered at higher doses. It is proposed that in heating at 480°C, ad species react with Ti³⁺ ions in the surface and produce –O–O– peroxy linkages and block the negatively charged sites while in heating at 540°C Ti₄O₇ phase is produced on the surface which adsorbs O₂ and provide large number of negatively charged sites. During -irradiation peroxy linkages are broken and the Ti₄O₇ phase is destroyed. Observed oscillatory variation in equilibrium EMF is explained on the basis of several reactions mentioned above proceeding at different rates during radiolysis.     

Radiation-Induced Transformations of Iron(II) Formate

The solid-phase decomposition of the iron formate crystal hydrate Fe(HCOO)₂ · 2H₂O under exposure to ⁶⁰Co -rays or 3.5-MeV electrons was studied. It was found that the irradiation of this salt to absorbed doses of 0.1–2 MGy resulted in the radiolysis of water of crystallization and the HCOO^– anion and in the reduction or oxidation of the Fe²⁺ cation. The composition of the solid-phase (-Fe, -Fe, FeO, -Fe -Fe₂O₃, Fe₃O₄, and FeCO₃) and gaseous (H₂O, CO, CO₂, HCOOH, and CH₄) radiolysis products of the substance was determined.     

Catalytic dehydration of isopropanol on neodymium-Y and X-zeolites and the effect of γ-irradiation

Four different samples of NdX, NdY, NdNH₄X and NdNH₄Y-zeolites were prepared by ionexchange methods. DTA and XRD analyses have been carried out for the samples. The thermally activated zeolites were irradiated by 1.5 and 10.0 Mrad -rays. The catalytic activities of these samples were tested in dehydration of isopropanol. The results of DTA indicated that all samples showed endothermic peaks at about 215 °C related to the release of physically adsorbed water and exothermic peaks at 850–950 °C indicating the collapses of the zeolite. The X-ray analysis revealed that the exchange of sodium by neodymium or ammonium followed by neodymium ions did not change the crystal structure but some decrease in the crystallinity was observed. The catalytic activities of these zeolites were measured in dehydration of isopropanol as a function of temperature. It was found that the activity of the prepared Nd-zeolites depends on the crystallinity of zeolites and on the condensation products formed on catalyst surface. However, the irradiated samples exhibited higher catalytic activities in isopropanol conversion than the unirradiated ones. The observed higher activity for irradiated samples was attributed to the increase of the number of acidic centers responsible for dehydration of alcohols. These centers were formed as a result of the formation of tricoordinate aluminium atoms in -irradiated zeolites.     

Effect of the Measurement Temperature on the Dispersive Component of the Surface Free Energy of a Heat Treated SiO2 Xerogel

The surface free energy of a monolithic silica xerogel treated at 1000°C has been measured by inverse gas chromatography in the temperature range 25–150°C using n-alkanes. Values of the dispersive component, _S ^D, vary from 49.07 mJ·m^–2 at 25°C to 17.20 mJ·m^–2 at 150°C. The _S ^D value obtained at 25°C is lower than that found for amorphous and crystalline silicas but higher than that found for glass fibres meaning that the heat treatment at 1000°C changes drastically the structure of the silica xerogel showing a surface similar to a glass. However, the higher value of _S ^D in comparison to glass fibres can be attributed to the mesoporous structure present in the silica xerogel. In the temperature range of 60–90°C there exists an abrupt change of the _S ^D values as well as in the dispersive component of the surface enthalpy, h _S ^D. Such abrupt change can be attributed to an entropic contribution of the surface free energy.     

Preparation and Characterization of Thin Optically Transparent Alumina and Ce-doped Alumina

Transparent and porous boehmite, -Al₂O₃ (500°C) and -Al₂O₃ (900° and 1000°C) thin sheets (50–100 m) have been prepared from boehmite sols. -Al₂O₃ shows about 48% porosity and 292 m²/g surface area. On transformation from -Al₂O₃ (500°C) to -Al₂O₃ (900°C), the porosity still remains high, i.e. 45%; however, the surface area becomes 138 m²/g. The porosity and surface area of -Al₂O₃ become about 41% and 97 m²/g respectively on further heating to 1000°C. A gradual increase of average pore radius during this thermal treatment suggests that coarsening of the pore occurred during the densification process. Both -Al₂O₃ and -Al₂O₃ show high degree of transmission from UV to NIR wavelength region. Cerium exists in +4 oxidation state in the boehmite as well as in the - and -Al₂O₃. The ultraviolet absorption edge of the alumina was tailored by varying the concentration of cerium.     

Single crystals of regio-selectively substituted cellulose hetero-esters

Lamellar single crystals of some regio-selectively substituted cellulose hetero-esters: cellulose propionate diacetate (CPDA, 2,3-di-O-acetyl-6-O-propionyl cellulose), cellulose acetate dipropionate (CADP, 6-O-acetyl-2,3-di-O-propionyl cellulose), cellulose butyrate diacetate (CBDA, 2,3-di-O-acetyl-6-O-butyryl cellulose) and cellulose acetate dibutyrate (CADB, 6-O-acetyl-2,3-di-O-butyryl cellulose), have been prepared at high temperature in a mixture of dibenzyl ether andn-tetradecane. The CPDA crystals were lozenge-shaped whereas those of CADP, CBDA and CADB had a ribbon morphology. CPDA crystals gave well-resolved electron diffractograms from which the reciprocal lattice parameters a^*=0.807 nm^–1,b ^*=0.400 nm^–1 and ^*=90° could be determined. Systematic absences occurred at every odd reflection along the two orthogonal axesa ^*andb ^*. Thus, the CPDA diffraction pattern is consistent with a p_gg symmetry. For CADP, the electron diffraction pattern is consistent with a p_mg two-dimensional space group withb the unique axis along the ribbon direction. The diagram yields the reciprocal lattice parameters a^* = 0.902 nm^–1,b ^*=0.651 nm^–1 and ^*=90°. The CBDA electron diffractogram yields the following cell parameters and two-dimensional space group:a ^*=0.482 nm^–1,b ^*=0.659 nm^–1 and ^*=90°, and a p_gg symmetry; and that of CADB:a ^*=0.834 nm^–1,b ^*=0.645 nm^–1 and ^*=90°, and a p_mg symmetry.     

Infrared spectral analysis during the thermal decomposition of pure and irradiated crystalline NH4ClO4

Variable temperature /303–553 K/ IR spectroscopic studies are made during thermal decomposition of pure and -treated ammonium perchlorate /AP/. Decomposition is enhanced by radiation or in the presence of an additive /Gd₂O₃/. Intensity of the stretching /1100 cm^–1/ and bending /625 cm^–1/ frequencies of ClO ₄ ^– decrease on heating the KBr matrix even below 360 K. Above this temperature, a broad band develops over 480–510 cm^–1 in the pure and -treated AP which is attributed to ClO ₃ ^– /₄/.     

Physicochemical properties of Ti-grafted SBA-15

Partial oxidation of n-heptane to syngas at 400–450°C was investigated over Rh and Rh-Ni based catalysts. The Rh/-Al₂O₃ catalyst exhibited much better catalytic activity than the Rh-Ni/-Al₂O₃ catalyst. A combination of the Rh-based catalyst with the WGS reaction catalyst (Fe₃O₄—Cr₂O₃) increases the hydrogen selectivity but has no distinct effect on shifting the balance of the partial oxidation of n-heptane.This revised version was published online in December 2005 with corrections to the Cover Date.     

Influence of MgO loading on the structure and catalytic performance of Pd/γ-Al2O3, I. Effect of interaction between MgO and γ-Al2O3

The influence of MgO dispersed on -Al₂O₃ in different amounts on the structure and performances of Pd/-Al₂O₃ catalysts has been studied by means of XRD, H₂–O₂ titration, BET and catalytic activity test for CO oxidation. It was found that introduction of MgO enhanced greatly the CO oxidation activity of catalyst. It seems that the enhanced activity stems from the stronger interaction between MgO and -Al₂O₃ at a given temperature (e.g. 450 °C).     

Cyclization of crotyl phenyl sulfide in the presence of acid catalysts

Crotyl phenyl sulfide is converted to 2-ethyl-2,3-dihydrobenzothiophene and 2- and 4-methylthiochromans in the presence of -Al₂O₃ and 5, 10, and 20% ZnCl₂/Al₂O₃ at 300°C and is also isomerized to 1-butenyl- and 3-butenyl phenyl sulfides and cleaved to thiophenol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1337–1339, October, 1973.     

Stereoselective hydrogenation of 2-hexyne on Cu/γ-Al2O3 catalysts

The stereoselective hydrogenation of 2-hexyne in ethanol on Cu/-Al₂O₃ catalysts (1–40 % Cu) at 4–10 atm and 80–120 °C has been studied. The reaction affordscis-2-hexene as the only reaction product in 100 % yield at [Cu] 30 %. For samples with 20 % Cu, hydrogenation proceeds in parallel with absorption of H₂ by the catalyst.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1314–1315, July, 1993.     

Regularities in gas formation at γ-radiolysis of coals and petroleum residues

The regularities of H₂, CO, and CH₄ formation at -radiolysis of brown coals, hard coal, petroleum-bituminous rock, petroleum bitumen, tar, and petroleum residue have been studied at room temperature, absorbed radiation dose 30–2400 kGy, dose intensity 1.6–21.1 kGy/h. The radiation-chemical yields of these gases were found to constitute °G^r0.005–0.07 mol/100 eV for coals, and °G^r0.3–0.6 mol/100 eV for petroleum residues.     

Sorption and desorption of radioiodine on calcareous soil and its solid components

The effect of different solid components of calcareous soil on the retention of I was investigated by a batch technique and selective extraction method, and the effect of -irradiation was also investigated. The sorption and desorption isotherms of I on the one untreated, three treated soils and the calcareous soil irradiated with -rays were determined at 30 °C, pH 8.1±0.2 and in the presence of 1.0×10^–4M or 0.67×10^–5M CaCl₂. It was found that the sorption-desorption hysteresis on the calcareous soil actually occurs on the same time scale, that iodine can be easily transported in the calcareous soil and that the exceptionally high contribution of organic matter to the iodine sorption is demonstrated.     

The properties of supported rhenium catalysts in the dehydrogenation of cyclohexane

The 2 % Re/sibunite catalyst is more active than 2 % Re/-Al₂O₃ and 2 % Re/-Al₂O₃ catalysts in the dehydrogenation of cyclohexane into benzene (T = 350 °C,w = 0.5 h–1). The substitution of NH₄ReO₄ by HReO₄ in the preparation of the catalyst enhances its activity by a factor of 1.3. Treatment with HNO₃ or oxalic acid increases the selectivity by a factor of 1.2 and 1.35, respectively, the overall conversion of cyclohexane being 32–40 %.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2119–2121, August, 1996.