N. N. Leont’eva

Formation of platinum sites on layered double hydroxides type basic supports: I. Effect of the nature of the interlayer anion on the structure characteristics of the layered aluminum-magnesium hydroxide and the formation of an oxide phase

A layered aluminum-magnesium hydroxide of the hydrotalcite type containing interlayer carbonate counterions (HT-CO3) and activated hydrotalcite containing interlayer OH− ions (HT-OH) were studied for the subsequent use as the precursors of supports for platinum catalysts. It was found that the nature of an interlayer anion in the composition of an aluminum-magnesium layered hydroxide is an important factor affecting both the formation of the oxide support and its texture characteristics. The replacement of the interlayer CO32− anion by OH− resulted in changes in the structural parameters of the initial double hydroxide: a decrease in the interlayer distance with the retention of the Mg/Al ratio and an increase in the imperfection of the layered material. X-ray diffraction studies in the temperature range of 30–900°C showed that HT-OH is characterized by the ability to form low-temperature spinel at 375°C. As a result, two types of aluminum-magnesium oxide supports, which were characterized by different pore space organizations at the same Mg: Al ratio, were obtained from the given layered hydroxides.

Formation of platinum sites on layered double hydroxide type basic supports: II. Effect of the nature of the interlayer anion of the layered aluminum-magnesium hydroxides on platinum binding and Pt/MgAlO x formation

The interaction of aqueous H2PtCl6 solutions with hydrotalcite-type aluminum-magnesium hydroxides differing in the nature of their interlayer anion is reported. In the case of CO32− as the interlayer anion, the introduction of the platinum(IV) chloro complex does exerts no significant effect on the structural properties of the support, on its thermal decomposition dynamics, and on the textural characteristics of the resulting oxide phase. The binding of the platinum complexes to “activated hydrotalcite” with interlayer OH− anions increases the interplanar spacing and enhances the thermal stability of the layered structure. This is accompanied by marked changes in textural characteristics of the material, leading to the formation of a nearly monodisperse mixed oxide phase. In the Pt/MgAlOx samples obtained by reductive treatment, a considerable proportion of platinum is in the form of planar particles, and this corroborates the hypothesis that the metal complex at the sorption stage is mainly localized in the interlayer space of this support. Platinum binds to the support as chloro complexes via rapid anion exchange, and these bound platinum species are characterized by a higher reduction temperature.

Influence of a doubly charged cation nature on the formation and properties of mixed oxides MAlOx (M = Mg2+, Zn2+, Ni2+) obtained from the layered hydroxide precursors

Influence of the nature of a doubly charged cation in the layered double hydroxides (LDH) on the conditions of formation and properties of mixed oxide phase MAlOx (M = Mg2+, Zn2+ and Ni2+), its ability to reconstruct the structure of the original precursor under contact with water has been studied. Hydrotalcite-like compounds and corresponding oxides with different M2+: M3+ ratio were investigated by XRD, TEM, TG-DTG-DTA, 27Al NMR, N2 adsorption, and differentiating dissolution. It has been found that the nature of the cation M2+ influences the conditions of LDH thermal decomposition, structural and textural characteristics of the formed mixed oxides. The obtained data can be used to synthesize the oxide supports with desired acid-base and adsorption properties.

Carbon deposits on a resistive FeCrAl catalyst for the suboxidative pyrolysis of methane

The carbon deposits forming upon the suboxidative pyrolysis of methane on resistive FeCrAl catalysts heated with electric current were studied. The suboxidative pyrolysis of methane was carried out in a flow reactor at the ratio CH4: O2 = 15: 1 in a catalyst-coil temperature range of 600–1200°C; a cold reaction mixture (∼20°C) was supplied. The morphology and structure of the carbon deposits and changes in the composition and structure of the catalyst were characterized by scanning electron microscopy, transmission electron microscopy with EDX analysis, Raman spectroscopy, and X-ray diffraction analysis. Various forms of carbon deposits, including branched nanotubes, and metal carbides formed by catalyst constituents were detected. It was found that the carbon deposits on the catalyst surface were morphologically different from the deposits on quartz reactor walls. The reasons for these differences were considered.

(CuO-CeO2)/glass cloth catalysts for selective CO oxidation in the presence of H2: The effect of the nature of the fuel component used in their surface self-propagating high-temperature synthesis on their properties

The potential of surface self-propagating high-temperature synthesis (SSHS) for obtaining (CuO-CeO2)/glass cloth catalysts is demonstrated. The dependence of the structural and catalytic properties of the catalysts on their preparation conditions (nature of the fuel component) is considered. X-ray diffraction, electron microscopy, and EXAFS data suggest that the short-term action of high temperature in the SSHS leads to the complete decomposition of the precursors and has an effect on the distribution of the resulting phases. According to H2 TPR and XPS data, the degree of dispersion of CuO and the electronic state of the reacting CuO and CeO2 phases depend on the choice of fuel. This is likely due to fuels varying in the amount of heat released in their combustion. The degree of dispersion of CuO and the total contribution from Cu1+ and Ce4+ to the electronic state of the active component increase as the standard enthalpy of combustion increases in the urea < glycerol < citric acid order. This leads to an increase in the catalytic activity of the (CuO-CeO2)/glass cloth system in selective CO oxidation.

Selective oxidation of carbon monoxide in hydrogen-containing gas on CuO-CeO2/Al2O3 catalysts prepared by surface self-propagating thermal synthesis

The CuO-CeO2/Al2O3 catalysts for the selective oxidation of CO in hydrogen-containing mixtures were prepared by surface self-propagating thermal synthesis (SSTS) with the use of cerium nitrate Ce(NO3)3, the ammonia complex of copper acetate [Cu(NH3)4](CH3COO)2, and citric acid C6H8O7 as a fuel additive. The effect of the C6H8O7/Ce(NO3)3 molar ratio on the catalyst activity and selectivity for oxygen was studied. The catalyst samples were studied by X-ray diffraction (XRD) analysis, temperature-programmed reduction (TPR-H2), IR spectroscopy of adsorbed CO, and transmission electron microscopy (TEM). It was found that an increase in the C6H8O7/Ce(NO3)3 ratio resulted in an increase in the degree of dispersion of the resulting CeO2 phase. The greatest amount of dispersed CuO particles, which are responsible for catalytic activity in the oxidation of CO, was formed at C6H8O7/Ce(NO3)3 = 1.

Mechanochemical synthesis of nanocrystalline nickel-molybdenum compounds, their morphology and application in catalysis: I. Effect of the Ni: Mo atomic ratio on the structure and properties of nickel-molybdenum compounds prepared under mechanochemical synthesis conditions

Mechanochemical activation in high-energy planetary activators was used for the preparation of highly dispersed nickel-molybdenum compounds. Nickel hydroxocarbonate [NiCO3 · 2Ni(OH)2 · nH2O] and ammonium paramolybdate [(NH4)6Mo7O24 · 4H2O] were chosen as starting compounds. The effect of the Ni: Mo atomic ratio on the composition and structure of products formed in the process of mechanochemical activation followed by calcination was studied. It was found that, at the Ni: Mo atomic ratios of 1.0 and 1.4, the mechanically activated product after calcination at 520°C contained 70–100% β-NiMoO4, which is a stable phase at temperatures lower than 180°C.

Structural phase transformations in tin dioxide under the action of a nanosecond high-power ion beam

Structural phase transformations in polycrystalline tin dioxide under the action of a nanosecond high-power ion beam with a current density of 50–150 A/cm2 are studied. It is found that the effect of a beam with a current density of 150 A/cm2 on SnO2 leads to the formation of submicron particles of tetragonal SnO with an average size of 210 nm on the exposed surface. The particles have a pronounced crystallographic facet pattern. Possible mechanisms of the observed transformations are discussed.

Influence of the Mg and Al ratio on the restructuring of hydrotalcite

The influence of the Mg : Al ratio on the phase composition and structure of the products of hydrotalcite restructuring was studied by X-ray diffraction. At a high Mg ion content, besides hydrotalcite, Mg(OH)2 and an interstratified phase consisting of hydrotalcite and Mg(OH)2 are also present. The real structure was studied by simulation of diffraction patterns using the DIFFaX program.

Preparing and studying Pt/WO3/ZrO2 catalysts for the isomerization of n-heptane

The effect of the temperature of WO3/ZrO2 support calcination in the range of 700–1000°C on the phase composition, acid, and catalytic properties of Pt/WO3/ZrO2 catalysts is studied. Using ammonia TPD, it is found that calcination in the temperature range of 850–950°C results in the formation of strong acid sites that increase the yield of the target products of the reaction of n-heptane isomerization: high octane di- and trimethylsubstituted isomers. DRIFT is used to determine the role of catalyst calcination in an air flow plays in the formation of charged platinum atoms, which results in higher catalyst activity.