G. S. Litvak

Preparation and Microstructural and Textural Characterization of Single-Phase Aluminum Oxides

Conditions for the preparation of single-phase η-, θ-, and χ-aluminas were determined. The structures of η- and χ-aluminas were characterized. With the use of high-resolution electron microscopy, it was found that η-Al2O3 particles exhibited the most developed {111} face and consisted of coherently joined domains with a pronounced platelet shape. Planar defects in the (111) plane occurred in the η-Al2O3 particles. Microstructural differences between single-phase η-Al2O3 and γ-Al2O3 with a defect spinel structure were revealed. It was found that the η-Al2O3, χ-Al2O3, and θ-Al2O3 oxides are characterized by uniformly porous structures with average pore diameters of 47, 55, and 110 Å, respectively.

Mechanochemical Synthesis and Catalytic Properties of the Calcium Ferrite Ca2Fe2O5

The formation of the real structure of calcium ferrite prepared by the calcination of a mechanochemically activated hydroxide mixture at 600–1100°C was studied by X-ray diffraction analysis, electron microscopy, thermal analysis, Moessbauer spectroscopy, IR spectroscopy, small-angle X-ray scattering, and secondary-ion mass spectrometry. It was found that low-temperature calcium ferrite is an anion-modified oxide, in which the ordering of oxygen vacancies was incomplete. Regions with a disordered structure were detected on the surface of crystallites. As the calcination temperature was increased, the brownmillerite crystal structure was improved and the intercrystalline boundaries were formed and then annealed. At the surface, these processes were accompanied by a change in the predominant form of adsorbed NO from nitrosyl to dinitrosyl species. An increase in the specific catalytic activity of samples with calcination temperature can be associated with the perfection of the brownmillerite structure and with a change in the state of adsorption centers.

Real structure of metastable forms of aluminum oxide

Differences in the real structure of γ-Al2O3 samples obtained by the thermal decomposition of pseudoboehmite and boehmite prepared by the hydrothermal treatment of bayerite were found. The transformations of these structures during their conversion to δ-Al2O3 as the treatment temperature increased were studied. The rate of conversion of metastable alumina species into the stable α-Al2O3 phase significantly depends on the real structure of samples. The rate of this transformation is drastically retarded in the presence of extended defects in the oxides originated from boehmite, and the stability of metastable alumina species increased as the degree of surface dehydroxylation increased.

Formation of vanadia-titania oxide catalysts

The formation of vanadia-titania catalysts was studied with a complex of physicochemical methods. The use of highly dispersed anatase with a defect structure results in the formation of coherent boundaries of coalescence of the V2O5 and TiO2 crystallites with the ratio V : Ti =1 : 1 in a wide range of vanadium and titanium concentrations. The catalysts containing coherent boundaries are active and selective in Β-picoline oxidation to nicotinic acid.

Scientific bases for the synthesis of highly dispersed framework zirconium phosphate catalysts for paraffin isomerization and selective oxidation

Results of the systematic study of the synthesis of highly dispersed framework zirconium phosphates stabilized by ammonium, lanthanum, aluminum, manganese, and cobalt cations are summarized. The synthesis involves the mechanochemical activation of a mixture of solid reactants (salts) or the sol–gel process each followed by the hydrothermal treatment (HTT) of obtained precursors in the presence of surfactants. The genesis of dispersed systems under investigation is studied by modern physical methods providing information on the state of the bulk and surface of the systems. It is found that the local structure of sol nanoparticles and zirconium phosphate crystalline nuclei arising from mechanochemical activation products depends on the nature of initial substances. This, in its turn, makes different crystallization mechanisms possible during the HTT process: the dissolution/precipitation mechanism or the mechanism of oriented mating of primary particles. The crystallization mechanism in HTT and the reaction system composition influence the nature of resulting complex zirconium phosphate phases, their thermal stability, dispersity, and porous structure parameters. The relationship between the bulk structure parameters of framework zirconium phosphates, which are controlled by varying the chemical composition and conditions of synthesis, and the surface characteristics of the systems (the strength and concentration of different Lewis and Br@nsted sites) is studied. It is shown that systems based on framework zirconium phosphates are promising catalysts for paraffin (pentane and hexane) isomerization, the selective oxidation of methane by oxygen into synthesis gas at short contact times, and the oxidative dehydrogenation of propane into propylene.

Synthesis of aluminum oxides from the products of the rapid thermal decomposition of hydrargillite in a centrifugal flash reactor: II. Physicochemical properties of the products obtained by the centrifugal thermal activation of hydrargillite

A variety of physicochemical methods were used to characterize the product of the rapid thermal decomposition of hydrargillite in a centrifugal flash reactor under the following conditions: the average particle size of the reactant, 80–120 μm; the temperature of the solid heating surface (plate or cylinder), 300–700°C; hot-zone residence time, ∼1 s; transfer of the product to the cooled zone of the reactor. The composition of the product and the extent of decomposition of hydrargillite were determined as a function of the processing temperature. The centrifugal thermal activation (CTA) of hydrargillite affords an X-ray-amorphous, highly reactive product with a developed surface and a disordered and inhomogeneous porous structure. This structure is capable of forming different modifications of aluminum hydroxide and oxide. The properties of the CTA product are compared with the properties of the earlier reported hydrargillite rapid decomposition products obtained using a gaseous heat-transfer agent (thermochemical activation product) or a fluidized bed of a granular heat-transfer agent (thermal dispersion product).

WO3/MO2 (M = Zr, Sn, Ti) heterogeneous acid catalysts: Synthesis, study, and use in cumene hydroperoxide decomposition

Thirty (5–40)% WO3/MO2 (M = Zr, Ti, Sn), heterogeneous acidic catalysts have been synthesized by two methods, specifically, via homogeneous acid solutions and from solutions brought to pH 9 with ammonia, both followed by calcination at 600–900°C. The catalysts have been characterized by IR spectroscopy and scanning electron microscopy, and their aqueous washings have been analyzed. Their acidity has been determined by the thermal analysis of samples containing adsorbed pyridine, and in terms of the proton affinity scale. Catalytic activities have been compared for cumene hydroperoxide (CHP) decomposition at 40°C in cumene and acetone. For all M, the catalysts are one type and contain W in strongly and weakly bound states, the latter being a polyoxometalate that can be washed off. Both tungstate phases are active in acid catalysis. Brønsted acid sites with a broad strength distribution have been found. The strongest of them are heteropolyacid protons. The catalysts 30% WO3/SnO2 and 20% WO3/ZrO2 (in acetone) and 10–20% WO3/TiO2 (in cumene) are the most active in CHP decomposition, and their activity is not related to their total acidity. Phases containing W6+ that form during the high-temperature synthesis are responsible for the high acidity, and additional protons that may appear owing to W6+ reduction can play only a minor role.

Influence of the heat treatment conditions on the activity of the CoMo/Al2O3 catalyst for deep hydrodesulfurization of diesel fractions

The effect of the heat treatment temperature on the sulfidation and activity of CoMo/Al2O3 catalysts designed for deep hydrodesulfurization of diesel fuel was studied. The catalysts were prepared using citric acid as a chelating ligand. The organic ligands present in the samples heat-treated at 110 and 220°C retard the decomposition of dimethyl disulfide and the formation of the sulfide phase but make the catalyst more active than the samples calcined at higher temperatures.

Structure of the metastable modification of iron(III) oxide

A new metastable modification of iron(III) oxide — protohematite — has_been studied. According to the X-ray diffractogram, protohematite (R3c) is identified as hematite (R3c) but characterized by other selection rules for IR and Raman active vibrations. Protohematite does not possess mechanical stability. The protohematite-hematite phase transition is initiated by heating above 900°C, or by pressure application, or by mechanochemical activation. The higher catalytic activity of protohematite compared to hematite may be explained by its structural features, namely, by lowered symmetry of the oxygen sublattice and by the effective tetrahedral environment of some iron cations.

Thermal transformations of α-H6P2Mo18O62·nH2O heteropolyacid

According to the 31P NMR spectroscopy, heteropolyacid (HPA) H6P2Mo18O62·nH2O (P2Mo18), α-isomer of the Dawson structure, transforms upon heating above 80 °C partially (up to 30%) to γ-isomer, in which both polar groups Mo3O13 of the heteropolyanion are turned by 60° around the N3 axis, and partially to β-isomer in which only one group is turned. The β- and γ-isomers of P2Mo18 have been found for the first time. Their transformation into the α-isomer occurs upon rehydration in one week in air and in 1 h in an aqueous solution. HPA P2Mo18 decomposes on heating up to 350 °C to HPA H3PMo12O40 (PMo12) and a previously unknown phase of the HPMo6I21 composition, which in its turn decomposes at ∼375 °C to molybdenyl phosphates and IiI3. The PMo12 decomposition occurs via two routes to form the same products at temperatures of ∼400 and 450 °C with corresponding exotherms of IiI3 crystallization.