Lattice Defects and Oxygen Absorption/Migration in Ceria/Ceria-Zirconia Solid Solutions: Analysis by Semiempirical Interacting Bonds Method

Semiempirical Interacting Bonds Method was used to calculate the enthalpies of oxygen removal from the bulk of ceria and ceria-zirconia solid solutions. The energy of the bulk reduction was obtained to agree reasonably with the experimental data when the complex defect comprised of the oxygen vacancy and interstitial oxygen atom surrounded by six cations was suggested to emerge due to an oxygen removal from the bulk. The zirconium cations dissolved in ceria affect the energies of the bulk reduction and bulk oxygen mobility due to a decrease in the local Me-O coordination number from 8 to 7.     

Cement-containing catalysts of ozone decomposition based on iron oxides

Cement-containing catalysts of ozone decomposition were synthesized on the basis of iron oxides obtained by ozonation of iron-containing aqueous solutions. X-ray diffraction analysis and Mössbauer spectroscopy showed that α-Fe₂O₃ occurs in the catalyst as highly dispersed nanoparticles. The catalysts obtained are efficient in the reaction of ozone decomposition and are as active as the best representatives of cement-containing catalysts of the GTT type.     

Synthesis and physicochemical properties of biomorphic zirconia fibers

Biomorphic zirconia fibers were prepared by successive carbonization and/or calcining of sawdust impregnated by a solution of zirconium oxynitrate. Pyrolysis was performed in nitrogen (500°C), and calcining, in air (600°C). The physicochemical characteristics of samples were studied by adsorption measurements, electron microscopy, and X-ray diffraction. The biomorphic fibers were composed of zirconia nanoparticles not larger than 12 nm. The samples had a uniform phase composition dominated by the tetragonal ZrO₂ phase; their specific surface area was 13–38 m²/g depending on the salt content in sawdust. It was assumed that the stabilization of the tetragonal phase could be related to the incorporation of mineral components (calcium, magnesium, and potassium compounds) of sawdust into zirconia; carbonization had no substantial effect on the properties of the resulting oxide. The method developed could be used to obtain tetragonal zirconia (without expensive reagents and water consumption) and utilize wood industry wastes.     

Interaction of positional isomers of dimethylbenzene with graphite

The optimized geometries and interaction energies of the intermolecular heterodimers of coronene with o-, m-, and p-dimethylbenzenes (xylenes) calculated by DFT in the PBE0 and B97D functionals were compared. The applicability of coronene as a model for qualitative assessment of the interaction of mononuclear aromatic compounds with the graphite surface was demonstrated. The necessity of including long-range dispersion interactions in DFT calculations of the dimerization energies of aromatic systems was shown. The sorption enthalpies of p- and m-xylenes were shown to be almost equal irrespective of the conditions of the chromatographic experiment. The preferred sorption of p- over m-xylene on graphite is solely due to the entropy factor.     

Catalytic activity of carbon nanotubes in the conversion of aliphatic alcohols

Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C₂–C₄ alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified.     

Adsorption of phenol on wood surfaces

Adsorption of phenol on aspen and pine wood is investigated. It is shown that adsorption isotherms are described by the Langmuir model. The woods’ specific surface areas and adsorption interaction constants are determined. It is found that the sorption of phenol on surfaces of aspen and pine is due to Van der Waals interactions (S_sp = 45 m²/g_odw for aspen and 85 m²/g_odw for pine). The difference between the adsorption characteristics is explained by properties of the wood samples’ microstructures.     

Enthalpies of the formation and decomposition of hydrogen trioxide HOOOH in an aqueous solution

The enthalpies of the formation and decomposition of hydrogen trioxide are estimated from the heating curves of peroxide-radical condensates synthesized from gaseous O₂ + H₂ mixtures. Enthalpy of decomposition Н₂О₃(aq.) → Н₂О(liq.) + О₂(gas) is ?31.2 ± 1.5 kcal/mol, and enthalpy of formation Δ_fH(H₂O₃, aq.) =–37.5 ± 1.6 kcal/mol. Both values correspond to the temperature range of 240–265 K.     

Effect of the morphology of structured carbon nanomaterials on their oxidizability

The oxidation of multi-walled carbon nanotubes (MCNTs), nanofibers (CNFs), and few-layer graphite fragments (FLGFs) with a nitric acid solution was studied. The oxygen content in the functionalized derivatives was determined by X-ray photoelectron spectroscopy and thermal analysis. The results were correlated with the structural features of the nanomaterials revealed by high-resolution transmission electron microscopy and X-ray diffraction. The highest content of carboxyl groups was achieved by functionalization of carbon nanotubes with the conical position of graphene layers.     

Coefficient of ozone mass transfer during its interaction with an aqueous solution of formic acid in a bubble column reactor

A way of determining the coefficient of ozone mass transfer between the gas phase and liquid aqueous phase using a test compound (formic acid) is described. The values of ozone mass transfer coefficient (in aqueous solutions of 0.1–0.55 М HClO₄ and 0–1 М НСООН, and in 0.75 М H₂SO₄, 0.125 М KHSO₄, and 0–2 М НСООН) are determined along with the rate constants of the reaction of О₃ with undissociated НСООН molecules and formate ions at 21 ± 1°С.