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Alkaline-earth metal oxide aerogels prepared by sol–gel method followed by autoclave drying are nanocrystalline mesoporous materials with high reactivity. Bulk solid-state reaction of MgO aerogels with CF2Cl2 takes place after a long induction period, during which the active sites are accumulated on the surface of the nanoparticles. It was found that vanadium addition has a promoting effect on this reaction accelerating the process of the active sites formation. A method for characterization of electron-acceptor sites by electron spin resonance spectroscopy using perylene as the spin probe was developed. A good correlation was observed between the rate of the CF2Cl2 destructive sorption and the concentration of weak electron-acceptor sites. Simplified models of such sites were suggested. The acid sites on the modified MgO surface were supposed to be originated from separation of the charged fragments resulting in the surface polarization. Uncompensated oxygen substitution for chlorine and/or fluorine ions leads to appearance of Lewis acid sites while HCl/HF chemisorption results in Bronsted acid sites formation.

Calcium aluminates (CA) with a mayenite structure have attracted a growing interest during the last decades. The present paper reports the preparation of vanadia-mayenite composites performed via an impregnation of pure CA with ammonium vanadate solution. The properties of the prepared materials were explored by a low-temperature nitrogen adsorption/desorption technique, X-ray diffraction analysis, transmission electron microscopy, and spin probe method. As revealed, the addition of vanadium significantly affects the textural properties and the porous structure of mayenite. The blockage of micropores by vanadium species is supposed. The spin probe electron paramagnetic resonance technique based on the adsorption of 1,3,5-trinitrobenzene, phenothiazine, and diphenylamine has been applied to study the active sites on the surface of the composite samples. The results demonstrated an increase in the concentration of weak electron-acceptor sites when the vanadium loading was 10 wt%. X-ray diffraction analysis and transmission electron microscopy studies showed that the composites consist of few phases including mayenite, CaO, and calcium vanadates. [ABSTRACT FROM AUTHOR]

A study is carried out on the reaction between CF2Cl with nanoscale MgO at 325 degree Celsius and higher temperature. The reaction results in the formation of MgFe2 as a predominant solid product, with CCl4, and CO2 formed as the main gaseous products when excess of halocarbons is used.

The HRTEM study indicates that the composition of the mineral constituent in the carbon-mineral materials was not changed by the carbon deposition. A singular balanced Lorentzian line owing to carbon deposits has been observed in the ESR range of the carbon-mineral materials.

Transformation of nanocrystalline Mg(OH)2 to MgO under dynamic vacuum in a temperature range of 570-770 K is studied by TGA-GCMS, FTIR, HREM, XRD, helium pycnometry, and nitrogen adsorption at 77 K. A new phenomenon of decrease of the interlayer distance in MgO crystallites with increase of the nanoparticle size was observed.

Alkaline-earth metal oxide aerogels prepared by sol-gel method followed by autoclave drying are nanocrystalline mesoporous materials with high reactivity. Bulk solid-state reaction of MgO aerogels with CF2Cl2 takes place after a long induction period, during which the active sites are accumulated on the surface of the nanoparticles. It was found that vanadium addition has a promoting effect on this reaction accelerating the process of the active sites formation. A method for characterization of electron-acceptor sites by electron spin resonance spectroscopy using perylene as the spin probe was developed. A good correlation was observed between the rate of the CF2Cl2 destructive sorption and the concentration of weak electron-acceptor sites. Simplified models of such sites were suggested. The acid sites on the modified MgO surface were supposed to be originated from separation of the charged fragments resulting in the surface polarization. Uncompensated oxygen substitution for chlorine and/or fluorine ions leads to appearance of Lewis acid sites while HCl/HF chemisorption results in Bronsted acid sites formation. [ABSTRACT FROM AUTHOR]

Cobalt-magnesium and vanadium magnesium oxide catalysts were prepared by aerogel method. The obtained nanocrystalline materials are characterized by uniform distribution of the active component, which is present in a finely dispersed state amorphous to X-rays. The oxides have unique morphology. The size of their nanoparticles does not exceed 10 nm. The aerogel synthesis method was successfully applied for synthesis of two-component CoO x·MgO and VO x·MgO catalysts active in CO oxidation and propane oxidative dehydrogenation, respectively. [ABSTRACT FROM AUTHOR]

High surface area nanocrystalline MgO, Al2O3, MgO·Al2O3, commercial MgO, and a series of 10% V/MgO samples were used as catalysts in one-step selective oxidative dehydrogenation of butane to butadiene in the presence of oxygen and iodine. Molecular iodine shifts the equilibrium of the dehydrogenation reactions to the right and makes it possible to achieve high butane conversion with high selectivity to butadiene. When excess oxygen is present in the feed, iodine is successfully regenerated and can be recycled. Butadiene selectivity as high as 64% has been achieved in the presence of small amounts of iodine (0.25 vol%) over a vanadia–magnesia catalyst at 82% butane conversion. The best performance was observed over a catalyst containing the magnesium orthovanadate phase. [Copyright &y& Elsevier]

Abstract: VO x /MgO aerogel catalysts were synthesized using three different preparation methods: by mixing the aerogel MgO support with dry ammonium vanadate, by vanadium deposition from a precursor solution in toluene, and by hydrolysis of a mixture of vanadium and magnesium alkoxides followed by co-gelation and supercritical drying. The latter aerogel technique allowed us to synthesize mixed vanadium–magnesium hydroxides with the surface areas exceeding 1300m2/g. The synthesized catalysts were studied by a number of physicochemical methods (XRD, Raman spectroscopy, XANES and TEM). A common feature of all synthesized samples is the lack of V2O5 phase. In all cases vanadium was found to be a part of a surface mixed V–Mg oxide (magnesium vanadate), its structure depending on the synthesis method. The VO x /MgO mixed aerogel sample had the highest surface area 340m2/g, showed higher catalytic activity and selectivity in oxidative dehydrogenation of propane compared to the catalysts prepared by impregnation and dry mixing. The addition of iodine vapor to the feed in 0.1–0.25 vol.% concentrations was found to increase to propylene yield by 40–70%. [Copyright &y& Elsevier]

Abstract: Several pure and doped alumina samples were characterized by EPR using spin probes and tested in ethanol dehydration. It was found that the concentrations of the electron acceptor sites and the catalytic activity increased when alumina was modified with chlorides and sulfates. Meanwhile, the number of the electron donor sites decreased. A very good correlation between the concentration of the weak acceptor sites and the catalytic activity of the acid-modified catalysts almost passing through the origin of the coordinates was obtained for all the studied samples. Alumina poisoning with sodium resulted in the decrease in the catalytic activity and the concentration of the weak acceptor sites. Therefore, it appears that the weak acceptor sites tested using anthracene are related to the sites active in the ethanol dehydration reaction. [Copyright &y& Elsevier]