No abstract

To develop new catalysts based on carbon nanomaterials with supported metal oxide nanoparticles for oxidative transformations of sulfur compounds, a series of metal oxide nanoparticle-decorated carbon nanotubes (MOx/CNTs) were prepared by incipient wetness impregnation at a variation of the active metal type (M = Ce, Mo, Cu). The thermal decomposition of bulk and CNT supported metal precursors used in the preparation of MOx/CNTs was analyzed under inert atmosphere employing several thermoanalytical techniques (thermogravimetry, differential thermogravimetry and differential scanning calorimetry) coupled with mass spectrometry. The thermolysis parameters of the bulk and supported metal precursors were compared and the effect of CNT support on the decomposition pattern of compounds was elucidated. It was established that the decomposition of metal precursors supported on CNTs was started and completed at temperatures of 15‒25 and 25‒70 °C lower, respectively, compared with the bulk active metal precursor. The enhancement of CNT support stability against thermal degradation is observed in the following row of metal cations: Ce < Cu < Мо < pristine and metal anions of precursor: nitrate < chloride < sulfate. The optimal mode of thermal treatment of catalyst and appropriate active metal precursors were selected for advanced synthesis of nanosized MOx/CNT catalyst.

Aerobic oxidative desulfurization of a model diesel fuel over MOx/CNTs catalysts (M = Ce, Cu, Mo) was studied to develop innovative technology for cleaning motor fuels to EURO-5 standard. It was shown that the thermal stability of catalysts improves in the following order of metal Сu < Сe < Мо. The disordering of the carbon matrix of support increases in the next row of M: Mo < Ce < Cu, which is accompanied by an increase in the specific surface area of the samples (40 → 105 m2/g). The forms of stabilization of the active component (CeO2, CuO/Cu2O/ Cu, or MoO3/MoO2) were revealed, indicating a partial reduction of the metal cations during the thermal decomposition of copper and molybdenum precursor compounds deposited on CNTs. In oxidative desulfurization of a model diesel fuel over MOx/CNTs catalysts at 150 °C the total conversion of dibenzothiophene increased in the next row of M: Се < Сu < Мо. It was found that at 150 °C over the optimum MoOx/CNTs catalyst the highest dibenzothiophene conversion 95–99% is observed. It was assumed that the high activity of MoOx/CNTs is associated with both the oxidizing ability and the tendency of MoOx to chemosorption of sulfur compounds.

No abstract