RESUMO
In this paper we show a very simple route for the incorporation of catalytically active niobium species on the surface of carbon materials, such as graphene oxide, carbon nanotubes and activated carbon. Some existing methods of incorporating a transition metal on a support have involved co-precipitation or wet impregnation, to obtain the corresponding oxides. These methods, however, cause reduction in the specific area of the support and can also form large metal oxide particles with loss of metal exposure. Therefore, here we present a novel way to add catalytically active species on the surfaces of different types of carbon through the formation of interaction complexes between the metal precursor and the functional groups of the carbon matrix. Because of the excellent catalytic properties exhibited by the niobium species we choose the NH4[NbO(C2O4)2(H2O)2]·2H2O salt as the model precursor. The characterization by XPS reveals the presence of the niobium species indicated by the displacement of the peaks between 206-212 eV related to the oxalate species according to the spectrum from pure niobium oxalate. Images obtained by TEM and SEM show the typical morphologies of carbonaceous materials without the niobium oxide formation signal, which indicates the presence of niobium complexes as isolated sites on the carbon surfaces. This new class of materials exhibited excellent properties as catalysts for pollutant oxidation. The presence of Nb promotes the catalytic activation of H2O2 generating hydroxyl radicals in situ, which allows their use in the organic compound oxidation processes. Tests for DBT oxidation indicate that Nb significantly improves the removal of such pollutants in biphasic reactions with removal around 90% under the tested conditions. Theoretical calculations showed that the most favorable adsorption model is an ionic complex presenting a ΔG = -108.7 kcal mol(-1) for the whole adsorption process.
RESUMO
In this work, the effect of incorporation of M2+ species, i.e. Co2+, Mn2+ and Ni2+, into the magnetite structure to increase the reactivity towards H2O2 reactions was investigated. The following magnetites Fe3-xMnxO4, Fe3-xCoxO4 and Fe3-xNixO4 and the iron oxides Fe3O4, gamma-Fe2O3 and alpha-Fe2O3 were prepared and characterized by Mössbauer spectroscopy, XRD, BET surface area, magnetization and chemical analyses. The obtained results showed that the M2+ species at the octahedral site in the magnetite strongly affects the reactivity towards H2O2, i.e. (i) the peroxide decomposition to O2 and (ii) the oxidation of organic molecules, such as the dye methylene blue and chlorobenzene in aqueous medium. Experiments with maghemite, gamma-Fe2O3 and hematite, alpha-Fe2O3, showed very low activities compared to Fe3O4, suggesting that the presence of Fe2+ in the oxide plays an important role for the activation of H2O2. The presence of Co or Mn in the magnetite structure produced a remarkable increase in the reactivity, whereas Ni inhibited the H2O2 reactions. The obtained results suggest a surface initiated reaction involving Msurf2+ (Fe, Co or Mn), producing HO radicals, which can lead to two competitive reactions, i.e. the decomposition of H2O2 or the oxidation of organics present in the aqueous medium. The unique effect of Co and Mn is discussed in terms of the thermodynamically favorable Cosurf3+ and Mnsurf3+ reduction by Femagnetite2+ regenerating the active species M2+.