Novel active heterogeneous Fenton system based on Fe3-xMxO4 (Fe, Co, Mn, Ni): the role of M2+ species on the reactivity towards H2O2 reactions

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+.