Book Description

In a political and legislative context promoting the use of abundant and non-toxic metals, different classes of transition metal catalysts have been developed and evaluated for two depollution reactions: (i) catalytic ozonation or activated persulfate for the elimination of pollutants containing nitrogen in the aqueous phase and (ii) the catalytic oxidation of volatile organic compounds in the gas phase. Structural spinel oxides AB2O4 and perovskites having the general formula ABO3 (where A and B are metal cations) are interesting candidates because of their safety and lower cost compared to platinum family metals. Moreover, the versatile properties of these mixed oxides, such as the numerous possible compositions and their associated surface states, have demonstrated their interest in heterogeneous catalysis. In the first reaction concerning advanced oxidation processes, spinel type mixed oxides have been studied to act as a degradation catalyst for organic pollutants (AO7 and bisphenol A). Two compositions, CuAl2O4 and CuFe2O4, have been isolated as active catalysts for the activation of ozone and peroxymonosulphate radical precursors. The combination of copper with aluminum or iron has been found to be beneficial in forming reactive radicals from ozone or peroxymonosulphate, significantly improving the degradation of targeted pollutants compared with simple oxides. In the second reaction involving the catalytic oxidation of formaldehyde in the gas phase, the perovskites and the manganese oxides were evaluated. A study dealing with the surface enrichment of the transition metal was carried out either by chemical treatment via acid washing of the perovskite precursor, or by a sub-stoechiometric approach used during the preparation. At the light of the experimental results, this enrichment improves drastically the elimination of formaldehyde towards low temperatures. These performances can be related to the cumulative effects associated with the formation of a morphology containing a multiple porosity following the acidic chemical treatment, the significant increase of the specific surface and the increase of the density of the surface redox sites highlighted by the Mn4 + / Mn3 + couple. Finally, the promotion of the catalytic support LaMnO3 by alkali and alkaline earth metals was carried out according to different conditions (La0.8A0.2MnO3 with A = K, Na, Sr, Ca). Based on the catalytic performances at a temperature giving a conversion of 50% of formaldehyde in CO2, potassium doping proved to be the most attractive doping agent (La0.8K0.2MnO3> La0.8Na0.2MnO3> La0.8Sr0.2MnO3> LaMnO3 = La0. 8Ca0.2MnO3= LMO-OH = LMO-Na). Chemical aging under wet and dry conditions has therefore been carried out on the best catalysts to evaluate their robustness. Despite a conservation of textural properties, a gradual deactivation of the doped perovskites (K, Na, Sr) was observed and related to a loss of surface active oxygen species and a reduction in the average degree of oxidation of manganese.