Oxydation catalytique des phenols par le peroxyde d'hydrogene: Etude structurale des catalyseurs Fe/Al2O3 et Fe-Cu/Al2O3 par spectroscopie Mossbauer

This study recalls the results obtained on the oxidation by hydrogen peroxide of a number of hydroxyl aromatic compounds with alumina supported catalysts and more particularly the structural study of these catalysts. The catalysts were prepared under different conditions: without thermic treatment, by oxidation in air at 450°C and by thermic reduction at 500 and 700°C, under hydrogen flow. The structural study by Mössbauer spectroscopy of the catalysts Fe/Al₂O₃ and Fe-Cu/Al₂O₃ made it possible to specify in what form was found the iron, as a function of the conditions under which the catalysts were prepared. For the catalyst prepared by impregnation without thermic treatment the iron on the support was in hematite form (α-Fe₂O₃) well crystallized in small particles with 10–20% iron which could be ferric ions (Fe³⁺) chemically adsorbed on alumina or iron within the structure of the alumina (Figs 7 and 8). Thermic oxidation in air brought about the appearance of hematite in the form of large particles (Fig. 9) whereas the thermic reduction under hydrogen flow led to the formation of crystallized metallic iron (α-Fe) (Fig. 12). The reducibility of iron on the support increased with the increase in temperature of reduction and with the presence of copper (Figs 11 and 13). As for the activity of the different catalysts in oxidation reactions of phenols by hydrogen peroxide, we notice that whatever the form of the catalyst, the activity was more important for pyrocatechol than for phenol (Fig. 3). As far as stability of the metals on the support was concerned, during the oxidation reaction we noticed that it was greater with an oxidized catalyst than with a reduced one (Figs 4 and 5). The comparison between the results obtained in a batch and in a continuous reactor made it possible to show that the first phase of the reaction was probably due to the superposition of the phenomena of homogeneous (by the Fe ions passed into solution) and heterogeneous catalysts (Fig. 6). The comparative structural study reduced before and after use was quite in agreement with the solubilization of iron that we observed during oxidation (Figs 15 and 13). However on the oxidized catalyst hematite was not modified after use and the most significant change on the spectrum was a slight decrease of E_Q (0.1 mm s^?1) in the central doublet (Figs 14 and 9).