Deactivation of Pt/MnOx–CeO2 catalysts for the catalytic wet oxidation of phenol: Formation of carbonaceous deposits and leaching of manganese

MnOx–CeO2 and Pt(2%)/MnOx–CeO2 catalysts were prepared and investigated in the catalytic wet oxidation (CWO) of phenol. The reaction was carried out in a high-pressure autoclave reactor operating at 140 °C and oxygen partial pressure of 2 MPa. The effect of a reduction pre-treatment at 350 °C on the catalytic performance of both, the platinum catalyst and the bare oxide was studied. Higher activities were found for the reduced catalysts, independently of the presence or absence of Pt. Formation of carbonaceous deposits on the catalytic surface and leaching of manganese was confirmed as the two major deactivation mechanisms occurring in CWO of phenol. The amounts of deposits formed and manganese leached were higher in the case of reduced samples. Different techniques (XRD, HREM, HAADF, EDS, ICP) were used to characterise the chemical and structural changes experimented by the catalysts during reaction. The behaviour of reduced catalysts was found to be associated to the presence of MnO. The formation of this manganese oxide phase during the reduction pre-treatment significantly influenced the catalytic performance and stability of the catalysts under operation conditions.