Insights into the Contribution of Oxidation-Reduction Pretreatment for Mn_0.2Zr_0.8O_2-δ Catalyst of CO Oxidation Reaction

A Mn_0.2Zr_0.8O_2-δ mixed oxide catalyst was synthesized via the co-precipitation method and studied in a CO oxidation reaction after different redox pretreatments. The surface and structural properties of the catalyst were studied before and after the pretreatment using XRD, XANES, XPS, and TEM techniques. Operando XRD was used to monitor the changes in the crystal structure under pretreatment and reaction conditions. The catalytic properties were found to depend on the activation procedure: reducing the CO atmosphere at 400-600 °C and the reaction mixture (O₂ excess) or oxidative O₂ atmosphere at 250-400 °C. A maximum catalytic effect characterized by decreasing T₅₀ from 193 to 171 °C was observed after a reduction at 400 °C and further oxidation in the CO/O₂ reaction mixture was observed at 250 °C. Operando XRD showed a reversible reduction-oxidation of Mn cations in the volume of Mn_0.2Zr_0.8O_2-δ solid solution. XPS and TEM detected the segregation of manganese cations on the surface of the mixed oxide. TEM showed that Mn-rich regions have a structure of MnO₂. The pretreatment caused the partial decomposition of the Mn_0.2Zr_0.8O_2-δ solid solution and the formation of surface Mn-rich areas that are active in catalytic CO oxidation. In this work it was shown that the introduction of oxidation-reduction pretreatment cycles leads to an increase in catalytic activity due to changes in the origin of active states.