Unravelling the Cu and Ce Effects in MnO₂-Based Catalysts for Low-Temperature CO Oxidation

Cu-containing and Ce-modified OMS-2 catalysts were prepared at various calcination temperatures using the hydrothermal method and tested for low-temperature CO oxidation. The structure, chemical compositions, and physical-chemical properties of the catalysts were characterized using XRD, N₂ physisorption, XRF, Raman spectroscopy, SEM, high-resolution TEM with EDX, TPR-H₂, and XPS. The incorporation of Cu into the Ce-OMS-2 sample facilitated the transformation of pyrolusite into cryptomelane, as confirmed by Raman spectroscopy data. In the light-off mode, the Cu/Ce-OMS-2-300 and Cu/OMS-2 samples exhibited higher activity in low-temperature CO oxidation (T₉₀ = 115 and 121 °C, respectively) compared to sample Cu/Ce-OMS-2-450. After a long-run stability test, the Cu/Ce-OMS-X samples demonstrated excellent performance: the T₈₀ increased by 16% and 7% for the samples calcined at 300 °C and 450 °C, respectively, while the T₈₀ for the Cu/OMS-2 increased by 40%. The Cu/OMS-2 and Cu/Ce-OMS-2-300 samples were found to have an increased content of nanodispersed copper sites on their surfaces. These copper sites contributed to the formation of the Cu²⁺-O-Mn⁴⁺ interface, which is responsible for the CO oxidation. The presence of Ce³⁺ in the catalyst was found to increase its stability in the presence of water vapor due to the higher reoxidation ability in comparison with Ce-free sample Cu/OMS-2.