Evolution hydrothermal aging resistance mechanism study of zirconium and manganese doped CeO2 catalysts in soot catalytic combustion based on low Miller indices crystal surface effect

The thermogravimetric analysis (TGA) experiments were carried out to reveal the mechanism of Zr and Mn doping on catalytic activity of CeO2 catalyst both fresh and after hydrothermal aging, and the lattice morphology and valence changes were characterized by means of Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and H2-temperature programmed reduction (H2-TPR). Density functional theory (DFT) and molecular thermodynamics calculations were applied to investigate the change in catalytic activity, crystal surface energy and crystal morphology caused by hydrothermal aging. The maximum reaction rate temperature of fresh Mn/CeO2 (389 °C) is similar to that of CeO2 (371 °C) and lower than that of Zr/CeO2 (447 °C), but the catalytic performance of CeO2 decreases more severely after hydrothermal aging. The catalyst crystals show different degrees of crystal surface migration after hydrothermal aging, which leads to the reduction of Ce3+/Ce4+ ratio and the active sites shift. DFT calculations indicate that the doping of Zr and Mn reduces the surface energy of the low Miller indices surface and increases the oxygen vacancy formation energy, leading to better thermal stability and lower catalytic activity. The Zr and Mn doping also changes the adsorption energy and Gibbs free energy of H2O, which dominates the migration of (1 1 1) to (1 1 0) and (1 0 0) in the vapor environment. The crystal surface migration mechanism of CeO2 catalysts doped with Zr and Mn induced by H2O molecules at high temperature obtained in this study can provide a valuable addition to the regeneration of CeO2 catalysts in the after-treatment systems of diesel engines.