Elucidating the intrinsic relationship between redox properties of CeO2 and CH4 oxidation activity: A theoretical perspective

Methane (CH4) oxidation is an important reaction to reduce the greenhouse effect caused by incomplete combustion of CH4. Here, we explored the mechanism of CH4 oxidation catalyzed by CeO2 and Ni-doped CeO2, focusing on the redox properties of these catalyst surfaces, using density functional theory (DFT). We found that the barriers for CH4* activation and H2O* formation are correlated with the surface redox capacity, which is enhanced by Ni doping. Furthermore, the complete reaction mechanism is explored by DFT calculations and microkinetic simulations on bare and Ni-doped CeO2 surfaces. Our calculations suggest that the doping of Ni leads to a much higher overall reactivity, due to a balance between the CH4* activation and H2O* formation steps. These results provide insights into the CH4 oxidation mechanism and the intrinsic relationship between redox properties and the activity of CeO2 surfaces.