A DFT+U revisit of reconstructed CeO₂(100) surfaces: structures, thermostabilities and reactivities

Cerium dioxide (CeO2) shows wide catalytic applications by virtue of its excellent oxygen storage capacity. The CeO2(100) surface has aroused particular interest because of its intrinsic polarity; however, it suffers from structural reconstruction, which consequently hinders experimental and theoretical studies. In this work, we performed density functional theory calculations with on-site Coulomb interaction correction to investigate and further correlate the geometric and catalytic properties of reconstructed CeO2(100) surfaces. By introducing CeO2 units on a previous O-terminal model, the surface exposed CeO4 pyramids with gradual increase in coverage and eventually transformed into a Ce-terminal structure. The corresponding thermostabilities were evaluated by calculating the surface energy and oxygen vacancy formation energy. We also showed that the CO oxidation on the reconstructed CeO2(100) surfaces favored the Mars-van-Krevelen mechanism. The most stable CeO4-terminal type of reconstruction, covered with a half overlayer of CeO4 pyramids on the surface, was capable of directly producing CO2 without forming bent CO2 intermediates and carbonate byproducts. Moreover, coordinatively unsaturated Ce ions at the pyramid apex provided extra accommodation to the reacting CO, thus lowering the reaction barrier of the key CO coupling step relative to that of the O-terminal surface. We finally generalized a unified picture of the dynamic changes in the thermostability and catalytic activity along with the structural reconstruction of the CeO2(100) surface. The CeO4-terminal type of reconstruction was theoretically predicted to be highly efficient for catalyzing CO oxidation.