Previous first-principles study on CO oxidation at CeO21 located the bent CO2 intermediate state species directly formed after CO reacts with surface lattice O. The bent CO2 species carries about 0.7e relative to the neutral CO2 species1, and the residual electron from the original surface O goes to the Ce 4f orbital, which reduces one surface Ce4+ to Ce3+. Actually, the bent CO2 species is faced with two different pathways: (i) to react with another surface O to form a surface carbonate (CO3) species; (ii) to discard the extra electron to become a linear CO2 species and desorb from the surface. It must be known that pathway (i) is thermodynamically more favorable in both clean CeO2(111) and (110) systems due to the unusual stability of surface CO3 species. However, accumulation of surface CO3 species can block the surface active sites. Accordingly, seeking an approach to skip the bent CO2 intermediate state can contribute to the continuous reaction. In our current work, we applies the transition metal-doped CeO2(111) as the model to solve such a problem. Density functional theory (DFT) calculations corrected by on-site Coulomb interaction (DFT+U) shows that new electron energy levels appears at doped CeO2(111). Intriguingly, these new energy levels have a strong capacity for modifying the electron distribution of the catalysis system under reaction; take their role in lowering the barrier and refraining from the formation of surface CO3 species.References(1) Chen, F.; Liu, D.; Zhang, J.; Hu, P.; Gong, X.-Q.; Lu, G. Phys. Chem. Chem. Phys. 2012 , 14, 16573-16580.

CO oxidation at transition metal-doped CeO<sub>2</sub>(111): An approach to avoid surface carbonate accumulation

248th National Meeting (2014)

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CO oxidation at transition metal-doped CeO2(111): An approach to avoid surface carbonate accumulation

CO oxidation at transition metal-doped CeO₂(111): An approach to avoid surface carbonate accumulation