(75f) Complementing Surface Science Experiment with Theory for Detailed Understanding of Surface Reactivity of CeO2(111)

Ceria is an abundant and widely used technological material owing to its ability to readily store and release oxygen and change oxidation state.  There is a growing body of studies indicating that ceria exhibits significantly different catalytic reactivity, including redox and C-C coupling reactions, toward a given organic molecule depending on the extent of reduction and crystalline orientation of the surface.  This suggests that ceria is a promising candidate for the development of heterogeneous catalysts for the conversion of organic compounds, if its reactivity can be understood and tailored at the atomic level.  In this talk I will discuss how density functional theory electronic structure calculations, combined with techniques such as microkinetic modeling and vibrational spectrum simulation, have been used in complement to surface science experiments to gain a detailed mechanistic understanding of how small organic oxygenates including acetaldehyde, formic acid, and acetic acid react on the CeO₂(111) surface.  Some aspects that will be highlighted include the role of oxygen vacancy, the pathway for C-C coupling, and the different reaction outcomes under UHV and finite pressure conditions.