Surface Effects in the Reactivity of Ceria: A First Principles Perspective

Synthesis of ceria nanostructures preferentially exposing particular surfaces has opened up new avenues to exploit ceria in catalysis. First principles density functional theory (DFT) simulations can examine the effect of surface structure on reactivity to help understand and guide this experimental work. This contribution to this volume discusses how important aspects of the reactivity of ceria, namely oxygen vacancy formation, interaction with molecules, and adsorption of metals and surface doping can be driven by the ceria surface structure. We discuss our understanding of oxygen vacancy formation in ceria surfaces from DFT. We describe how the interaction of CO and its oxidation is dependent on the surface structure. We highlight that reoxidation of reduced ceria and enhanced reactivity arising from surface doping are essentially independent of the surface considered. Thus surface effects are key for reactions involving the reduction of ceria, an important finding to which DFT has made many contributions.