Theory of gold on ceria

Abstract

The great promise of ceria-supported gold clusters as catalysts of the future for important industrial processes, such as the water gas shift reaction, has prompted a flurry of activity aimed at understanding the molecular-level details of their operation. Much of this activity has focused on experimental and theoretical studies of the structure of perfect and defective ceria surfaces, with and without gold clusters of various sizes. The complicated electronic structure of ceria, particularly in its reduced form, means that at present it is highly challenging to carry out accurate electronic structure simulations of such systems. To overcome the challenges, the majority of recent theoretical studies have adopted a pragmatic and often controversial approach, applying the so-called DFT + U technique. Here we will briefly discuss some recent studies of Au on CeO₂{111} that mainly use this methodology. We will show that considerable insight has been obtained into these systems, particularly with regard to Au adsorbates and Au cluster reactivity. We will also briefly discuss the need for improved electronic structure methods, which would enable more rigorous and robust studies in the future.