The influence of the Hubbard U parameter in simulating the catalytic behaviour of cerium oxide.

The seemingly unique redox and oxygen storage properties of cerium oxide (ceria) lead to broad practical application. However, the theoretical treatment of ceria can be troublesome due to the localised nature of the f-electrons and the self-interaction error associated with Density Functional Theory (DFT). DFT + U has been a widely used method to correct for these errors when probing specific physical material properties. However, due to the empirical nature of the U correction it is not immediately obvious that correcting certain bulk properties leads to the correct description of catalytic reactivity at surfaces. We propose an approach to choosing the U parameter using adsorption properties that provides a consistent method to simulate catalytic properties of ceria. We go on to show that combining the derived ceria energetics with those of adsorption at metal surfaces, allow us to construct transition metal-oxide pairings to develop a redox screening model for catalysis.