Grain-boundary-dependent segregation and phase separation in ceria–zirconia from atomistic simulation

Doping is the most common strategy employed in the development of new and improved materials. However, predicting the effects of doping on the atomic-scale structure of a material is often difficult or limited to high-end experimental techniques. Doping can induce phase separation in a material, undermining the material’s stability. A further complication is that dopant atoms can segregate to interfaces in a material such as grain boundaries (GBs), with consequences for key macroscopic properties of the material such as its conductivity. Here, we demonstrate a computational methodology based on semi-grand canonical Monte Carlo which can be used to probe these phenomena at the atomic scale for metal oxide solid solutions. The methodology can provide precise predictions of the thermodynamic conditions at which phase separation occurs. It can also provide the segregation patterns exhibited by GBs at given conditions. We apply the methodology to one of the most important catalytic materials, ceria-zirconia. Our calculations reveal an interesting richness in the GB segregation in this system. Most GBs we examined exhibited continuous increases in Zr segregation upon Zr doping, with a concomitant reduction in the formation enthalpies of the GBs. However, a few GBs exhibited no segregation at low temperatures. We also observed evidence of first-order complexion transitions in some GBs.