Ceria in an oxygen environment: Surface phase equilibria and its descriptors

Ceria offers great promise in catalysis, due to its facile switchable oxidation state manifested from its oxygen buffering capability. This work presents the first equilibrium surface phase diagram of ceria exposed to various oxygen providing reservoirs (e.g., a pure O2 reservoir as well as NO/NO2, H2/H2O, or CO/CO2 redox environments) using first principles thermodynamics. For a pure O2 environment, the stoichiometric ceria (111) surface is favored at ambient conditions. Any appreciable surface reduction is observed only at ultra-low oxygen partial pressures (< 10− 30 atm) and room temperature or at temperatures > 2000 K and ambient pressures. On the other hand, a redox environment promotes surface reduction at temperatures as low as 300 K. Semi-local, Hubbard modified semi-local, and hybrid electronic exchange-correlation functionals are used to capture the energetics and phase transitions. We observe no difference between the three theories in the energetics governing ceria surface reduction in the dilute limit. The predicted phase transitions by all levels of theory are in agreement with each other and in excellent agreement with literature experimental data. Creation of oxygen vacancies in the sub-surface is energetically favored over surface vacancies, and is pivotal in determining the key features of the surface phase diagram. Consequently, we identify the oxygen vacancy formation energy as a descriptor for the surface reactivity of ceria in various oxygen environments. This single governing factor could be used in future studies to probe the surface reactivity of ceria and also to design improved ceria-based materials for redox reactions.