Abstract
Perovskite SrCoO3 is a potentially useful material for promoting the electrocatalytic oxygen evolution reaction, with high activities predicted theoretically and observed experimentally for closely related doped perovskite materials. However, complete stoichiometric oxidation is very difficult to realize experimentally in almost all cases there are significant fractions of oxygen vacancies present. Here, using first-principles calculations we study oxygen vacancies in perovskite SrCoO3 from thermodynamic, electronic, and kinetic points of view. We find that an oxygen vacancy donates two electrons to neighboring Co sites in the form of localized charge. The formation energy of a single vacancy is very low and is estimated to be 1.26 eV in the dilute limit. We find that a vacancy is quite mobile with a migration energy of similar to 0.5 eV. Moreover, we predict that oxygen vacancies exhibit a tendency toward clustering, which is in accordance with the material's ability to form a variety of oxygen-deficient structures. These vacancies have a profound effect on the material's ability to facilitate OER, increasing the overpotential from similar to 0.3 V for the perfect material to similar to 0.7 V for defective surfaces. A moderate compressive biaxial strain (2%) is predicted here to increase the surface oxygen vacancy formation energy by ca. 30%, thus reducing the concentration of surface vacancies and thereby preserving the OER activity of the material.