Understanding Structure–Activity Relationships in Sr1–xYxCoO3−δ through in Situ Neutron Diffraction and Electrochemical Measurements

In this work, we report a systematic study on temperature-dependent local structural evolution, oxygen stoichiometry, and electrochemical properties of an oxygen-deficient perovskite Sr_0.7Y_0.3CoO_3−δ (SYC30) for oxygen electrocatalysis. The obtained results are then closely compared with its analogue Sr_0.9Y_0.1CoO_3−δ (SYC10) of different crystal structures to establish structure–activity relationships. The comparison shows that both SYC30 and SYC10 consist of alternate layers of oxygen-deficient Co1-polyhedra and oxygen-saturated Co2-octahedra with Co1-polyhedra being responsible for V_o^•• migration. It is also found that the distribution and concentration of oxygen vacancies within the Co1-layer are, respectively, less symmetrical and lower in SYC30 than those in SYC10, making the former unfavorable for oxygen transport. A molecular orbital energy analysis reveals that the energy gap between Fermi level and O 2p level in the active Co1-polyhedra is larger in SYC30 than that in SYC10, further suggesting that SYC10 is a better oxide-ion conductor and thus a better electrocatalyst for oxygen reduction reaction, which is unambiguously confirmed by the subsequent electrochemical measurements.