Bifunctional mechanism of oxygen evolution reaction and oxygen reduction reaction induced by surface reconstruction in Perovskite electrocatalysts

Elucidation of the relationship among crystal structure, material compositions, and electrocatalytic performance is beneficial to the design of electrocatalysts with high activity. Specially, for bifunctional electrocatalysts, there is a lack of the unified understanding of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) mechanisms. Based on the first-principles calculations, LaCoO3 surface reconstructions with different OH coverage under OER/ORR condition are determined. Thereby, the different reaction pathways for OER and ORR with the cooperation of Co and O sites are revealed, under which Co and lattice O sites are activated dynamically, and an overpotential of 0.35 V for the OER and 0.44 V for the ORR are obtained. Furthermore, the octahedra lattice distortion-related bifunctional mechanism (DRBM) is proposed from electron structure analysis, and the bifunctional activity of different B-site doped LaCoO3 (LaCoMO3) are studied. Based on this mechanism, we find that OER, ORR, and their bifunctional activity of LaCoMO3 all exhibit a volcano trend as a function of the O-B-O bond angle formed by Co and lattice oxygen. Consequently, we predict that Mn, Cr, Fe, and Ti doped LaCoO3 electrocatalysts exhibit remarkable bifunctional activity, which is corroborated by the reported experimental results.