Ab initio study of changing the oxygen reduction activity of Co-Fe-based perovskites by tuning the B-site composition

Perovskite oxides are promising low-cost and stable alternative electrocatalysts for the oxygen reduction reaction (ORR), relative to the precious metal-based electrocatalysts. Despite the experimental research on substituting various transition metals into the B-site of perovskite catalysts to improve the ORR performance, the detailed ORR mechanism due to the substitution process is rarely studied. In this paper, the ORR activity of La_0.5Sr_0.5CoFe_1-O₃ perovskites (x = 0, 0.25, 0.5, 0.75, and 1) is studied by density functional theory (DFT). The ORR mechanism in alkaline solution is theoretically examined as a function of the Co/Fe composition at different potentials. The substitution of Co for Fe at the B-site of the perovskites dramatically changes the theoretical overpotential and enhances the activity. The HOO* formation is the potential-determining step for all the Co/Fe compositions. In comparison with the other compositions, the Co_0.5/Fe_0.5 composition exhibits the lowest overpotential and bonding with the reaction intermediates moderately. Furthermore, the oxygen binding energy is correlated with the bulk oxygen p-band center relative to the Fermi level. Among all the Co/Fe compositions, the Co_0.5/Fe_0.5 composition shows neither too low nor too high oxygen p-band center value. These results provide deep insights into the ORR mechanism on B-site substituted perovskites and guidelines for the design of cost-effective and Pt-free electrocatalysts for oxygen reduction.