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 0.5 Sr 0.5 Co x Fe 1- x O 3 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.