Identifying the Zn-Co binary as a robust bifunctional electrocatalyst in oxygen reduction and evolution reactions via shifting the apexes of the volcano plot

Abstract The performance of an electrocatalyst is closely correlated with the binding strength of key oxygen-containing intermediates, i.e., *OOH, *O and *OH, in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Facile strategies to achieve favorable binding strength of these oxygen-containing species are urgently demanded, yet it still remains great challenges. Herein, the Zn-Co bimetallic isolation, which serves as an ideal model, is studied systematically by the density functional theory (DFT). Reaction activity volcano plots are built from 48 models, among them the ZnCoN6-gra(I) configuration is confirmed to be the most stable, featured of the strongest interaction with the oxygen-containing species. Optimal ΔG*O (free energy change of an atomic oxygen containing intermediate) is facilitated, which effectively drifts the volcano peaks of ORR and OER closer to each other, enabling promising bifunctional catalyst. Moreover, the small overpotential in the simulation of protonation and oxidation by hydroxy groups rationalizes the durability of the catalyst in both acid and alkaline media.