Co-Fe₃C pair sites catalyst with heterometallic dual active sites for efficient oxygen reduction reaction

Newly emerging metal-based pair sites catalysts show great potential because they can provide more metal active centers with synergistic effect for green catalysis, compared with single site catalysts. However, both the synthesis and catalytic mechanisms of the pair sites catalyst with new structural features need to be developed vigorously to promote the desired chemical reactions, especially carbon-based metal catalysts for green energy storage and conversion devices. Herein, we constructed highly active Co-Fe₃C pair sites on N-doped graphite catalyst (CNCo-Fe₃C) by a two-step strategy, which have electron interactions of heterometallic atoms and can play better synergistic effect. X-ray absorption spectra and density functional theory (DFT) calculation further identify the presence of heterometallic active sites in the pair sites catalyst, resulting in electron redistribution and positive d-band center due to the electron interactions. The more positive d-band center model predicts the optimization of the adsorption energy of oxygen-containing intermediates, and reduces the energy barrier of the determining step. This further results in superior oxygen reduction reaction (ORR) performance with a half-wave potential of 0.90 V versus reversible hydrogen electrode (vs.RHE) and superior long-term stability for about 20 h with only 2.3 % decrease at 0.75 V vs.RHE in 0.1 M KOH solution. Additionally, it also shows significant peak power density of 124 mW cm^-2 and prominent cycling stability performance exceeding 400 h at 5 mA cm^-2 in the Zn-air battery (ZAB) test, which is higher than that of Pt/C catalyst. This work provides a new idea for the regulation of intrinsic activity of non-noble metal ORR catalysts through the synergistic effect of the pair sites.