As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O2 reduction preferentially takes place on FeIII in the FeN4 /C system with intermediate spin state which possesses one eg electron (t2g4eg1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the FeIII sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO4), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm−2 and long-term durability in reversible zinc–air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts.

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Understanding the relationship between the electronic state of active sites and N 2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well-defined FeN 4 and MoN 4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN 4 on NRR behavior. The neighboring MoN 4 can regulate the spin state of Fe center in FeN 4 from high-spin (d xy 2 d yz 1 d xz 1 d z 2 1 d x 2 −y 2 1 ) to medium-spin (d xy 2 d yz 2 d xz 1 d z 2 1 ), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN 4 instead of MoN 4 , and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N 2 . As a result, FeMoPPc with medium-spin FeN 4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH 3 yields for NRR than FePPc with high-spin FeN 4 and MoPPc with MoN 4 , respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.