Engineering Energy Level of FeN4 Sites via Dual-Atom Site Construction Toward Efficient Oxygen Reduction

Single-atom catalysts based on metal-N-4 moieties and embedded in a graphite matrix (defined as M-N-C) are promising for oxygen reduction reaction (ORR). However, the performance of M-N-C catalysts is still far from satisfactory due to their imperfect adsorption energy to oxygen species. Herein, single-atom Fe-N-C is leveraged as a model system and report an adjacent Ru-N-4 moiety modulation effect to optimize the catalyst's electronic configuration and ORR performance. Theoretical simulations and physical characterizations reveal that the incorporation of Ru-N-4 sites as the modulator can alter the d-band electronic energy of Fe center to weaken the Fe-O binding affinity, thus resulting in the lower adsorption energy of ORR intermediates at Fe sites. Thanks to the synergetic effects of neighboring Fe and Ru single-atom pairs, the FeN4/RuN4 catalyst exhibits a half-wave potential of 0.958 V and negligible activity degradation after 10 000 cycles in 0.1 m KOH. Metal-air batteries using this catalyst in the cathode side exhibit a high power density of 219.5 mW cm(-2) and excellent cycling stability for over 2370 h, outperforming the state-of-the-art catalysts.