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Highlights: Engineering Fe-N4 electronic structure with adjacent Co-N2C2 and Co sub-nanoclusters to optimize the electronic structure of the Fe-N4 active center is first demonstrated. Electrochemical studies reveal that the amorphous carbon corrosion leads to significantly increased charge- and mass-transport resistances. The operando X-ray absorption spectroscopy allows an investigation of the effect of highly oxidative environments on electrochemical behavior. Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement. Unlike the previously reported single-atom or dual-atom configurations, we designed a new type of binary-atom catalyst, through engineering Fe-N4 electronic structure with adjacent Co-N2C2 and nitrogen-coordinated Co nanoclusters, as oxygen electrocatalysts. The resultant optimized electronic structure of the Fe-N4 active center favors the binding capability of intermediates and enhances oxygen reduction reaction (ORR) activity in both alkaline and acid conditions. In addition, anchoring M–N–C atomic sites on highly graphitized carbon supports guarantees of efficient charge- and mass-transports, and escorts the high bifunctional catalytic activity of the entire catalyst. Further, through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses, the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed. This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior. It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M–N–C catalysts. [ABSTRACT FROM AUTHOR]

Highlights: Three-dimensional (3D) core‐shell heterostructured NixSy@MnOxHy nanorods grown on nickel foam (NixSy@MnOxHy/NF) were successfully fabricated via a simple hydrothermal reaction and a subsequent electrodeposition process. The fabricated NixSy@MnOxHy/NF shows outstanding bifunctional activity and stability for hydrogen evolution reaction and oxygen evolution reaction, as well as overall‐water‐splitting performance. The main origins are the interface engineering of NixSy@MnOxHy, the shell‐protection characteristic of MnOxHy, and the 3D open nanorod structure, which remarkably endow the electrocatalyst with high activity and stability. Exploring highly active and stable transition metal-based bifunctional electrocatalysts has recently attracted extensive research interests for achieving high inherent activity, abundant exposed active sites, rapid mass transfer, and strong structure stability for overall water splitting. Herein, an interface engineering coupled with shell-protection strategy was applied to construct three-dimensional (3D) core‐shell NixSy@MnOxHy heterostructure nanorods grown on nickel foam (NixSy@MnOxHy/NF) as a bifunctional electrocatalyst. NixSy@MnOxHy/NF was synthesized via a facile hydrothermal reaction followed by an electrodeposition process. The X-ray absorption fine structure spectra reveal that abundant Mn‐S bonds connect the heterostructure interfaces of NixSy@MnOxHy, leading to a strong electronic interaction, which improves the intrinsic activities of hydrogen evolution reaction and oxygen evolution reaction (OER). Besides, as an efficient protective shell, the MnOxHy dramatically inhibits the electrochemical corrosion of the electrocatalyst at high current densities, which remarkably enhances the stability at high potentials. Furthermore, the 3D nanorod structure not only exposes enriched active sites, but also accelerates the electrolyte diffusion and bubble desorption. Therefore, NixSy@MnOxHy/NF exhibits exceptional bifunctional activity and stability for overall water splitting, with low overpotentials of 326 and 356 mV for OER at 100 and 500 mA cm–2, respectively, along with high stability of 150 h at 100 mA cm–2. Furthermore, for overall water splitting, it presents a low cell voltage of 1.529 V at 10 mA cm–2, accompanied by excellent stability at 100 mA cm–2 for 100 h. This work sheds a light on exploring highly active and stable bifunctional electrocatalysts by the interface engineering coupled with shell-protection strategy. [ABSTRACT FROM AUTHOR]