Engineering d-band center of FeN4 moieties for efficient oxygen reduction reaction electrocatalysts

Atomically-dispersed FeN4 moieties are emerging as low-cost electrocatalysts for oxygen reduction reaction (ORR), which can be applied in fuel cells and metal-air batteries. Whereas, the unsatisfactory position of the d-band center from the metal sites offered by FeN4 affects the adsorption-desorption behaviors of oxygenated intermediates, further impeding the improvement of their ORR performances. Herein, we report a well-designed diatomic Fe/Zn-CNHC catalyst on a microporous hollow support. This strategy drives the position of the d-band center of Fe upward, thus making FeN4 active sites more favorable and stable during the ORR kinetic processes. The material exhibits an excellent ORR activity with a half-wave potential of 0.91 V and excellent stability (insignificant attenuation after 5,000 cycles), surpassing commercial Pt/C and many other single-atom catalysts. DFT calculations further indicate that the tuning effect of Zn on the d-orbital electron distribution of Fe facilitates the stretching and cleavage of Fe-O, thus accelerating the rate-determining step. This work presents a simple strategy to fabricate well-defined diatomic coordination in single-atom ORR electrocatalysts and inspires future research on developing new syntheses to control the coordination of single-atom electrocatalysts.