Abstract

Abstract High‐performance bifunctional electrocatalyst for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the keystone for the industrialization of rechargeable zinc‐air battery (ZAB). In this work, the modulation in the spin state of Fe single atom on nitrogen doped carbon (Fe 1 ‐NC) is devised by Co 3 O 4 (Co 3 O 4 @Fe 1 ‐NC), and a mediate spin state is recorded. Besides, the d band center of Fe is downshifted associated with the increment in e g filling revealing the weakened interaction with OH * moiety, resulting in a boosted ORR performance. The ORR kinetic current density of Co 3 O 4 @Fe 1 ‐NC is 2.0‐ and 5.6 times higher than Fe 1 ‐NC and commercial Pt/C, respectively. Moreover, high spin state is found for Co in Co 3 O 4 @Fe 1 ‐NC contributing to the accelerated surface reconstruction of Co 3 O 4 witnessed by operando Raman and electrochemical impedance spectroscopies. A robust OER activity with overpotential of 352 mV at 50 mA cm −2 is achieved, decreased by 18 and 60 mV by comparison with Co 3 O 4 @NC and IrO 2 . The operando Raman reveals a balanced adsorption of OH * species and its deprotonation leading to robust stability. The ZAB performance of Co 3 O 4 @Fe 1 ‐NC is 193.2 mW cm −2 and maintains for 200 h. Furthermore, the all‐solid‐state ZAB shows a promising battery performance of 163.1 mW cm −2 .