Defect‐Rich Nitrogen Doped Co₃O₄/C Porous Nanocubes Enable High‐Efficiency Bifunctional Oxygen Electrocatalysis

Abstract

Abstract Heteroatom doping plays a significant role in optimizing the catalytic performance of electrocatalysts. However, research on heteroatom doped electrocatalysts with abundant defects and well‐defined morphology remain a great challenge. Herein, a class of defect‐engineered nitrogen‐doped Co 3 O 4 nanoparticles/nitrogen‐doped carbon framework (N‐Co 3 O 4 @NC) strongly coupled porous nanocubes, made using a zeolitic imidazolate framework‐67 via a controllable N‐doping strategy, is demonstrated for achieving remarkable oxygen evolution reaction (OER) catalysis. X‐ray photoelectron spectroscopy, X‐ray absorption fine structure, and electron spin resonance results clearly reveal the formation of a considerable amount of nitrogen dopants and oxygen vacancies in N‐Co 3 O 4 @NC. The defect engineering of N‐Co 3 O 4 @NC makes it exhibit an overpotential of only 266 mV to reach 10 mA cm −2 , a low Tafel slope of 54.9 mV dec −1 and superior catalytic stability for OER, which is comparable to that of commercial RuO 2 . Density functional theory calculations indicate N‐doping could promote catalytic activity via improving electronic conductivity, accelerating reaction kinetics, and optimizing the adsorption energy for intermediates of OER. Interestingly, N‐Co 3 O 4 @NC also shows a superior oxygen reduction reaction activity, making it a bifunctional electrocatalyst for zinc–air batteries. The zinc–air battery with the N‐Co 3 O 4 @NC cathode demonstrates superior efficiency and durability, showing the feasibility of N‐Co 3 O 4 /NC in electrochemical energy devices.