Ionic Covalent Organic Frameworks‐Derived Cobalt Single Atoms and Nanoparticles for Efficient Oxygen Electrocatalysis

Abstract Metal single atoms show outstanding electrocatalytic activity owing to the abundant atomic reactive sites and superior stability. However, the preparation of single atoms suffers from inexorable metal aggregation which is harmful to electrocatalytic activity. Here, ionic covalent organic frameworks (iCOFs) are employed as the sacrificial precursor to mitigate the metal aggregation and subsequent formation of bulky particles. Molecular dynamics simulation shows that iCOFs can trap and confine more Co ions as compared to neutral COFs, resulting in the formation of a catalyst composed of Co single atoms and uniformly distributed Co nanoparticles (Co_SA&Co_NP‐10). However, the neutral COFs derive a catalyst composed of Co atomic clusters and large Co nanoparticles (Co_AC&Co_NP‐25). The Co_SA&Co_NP‐10catalyst exhibits higher oxygen bifunctional electrocatalytic activities than Co_AC&Co_NP‐25, coinciding with the density functional theory results. Taking the Co_SA&Co_NP‐10as the air cathode in Zn–air batteries (ZABs), the aqueous ZAB presents a high power density of 181 mW cm⁻², a specific capacity of 811 mAh g⁻¹as well as a long cycle life of 407 h at a current density of 10 mA cm⁻², while the quasi‐solid state ZAB displays a power density of 179 mW cm⁻²and the cycle life of 30 h.