Bifunctional Covalent Organic Framework‐Derived Electrocatalysts with Modulated p‐Band Centers for Rechargeable Zn–Air Batteries

Fine control over the physicochemical structures of carbon electrocatalysts is important for improving the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Zn–air batteries. Covalent organic frameworks (COFs) are considered good candidate carbon materials because their structures can be precisely controlled. However, it remains a challenge to impart bifunctional electrocatalytic activities for both the ORR and OER to COFs. Herein, a pyridine‐linked triazine covalent organic framework (PTCOF) with well‐defined active sites and pores is readily prepared under mild conditions, and its electronic structure is modulated by incorporating Co nanoparticles (CoNP‐PTCOF) to induce bifunctional electrocatalytic activities for the ORR and OER. The CoNP‐PTCOF exhibits lower overpotentials for both ORR and OER with outstanding stability. Computational simulations find that the p‐band center of CoNP‐PTCOF down‐shifted by charge transfer, compared to pristine PTCOF, facilitate the adsorption and desorption of oxygen intermediates on the pyridinic carbon active sites during the reactions. The Zn–air battery assembled with bifunctional CoNP‐PTCOF exhibits a small voltage gap of 0.83 V and superior durability for 720 cycles as compared with a battery containing commercial Pt/C and RuO2. This strategy for modulating COF electrocatalytic activities can be extended for designing diverse carbon electrocatalysts. Pyridine‐linked triazine covalent organic framework (PTCOF) with well‐defined carbon active sites and pores is readily prepared, and its electronic structure is effectively modulated by incorporating Co nanoparticles into the framework (CoNP‐PTCOF) to improve the bifunctional electrocatalytic activity for the oxygen reduction reaction and oxygen evolution reaction in Zn–air batteries. A rechargeable Zn–air battery with bifunctional CoNP‐PTCOF exhibits outstanding performance with superior durability.