Abstract
Covalent organic frameworks (COFs) are promising materials for oxygen catalysis. Here, a novel, highly stable, conjugated two-dimensional poly(benzimidazole porphyrin-cobalt) (PBIPorCo) with a large delocalization energy is synthesized using meso-5,10,15,20-tetra (4-cyano-phenylporphyrin) cobalt (TCNPorCo) and 3,3'-diaminobenzidine (DAB). The decrease in energy between the HOMO and LUMO orbitals of PBIPorCo could enhance the capability for the gain and loss of electrons during the catalytic process. In a nitrogen-rich environment, a benzimidazole (BI) group can transfer electrons to the Co-N(4) site and enhance the protonation process in the oxygen reduction reaction (ORR). The π-π interactions between PBIPorCo and three-dimensional graphene (3D-G) form an "electron donor-π-electron acceptor" structure to boost the bifunctional oxygen catalysis process. PBIPorCo/3D-G exhibits outstanding bifunctional oxygen catalytic performance (ΔE = 0.62 V) and outstanding performance in zinc-air batteries. It exhibits satisfactory potential for application in fuel cells (FCs) and overall water splitting (OWS). This work presents a promising strategy for the design of novel COFs as bifunctional oxygen catalysts.