Incorporation of Cu–Nx cofactors into graphene encapsulated Co as biomimetic electrocatalysts for efficient oxygen reduction

Abstract

Unlike metals with incomplete d-shells such as Pt and Fe, copper (Cu) with a filled d-electron shell is generally regarded as a sluggish oxygen reduction reaction (ORR) electrocatalyst. However, laccase and other copper enzymes could catalyze the ORR efficiently in nature. Inspired by this, we incorporated Cu–N_x cofactors (Cu–N₂ and Cu–N₄) into graphene encapsulated Co frameworks by direct annealing of MOFs with a post etching process. The bioinspired electrocatalyst exhibits excellent performance and stability for ORR which is comparable to or even better than Pt/C. Meanwhile, it also illustrates a fantabulous performance in a zinc–air battery device. The excellent performance can be ascribed to the abundant atomically dispersed Cu–N_x cofactors in the graphene frameworks confirmed by aberration corrected HAADF-STEM and XAFS analyses. Density functional theory calculations suggest that when Cu atoms are coordinated with the surrounding N atoms, the valence electrons of Cu atoms will transfer to nitrogen atoms, simultaneously tuning the d electronic states near the Fermi level to realize fast ORR kinetics.