Boosting oxygen-reduction catalysis over mononuclear CuN2+2 moiety for rechargeable Zn-air battery

Abstract Endowing the transition-metal-nitrogen-carbon (M-N-Cs) electrocatalysts with high oxygen reduction activity for sustainable energy conversion, is a field of intense research while remains elusive. Here we exploit the variable configuration of atomically dispersed Cu1 centers on carbon support via rationally constructing prototypical CuN2+2 active sites to boost the kinetically sluggish electrochemical oxygen reduction. Density functional theory reveals the modified electronic structure of active Cu site and its derived orbital overlap through right symmetry with the degenerate π* orbital of O2 molecule, which more effectively facilitates O2 activation compared with CuN4 counterpart. The targeted electrocatalyst delivers superior alkaline ORR activity with a half-wave potential of 0.88 V and superior kinetics with Tafel slope of 48 mV dec−1, outperforming those of benchmark Pt/C. Remarkably, further demonstrated excellent peak power density and long-term durability in both primary liquid and flexible solid-state Zn-air battery assemblies signify the potential for practical applications.