Self-templated formation of ZnNC microtube with high oxygen reduction reaction overpotential for Zn-based catalyst

Abstract

The synthesis of hollow morphologies without employing templates and addressing the high overpotential of the oxygen reduction reaction in Zn-N4-C-based materials poses a significant challenge. In this study, we present a straightforward yet robust approach based on a self-templated metal-organic framework (MOF-based) to synthesize ZnNC microtubes and explore the reason behind its high oxygen reduction (ORR) overpotential through density functional theory (DFT) calculation. ZnNC microtubes, benefiting from the abundant Zn-N4 active sites, hierarchical porosity, and a reasonable degree of graphitization, exhibited superior ORR activity and methanol tolerance compared to the traditional precious Pt/C catalyst. On the other hand, DFT calculation shows that Zn exhibits a d10 electronic configuration and diamagnetic nature in Zn-N4 moieties confirmed by the partial density of state (PDOS), hence the main reason behind the high ORR overpotential. This study provides a novel roadmap for further engineering efforts to achieve an ideal ORR catalyst in Zn-based materials.