MOF Structure Engineering to Synthesize CoNC Catalyst with Richer Accessible Active Sites for Enhanced Oxygen Reduction

Abstract

Single-atom cobalt-based CoNC are promising low-cost electrocatalysts for oxygen reduction reaction (ORR). However, further increasing the single cobalt-based active sites and the ORR activity remain a major challenge. Herein, an acetate (OAc) assisted metal-organic framework (MOF) structure-engineering strategy is developed to synthesize hierarchical accordion-like MOF with higher loading amount and better spatial isolation of Co and much higher yield when compared with widely reported polyhedron MOF. After pyrolysis, the accordion-structured CoNC (CoNC (A)) is loaded with denser CoN₄ active sites (Co: 2.88 wt%), approximately twice that of Co in the CoNC reported. The presence of OAc in MOF also induces the generation of big pores (5-50 nm) for improving the accessibility of active sites and mass transfer during catalytic reactions. Consequently, the CoNC (A) catalyst shows an admirable ORR activity with a E_1/2 of 0.89 V (40 mV better than Pt/C) in alkaline electrolytes, outstanding durability, and absolute tolerance to methanol in both alkaline and acidic media. The CoNC-based Zn-air battery exhibits a high specific capacity (976 mAh g^-1 _Zn ), power density (158 mW cm^-2 ), rate capability, and long-term stability. This work demonstrates a reliable approach to construct single atom doped carbon catalysts with denser accessible active sites through MOF structure engineering.

Keywords: ORR; metal-air batteries; metal-organic frameworks; single atoms; structure engineering.