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

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 E1/2 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−1Zn), 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. A new accordion‐like zeolitic‐imidazole framework (ZIF) with high Co ion loading amount and dispersity is prepared by metal–organic framework (MOF) structure engineering. The acetate (OAc) plays an important role in stabilization of more Co ions and formation of large pores during carbonization. The obtained CoNC (A) contains high density of accessible single atom Co‐based active sites and exhibits greatly enhanced oxygen reduction reaction (ORR) activity.