A carboxylate linker strategy mediated densely accessible Fe-N₄ sites for enhancing oxygen electroreduction in Zn-air...

Iron-nitrogen-carbon single-atom catalysts derived from zeolitic-imidazolate-framework-8 (ZIF-8) have presented its great potential for the oxygen reduction reaction (ORR) in Zn-air batteries (ZABs). However, due to insufficient active Fe-N sites, its ORR activity is inferior to Pt-based catalysts. Herein, a carboxylate (OAc) linker strategy is proposed to design a ZIF-8-derived FeNCOAc catalyst with abundant accessible Fe-N₄ single-atom sites. Except that imidazole groups can coordinate with Fe ions, the OAc linker on the unsaturated coordination Zn nodes can anchor and coordinate with more Fe ions, resulting in a significant increase in Fe-N₄ site density. Meanwhile, the corrosion of carbon skeleton by OAc oxidation during heat-treatment leads to improved porosity of catalyst. Benefitting from the highly dense Fe-N₄ sites and hierarchical pores, the FeNCOAc endows superior performance in alkaline medium (E_1/2 = 0.906 V), which is confirmed by density functional theory calculation results. Meanwhile, the assembled liquid ZAB delivers a favorable peak power density of 173.9 mW cm^-2, and a high specific capacity of 770.9 mAh g^-1 as well as outstanding durability. Besides, the solid-state ZAB also shows outstanding discharge performance.