Densely accessible Fe/Co–Nx dual-atom site coupled core–shell Co3Fe7@C as an efficient bifunctional oxygen electrocatalyst for rechargeable zinc–air batteries

Abstract

The urgent demand for stable and highly efficient bifunctional electrocatalysts for the oxygen reduction/evolution reactions (ORR/OER) is pivotal in advancing energy conversion and storage technologies. Herein, we introduce a metal–organic framework (MOF)-derived bifunctional electrocatalyst Fe₃Co-NC@900, featuring synergistically coupled dual single-atom sites (Fe/Co–N_x) and core–shell Co₃Fe₇@C nanoparticles. Leveraging the synergistic interactions of Fe–N_x sites with associated Co–N_x sites and core–shell nanoparticles within the MOF-derived nitrogen-doped mesoporous sheets and nanotubes, Fe₃Co-NC@900 demonstrates outstanding ORR and OER performance, outpacing the Fe-NC@900 catalyst fabricated without Co incorporation. Specifically, it demonstrates superior ORR performance with a higher half-wave potential (E_1/2) of 0.88 V and a small Tafel slope of 62.1 mV dec⁻¹, surpassing the Pt/C benchmark (E_1/2 of 0.82 V) and Fe-NC@900 (E_1/2 of 0.788 V). Additionally, it demonstrates noteworthy OER performance, requiring a 1.572 V overpotential at 10 mA cm⁻² current density, resulting in a significant bifunctional activity with a potential gap (ΔE) of 0.692 V, surpassing the Pt/C + Ir/C combination (ΔE = 0.748 V). Moreover, serving as a bifunctional air electrode, Fe₃Co-NC@900 exhibits excellent performance in lab-made Zn–air batteries, with outstanding open circuit voltage, specific capacity, and cycling stability (>650 cycles), outpacing the Pt/C + Ir/C-based battery.