A Single-Atom Fe-N-C Catalyst with Ultrahigh Utilization of Active Sites for Efficient Oxygen Reduction

Fe-N-C single-atom catalysts (SACs) are emerging as a promising class of electrocatalysts for the oxygen reduction reaction (ORR) to replace Pt-based catalysts. However, due to the limited loading of Fe for SACs and the inaccessibility of internal active sites, only a small portion of the sites near the external surface are able to contribute to the ORR activity. Here, this work reports a metal-organic framework-derived Fe-N-C SAC with a hierarchically porous and concave nanoarchitecture prepared through a facile but effective strategy, which exhibits superior electrocatalytic ORR activity with a half-wave potential of 0.926 V (vs RHE) in alkaline media and 0.8 V (vs RHE) in acidic media while maintaining excellent stability. The superior ORR activity of the as-designed catalyst stems from the unique architecture, where the hierarchically porous architecture contains micropores as Fe SAC anchoring sites, meso-/macro-pores as accessible channels, and concave shell for increasing external surface area. The unique architecture has dramatically enhanced the utilization of previously blocked internal active sites, as confirmed by a high turnover frequency of 3.37 s(-1) and operando X-ray absorption spectroscopy analysis with a distinct shift of adsorption edge.

Automated summary

This work reports the synthesis of a metal-organic framework-derived Fe-N-C single-atom catalyst with a hierarchically porous and concave nanoarchitecture, which exhibits superior electrocatalytic oxygen reduction reaction (ORR) activity in both alkaline and acidic media while maintaining excellent stability. The superior activity is attributed to the unique architecture, where the hierarchically porous structure provides increased surface area and utilization of internal active sites.