MIL-101-Derived Mesoporous Carbon Supporting Highly Exposed Fe Single-Atom Sites as Efficient Oxygen Reduction...

Fe single-atom catalysts (Fe SACs) with atomic FeN_x active sites are very promising alternatives to platinum-based catalysts for the oxygen reduction reaction (ORR). The pyrolysis of metal-organic frameworks (MOFs) is a common approach for preparing Fe SACs, though most MOF-derived catalysts reported to date are microporous and thus suffer from poor mass transfer and a high proportion of catalytically inaccessible FeN_x active sites. Herein, NH₂ -MIL-101(Al), a MOF possessing a mesoporous cage architecture, is used as the precursor to prepare a series of N-doped carbon supports (denoted herein as NC-MIL101-T) with a well-defined mesoporous structure at different pyrolysis temperatures. The NC-MIL101-T supports are then impregnated with a Fe(II)-phenanthroline complex, and heated again to yield Fe SAC-MIL101-T catalysts rich in accessible FeN_x single atom sites. The best performing Fe SAC-MIL101-1000 catalyst offers outstanding ORR activity in alkaline media, evidenced by an ORR half-wave potential of 0.94 V (vs RHE) in 0.1 m KOH, as well as excellent performance in both aqueous primary zinc-air batteries (a near maximum theoretical energy density of 984.2 Wh kg_Zn ^-1 ) and solid-state zinc-air batteries (a peak power density of 50.6 mW cm^-2 and a specific capacity of 724.0 mAh kg_Zn ^-1 ).