Abstract

Fe–N–C electrocatalysts, as a representative of platinum group metal-free (PGM-free) catalysts, exhibit a comparable oxygen reduction reaction (ORR) activity but insufficient stability to that of commercial Pt/C in proton-exchange membrane fuel cells (PEMFCs), due to the unavoidable Fenton's reactions. Herein, we report a hard-template approach to synthesize the rare-earth single-cerium-atom-doped metal–organic frameworks with a hierarchically macro–meso–microporous structure. Spherical aberration correction electron microscopy confirms the atomic dispersion of Ce sites. Additionally, X-ray absorption spectroscopy (XAS) was employed to further verify the coordination environment of Ce sites, which were stabilized by four-coordinated nitrogen atoms and six-oxygen atoms (Ce–N4/O6). The Ce sites were embedded in a hierarchically macro–meso–microporous N-doped carbon (Ce SAS/HPNC) catalyst, which exhibits a half-wave potential of 0.862 V in ORR and the highest power density of 0.525 W cm–2 under 2.0 bar H2/O2 in the fuel cell test.