Markedly Enhanced Oxygen Reduction Activity of Single-Atom Fe Catalysts via Integration with Fe Nanoclusters.

Single-atom catalysts (SACs) have emerged as one of the most promising alternatives to noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). While SACs can offer notable benefits in terms of lowering overall catalyst cost, there is still room for improvement regarding catalyst activity. To this end, we designed and successfully fabricated an ORR electrocatalyst in which atomic clusters are embedded in an atomically dispersed Fe-N-C matrix (FeAC@FeSA-N-C), as shown by comprehensive measurements using aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption spectroscopy (XAS). The half-wave potential of FeAC@FeSA-N-C is 0.912 V (versus reversible hydrogen electrode (RHE)), exceeding that of commercial Pt/C (0.897 V), FeSA-N-C (0.844 V), as well as the half-wave potentials of most reported non-platinum-group metal catalysts. The ORR activity of the designed catalyst stems from single-atom active centers but is markedly enhanced by the presence of Fe nanoclusters, as confirmed by both experimental measurements and theoretical calculations.