Oxygen Coordination on Fe–N–C to Boost Oxygen Reduction Catalysis

The coordination environments of iron (Fe) in Fe-N-C catalysts determine their intrinsic activities toward oxygen reduction reactions (ORR). The precise atomic-level regulation of the local coordination environments is thus of critical importance yet quite challenging to achieve. Here, atomically dispersed Fe-N-C catalyst with O-Fe-N₂C₂ moieties is thoroughly studied for ORR catalysis. Advanced synchrotron X-ray characterizations, along with theoretical modeling, explicitly unraveled the penta-coordinated nature of the Fe center in the catalytic domain and the energetically optimized ORR pathways on the well-tailored O-Fe-N₂C₂ moieties. The combined structure identification from both experiments and theory provides an opportunity to understand the role of the coordination environments in directing the catalytic activity of single-atom or single-site catalysts; not only the center metal atom but also the whole coordinating atoms participate in the catalytic cycle.