The Evolution Pathway from Iron Compounds to Fe1(II)-N4 Sites Through Gas-Phase Iron During Pyrolysis

Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap ob- scures the connections between the input precursors and output products, clouding the pathway toward Fe-N-C catalyst improve- ment. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single atom Fe1(II)- N4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C, and then to tetrahedral Fe1(II)-O4 via a crystal-to-melt-like transformation below 600 °C. The Fe1(II)-O4 releases a single Fe atom that flows into the N-doped carbon defect forming Fe1(II)-N4 above 600 °C. This vapor phase single Fe atom transport mechanism is verified by synthesizing Fe1(II)-N4 sites via “non-contact pyrolysis” wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis.