Highly Strong Interaction between Fe/Fe3C Nanoparticles and N‐Doped Carbon toward Enhanced Oxygen Reduction Reaction Performance

Transition metal compounds anchored on N‐doped carbon (NC) show intrinsic activity and stability for oxygen reduction reaction (ORR). However, the interaction between the transition metal compounds and NC still needs to be strengthened for electron transfer at the compounds/carbon interface. Herein, Fe/Fe3C hybrid nanoparticles encapsulated into N‐doped carbon (Fe@NC) are used as high‐performance ORR catalysts. Benefiting from the strong interaction at Fe/Fe3C nanoparticles/NC interface, the electrons can transfer from Fe/Fe3C hybrid nanoparticles to NC, redistributing the electron density of active sites and promoting the ORR process. The as‐synthesized Fe@NC exhibits outstanding ORR catalytic activity with an onset potential of 1.01 V and a half‐wave potential of 0.92 V in alkaline media. It also shows prominent cycling stability and tolerance to methanol crossover, superior to Pt/C catalyst. The theoretical analysis reveals that the Fe nanoparticles have regulated the electron distributions at the heterojunction interface. The Gibbs free energy diagrams for ORR illustrate that the rate‐determining step is the conversion of OH* to OH−. In situ Raman spectra give evidence of O‐containing intermediates to prove the ORR process. The encapsulation of Fe/Fe3C nanoparticles into N‐doped carbon induces a strong interaction between Fe species and carbon matrix, which is beneficial for electron transfer and endows the catalyst with enhanced catalytic activity toward oxygen reduction reaction.