Atomic Arrangement Modulation in CoFe Nanoparticles Encapsulated in N-Doped Carbon Nanostructures for Efficient Oxygen Reduction Reaction

The properties and, hence, the application of materials are dependent on the way their constituent atoms are arranged. Here, we report a facile approach to produce body-centered cubic (bcc) and face-centered cubic (fcc) phases of bimetallic FeCo crystalline nanoparticles embedded into nitrogen-doped carbon nanotubes (NCNTs) with equal loading and almost similar particle size for both crystalline phases by a rational selection of precursors. The two electrocatalysts with similar composition but different crystalline structures of the encapsulated nanoparticles have allowed us, for the first time, to account for the effect of crystal structure on the overall work function of electrocatalysts and the concomitant correlation with the oxygen reduction reaction (ORR). This study unveils that the electrocatalysts with lower work function show lower activation energy to facilitate the ORR. Importantly, the difference between the ORR activation energy on electrocatalysts and their respective work functions are found to be identical (∼0.2 eV). A notable decrease in the ORR activity after acid treatment indicates the significant role of encapsulated FeCo nanoparticles in influencing the oxygen electrochemistry by modulating the material property of overall electrocatalysts.