PtFe and Fe₃C nanoparticles encapsulated in Fe–N-doped carbon bowl toward the oxygen reduction reaction

The high-temperature calcination strategy facilitates the formation of alloy atoms but inevitably results in the aggregation and deactivation of the metal particles for the oxygen reduction reaction (ORR) electrocatalysts. Herein, we report the successful encapsulation of Platinum–Iron (PtFe) nanoparticles (∼4.7 nm) in the N-doped hollow carbon hemisphere matrix (NCB) containing Fe–N and Fe₃C without employing high-temperature pyrolysis, which effectively facilitates the well-dispersed Pt nanoparticles and the formation of PtFe nanoalloys. The hollow carbon hemisphere structure contributes to the expansion of the specific surface area and exposure of active sites of the catalyst, meanwhile, the modification of the surface of the carbon nano-bowl from a predominantly Fe to a functional electrocatalyst with a primarily PtFe alloy can boost the ORR catalytic activity and stability. It is found that the Pt3Fe/Fe₃C-NCB catalyst exhibits the optimum ORR performance with a mass activity (0.97 A mg⁻¹_Pt), 5.10 times higher than the commercial Pt/C (0.19 A mg⁻¹_Pt). Pt3Fe/Fe₃C-NCB also displays excellent durability in comparison to the commercial Pt/C after 20,000 potential cycles. Combined with the Physical characterization and the electrochemical test results, Fe₃C-NCB plays a strong metal-support role for the encapsulated PtFe nanoparticles structure, thereby preventing nanoparticle migration and corrosion. Experimental characterization and theoretical calculations show that the appropriate PtFe alloy composition and the strain effect induced by Fe–N/Fe₃C active sites are sufficient to accelerate the detachment of oxygenated species from the alloy surface, resulting in a catalyst with excellent ORR performance.