Rational syntheses of core-shell Fex@Pt nanoparticles for the study of electrocatalytic oxygen reduction reaction

We report on the syntheses of core-shell Fe-x@Pt (x = 0.4-1.2) nanoparticles (NPs) with Pt-shell thickness systematically controlled while the overall particle size is constant. The syntheses were achieved via one-pot ultrasound-assisted polyol synthesis (UPS) reactions. Fe-1.2@Pt showed a record-breaking high core-element content (55 at%) of core-shell NPs. Based on observations from a series of control experiments, we propose a mechanism of the NPs' formation that enables control of shell thickness in UPS reactions. Fe-x@Pt NPs showed drastic enhancements in mass and specific activity for oxygen reduction reaction (ORR) and significantly enhanced durability compared to commercial Pt NPs. Fe-x@Pt with a 1 (monolayer) ML Pt shell showed the highest activity. The ab initio density functional theory calculations on the binding energies of oxygen species on the surfaces of Fe-x@Pt NPs showed that the 1 ML case is most favourable for the ORR, and in good agreement with the experimental results.