Island-in-Sea Structured PtFe Nanoparticles-in-Fe Single Atoms Loaded in Carbon Materials as Superior Electrocatalysts toward Alkaline HER and Acidic ORR.

In this work, PtFe nanoparticles (PtFe NPs) with the ordered internal structure and Pt-rich shells surrounded by plenty of Fe single atoms (Fe SAs) as active species (PtFe NP-in-Fe SA) loaded in the carbon materials are successfully fabricated, which are abbreviated as island-in-sea structured (IISS) PtFe NP-in-Fe SA catalysts. Moreover, the synergistic effect of O-bridging between PtFe NPs and Fe SAs, and the ordered internal structured PtFe NPs with Pt-rich shells of an optimal thickness contributes to the achievement of the local acidic environments on the surfaces of PtFe NPs in the alkaline hydrogen evolution reaction (HER) and the enhancement of the desorption rate of *OH intermediate in the acidic oxygen reduction reaction (ORR). In addition, the electronic interactions between PtFe NPs and dispersed Fe SAs cannot only provide efficient electrons transfer, but also prevent the aggregation and dissolution of PtFe NPs. Furthermore, the overpotential and the half wave potential of the as-prepared IISS PtFe NP-in-Fe SA catalysts toward the alkaline HER and toward the acidic ORR are 8 mV at a current density of 10 mA cm and 0.933 V, respectively, which is 29 lower and 86 mV higher than those (37 mV and 0.847 V) of commercial Pt/C catalysts.