Surface Segregation of Fe in Pt–Fe Alloy Nanoparticles: Its Precedence and Effect on the Ordered-Phase Evolution during Thermal Annealing

Coupling electron microscopy techniques with in situ heating ability allows us to study phase transformations on the single-nanoparticle level. We exploit this setup to study disorder-to-order transformation of Pt–Fe alloy nanoparticles, a material that is of great interest to fuel-cell electrocatalysis and ultrahigh density information storage. In contrast to earlier reports, we show that Fe (instead of Pt) segregates towards the particle surface during annealing and forms a Fe-rich FeO(x) outer shell over the alloy core. By combining both ex situ and in situ approaches to probe the interplay between ordering and surface-segregation phenomena, we illustrate that the surface segregation of Fe precedes the ordering process and affects the ordered phase evolution dramatically. We show that the ordering initiates preferably at the pre-existent Fe-rich shell than the particle core. While the material-specific findings from this study open interesting perspectives towards a controlled phase evolution of Pt–Fe nanoalloys, the characterization methodologies described are general and should prove useful to probing a wide-range of nanomaterials.