Variable temperature in situ TEM mapping of the thermodynamically stable element distribution in bimetallic Pt-Rh nanoparticles.

We report here the first variable temperature in situ transmission electron microscopy (TEM) study on smaller Pt-Rh nanoparticles (≤24 nm) under vacuum conditions. Well-defined 50 at% Pt/50 at% Rh Pt-Rh solid solution and Rh(core)-Pt(shell) nanoparticles, obtained via colloidal synthesis routes, were investigated between room temperature and 650 °C to elucidate the tendency of elemental mixing/segregation. Key findings are that Pt-Rh nanoparticles <13 nm are stable in a solid solution configuration over the entire studied temperature range, whereas nanoparticles >13 nm tend to segregate upon cooling. Such a cross-over in element distribution with nanoparticle size has not been reported for the Pt-Rh system previously. The results demonstrate the technique's ability to extract valuable information concerning the intricate dynamic processes that take place in the bimetallic Pt-Rh system at the nanoscale, which may be indispensable when optimizing, e.g. , the metal composition in catalytically active materials.