Carbon support effects on bimetallic Pt-Ru nanoparticles formed from molecular precursors

We describe the preparation, structural characterization, and support interactions experienced by two different compositions of Pt-Ru nanoparticles supported on several carbons (carbon black, fullerene soot, and desulfurized carbon black). The bimetallic nanoparticles, obtained by reduction of the neutral molecular precursors PtRu5C(CO)(16) and Pt2Ru4(CO)(18) (the latter of which lacks a central "stabilizing" carbide core) at elevated temperatures in a hydrogen atmosphere, show a structural homology, exhibiting exceptionally narrow size and compositional distributions. A detailed structural picture of the nanoparticles has been deduced on the basis of in-situ extended X-ray absorption fine structure (EXAFS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray analysis (EDX), and X-ray absorption near edge structure (XANES). These techniques reveal that the bimetallic nanoparticles have Pt/Ru compositions of 1:5 and 2:4, respectively, and average diameters lying between 1.0 and 1.5 nm. The local metal coordination environments reveal a nonstatistical distribution of the two metals in the nanoparticles. Specifically, Pt shows a marked preference for segregation to the particle surfaces under an Hz atmosphere. The data also reveal a difference in the structural environment of the nanoparticles when formed on the fullerene soot support. Interactions between Ru and low-Z atoms are revealed through XANES, which, taken collectively with the other data presented, leads us to propose a possible Ru-C compound formation on this latter support phase.