Revealing chemical ordering in Pt–Co nanoparticles using electronic structure calculations and X-ray photoelectron spectroscopy†
The high catalytic activity of Pt–Co nanoalloys in oxygen reduction and other reactions is usually attributed to their Pt-rich surfaces. However, identification of the precise near-surface structure is by no means easily achievable experimentally. In this work we systematically analyzed the chemical ordering and surface composition of PtXCo79−X and PtXCo140−X bimetallic nanoparticles by means of a recently developed method based on topological energy expressions and electronic structure calculations. Pt is found to segregate on the surface, especially on corner and edge sites, forming a one atomic layer thick skin independent of the size and composition of the nanoparticle. In turn, the subsurface shell of the particle is composed mostly of Co, whereas the core area has a mixed composition, which depends on the overall stoichiometry. The formation of an outer Pt shell is corroborated by thoroughly analyzed data of X-ray photoelectron spectroscopy experiments performed with various photon energies on annealed Pt–Co particles prepared in vacuum by magnetron sputtering. The core–shell structure of Pt–Co particles is calculated to be more stable than the respective L10 structure. The obtained topological energy expressions are shown to depend only very moderately on the nanoparticle size, which allowed us to apply them to determine the ordering in ∼4 nm big PtXCo1463−X species. The presented results deepen our understanding of the intrinsic structure of Pt–Co nanoparticles depending on their size and composition.
- This article is part of the themed collection: Recent advances in the chemical physics of nanoalloys