Size-Dependent Morphology of Dealloyed Bimetallic Catalysts: Linking the Nano to the Macro Scale

Chemical dealloying of Pt binary alloy precursors has emerged as a novel and important preparation process for highly active fuel cell catalysts. Dealloying is a selective (electro)­chemical leaching of a less noble metal M from a M rich Pt alloy precursor material and has been a familiar subject of macroscale corrosion technology for decades. The atomic processes occurring during the dealloying of nanoscale materials, however, are virtually unexplored and hence poorly understood. Here, we have investigated how the morphology and intraparticle composition depend on the particle size of dealloyed Pt–Co and Pt–Cu alloy nanoparticle precursor catalysts. To examine the size–morphology–composition relation, we used a combination of high-resolution scanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), electron energy loss (EEL) spectroscopy, energy-dispersive X-ray spectroscopy (EDS), and surface-sensitive cycling voltammetry. Our results indicate the existence of three distinctly different size-dependent morphology regimes in dealloyed Pt–Co and Pt–Cu particle ensembles: (i) The arrangement of Pt shell surrounding a single alloy core (“single core–shell nanoparticles”) is exclusively formed by dealloying of particles below a characteristic diameter d_{multiple cores} of 10–15 nm. (ii) Above d_{multiple cores}, nonporous bimetallic core–shell particles dominate and show structures with irregular shaped multiple Co/Cu rich cores (“multiple cores–shell nanoparticles”). (iii) Above the second characteristic diameter d_pores of about 30 nm, the dealloyed Pt–Co and Pt–Cu particles start to show surface pits and nanoscale pores next to multiple Co/Cu rich cores. This structure prevails up to macroscopic bulklike dealloyed particles with diameter of more than 100 nm. The size–morphology–composition relationships link the nano to the macro scale and provide an insight into the existing material gap of dealloyed nanoparticles and highly porous bulklike bimetallic particles in corrosion science.