Tailoring Au-core Pd-shell Pt-cluster nanoparticles for enhanced electrocatalytic activity

We have rationally synthesized and optimized catalytic nanoparticles consisting of a gold core, covered by a palladium shell, onto which platinum clusters are deposited (Au@Pd@Pt NPs). The amount of Pt and Pd used is extremely small, yet they show unusually high activity for electrooxidation of formic acid. The optimized structure has only 2 atomic layers of Pd and a half-monolayer equivalent of Pt (θPt ≈ 0.5) but a further increase in the loading of Pd or Pt will actually reduce catalytic activity, inferring that a synergistic effect exists between the three different nanostructure components (sphere, shell and islands). A combined electrochemical, surface-enhanced Raman scattering (SERS) and density functional theory (DFT) study of formic acid and CO oxidation reveals that our core–shell–cluster trimetallic nanostructure has some unique electronic and morphological properties, and that it could be the first in a new family of nanocatalysts possessing unusually high chemical reactivity. Our results are immediately applicable to the design of catalysts for direct formic acid fuel cells (DFAFCs).