Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

•Synthesis of carbon supported PdRu, Pd3Ru, and Pd9Ru nanoparticles for oxygen reduction reaction in acidic electrolytes.•X-ray absorption spectroscopy indicates the as-synthesized samples are Ru-enriched on surface.•Synthesis of core@shell (Pd9Ru@Pt) nanoparticles for enhanced oxygen reduction catalysis with reduced Pt consumption.

Nanoparticles of PdRu, Pd3Ru, and Pd9Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x = 1/3/9), suggest successful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd9Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO4 solution. Subsequently, the Pd9Ru/C undergoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd9Ru surface (Pd9Ru@Pt). The Pd9Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg−1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg−1Pt). The mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core–shell Pd9Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

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