Synthesis and composition evolution of bimetallic Pd-Pt alloy nanoparticles

摘要

This paper reports a study on the synthesis of Pd-Pt alloy nanoparticles and composition evolution of the alloys. The synthesis involves Pd and Pt acetylacetonate as the metal precursors and trioctylphosphine ( TOP) as the solvent. Thermal decomposition of the Pd-TOP complex resulted in Pd nanoparticles, while substitution of Pt in the Pt-TOP complex by Pd allowed formation of the Pd-Pt alloys. It was observed that the Pd-Pt nanoparticles formed at the very beginning in the synthesis process are Pd rich with various nanoparticle sizes ranging from 1.5 to 25 nm in diameter. These nanoparticles averaged out through a digestive ripening process and reached a final size of 3.5 nm in about 10 min. The alloy compositions evolved throughout the synthesis process and only reached the preset Pd to Pt ratio of the precursors in 120 min. It was found that Pt acetylacetonate alone in TOP cannot produce Pt nanoparticles, which was attributed to the formation of a Pt-TOP complex and a strong coordination of Pt to the phosphine. This observation led us to propose an atomic exchange process between the Pt-TOP complex and the Pd atoms at the nanoparticle surface. As a result, the alloy formation process is limited by a substitution and diffusion rate of the Pt atoms at the surface of the alloy nanoparticles.