Octahedral Growth of PtPd Nanocrystals

Abstract

PtPd nanoparticles are among the most widely studied nanoscale systems, mainly because of their applications as catalysts in chemical reactions. In this work, a combined experimental-theoretical study is presented about the dependence of growth shape of PtPd alloy nanocrystals on their composition. The particles are grown in the gas phase and characterized by STEM-HRTEM. PtPd nanoalloys present a bimodal size distribution. The size of the larger population can be tuned between 3.8 ± 0.4 and 14.1 ± 2.0 nm by controlling the deposition parameters. A strong dependence of the particle shape on the composition is found: Pd-rich nanocrystals present more rounded shapes whereas Pt-rich ones exhibit sharp tips. Molecular dynamics simulations and excess energy calculations show that the growth structures are out of equilibrium. The growth simulations are able to follow the growth shape evolution and growth pathways at the atomic level, reproducing the structures in good agreement with the experimental results. Finally the optical absorption properties are calculated for PtPd nanoalloys of the same shapes and sizes grown in our experiments.