Synthesis and Characterization of Pt Dendrimer-Encapsulated Nanoparticles: Effect of the Template on Nanoparticle Formation

In this article, we provide a detailed description of the synthesis and properties of Pt dendrimer-encapsulated nanoparticles (DENs) prepared using sixth-generation, hydroxyl-terminated, poly(amidoamine) (PAMAM) dendrimers (G6−OH) and three different PtCl 4 2− /G6−OH ratios: 55, 147, and 240. Results obtained from UV−vis spectroscopy, X-ray photoelectron spectroscopy, electron microscopy, X-ray absorption spectroscopy, and high-energy X-ray diffraction show that only a fraction of the Pt 2+ /dendrimer precursors are reduced by BH 4 − and that the reduction process is highly heterogeneous. That is, after reduction each Pt 2+ /dendrimer precursor complex is either fully reduced, to yield a DEN having a size and structure consistent with the original PtCl 4 2− /dendrimer ratio used for the synthesis, or the precursor is not reduced at all. This result is consistent with an autocatalytic process that entails slow formation of a nascent catalytic Pt seed within the dendrimer, followed by rapid, catalytic reduction of nearby Pt 2+ ions. Details concerning the formation of the Pt 2+ /dendrimer precursor are also discussed.