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 PtCl4 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 Pt2+/dendrimer precursors are reduced by BH4 − and that the reduction process is highly heterogeneous. That is, after reduction each Pt2+/dendrimer precursor complex is either fully reduced, to yield a DEN having a size and structure consistent with the original PtCl4 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 Pt2+ ions. Details concerning the formation of the Pt2+/dendrimer precursor are also discussed.

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As nanoparticle synthesis capabilities advance, there is an increasing need for reliable nanoparticle size distribution analysis. Transmission electron microscopy (TEM) can be used to directly image nanoparticles at scales approaching a single atom. However, the advantage gained by being able to "see" these nanoparticles comes with several tradeoffs that must be addressed and balanced. For effective nanoparticle characterization, the proper selection of imaging type (bright vs dark field), magnification, and analysis method (manual vs automated) is critical. These decisions control the measurement resolution, the contrast between the particle and background, the number of particles in each image, the subsequent analysis efficiency, and the proper determination of the particle-background boundary and affect the significance of electron beam damage to the sample. In this work, the relationship between the critical decisions required for TEM analysis of small nanoparticles and the statistical effects of these factors on the resulting size distribution is presented.