The functional property of the PAMAM-containing film as a sequestering agent for metallic nanoparticles was exploited by the introduction of copper acetylacetonate (Cu(acac)2) as a precursor for copper nanoparticles. Introduction of the nanoparticle precursors into the matrix was performed in SCCO2 as well as in a conventional solvent medium (tetra hydro furan-THF). The precursors were subsequently reduced to form the nanoparticles. Formation of Cu nanoparticles within the dendrimer films is confirmed by X-ray photoelectron spectroscopy (XPS), UV-visible absorption spectroscopy, Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Atomic force microscopy (AFM), and ellipsometry. Processing in the supercritical phase resulted in a higher yield and a denser and more stable distribution of nanoparticles than when THF was employed, possibly due to rapid solvent separation and accelerated reaction rates available in SCF media. TEM images revealed that the embedded nanoparticles are fairly tightly distributed in terms of size with an average diameter of 7 nm. The SCF processed film exhibited good stability towards polar solvent attack when compared to the THF-processed film
We have also demonstrated the formation of monometallic (Pd, and Pt) and bimetallic Pd-Pt nanoparticles with various metal compositions within the dendrimer films in SCCO2. These nanoparticles are prepared by sequestering acetylacetonate complexes (Pd(acac)2 and Pt(acac)2) within the dendrimer film followed by thermal reduction of the complexes to yield the corresponding nanoparticles. XPS and UV-visible absorption spectroscopy confirm that the metal complexes are completely reduced to zerovalent nanoparticles. TEM, FESEM, and AFM study show the Pd, Pt, and Pd-Pt nanoparticles are well separated and are of average sizes 1.3 nm, 1.6 nm and 8 nm, respectively. FESEM and TEM-EDX analyses of individual nanoparticles confirm that the films contain both Pd and Pt atoms and have approximately the same atomic compositions as the ratio of the acetylacetonates loaded into the SCCO2 stream. The spatial distribution of the bimetallic nanoparticles depends on the proportion of the metal precursors loaded into the dendrimer matrix. This study also suggests that the other metal nanoparticles with a narrow size distribution can be synthesized in SCCO2 using corresponding organometallic compounds.