This thesis reports on the synthesis and characterization of PtNi dendrimer-encapsulated nanoparticles (DENs) containing on average 147 atoms. This is significant because PtNi DENs have not yet been reported. The DENs were prepared by first complexation of Pt²⁺ to the interior tertiary amines of a sixth-generation, hydroxyl-terminated (G6-OH) poly(amidoamine) (PAMAM) dendrimer template, followed by chemical reduction in the presence of free Ni²⁺ to yield PtNi DENs. UV-visible (UV-vis) absorbance measurements exhibit a broad, monotonically decreasing band characteristic of nanoparticle formation. Upon dialysis in both H₂ and O₂ this band is observed to decrease in absorbance. Transmission electron microscopy (TEM) studies indicate that particles have been synthesized and are 1.8 + 0.2 nm before dialysis and 1.9 + 0.2 nm after dialysis under H₂. Results obtained from X-ray photoelectron spectroscopy (XPS) show that Pt is present and the Pt(4f7/2) binding energy is observed at 72.0 eV before dialysis and 71.5 eV after dialysis under H₂. XPS shows that Ni is present and the Ni(2p3/2) binding energy is centered at 857.0 eV before dialysis and 856.6 eV after dialysis under H₂. Finally, oxidative electrochemical stripping is observed at 1.07 V (vs NHE) for PtNi DENs immobilized on glassy carbon electrodes (GCE) and is tentatively assigned to Ni. / text

Dendrimer-encapsulated nanoparticles (DENs) were prepared, characterized, and immobilized on solid surfaces. The resulting films were applied as electrocatalysts for the oxygen reduction reaction (ORR). First, the synthesis, physical and chemical properties, and stability of Pd DENs prepared within poly(amidoamine) (PAMAM) dendrimers were studied in aqueous solution. In this part of the study, the following new findings were reported: (1) the maximum Pd ion loading in the dendrimer was correlated to the number of interior amines available for complexation; (2) Pd DENs could be synthesized within amine-terminated Pd DENs by controlling the solution pH; (3) the oxidative stability of Pd DENs was significantly improved by removing solution-phase impurities; (4) exposure to hydrogen gas reversibly converts partially oxidized Pd DENs back to the zerovalent state. Second, Pt and Pd DENs were prepared using amine-terminated PAMAM dendrimers, and then the free amine groups on the periphery were used to immobilize Pt and Pd DENs onto Au surfaces via an intermediate self-assembled monolayer. The resulting DEN films were more robust and had higher coverages of DENs compared to the DEN films prepared via physisorption. Third, Pt DENs were prepared and immobilized on glassy carbon electrodes using an electrochemical coupling method. The resulting films were electrochemically active for the ORR. These electrocatalytic monolayers were also robust, surviving up to 50 consecutive electrochemical scans for ORR and sonication in acid solution with no significant change in activity. Finally, PtPd bimetallic nanoparticles containing an average of 180 atoms (~1.8 nm in diameter) and composed of seven different Pt:Pd ratios were prepared within sixth-generation, hydroxyl-terminated PAMAM dendrimers. Transmission electron microscopy and single-particle energy dispersive spectroscopy confirmed the sizes and compositions of the particles. These DENs were immobilized on glassy carbon electrodes, and their electrocatalytic properties were evaluated as a function of composition using cyclic voltammetry and rotating disk voltammetry. The results showed that the maximum rate for the ORR occurs at a Pt:Pd ratio of 5:1, which corresponds to a relative mass activity enhancement of 2.5 compared to otherwise identical monometallic Pt nanoparticles.

Dendrimer-encapsulated nanoparticles (DENs) were prepared, characterized, and immobilized on solid surfaces. The resulting films were applied as electrocatalysts for the oxygen reduction reaction (ORR). First, the synthesis, physical and chemical properties, and stability of Pd DENs prepared within poly(amidoamine) (PAMAM) dendrimers were studied in aqueous solution. In this part of the study, the following new findings were reported: (1) the maximum Pd ion loading in the dendrimer was correlated to the number of interior amines available for complexation; (2) Pd DENs could be synthesized within amine-terminated Pd DENs by controlling the solution pH; (3) the oxidative stability of Pd DENs was significantly improved by removing solution-phase impurities; (4) exposure to hydrogen gas reversibly converts partially oxidized Pd DENs back to the zerovalent state. Second, Pt and Pd DENs were prepared using amine-terminated PAMAM dendrimers, and then the free amine groups on the periphery were used to immobilize Pt and Pd DENs onto Au surfaces via an intermediate self-assembled monolayer. The resulting DEN films were more robust and had higher coverages of DENs compared to the DEN films prepared via physisorption. Third, Pt DENs were prepared and immobilized on glassy carbon electrodes using an electrochemical coupling method. The resulting films were electrochemically active for the ORR. These electrocatalytic monolayers were also robust, surviving up to 50 consecutive electrochemical scans for ORR and sonication in acid solution with no significant change in activity. Finally, PtPd bimetallic nanoparticles containing an average of 180 atoms (~1.8 nm in diameter) and composed of seven different Pt:Pd ratios were prepared within sixth-generation, hydroxyl-terminated PAMAM dendrimers. Transmission electron microscopy and single-particle energy dispersive spectroscopy confirmed the sizes and compositions of the particles. These DENs were immobilized on glassy carbon electrodes, and their electrocatalytic properties were evaluated as a function of composition using cyclic voltammetry and rotating disk voltammetry. The results showed that the maximum rate for the ORR occurs at a Pt:Pd ratio of 5:1, which corresponds to a relative mass activity enhancement of 2.5 compared to otherwise identical monometallic Pt nanoparticles.

The synthesis and characterization of Pt core/ Cu shell (Pt@Cu) dendrimer-encapsulated nanoparticles (DENs) having full and partial Cu shells deposited via electrochemical underpotential deposition (UPD) is described. Pt DENs containing averages of 55, 147, and 225 Pt atoms immobilized on glassy carbon electrodes served as the substrate for the UPD of a Cu monolayer. This results in formation of Pt@Cu DENs. Evidence for this conclusion is based on results from the analysis of cyclic voltammograms (CVs) for the UPD and stripping of Cu on Pt DENs, and from experiments showing that the Pt core DENs catalyze the hydrogen evolution reaction before Cu UPD, but that after Cu UPD this reaction is inhibited. Results obtained by in-situ electrochemical X-ray absorption spectroscopy (XAS) confirm the core@shell structure. Calculations from density functional theory (DFT) show that the first portion of the Cu shell deposits onto the (100) facets, while Cu deposits lastly onto the (111) facets. The DFT-calculated energies for Cu deposition on the individual facets are in good agreement with the peaks observed in the CVs of the Cu UPD on the Pt DENs. Finally, structural analysis of Pt DENs having just partial Cu shells by in-situ XAS is consistent with the DFT-calculated model, confirming that the Cu partial shell selectively decorates the (100) facets. These results are of considerable significance because site-selective Cu deposition has not previously been shown on nanoparticles as small as DENs. In summary, the application of UPD as a synthetic route and characterization tool for core@shell DENs having well defined structures is established. A study of the degradation mechanism and degradation products of Pd DENs is provided as well. These DENs consisted of an average of 147 atoms per dendrimer. Elemental analysis and UV-vis spectroscopy indicate that there is substantial oxidation of the Pd DENs in air-saturated solutions, less oxidation in N₂-saturated solution, and no detectable oxidation when the DENs are in contact with H₂. Additionally, the stability improves when the DEN solutions are purified by dialysis to remove Pd²⁺-complexing ligands such as chloride. For the air- and N₂-saturated solutions, most of the oxidized Pd recomplexes to the interiors of the dendrimers, and a lesser percentage escapes into the surrounding solution. The propensity of Pd DENs to oxidize so easily is a likely consequence of their small size and high surface energy. Calculations from density functional theory (DFT) show that the first portion of the Cu shell deposits onto the (100) facets, while Cu deposits lastly onto the (111) facets. The DFT-calculated energies for Cu deposition on the individual facets are in good agreement with the peaks observed in the CVs of the Cu UPD on the Pt DENs. Finally, structural analysis of Pt DENs having just partial Cu shells by in-situ XAS is consistent with the DFT-calculated model, confirming that the Cu partial shell selectively decorates the (100) facets. These results are of considerable significance because site-selective Cu deposition has not previously been shown on nanoparticles as small as DENs. In summary, the application of UPD as a synthetic route and characterization tool for core@shell DENs having well defined structures is established. A study of the degradation mechanism and degradation products of Pd DENs is provided as well. These DENs consisted of an average of 147 atoms per dendrimer. Elemental analysis and UV-vis spectroscopy indicate that there is substantial oxidation of the Pd DENs in air-saturated solutions, less oxidation in N2-saturated solution, and no detectable oxidation when the DENs are in contact with H2. Additionally, the stability improves when the DEN solutions are purified by dialysis to remove Pd2+-complexing ligands such as chloride. For the air- and N2-saturated solutions, most of the oxidized Pd recomplexes to the interiors of the dendrimers, and a lesser percentage escapes into the surrounding solution. The propensity of Pd DENs to oxidize so easily is a likely consequence of their small size and high surface energy. / text