Structural and electrocatalytic properties of dendrimer-encapsulated nanoparticles




Yancey, David Francis

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As computational methods for the prediction of metallic nanoparticle structure and reactivity continue to advance, a need has developed for simple experimental models that can mimic and confirm theoretical predictions. Dendrimer-encapsulated nanoparticles, or DENs, are ideal to fill this role. DENs are synthesized within poly(amido amine) dendrimer templates which allows for the controlled synthesis of monodisperse nanoparticles in the 50-250 atom (1-2 nm) size range. These are small enough to be accessible to high-level theoretical calculations while being large enough to study experimentally. The research reported here consists of several independent but closely related studies. First, the synthesis, structural, and electrochemical properties of Au@Pt (core@shell) DENs are described. These materials are prepared by underpotentially depositing Cu onto Au DENs followed by galvanic exchange of Cu for Pt. Second, Pb UPD onto Au DENs and a detailed experimental and theoretical study of the resulting core@shell particle structures and catalytic activity is discussed. It is found that no matter how much Pt is deposited onto the surface of Au₁₄₇ DENs, a surface reorganization occurs resulting in similar electrocatalytic activity for the oxygen reduction reaction. Third, an in-depth X-ray absorption spectroscopy study of the structural properties of thiol-capped Au₁₄₇ DENs is described. Here, the surfaces of uncapped Au₁₄₇ nanoparticles are titrated with strongly binding thiol ligands to tune the extent of surface disorder. The effect of the increased surface disorder on the standard EXAFS fitting results is discussed from experimental and theoretical perspectives. Lastly, an in-situ electrochemical study of Au₁₄₇ DENs structure is reported. The key result is that the Au lattice expands during electrochemical surface oxidation. This is an important result for understanding electrocatalytic processes on Au nanoparticle




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