Using Core-Shell Nanocatalysts to Unravel the Impact of Surface Structure on Catalytic Activity

Abstract

The high surface area and atomic-level tunability offered by nanoparticles has defined their promise as heterogeneous catalysts. While initial studies began with nanoparticles of a single metal assuming thermodynamic shapes, modern work has focused on using nanoparticle composition and geometry to optimize nanocatalysts for a wide variety of reactions. Further optimization of these refined nanocatalysts remains difficult, however, as the factors that determine catalytic activity are intertwined and a fundamental understanding of each remains elusive. In this work, precise synthetic methods are used to tune a number of factors, including composition, strain, metal-to-metal charge transfer, atomic order, and surface faceting, and understand their impact on catalysis. The first chapter focuses on current achievements and challenges in the synthesis of intermetallic nanocatalysts, which offer long-range order that allows for total control of surface structure. A particular focus is given to the impact of the synthetic approach on the activity of the resulting nanoparticles. In the second chapter, multilayered Pd-(Ni-Pt)x nanoparticles serve as a controlled arena for the study of metallic mixing and order formation on the nanoscale. The third chapter controls the shell thickness of Au@PdPt core-alloyed shell nanoparticles on a nanometer scale to isolate strain at the nanoparticle surface. In the fourth chapter, the synthetic approaches of chapters two and three are applied to catalysis. In totality, the work presented here represents a brick in the foundation of understanding and exploiting structure-function relationships on the nanoscale, with an eye toward the rational design of tailored nanocatalysts.