Due to the ever-increasing desire for catalysts that possess high activities and selectivities for industrially relevant reactions, much effort is being spent on the synthesis of mono and bimetallic nanoparticles with tunable characteristics such as size, shape and bimetallic composition. Understanding how these characteristics influence catalytic performance is the key to rationally designing catalysts for a specific reaction. While significant breakthroughs have been made, particularly in the area of monometallic nanoparticles with regard to shape and size, relating the bimetallic structure, i.e., core@shell or alloy to a specific reactivity remains a difficult task.

Work presented in this thesis describes the synthesis, characterization and catalytic properties of mono and bimetallic nanoparticles. Our efforts were motivated by the desire to understand the relationships that exist between metallic nanoparticle structure and their function as catalysts. This work also seeks to better understand the dynamic changes a nanoparticle's structure undergoes during typical catalytic operating conditions. Our approach is to use a wide array of analytical tools including optical methods, electron microscopy, XRD and mass spectrometry to provide an interlocking description of nanoparticle structure, function and durability.

We show how the polymer coatings and degraded carbonaceous deposits affect propene hydrogenation catalytic activity of Pt nanoparticles. We also present a unique view of the interplay between thermodynamic and kinetic variables that control bimetallic nanoparticle alloy structures by looking at ordered and disordered PdCu alloy nanoparticles as a function of particle size.

In another study we show that Ru@Pt and PtRu alloy nanoparticle catalysts have similar surface structures under oxidizing conditions but completely different surface structures under reducing conditions as probed by vibrational spectroscopy. These differences and similarities in surface composition correlate very well to their catalytic activity for CO oxidation under oxidizing and reducing environments, respectively.

Finally, we present the synthesis and characterization of Cu@Pt nanoparticles with a particular focus on the core@shell formation mechanism. We also show how dramatic changes in the surface electronic structure of Cu versus Cu@Pt nanoparticles can affect their ability to transform light into heat by using Raman spectroscopy to observe graphite formation on the surface of these nanoparticles.