Nanomaterials in 0, 1, 2, and 3-Dimensions

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Nanomaterials are key elements of a number of developing technologies including energy storage, biomedical devices, chemical catalysis, and advanced materials. This research program focuses on the synthesis and reactivity of two of the most important nanomaterial systems - self assembled monolayers (2D SAMs) and ligand-capped metal nanoparticles (NPs with 3D SAMs). Research will be directed to obtaining a comprehensive mechanism-based understanding of the formation and stability of multicomponent thiol-based 2D self assembled monolayers. Particular emphasis will be directed to the use of electrochemical methods to make multicomponent 2D SAMs. Potential-assisted exchange (or replacement) reactions offer the possibility a controlled entry to derivatize mono- and multi-composition SAMs in a reproducible manner. Potential control will thus be explored in detail as a means to prepare binary and ternary SAMs with a large number of RSH pairs or trios. This knowledge will provide an entry to the generation of functional nanoscale patterns in 2D SAMs. In parallel, the factors which determine metal nanoparticle growth and dispersion will be determined, with an emphasis on the role played by the NP capping ligand, or 3D SAM. In particular, the concept of a charge density-limited equilibrium size will be explored by developing an extensive structure (e.g. ligand species) –property (e.g. metal core size) map, using a wide selection of ligands. This knowledge will lead to an understanding of ligand stability and activation toward replacement reactions, and will enable methods to achieve equilibrium phase separation of a multicomponent 3D SAM into a range of nanoscale patterns.