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

纳米材料是许多发展中技术的关键要素，包括能量存储、生物医学设备、化学催化和先进材料。该研究计划的重点是两个最重要的纳米材料系统的合成和反应性-自组装单分子层（2D SAM）和配体覆盖的金属纳米颗粒（NPs与3D SAM）。研究将致力于获得一个全面的机制为基础的理解的形成和稳定性的多组分硫醇为基础的二维自组装单分子膜。特别强调将针对使用电化学方法，使多组分的二维自组装膜。电位辅助交换（或置换）反应提供了以可再现的方式衍生单组分和多组分SAM的受控进入的可能性。因此，潜在的控制将被详细探讨作为一种手段，以准备大量的RSH对或trios的二元和三元SAM。这方面的知识将提供一个入口的功能纳米级图案的生成2D SAM。同时，将确定决定金属纳米颗粒生长和分散的因素，重点是NP封端配体或3D SAM所起的作用。特别是，电荷密度限制的平衡尺寸的概念将探索通过开发一个广泛的结构（如配体物种）-性质（如金属核尺寸）的地图，使用广泛的选择配体。这些知识将导致对配体稳定性和置换反应活化的理解，并将使方法能够实现多组分3D SAM的平衡相分离成一系列纳米级图案。

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.