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

纳米材料是许多发展中的技术的关键元素，包括储能、生物医学设备、化学催化和先进材料。这项研究计划重点研究两个最重要的纳米材料系统--自组装单分子膜(2D SAM)和带有配体的金属纳米颗粒(NPs与3D SAM)的合成和反应性。*研究将致力于从机理上全面了解基于硫醇的多组分2D自组装单分子膜的形成和稳定性。将特别强调使用电化学方法来制造多组分2D自组装膜。电位辅助的交换(或取代)反应提供了一种可控制的进入，以可重复的方式衍生化单组分和多组分的自组份自组装膜。因此，将详细探索电位控制作为制备具有大量RSH对或三元的二元和三元自组装膜的手段。这一知识将为在2DSAM中产生功能纳米级图案提供入口。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封顶配体或3DSAM所起的作用。特别是，电荷密度受限平衡尺寸的概念将通过使用广泛的选择的配体来开发广泛的结构(例如，配体种类)-性质(例如，金属核心尺寸)图来探索。这一知识将导致对配体稳定性和取代反应活化的理解，并将使方法能够实现将多组分3D SAM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.***