Entrapment, Manipulation and Reactions of Molecules at the Nanoscale

这个项目解决了一个最基本的科学挑战，涉及到在纳米尺度上控制分子的位置、方向和动能。该项目将开发一维（纳米管）和二维（石墨烯）纳米材料中分子约束的创新方法，以研究它们的行为并利用它们的功能特性。单壁碳纳米管（内径1-2纳米）是世界上最小的试管，它可以有效地将分子包裹在圆柱形腔中，而圆柱形腔的自由度受到很大限制。例如，富勒烯在以前的研究中被用作模型分子，已经清楚地表明分子的位置、方向、平移和旋转运动——都受到宿主纳米管的显著影响[Acc]。化学。文献资料，2005,38(1):1 - 9。在这个项目中，我们将扩展这一概念并引入分子行为的主动控制，使用纳米管作为电子或声子的纳米级管道，或纳米天线收集电磁辐射并将能量传递给被捕获的分子。其中一个目标是触发和控制分子的反应，并在单分子水平上引导它们转化为所需的产物[ACS Nano， 2017，出版中，http://pubs.acs.org/doi/abs/10.1021/acsnano.6b08228]，这可能会彻底改变我们研究化学反应和制造材料的方式。本项目中为纳米管开发的方法将转移到石墨烯单层或石墨烯双层上的分子，其中纳米管中的一维约束原理将在二维中得到扩展和探索。特别是，分子间反应导致1D [Nature Mater]中的链状或带状产物。[j], 2011, 10, 687]将利用石墨烯上的分子来构建具有定制结构和组成以及可调谐电子和光学特性的共价有机框架（COF）材料，从而解决石墨烯技术最关键的挑战之一。

This project addresses one of the most fundamental challenges of science related to control of positions, orientations and kinetic energy of molecules at the nanoscale. Innovative methodologies for confinement of molecules in 1D (nanotube) and 2D (graphene) nanomaterials will be developed in this project in order to study their behaviour and to harness their functional properties.Single-walled carbon nanotubes (internal diameter 1-2 nm) are the world's tiniest test tubes which allow effective entrapment of molecules in cylindrical cavities, where degrees of freedom are significantly limited. Fullerenes, for example, employed as a model molecules in previous studies have clearly demonstrated that positions, orientations, translational and rotational motions of the molecules - all are significantly influenced by the host nanotube [Acc. Chem. Res., 2005, 38, 901]. In this project, we shall expand this concept and introduce active control of the molecular behaviour, using the nanotube as a nanoscale conduit of electrons or phonons, or a nano-antenna harvesting electromagnetic radiation and transferring the energy to entrapped molecules. One of the objectives is to trigger and control reactions of the molecules, and to steer their transformations to desired products at the single-molecule level [ACS Nano, 2017, in press, http://pubs.acs.org/doi/abs/10.1021/acsnano.6b08228 ], which can potentially revolutionise the way we study chemical reactions and make materials.The approaches developed for nanotubes in this project will be transferred to molecules entrapped on graphene monolayer or within graphene bi-layer, where the principles of 1D confinement in nanotubes will be expanded and explored in 2D. In particular, intermolecular reactions leading to chain-like or ribbon-like products in 1D [Nature Mater., 2011, 10, 687] will be harnessed for molecules on graphene to construct covalent organic framework (COF) materials with bespoke structure and composition, and tuneable electronic and optical properties, thus addressing one of the most critical challenges of the graphene technology.