New Frontiers in Metal-Organic Frameworks: Chemical, Optical, and Electrochemical Control of Pore Size/Aperture

金属有机框架的新领域：孔径/孔径的化学、光学和电化学控制

• 批准号: RGPIN-2015-06625
• 负责人: Katz, Michael
• 金额: $ 2.4万
• 依托单位: Memorial University of Newfoundland
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=614258
• 关键词: New; Frontiers; Metal; Organic; Frameworks; New; Frontiers; Metal; Organic; Frameworks

The research program focuses on using porous materials to address challenges in sustainable chemistry. For example, sponges are porous materials. A sponge can be characterized by how much water it can absorb. In my lab, we will work on porous materials known as Metal-Organic Frameworks (MOFs). MOFs are made from inorganic metals (nodes) which are connected to one another by organic molecules (linkers). In MOFs, 80% of the crystal is empty. This 80 % is available for me as a researcher to investigate. Unlike the sponge example, the advantage of MOFs is that their pores are very regular and well defined. A well-defined pore has an internal volume and a pore aperture (i.e., the size of the opening into the pore). My research team will focus on tuning the volume of the pore and the opening of the pore in order to change how molecules are stored or interact with the MOF. The research program will focus on 2 objectives. The research team and I will utilize a MOF known as UiO-66. UiO-66 is a very sturdy MOF, making it ideal for a variety of industrial applications. When the MOF is heated, two water molecules are removed from each node. Although this reaction is reversible, we will explore how alcohols, instead of water molecules, are attached to the node. In this objective, the node will present a carbon chain into the pore instead of a hydrogen atom from the water molecule. By changing the length of the carbon chain, then the pore size can be tuned for applications in gas storage (e.g., CO2 sequestration), and water purification (e.g., mercury adsorption). The previous portion of the objective focused on adjusting every pore inside the MOF. However, if the alcohol that is being used is long enough, then only the outside of the MOF particle will be modified. Depending on the type of alcohol used, we will make MOFs that are soluble in water so that they can be easily processable into films, or easily incorporated into plastics. The research team and I will investigate MOFs which have switches built into them. Switching molecules change their shape when they are exposed to light. This switching is reversible. The switch will be placed in one of two places of the MOF. If the switch is placed by the aperture of the MOF, then the switch can be used to open and close, or, at the very least, constrict the size of the aperture. In this system, molecules can be trapped inside the MOF by simply shining light on it. Molecules used for gas-storage (e.g., methane for methane-powered cars), catalysts, and potentially even drugs can be stored in these MOFs. In the second type of switchable MOFs, the switch will point into the middle of the pore. In this system, the research team will tackle conducting MOFs in which the conductivity of the MOF can be turned on and off. The switching will occur inside the pore, and thus the pore size itself will change. The impact of this research program is that two new tools will be explored and utilized for applications in sustainability chemistry.

该研究计划着重于使用多孔材料来应对可持续化学的挑战。例如，海绵是多孔材料。海绵的特征是它可以吸收多少水。在我的实验室中，我们将使用称为金属有机框架（MOF）的多孔材料。 MOF由无机金属（节点）制成，它们通过有机分子（接头）相互连接。在MOF中，80％的晶体为空。作为研究人员，我可以使用80％的人来调查。与海绵示例不同，MOF的优点是它们的毛孔非常规定且定义得很好。定义明确的孔具有内部体积和一个孔径（即开口大小到孔中的大小）。我的研究团队将专注于调整孔的体积和孔的打开，以改变分子的存储方式或与MOF相互作用。 研究计划将重点关注两个目标。 研究团队和我将使用称为UIO-66的MOF。 UIO-66是一个非常坚固的MOF，非常适合各种工业应用。加热MOF时，从每个节点中除去两个水分子。尽管这种反应是可逆的，但我们将探讨如何将酒精而不是水分子附着在节点上。在这个目标中，节点将碳链呈现到孔中，而不是水分子的氢原子。通过更改碳链的长度，可以将孔径调整为用于在气体存储中的应用（例如CO2固存）和水纯化（例如汞吸附）。 目标的先前部分集中于调整MOF内部的每个孔。但是，如果使用的酒精足够长，则只有MOF粒子的外部才会被修改。根据所使用的酒精类型，我们将制造可溶于水的MOF，以便它们可以轻松地加工成薄膜，或者很容易被掺入塑料中。 研究团队和我将调查内置开关的MOF。开关分子在暴露于光线时会改变形状。此切换是可逆的。该开关将放置在MOF的两个地方之一。如果开关是通过MOF的光圈放置的，则可以使用开关打开和关闭，或者至少收缩了孔径的大小。在该系统中，可以通过简单地在其上闪耀光线来将分子捕获在MOF中。用于燃气存储的分子（例如，用于甲烷驱动的汽车的甲烷），催化剂甚至可能储存在这些MOF中。在第二种类型的可开关MOF中，开关将指向孔的中间。在该系统中，研究团队将解决指导MOF，其中可以打开和关闭MOF的电导率。切换将发生在孔内，因此孔径本身将改变。 该研究计划的影响是，将探索和用于可持续性化学应用程序的应用。