Engineering Metal-Organic Framework Catalysts using Advance Functionalization Techniques

使用先进功能化技术工程金属有机框架催化剂

• 批准号: 1359906
• 负责人: Seth Cohen
• 金额: $ 45万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-06-15 至 2017-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1359906&HistoricalAwards=false
• 关键词: Engineering; Metal; Organic; Framework; Catalysts

In this project funded by the Chemical Catalysis program of the Chemistry Division, Prof. Seth Cohen of the University of California, San Diego seeks to develop high value catalysts using metal-organic frameworks (MOFs), which are a type of porous solid. By incorporating metals into the MOFs very robust selective catalysts can be developed. (Catalysts are species that facilitate chemical processes, thus saving energy and time.) Catalysis is needed for activities ranging from pharmaceutical synthesis to advanced energy. The development of new catalysts that can perform important transformations and be readily separated from products, recovered, and recycled is of value for process efficiency and greener chemistry. The MOF-based catalysis developed in this project will help realize these goals. This proposal also includes teaching activities involving a Science Policy Internship Program (SPIP). The SPIP supports undergraduate STEM (science, technology, engineering, math) students at the University of California Center in Washington D.C. This program educates STEM students on the importance of science in pubic policy. This program has recruited both underrepresented and women students, across the University of California system, to help to create a generation of scientists that better appreciate their role in society and government. The MOF materials targeted in this study are being developed to catalyze reactions where the advantages of a heterogeneous (i.e. solid state) catalyst can be exploited. In this study chiral substituents, organocatalytic groups, organometallics, and oxidizing metal centers are introduced into several known MOFs to produce single-site, catalytically active species. The project has three specific goals: 1. Modify the MOFs to generate organometallic active sites for transition metal catalyzed transformations; 2. Prepare MOFs that contain redox-active monocatecholato-metal sites that can perform oxidation reactions; and 3. Prepare MOFs with strong hydrogen-bonding groups, including squaramides, that can demonstrate significant organocatalytic behavior. These MOFs are attractive as catalysts because they can easily be isolated and separated from homogenous reaction mixtures by filtration, they contain well-ordered pores for potential size and shape selective reactions, and that they can be used to generate isolated active sites, reducing the chance of unfavorable interactions between catalytic sites.

在这个由化学学部化学催化项目资助的项目中，加州大学圣地亚哥分校的Seth Cohen教授试图利用金属有机框架（MOFs）开发高价值的催化剂，这是一种多孔固体。通过将金属掺入mof中，可以开发出非常坚固的选择性催化剂。（催化剂是促进化学过程，从而节省能源和时间的物质。）从药物合成到先进能源的各种活动都需要催化。开发能够进行重要转化并易于从产品中分离、回收和再循环的新型催化剂对提高工艺效率和绿色化学具有重要价值。本项目开发的基于mof的催化剂将有助于实现这些目标。该建议还包括涉及科学政策实习计划（SPIP）的教学活动。SPIP支持位于华盛顿特区的加州大学中心的STEM（科学、技术、工程、数学）本科生。该项目教育STEM学生科学在公共政策中的重要性。这个项目在整个加州大学系统中招募了代表性不足的学生和女性学生，以帮助培养一代科学家，让他们更好地认识到自己在社会和政府中的作用。这项研究的目标是开发MOF材料来催化反应，在这些反应中可以利用非均相（即固态）催化剂的优势。在本研究中，手性取代基、有机催化基团、有机金属和氧化金属中心被引入到几种已知的mof中，以产生单位点、催化活性的物质。该项目有三个具体目标：1。修饰mof以生成有机金属活性位点，用于过渡金属催化转化；2. 制备含有可进行氧化反应的氧化还原活性单儿茶酚金属位点的mof；和3。制备具有强氢键基团的mof，包括能表现出显著有机催化行为的角酰胺。这些MOFs作为催化剂很有吸引力，因为它们可以很容易地通过过滤从均相反应混合物中分离出来，它们含有有序的孔，可以进行潜在的尺寸和形状选择反应，它们可以用来产生分离的活性位点，减少催化位点之间不利相互作用的机会。