Engineering Metal-Organic Framework Catalysts using Advance Functionalization Techniques

在这个由化学部化学催化计划资助的项目中，加州大学圣地亚哥分校的Seth Cohen教授试图使用金属有机框架（MOFs）开发高价值催化剂，MOFs是一种多孔固体。通过将金属结合到M0 F中，可以开发非常稳健的选择性催化剂。（催化剂是促进化学过程的物质，从而节省能源和时间。从药物合成到先进能源的活动都需要催化。 开发能够进行重要转化并易于从产品中分离、回收和再循环的新催化剂对于提高工艺效率和实现更环保的化学过程具有重要价值。 本项目开发的基于MOF的催化剂将有助于实现这些目标。 该提案还包括涉及科学政策实习计划（SPIP）的教学活动。 SPIP支持华盛顿特区的加州大学中心的本科STEM（科学、技术、工程、数学）学生。 该计划在整个加州大学系统招募了代表性不足的学生和女学生，以帮助培养一代更好地理解他们在社会和政府中的作用的科学家。本研究中的目标MOF材料正在开发用于催化反应，其中可以利用非均相（即固态）催化剂的优点。 在这项研究中，手性取代基，有机催化基团，有机金属化合物，和氧化金属中心被引入到几个已知的MOFs生产单位点，催化活性物种。该项目有三个具体目标：1。修饰MOFs以产生用于过渡金属催化转化的有机金属活性位点; 2.制备含有可进行氧化反应的氧化还原活性单儿茶酚合金属位点的M0 F;以及3.制备具有强氢键基团（包括方酰胺）的MOF，其可以表现出显著的有机催化行为。这些M0 F作为催化剂是有吸引力的，因为它们可以容易地通过过滤从均相反应混合物中分离和分离，它们含有用于潜在的尺寸和形状选择性反应的有序孔，并且它们可以用于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。

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.