Engineering Metal-Organic Framework Catalysts using Advance Functionalization Techniques

在这个由化学系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教授试图利用金属有机骨架(MOF)开发高价值催化剂，MOF是一种多孔固体。通过在MOF中加入金属，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的物种，从而节省能源和时间。)从药物合成到高级能源的各种活动都需要催化。开发能够进行重要转化并且容易从产品中分离、回收和再循环的新型催化剂对工艺效率和更绿色的化学具有价值。本项目开发的MOF基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支持位于华盛顿特区的加州大学中心的本科生STEM(科学、技术、工程、数学)学生。该项目教育STEM学生科学在公共政策中的重要性。该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学生，以帮助培养更好地认识到他们在社会和政府中的作用的一代科学家。本研究的目标是开发MOF材料来催化反应，其中可以利用多相(即固态)催化剂的优势。在这项研究中，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个已知的MOF中，以产生单一中心的催化活性物种。该项目有三个具体的目标：1.修饰MOF以生成过渡金属催化转化的有机金属活性中心；2.制备含有氧化还原活性的单金属中心的MOF；以及3.制备具有强氢键基团的MOF，包括方酰胺，可以表现出显著的有机催化行为。这些MOF作为催化剂很有吸引力，因为它们可以很容易地从均相反应混合物中分离出来，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，可以用于潜在的大小和形状选择反应，并且它们可以用来产生孤立的活性中心，减少催化中心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.