Multifunctional Metal-Organic Frameworks for Cooperative Catalysis

在化学系化学催化计划的支持下，芝加哥大学林文斌教授正在开发新的金属-有机骨架(MOF)作为化学合成的合作催化剂。协作型催化剂可同时加速两步或多步反应，从而提高化学键的构筑效率，从而促进多步反应。虽然固体催化剂被用于许多催化反应，但由于不能安装空间可控的催化中心，它们很难精确地设计用于协同催化。林教授和他的研究小组正在利用MOF的最新进展来解决这个问题，以构建用于合作催化的多功能MOF。一种自下而上的方法被用来构建可回收和可重复使用的、具有合作催化中心的多功能MOF，并优化这些结构，用于制药、农用化学品和精细化工等重要的化学合成应用。正在研究MOF和目标催化过程之间的结构-功能关系，以支持继续改进设计。这些活动进一步被用来支持本科生和高中生的研究机会，以提高对STEM学科的参与度。许多天然酶具有多个精确设计的活性部位，可以高效和选择性地协同催化二氧化碳等简单分子向碳水化合物等复杂分子的多种转化。尽管固体催化剂在商品化学品的生产中很重要，但由于缺乏在这些固体中以空间可控的方式精确设计均匀和协同催化中心的方法，它们不能用于协同催化。林教授和他的研究小组将利用合成策略来制备具有大开放通道/孔和多功能活性中心的新型MOF，用于合作催化剂组合，包括：(Ii)Lewis酸和过渡金属催化剂，(Ii)光氧化还原和过渡金属催化剂，或(Iii)光氧化还原和Lewis/Brronsted酸催化剂。然后将检查这些MOF的C-C和C-杂原子交叉偶联、烯烃歧化和烯烃齐聚反应。人们正在利用MOF固有的性质，目的是发现可行的新催化体系，并开发具有合作功能的仿生材料。该研究项目还将为不同的博士后研究人员和研究生提供重要的培训，以开发用于环境管理的可持续化学过程。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Wenbin Lin of the University of Chicago is developing new metal-organic frameworks (MOFs) as cooperative catalysts for chemical synthesis. Cooperative catalysts accelerate two or more steps in concert, which increases the efficiency of chemical bond construction and thereby facilitates multi-step processes. Although solid catalysts are used in many catalytic reactions, they are difficult to precisely engineer for cooperative catalysis due to the inability to install spatially-controlled catalytic sites. Professor Lin and his research group are addressing this problem by using recent advances in MOFs to build multifunctional MOFs for cooperative catalysis. A bottom-up approach is being used to build recyclable and reusable multifunctional MOFs with cooperative catalytic sites and to optimize these structures for important chemical synthesis applications in the pharmaceutical, agrochemical, and fine-chemical industries. The structure-function relationships between the MOFs and the targeted catalytic processes are being studied to support continued design improvements. These activities are further being used to support research opportunities for undergraduate and high school students to improve engagement in STEM disciplines.Many natural enzymes possess multiple precisely engineered active sites to cooperatively catalyze multiple transformations of simple molecules, such as carbon dioxide, to complex molecules, such as carbohydrates, with high efficiency and selectivity. Despite the importance of solid catalysts in the production of commodity chemicals, they cannot be used for cooperative catalysis because of the lack of methods to precisely engineer uniform and synergistic catalytic centers in a spatially controlled manner in these solids. Professor Lin and his research group will utilize synthetic strategies to prepare new MOFs with large open channels/pores and multifunctional active sites for cooperative catalyst combinations including: (ii) Lewis acid and transition metal catalysts, (ii) photoredox and transition metal catalysts, or (iii) photoredox and Lewis/Bronsted acid catalysts. These MOFs will then being examined for C-C and C-heteroatom cross-coupling, olefin metathesis, and olefin oligomerization reactions. The intrinsic MOF properties are being leveraged with the aim of discovering viable new catalytic systems and developing biomimetic materials with cooperative functions. This research program will also provide important training for a diverse group of postdoctoral researchers and graduate students in the development of sustainable chemical processes for environmental stewardship.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.