Developing Late Metal Catalytic Systems for Aerobic Partial Oxidation of Alkanes

在化学系化学催化和化学结构、动力学和机制B项目的支持下，宾夕法尼亚大学的Karen Goldberg教授正在研究将促进天然气选择性转化为有用化学品的催化剂的开发。甲烷是天然气的最大成分，是气候变化的重要贡献者。目前，大量天然气被燃烧(在没有能量捕获的情况下燃烧以产生二氧化碳和水)，因为甲烷是一种比二氧化碳更强的温室气体，将其作为气体运输或在现场将其转化为液体是无利可图的。该项目的研究人员正在努力设计金属化合物，这些化合物将作为催化剂，在温和的条件下利用空气中的氧气直接将天然气转化为更高价值的产品。将对特定金属化合物的选择性裂解和关键化学键的形成进行详细研究，以确定这些催化剂的重要设计原则。在强调增加科学多样性的同时，该项目还在培训研究生，并为他们提供创造性地应对未来社会面临的挑战所需的研究技能。过渡金属配合物具有选择性地激活烷烃的C-H键的独特能力。然而，许多这种选择性的C-H键裂解反应在空气或氧气存在下是不可行的。这种情况阻碍了大规模进行烷烃选择性部分氧化的技术的发展，因为氧气被认为是最有希望的氧化剂。这个项目的目标是开发过渡金属络合物，它可以使用空气或氧气作为氧化剂，选择性地激活和官能化C-H键。Goldberg团队的研究人员将探索在氧气和水存在的情况下激活烷烃C-H键的新机制。将对烷烃C-H活化的产物金属烷基和氢化物与氧的反应进行详细的机理研究，以了解如何在天然气改质中加入氧作为氧化剂。参与这些活动的学生将学习合成技能和假说驱动的机械方法来发现和优化催化剂，同时参与推广活动，并被鼓励参与拓宽化学领域的包容性思维。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 and the Chemical Structure, Dynamics, and Mechanism B Programs in the Division of Chemistry, Professor Karen Goldberg of the University of Pennsylvania is studying the development of catalysts that will promote the selective conversion of natural gas to useful chemicals. Methane, the largest component of natural gas, is a significant contributor to climate change. Currently large amounts of natural gas are flared (burned without energy capture to produce carbon dioxide and water) because methane is a more potent greenhouse gas than carbon dioxide, and it is not profitable to transport it as a gas or convert it onsite to a liquid. The researchers on this project are working to design metal compounds that will act as catalysts to directly convert natural gas to higher-value products under mild conditions using the oxygen in air. Detailed studies of the selective cleavage and formation of key chemical bonds by specific metal compounds will be carried out to determine the important design principles for these catalysts. With a strong emphasis on increasing diversity in science, this project is also training graduate students and providing them with the research skills needed to creatively address future challenges facing society. Transition metal complexes have shown a unique ability to selectively activate the C-H bonds of alkanes. However, many of these selective C-H bond cleavage reactions are not viable in the presence of air or oxygen. This condition presents an impediment to the development of technologies to carry out the selective partial oxidation of alkanes on a large scale, where oxygen is considered the most promising oxidant. This project targets the development of transition metal complexes that can selectively activate and functionalize C-H bonds using air or oxygen as the oxidant. The researchers on the Goldberg team will explore new mechanisms for the activation of alkane C-H bonds that proceed in the presence of oxygen and water. Detailed mechanistic studies of the reactions of metal alkyl and hydride complexes, the products of alkane C-H activation, with oxygen will be carried out to learn how to incorporate oxygen as the oxidant in natural gas upgrading. Students involved in these activities will learn synthetic skills and a hypothesis-driven mechanistic approach to catalyst discovery and optimization, while participating in outreach activities and being encouraged to participate in broadening inclusive thinking in chemistry.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.