Catalytic Oxidations with Lignin-Based Ligands

国家科学基金会化学部的催化计划支持加州大学圣巴巴拉分校的马赫迪·阿布-奥马尔教授的研究计划。该项目侧重于可持续发展或“绿色化学”领域。该项目寻求生产具有重要工业意义的化学品和燃料的新方法。这项工作与全球最大的化学产品生产国美国的经济有关。化学品生产商寻求可再生的起始材料。他们还寻求在可能的情况下利用丰富的资源。化学过程中的安全是第三个考虑因素。这些目标推动了对环境友好的化学反应的研究。阿布-奥马尔教授的项目使用廉价而丰富的元素，如锰和铁，以及以植物为基础的基团来形成新的催化剂，进而加速预期的反应。对这些化学反应速率的详细分析可以深入了解催化剂在原子水平上是如何工作的。为了支持该项目的更广泛影响，阿布-奥马尔博士积极参与了一项让社区大学(CC)学生参与实验室研究的外展计划，这些学生大多来自代表性不足的群体。在化学系化学催化项目的资助下，加州大学圣巴巴拉分校(UCSB)的Mahdi Abu-Omar博士正在设计和合成基于第一排过渡金属的催化剂，特别是锰和铁。这些催化剂进一步使用基于木质素的配体(LBL)进行设计。LBL的合成是高产率的，原子经济的，并且满足绿色化学的许多原则。LBL的设计提供了一个非常适合配位化学但又抗氧化降解的基序。然后利用铁和锰-LBL络合物在常温和中性pH条件下从水溶液中的亚氯酸盐按需生成二氧化氯。二氧化氯生产的一个重要改进是避免了氧原子从催化剂转移到亚氯酸盐以生成氯酸盐，氯酸盐是一种持久性污染物。正在研究的是原位生成的二氧化氯对菲和苯酚(芳香族化合物)的氧化。在一种独特的方法中，两个催化循环串联在一起，以氧气作为化学计量氧化剂进行氧化。这一奖项反映了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。

The Catalysis Program of the Chemistry Division of the National Science Foundation supports the research program of Professor Mahdi Abu-Omar of the University of California, Santa Barbara. This project is focused on the area of sustainability or "Green Chemistry". The project seeks new ways to produce industrially important chemicals and fuels. This work is relevant to the economy of United States, the largest producer of chemical products globally. Chemical producers seek renewable starting materials. They also seek to use abundant resources when possible. Safety in a chemical process is a third consideration. These goals motivate research on chemical reactions that are environmentally friendly. Professor Abu-Omar's project uses cheap and abundant elements such as manganese and iron along with plant-based groups to form the new catalysts that in turn, speed up the desired reactions. Detailed analyses of the rates of these chemical reactions give insights into how the catalyst works on an atomic level. In support of the broader impacts of the project, Dr. Abu-Omar is actively engaged in an outreach program involving community college (CC) students, who are largely from underrepresented groups, in laboratory research. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Mahdi Abu-Omar of the University of California, Santa Barbara (UCSB) is designing and synthesizing catalysts based on first row transition metals, specifically manganese and iron. These catalysts are further designed using lignin-based ligands (LBL). The synthesis of LBL is high yielding, atom economical, and satisfies many of the Principles of Green Chemistry. The design of LBL provides a motif that is highly suited for coordination chemistry but yet resistant to oxidative degradation. Iron- and manganese-LBL complexes are then employed to generate chlorine dioxide on-demand from chlorite in aqueous solution under ambient temperature and at neutral pH. A significant improvement in chlorine dioxide production is to avoid oxygen atom transfer (OAT) from the catalyst to chlorite to make chlorate, which is a persistent pollutant. Under investigation is the oxidation of phenanthrene and phenols (aromatic compounds) by in situ generated chlorine dioxide. In a unique approach, two catalytic cycles are coupled in tandem to achieve oxidations with dioxygen as the stoichiometric oxidant.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.