Heterogeneous Alkene Epoxidation Catalysts Derived via Immobilization of Tripodal Titanium Silsesquioxane Complexes

化学催化计划支持肯塔基大学的Folami T.Ladipo教授和Mark Crocker教授，他们建议的研究描述了设计含有三脚架钛倍半硅氧烷部分的多相催化剂的策略，以及全面评估所产生的催化剂在要求苛刻的底物环氧化中的合成潜力。本研究的最终目标是设计和制备比现有催化剂具有更高的活性、选择性和耐用性的多相烯环氧化催化剂。这些催化剂可用于以H_2O_2和H_2/O_2为氧化剂的烯烃环氧化反应。他们的研究将集中在通过物理包裹在聚二甲基硅氧烷(PDMS)膜中固定三脚架钛硅氧烷配合物。这还包括将钛倍半硅氧烷部分锚定到负载金(Au)纳米颗粒上，通过Au催化的H2和O2反应原位生成H2O2。关于要求苛刻的底物的环氧化反应，我们将探索所得到的催化剂的性质。这将包括在环氧化反应中电子和/或空间失活的烯烃，如烯丙醇。Folami T.Ladipo教授和Mark Crocker教授将为烯烃环氧化设计改进的催化剂。这些催化剂有望既适用于精细化学品的合成，也适用于简单脂肪族环氧化物的大规模生产。该项目将是化学系的拉迪波教授和肯塔基大学应用能源研究中心的克罗克教授之间的积极合作。这项研究将在两个地点进行，共同负责研究生和本科生的方向。因此，这项研究将为学生提供传统的以化学为基础的项目所不具备的多学科培训机会。这项拟议研究的另一个重要目标是利用研究培训来指导来自传统上在科学领域代表性不足的群体的学生。通过与历史上的黑人学院和大学(HBCU)以及地区性大学的同事合作，将招募有才华的非裔美国人和阿巴拉契亚本科生参与拟议的研究。

The Chemical Catalysis Program supports Professors Folami T. Ladipo and Mark Crocker, both at the University of Kentucky whose proposed research describes strategies for the design of heterogeneous catalysts incorporating tripodal Ti silsesquioxane moieties, and for fully assessing the synthetic potential of the resulting catalysts in the epoxidation of demanding substrates. The ultimate goal of the proposed research is the design and preparation of heterogeneous alkene epoxidation catalysts possessing improved activity, selectivity, and durability relative to current catalysts. These catalysts should be useful in alkene epoxidation using H2O2 and H2/O2 as the oxidant. Their research will focus on the immobilization of tripodal Ti silsequioxane complexes via physical encapsulation in polydimethylsiloxane (PDMS) membranes. This also includes anchoring the Ti silsesquioxane moieties to supported Gold (Au) nanoparticles with in situ generation of H2O2 via the Au-catalyzed reaction of H2 with O2. The properties of the resulting catalysts will be explored with regard to epoxidation of demanding substrates. These will include alkenes that are electronically and/or sterically "deactivated" with respect to epoxidation, such as allylic alcohols. Professors Folami T. Ladipo and Mark Crocker will design improved catalysts for olefin epoxidation. These catalysts are anticipated to be applicable to both fine chemicals synthesis and bulk production of simple aliphatic epoxides. The project will be an active collaboration between Professor Ladipo at the Department of Chemistry and Professor Crocker at the University of Kentucky's Center for Applied Energy Research. The research will be conducted at both locations, with joint responsibility for the direction of graduate and undergraduate students. Thus, this research will provide multidisciplinary training opportunities to students that would not be typically available in a traditional chemistry based project. Another vital objective of the proposed research is using research training to mentor students from groups traditionally under-represented in science. Through collaborations with colleagues at historically black colleges and universities (HBCUs) as well as regional universities, talented African American and Appalachian undergraduate students will be recruited to participate in the proposed research.