EAGER: Directed Ozonolysis in Liquid Carbon Dioxide

PI：Bala Subramanian Institution：堪萨斯大学研究中心。建议编号：1128186标题：EIGER：液态碳二氧化碳中的定向臭氧分解目标和目标：这个迫切的项目旨在为建立臭氧分解作为生产工业化学品和燃料的可行技术奠定基础。最近的发现表明，与传统溶剂相比，臭氧在液态二氧化碳中的溶解度大大提高。这一发现促使了这项旨在探索在液体二氧化碳中进行受控臭氧化是否可以在广泛的底物上进行的调查。因此，具体目标是研究(A)臭氧在惰性溶剂中的相容性和稳定性，目的是建立适合臭氧分解的介质；(B)在液体二氧化碳中脂肪酸甲酯和芳香族结构(含C=C键)的臭氧降解过程中获得的转化率和选择性。意义：臭氧分解能够通过氧化裂解多芳烃结构(如木质素)中的C=C键和直链碳氢化合物，生成丰富的有价值的中间体，如羧酸和醛。然而，由于保护反应中间体免受进一步氧化和寻找对臭氧具有惰性的可行溶剂的挑战，工业应用相对较少。研究活动：将利用一套日益复杂的模型底物来实现上述目标。初始底物将包括：(A)二苯乙烯和环己烯；(B)硬脂酸甲酯和油酸甲酯作为饱和和不饱和脂肪酸的模型；以及(C)代表木质素衍生天然产品中常见功能的芳香化合物。实验研究将得到最先进的研究基础设施的支持，该基础设施包括配备现场UV-Vis光谱的高压观察室、超声波使能的混合和用于执行反应和相平衡研究的在线采样功能。智能优点：成功完成将为臭氧在工业化学品和燃料加工中的广泛应用奠定基础，具有以下促进可持续发展的属性：在相对温和的条件下(数十巴和近环境温度)进行过程强化，高效地利用臭氧以最大化所需的产品，最大限度地减少废物和固有安全。与脂肪酸甲酯和多芳烃底物相关的成果将为木质纤维素生物质和天然油转化为燃料和化学品提供一条迄今尚未探索的反应途径。负面影响：环境催化中心的教职员工、学生和工业研究人员在跨学科环境下的协同互动预计将培养出一批经过独特培训的多样化学生，通过环境催化中心的多元化招聘工作招募。国际学生联合会有培训来自代表性不足群体的学生的历史，包括妇女和少数族裔学生，这些学生是从与Prairie View A&amp；M大学和波多黎各大学的持续伙伴关系中招募的。技术成果将被整合到正在进行的名为可持续化学过程开发的研究生课程中，该课程由化学家和工程师团队授课。

PI: Bala Subramanian Institution: University of Kansas Center for Research Inc.Proposal Numbers: 1128186Title: EAGER: Directed Ozonolysis in Liquid Carbon DioxideGoals and Objectives: This EAGER project is aimed at laying the foundation to establish ozonolysis as a viable technology for producing industrial chemicals and fuels. Recent finding indicate that O3 solubility is dramatically enhanced in liquid CO2 compared to conventional solvents. This finding has prompted this investigation aimed at exploring whether controlled ozonolysis in liquid CO2 can be performed with a broad range of substrates. Specific objectives are therefore to investigate (a) ozone miscibility and stability in inert solvents such as dense CO2 aimed at establishing appropriate media for ozonolysis; (b) the conversion and selectivities obtained during ozonolysis of fatty acid methyl esters and aromatic structures (containing C=C bonds) in liquid CO2.Significance: Ozonolysis is capable of producing a rich variety of valuable intermediates such as carboxylic acids and aldehydes by oxidative cleavage of C=C bonds and linear hydrocarbons from polyaromatic structures such as lignin. However, there are relatively few industrial applications because of the challenges to protect reaction intermediates from further oxidation and to find viable solvents that are inert to ozone. Research Activities: The aforementioned objectives will be pursued with a suite of model substrates of increasing complexity. Initial substrates will include: (a) stilbene and cyclohexene; (b) methyl stearate and methyl oleate as model saturated and unsaturated fatty acids; and (c) aromatic compounds representative of functionalities commonly found in natural products derived from lignin. The experimental investigations will be supported by a state-of-the-art research infrastructure that includes high-pressure view cells equipped with in situ UV-Vis spectroscopy, ultrasound-enabled mixing and in-line sampling features for performing the reaction and phase equilibrium studies.Intellectual Merit: Successful completion will lay the foundation for widespread applications of ozone in industrial chemicals and fuels processing, with the following attributes that promote sustainability: process intensification at relatively mild conditions (tens of bars and near-ambient temperatures), efficient O3 utilization for maximizing the desired products, waste minimization and inherent safety. The outcomes associated with fatty acid methyl esters and polyaromatic substrates will provide a hitherto unexplored reaction pathway for transforming lignocellulosic biomass and natural oils to fuels and chemicals.Broader Impacts: The synergistic interactions between faculty, students and industrial researchers in a cross-disciplinary setting at the Center for Environmentally Catalysis (CEBC) is expected to produce a diverse cadre of uniquely trained students, recruited through the CEBC?s diversity recruitment efforts. The PI has a history of training students from under-represented groups including women and minority students recruited from ongoing partnerships with Prairie View A&M University and the University of Puerto Rico. The technical outcomes will be integrated into an ongoing graduate course titled Development of Sustainable Chemical Processes, which is team-taught by chemists and engineers.