CAREER:Revolutionizing Propylene Production via Oxidative Dehydrogenation and CO2 Dissociation in Tandem

由于页岩气资源丰富，开发低烷烃转化为烯烃的催化途径具有很高的潜在回报，是一个具有挑战性的问题。该项目的总体目标是通过创新的串联催化反应方案，提高整体转化率和选择性，彻底改变烷烃丙烯生产。该项目基于一种潜在的变革性方法，其中反应机制的新范式指导催化剂合成。将开发一个分级框架，用于合理设计和表征催化剂，这些催化剂在美国工业的能源，石化和化学部门具有重大的潜在更广泛的影响。该项目的主要目标是开发一种基于亚化学计量纳米相金属氧化物的新型双功能催化剂，该催化剂将在串联反应方案中工作，其中烷烃的氧化脱氢和二氧化碳的还原，通过解离吸附，将同时发生，而不会产生合成气。提出的新型串联反应方案有可能通过防止副反应（如焦炭的形成）和丙烯的进一步芳构化来加强丙烯的生产。提出了一种以高无定形可溶性纤维素为牺牲模板制备缺氧锐钛矿纳米片催化剂的简便合成方法。提出的实验框架是基于光学反应器原型和Operando光谱，在实际工作条件下，通过时间和空间分辨拉曼光谱在单个光学电池中同时研究金属氧化物催化剂的分子结构和反应性。研究和教育的整合重点是现代化的化学反应工程课程与教学模块的Operando光谱学。拓展工作旨在通过开发一款教授分子对称和光谱学原理的免费电脑游戏，吸引包括代表性不足的少数民族在内的K-12学生。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

The development of catalytic routes for converting lower alkanes to olefins is a challenging problem with high potential payoff due to the vast shale gas resources that have recently become available. The overarching goal of this project is to revolutionize propylene production from alkanes through an innovative tandem catalytic reaction scheme that improves overall conversion and selectivity. The project is based on a potentially transformative approach where new paradigms in reaction mechanisms guide catalyst synthesis. A hierarchical framework will be developed for rational design and characterization of catalysts with significant potential broader impact in the energy, petrochemical and chemical sectors of the US industry.The main objective of this project is to develop a new class of bifunctional catalysts based on sub-stoichiometric nanophase metal oxides that will work in a tandem reaction scheme, where oxidative dehydrogenation of alkanes and carbon dioxide reduction, via dissociative adsorption, will occur simultaneously without producing syngas. The proposed novel tandem reaction scheme has the potential to intensify on-purpose propylene production by preventing side reactions, such as coke formation, and further aromatization of propylene. A new facile synthesis method for producing oxygen-deficient anatase nanosheet catalysts is proposed by utilizing highly amorphous solubilized cellulose as a sacrificial template. The proposed experimental framework is based on optical reactor prototyping and Operando spectroscopy, where the molecular structure and reactivity of the metal oxide catalysts are studied simultaneously in a single optical cell by time- and spatially-resolved Raman spectroscopy under real working conditions. Integration of research and education is focused towards modernizing the chemical reaction engineering curriculum with teaching modules on Operando spectroscopy. Outreach efforts are aimed at engaging K-12 students, including underrepresented minorities, by developing a freeware computer game that teaches principles of molecular symmetry and spectroscopy.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.