EAGER: Catalysis Fundamentals of Selective Hydrogenation of Aromatic Hydrocarbons

催化剂加速化学反应，同时促进原料选择性转化为所需产品。环烯烃化合物是一类广泛应用于化学、制药和食品工业的化合物。然而，他们目前的制造依赖于低效的催化剂和多步骤的过程，产生不需要的副产品，包括危险和对环境不友好的化学物质。此外，目前的原料主要由来自化石来源的芳香烃组成。该项目解决了对与环烯烃制造相关的催化化学的更好的基本理解的需要。这些基本见解将支持能够预测催化剂配方和工艺条件的模型的发展，从而在节能的单步反应中产生高产量的目标产品。这些模型将扩展到生物质和其他可再生原料，以提高绿色化学和能源的可持续性。过渡金属催化剂的结构与芳烃反应性之间的基本关系将在分子水平上通过集中于烃类（含一个芳烃环）单步选择性加氢生成环烯烃的综合实验-理论研究建立。四氢化萘选择性加氢为辛酞将作为一个模型反应。最初的实验将集中在先前确定的由负载的Pd-Pt和Ni-Sn纳米颗粒组成的有前途的催化剂上。将根据初步结果选择其他催化剂配方。实验研究将为校准分子模型的建立提供信息，从而更好地解释实验结果，并指导后续实验的选择，从而在迭代周期中进一步完善模型。该研究将协同和迭代地结合：(1)稳态和瞬态条件下的动力学反应测量，(2)原位拉曼和红外振动光谱测量，(3)用于解释振动光谱的量子化学计算，以及用于识别反应机制的过渡态计算。反应工程的要素将通过从温度、反应物分压和反应时间数据中获得的动力学模型进行整合。除了技术方面，该项目还将使学生掌握在21世纪国际经济中竞争和成功贡献所需的关键技能，特别是在可持续化学生产和纳米技术等重要领域。研究小组还将支持研究者所在机构的本科和K-12教育推广项目。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。

Catalysts speed up chemical reactions while promoting the selective conversion of feedstocks to desired products. Cyclic olefin compounds are a class of chemical compounds that are used widely in the chemical, pharmaceutical, and food industries. Their current manufacture, however, relies on inefficient catalysts and multistep processes that produce unwanted by-products, including hazardous and environmentally-unfriendly chemicals. Moreover, current feedstocks primarily consist of aromatic hydrocarbons derived from fossil sources. The project addresses the need for better fundamental understanding of the catalytic chemistry associated with cycloolefin manufacture. The fundamental insights will support development of models capable of predicting catalyst formulations and process conditions tuned to produce high yields of targeted products in energy-efficient single-step reactions. The models will be extended to biomass and other renewable feedstocks to enhance green chemistry and energy sustainability. Fundamental relationships between the structure of transition-metal catalysts and reactivity of aromatic hydrocarbons will be established at the molecular level via an integrated experimental-theoretical study focusing on single-step selective hydrogenation of hydrocarbons (containing one aromatic ring) to cycloolefins. Selective hydrogenation of tetralin to octalin will be used as a model reaction. Initial experiments will focus on previously identified promising catalysts consisting of supported Pd-Pt and Ni-Sn nanoparticles. Additional catalyst formulations will be selected based on the initial results. Experimental studies will provide information for the development of calibrated molecular models, which in turn will provide a better interpretation of the experimental results, and guide the selection of follow-up experiments to further improve the models in an iterative cycle. The study will synergistically and iteratively combine: (1) kinetic reaction measurements at steady-state and transient conditions, (2) in situ Raman and infrared vibrational spectroscopic measurements and (3) quantum-chemical calculations for interpretation of vibrational spectra, and transition state calculations for identification of reaction mechanisms. Elements of reaction engineering will be incorporated through kinetic models developed from data obtained over a range of temperature, reactant partial pressure, and reaction-time data. In addition to the technical aspects, the project will enable students to master critical skills needed to compete and contribute successfully in the international economy of the 21st century, particularly in the vital fields of sustainable chemical production and nanotechnology. The research team will also support undergraduate and K-12 educational outreach programs at the investigator’s institution.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.