The Role of Substrate in Accelerating the Reactivity of Graphene in Diels Alder Reactions

底物在加速狄尔斯阿尔德反应中石墨烯反应活性中的作用

• 批准号: 2305006
• 负责人: Mingdi Yan
• 金额: $ 48万
• 依托单位: University of Massachusetts Lowell
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-15 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2305006&HistoricalAwards=false
• 关键词: Role; Substrate; Accelerating; Reactivity; Graphene

With support from the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry, Mingdi Yan and Lawrence Wolf from the University of Massachusetts-Lowell will explore the transformation of monolayer pristine graphene nanocarbon monolayer sheets in a controlled fashion through organic synthesis with a particular focus on the Diels-Alder reaction. Local hot spots of curved distorted sites will be created on the graphene surface over nano-featured substrates. Theoretical computations will be used to aid in rationally designing these graphene sheets with curved features. Pristine graphene has the potential to impact many technologically important applications, such as in display screens, nanoelectronics, solar cells, and various others and functionalized graphene has similar and yet to be discovered applications. The ability to functionalize graphene with well-defined chemical functionalities and in a controlled fashion is a frontier goal in the field and has the potential to provide access to novel materials with great potential for technological application. As part and parcel of this research project, graduate and undergraduate students will be trained in multidisciplinary research; specialized courses related to the research will also be developed. Furthermore, high school students of diverse backgrounds will be provided with summer research experience and K-12 students will be engaged through science presentations and workshop demonstrations. This project will integrate theory and experiment to provide mechanistic insights on how surface curvature enhances the reactivity of graphene and which substrate configurations best accelerate Diels-Alder and other cycloaddition reactions. In Aim 1, monolayer graphene supported on a metallic or insulating substrate having well-defined surface topography will be fabricated. Subsequently, Diels-Alder reactions will be carried out, and the extent of graphene functionalization will be determined to test the hypothesis that the reactivity of graphene will increase by introducing surface curvature and will further increase by using a metal substrate. In Aim 2, combined atomistic and larger scale computational methods, including density functional theory, semi-empirical, and molecular mechanics methods, will be developed and used to investigate the origins of the reactivity enhancement by surface curvature and the role of surface curvature and the resulting distorted electronic structure on the reactivity of graphene in cycloaddition reactions.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.

在化学划分的大分子，超分子和纳米化学（MSN）计划的支持下，马萨诸塞州 - 洛威尔大学的Mingdi Yan和Lawrence Wolf将探索通过有机化的焦点构成的Pocutnerssississ，探索单层原始石墨烯纳米碳单层单层纸的单层原始石墨烯纳米碳单层纸的转变。 将在纳米功能的底物上的石墨烯表面上创建弯曲扭曲位点的局部热点。 理论计算将用于协助以弯曲特征为合理设计这些石墨烯片。 原始石墨烯具有影响许多在技术上重要的应用，例如在显示屏，纳米电子，太阳能电池以及其他各种和功能化的石墨烯具有相似且尚未被发现的应用中。 通过定义明确的化学功能和受控的方式使石墨烯官能化的能力是该领域的前沿目标，并且有可能提供具有技术应用潜力的新型材料。 作为该研究项目的一部分，研究生和本科生将接受多学科研究的培训；还将开发与研究有关的专门课程。此外，将为具有不同背景的高中学生提供夏季研究经验，K-12学生将通过科学演示和讲习班演示来参与。 该项目将整合理论和实验，以提供有关表面曲率如何增强石墨烯反应性以及哪些底物配置最佳加速Diels-Alder和其他Cycloadition反应的机械见解。在AIM 1中，将制造在具有明确表面地形的金属或绝缘底物上支撑的单层石墨烯。随后，将执行Diels-Alder反应，并将确定石墨烯功能化的程度来检验假设，即石墨烯的反应性将通过引入表面曲率增加，并通过使用金属底物进一步增加。在AIM 2中，将开发并使用组合的原子和较大规模的计算方法，包括密度功能理论，半经验和分子力学方法，并使用表面曲率曲率的作用以及表面曲率的作用以及由此产生的扭曲的反应量的反应性，并在表面弯曲的作用以及对cycloadition rections的反应率的扭曲反应性的反应性的反应性的反应性上的作用。通过使用基金会的智力优点和更广泛影响的评论标准进行评估。