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

在化学系大分子、超分子和纳米化学（MSN）项目的支持下，来自马萨诸塞大学洛厄尔分校的闫明迪和劳伦斯·沃尔夫将通过有机合成，以可控的方式探索单层原始石墨烯纳米碳单层片的转化，并特别关注Diels-Alder反应。弯曲扭曲点的局部热点将在石墨烯表面的纳米基板上产生。理论计算将用于帮助合理设计具有弯曲特征的石墨烯片。原始石墨烯具有影响许多重要技术应用的潜力，例如在显示屏、纳米电子、太阳能电池和各种其他领域，功能化石墨烯具有类似的尚未被发现的应用。以可控的方式使石墨烯具有明确的化学功能是该领域的前沿目标，并有可能提供具有巨大技术应用潜力的新材料。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方面的培训；还将制定与这项研究有关的专门课程。此外，将为不同背景的高中生提供暑期研究经验，K-12学生将通过科学演讲和研讨会示范参与其中。该项目将结合理论和实验，提供关于表面曲率如何增强石墨烯反应性的机理见解，以及哪种衬底构型最能加速Diels-Alder反应和其他环加成反应。在目标1中，将制造支撑在具有明确表面形貌的金属或绝缘衬底上的单层石墨烯。随后，将进行Diels-Alder反应，并确定石墨烯的功能化程度，以验证石墨烯的反应性将通过引入表面曲率而提高，并通过使用金属衬底进一步提高的假设。在目标2中，结合原子和更大规模的计算方法，包括密度泛函理论、半经验和分子力学方法，将被开发并用于研究表面曲率增强反应性的起源，以及表面曲率和由此产生的扭曲电子结构对石墨烯在环加成反应中的反应性的作用。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。

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.