Substrate-Enhanced reactivity of pristine graphene in cycloaddition reactions

原始石墨烯在环加成反应中的基质增强反应性

• 批准号: 1808671
• 负责人: Mingdi Yan
• 金额: $ 36万
• 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: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2022-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808671&HistoricalAwards=false
• 关键词: Substrate; Enhanced; reactivity; pristine; graphene

Professors Mingdi Yan and Lawrence Wolf of the University of Massachusetts Lowell are supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) Program of the Division of Chemistry to develop experimental and computationally guided approaches to enhance the reactivity of pristine graphene (a defect-free single layer, two-dimensional carbon material). The integration of theory with experiment provides a comprehensive, fundamental understanding of the reactions leading to the acceleration of discovery. The results have a direct impact on the practical utilization of this material, which exhibit extraordinary mechanical, electrical and thermal properties. Pristine graphene has the potential to impact many technologically important applications, such as in display screens, nanoelectronics, solar cells, and various others. Pristine graphene offers advantages over other forms of graphene, which are either oxidized or contain many defects. The computational modeling techniques used are incorporated in the curriculum of new computational chemistry courses offered to both undergraduate and graduate students. The students involved in the project receive training in research planning and evaluation through individualized development plans. Under-represented and female undergraduate students are recruited to participate in the project. This project aims to expand the chemical space of pristine graphene. Specifically, the impacts of substrate and interface on the reactivity of pristine graphene in cycloaddition reactions is investigated both experimentally and computationally. Pristine graphene is fabricated on different surfaces by chemical vapor deposition or by transfer. Cycloaddition reactions, with initial focus on the (2+1) cycloaddition with perfluoroaryl azides, are carried out and the products are characterized. The study aims to shed light on the relationship between the reactivity of graphene and its supporting substrate interface. The reactivity of pristine graphene in other cycloaddition reactions is also a subject of this investigation. The theoretical underpinnings of the cycloaddition substrate/reactivity relationships with pristine graphene is established using density functional theory through the development and application of modern reactivity models. Pristine graphene is fairly inert chemically due to the large resonance stabilization resulting from the delocalization of its conjugated pi electrons over the entire two-dimensional network. Overcoming these inherent reactivity challenges offers the ability to introduce into pristine graphene well-defined functionalities. Other benefits include modulating graphene solubility and bandgap, and enabling its integration into high performance composite materials and devices.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.

马萨诸塞州洛厄尔大学的明迪·杨教授和劳伦斯·沃尔夫教授得到了化学部的大分子，超分子和纳米化学（MSN）计划，以开发实验性和计算指导性方法，以增强原始石墨烯的反应性（一种缺乏自然的单层单层），两层carbon carbon carbon corbon carbon carbon carbon carbon carbon corbon carbon carbon。 理论与实验的整合提供了对导致发现加速的反应的全面，基本的理解。 结果对该材料的实际利用产生了直接影响，该材料具有非凡的机械，电和热性能。 原始石墨烯有可能影响许多在技术上重要的应用，例如在显示屏，纳米电子，太阳能电池等。 原始石墨烯比其他形式的石墨烯具有优势，这些石墨烯要么被氧化或包含许多缺陷。 所使用的计算建模技术纳入了为本科和研究生提供的新计算化学课程的课程中。参与该项目的学生通过个性化的发展计划接受研究计划和评估的培训。招募了代表性不足和女性本科生参加该项目。该项目旨在扩大原始石墨烯的化学空间。具体而言，在实验和计算上研究了底物和界面对原始石墨烯在环加成反应中反应性的影响。原始石墨烯是通过化学蒸气沉积或通过转移在不同表面上制造的。在（2+1）和全氟叠氮化物的（2+1）环加成上，进行了环加成反应，并将其表征。 该研究旨在阐明石墨烯的反应性与其支持的底物界面之间的关系。 原始石墨烯在其他环加成反应中的反应性也是该研究的主题。 通过建立和应用现代反应性模型的开发和应用，使用密度功能理论建立了环加成底物/反应性关系的理论基础。 由于其在整个二维网络中其共轭PI电子的定位，因此原始石墨烯是化学上相当惰性的。克服这些固有的反应性挑战提供了将原始石墨烯定义明确的功能引入的能力。 其他好处包括调节石墨烯的溶解度和带量，并促进其整合到高性能复合材料和设备中。该奖项反映了NSF的法定任务，并认为使用基金会的知识分子和更广泛的影响审查标准，认为值得通过评估来获得支持。

项目成果

Removing contaminants from transferred CVD graphene

• DOI: 10.1007/s12274-020-2671-6
• 发表时间: 2020-02
• 期刊: Nano Research
• 影响因子: 9.9
• 作者: Xiaojiang Yang;Mingdi Yan

Carbohydrate Functionalization of Few-Layer Graphene through Microwave-Assisted Reaction of Perfluorophenyl Azide

全氟苯基叠氮化物微波辅助反应对少层石墨烯进行碳水化合物功能化

• DOI: 10.1021/acsabm.8b00597
• 发表时间: 2019-01-22
• 期刊: ACS APPLIED BIO MATERIALS
• 影响因子: 4.7
• 作者: Kong, Na;Park, JaeHyeung;Yan, Mingdi
• 通讯作者: Yan, Mingdi

Using metal substrates to enhance the reactivity of graphene towards Diels–Alder reactions

使用金属基底增强石墨烯对狄尔斯-阿尔德反应的反应活性

• DOI: 10.1039/d2cp01842j
• 发表时间: 2022
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Yang, Xiaojian;Chen, Feiran;Kim, Min A.;Liu, Haitao;Wolf, Lawrence M.;Yan, Mingdi
• 通讯作者: Yan, Mingdi

Synthesis of Carbohydrate-Grafted Glycopolymers Using a Catalyst-Free, Perfluoroarylazide-Mediated Fast Staudinger Reaction

• DOI: 10.3390/molecules24010157
• 发表时间: 2019-01
• 期刊: Molecules
• 影响因子: 4.6
• 作者: William Ndugire;Bin Wu;Mingdi Yan