Research Initiation Award - Beyond Traditional Dynamic Linkages: Reinforcing Chemical Stability and Complexity in Next-generation Covalent Organic Frameworks

研究启动奖为历史上黑人学院和大学的初级和中级职业教师提供支持，他们正在建立新的研究项目或重新定向和重建现有的研究项目。预计该奖项将有助于进一步提高教师的研究能力和效率，改善家庭机构的研究和教学，并使本科生参与研究经验。授予克拉克亚特兰大大学的奖项有可能扩大在几个领域的影响。拟议的研究旨在开发和表征在固态化学中重要的新型结晶多孔材料。该研究将为本科生提供一个多学科平台，探索尖端材料科学，并与国家实验室的研究人员合作。拟议的工作旨在开发下一代共价有机框架（COFs），以消除对传统动态连接（如硼和氮基连接）的共同依赖。COF是完全由轻质有机元素组成的2D和3D结晶多孔材料。由于其独特的结构特征，如高结晶度，超低密度，大表面积，多功能合成和可预先设计的结构，COFs在过去十年中一直处于多孔材料化学的前沿，并在广泛的领域获得了巨大的关注。然而，固有的化学不稳定性和结构复杂性不足阻碍了COFs的充分开发。为此，这项工作旨在通过使用有限可逆性的反应，即，亲核芳香取代和羟醛缩合。通过溶剂热法和机械化学法合成了一系列未被发现的芳基醚连接的COFs和未被取代的sp2碳共轭COFs。除了实验合成外，这项工作还将通过多管齐下的方法揭示新COF形成的潜在机制，包括模型类似物中的交换反应，计算模拟和动力学研究以及原位表征。最后，这项研究将推进下一代COFs在多相催化中的应用，并阐明迄今为止尚不清楚的结构-催化相关性，这将指导COFs的合成和增强。该项目挑战了COF化学的传统，并将生产一系列具有特殊性能的坚固有序的多孔材料，从而在广泛的应用中开辟了许多可能性，即使在恶劣的操作环境中，该奖项反映了NSF的法定使命，并被认为是值得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的支持。

Research Initiation Awards provide support for junior and mid-career faculty at Historically Black Colleges and Universities who are building new research programs or redirecting and rebuilding existing research programs. It is expected that the award helps to further the faculty member's research capability and effectiveness, improve research and teaching at the home institution, and involves undergraduate students in research experiences. The award to Clark Atlanta University has potential to broaden impacts in several areas. The proposed study intends to develop and characterize new crystalline porous materials that are important in solid state chemistry. The research will provide a multidisciplinary platform for undergraduate students to explore cutting-edge materials science and collaborate with researchers at national laboratories. The proposed work intends to develop next-generation covalent organic frameworks (COFs) that obviate the common reliance upon traditional dynamic linkages such as boron and nitrogen-based linkages. COFs are 2D and 3D crystalline porous materials entirely composed of lightweight organic elements. Due to their unique structural features such as high crystallinity, ultralow density, large surface areas, versatile synthesis, and predesignable structures, COFs have been at the forefront of porous material chemistry in the past decade and garnered enormous attention in widespread areas. However, the inherent chemical instability and inadequate structural complexity are hindering the fullest exploration of COFs. To this end, the work aims to develop the next-generation COFs beyond traditional dynamic linkages by using reactions with limited reversibility, i.e., nucleophilic aromatic substitution and aldol condensation. A series of as-yet-undiscovered aryl ether-linked COFs and unsubstituted sp2 carbon-conjugated COFs will be produced via conventional solvothermal and mechanochemical synthesis. Besides experimental synthesis, the work will unveil the underlying mechanism of new COF formation through multipronged approaches, including exchange reactions in model analogs, computational simulation, and kinetic studies coupled with in situ characterizations. Lastly, the research will advance the use of next-generation COFs in heterogeneous catalysis and elucidate hitherto poorly understood structure-catalysis correlations, which will guide the synthesis and enhancement of COFs for catalysis and beyond. This project challenges the convention of COF chemistry and will produce a series of robust well-ordered porous materials with peculiar properties, thus opening numerous possibilities in widespread applications even in harsh operating environments, which are off-limits of current COF systems.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.