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

研究启动奖为历史悠久的黑人学院和大学的初级和职业生涯中期教师提供支持，这些教师正在建立新的研究计划或重新定向和重建现有的研究计划。预计该奖项有助于进一步提高教师的研究能力和有效性，改善所在机构的研究和教学，并让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几个领域的影响。这项拟议的研究旨在开发和表征在固态化学中重要的新的晶态多孔材料。这项研究将为本科生提供一个多学科的平台，让他们探索尖端材料科学，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(COF)，以消除对传统动态联系的共同依赖，如基于硼和基于氮的联系。COF是完全由轻质有机元素组成的2D和3D晶态多孔材料。由于其独特的结构特征，如高结晶度、超低密度、大比表面积、合成方法多样、结构可预先设计等，在过去的十年里，COF一直处于多孔材料化学的前沿，引起了广泛领域的极大关注。然而，固有的化学不稳定性和不充分的结构复杂性阻碍了对COFS的最充分探索。为此，这项工作旨在通过使用可逆性有限的反应，即亲核芳香取代和羟醛缩合，开发出超越传统动态连接的下一代COFS。通过传统的溶剂热法和机械力化学合成法将合成一系列尚未发现的芳基醚连接的COF和未被取代的SP2碳共轭COF。除了实验合成，这项工作还将通过多管齐下的方法揭示新的COF形成的潜在机制，包括模型模拟中的交换反应、计算模拟、动力学研究以及现场表征。最后，该研究将推进下一代COF在多相催化中的应用，并阐明迄今知之甚少的结构-催化相关性，这将指导COF的合成和增强用于催化及其他领域。该项目挑战了COF化学的传统，将生产一系列具有特殊性质的坚固有序的多孔材料，从而在广泛应用中开辟了无数可能性，即使在恶劣的操作环境中也是如此，这是当前COF系统的禁区。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.