RUI: Mechanistic Elucidation of the Formation of Metal-organic Frameworks: A Spectroscopic, Synthetic, and Computational Approach

金属有机框架（MOFs）是一类在碳捕获、水净化和催化等几个工业和社会相关应用中显示出前景的材料。除了选定的例子，一般的和强大的大规模的MOFs合成的发展已被证明是难以捉摸的，限制了广泛的实施，以更大的社区。目前优化MOF合成以扩大规模的努力通常集中在试错型方法上，这可能是耗时且昂贵的。通过这个项目，在材料研究部的固态和材料化学计划的支持下，道格拉斯Genna教授和他在扬斯敦州立大学的研究小组结合了合成，光谱和计算建模的工具，开发成功和不成功的MOF合成反应的机理模型。这些机理模型将确定成功所需的化学物质，并阐明导致合成尝试失败的有害物质。然后，从业者可以使用这些信息来为现有的MOF材料开发稳健的合成方案，并为探索新的化学空间提供机会和指导，同时限制猜测。MOFs是一类在催化、药物输送、分子分离和能量存储等领域继续显示出前景的材料，其应用领域包括催化、药物输送、分子分离和能量存储等。虽然在MOF自组装的机制上已经进行了出色的工作，但这仍然是一个研究不足的研究领域。该项目由材料研究部的固态和材料化学计划支持，重点是了解金属有机框架（MOFs）形成的溶液相机制。具体而言，MOFs组成的第13族金属（Al，Ga和In）的合成，密度泛函理论（DFT）和原位拉曼光谱的工具进行了研究。使用DFT研究In衍生的无限链和阳离子三聚体（目标1）和阴离子Ga-MOFs（目标2）的形成，以识别用于合成的潜在分子和聚合物中间体目标。使用原位拉曼光谱来询问所述中间体在溶液中的存在。使用拉曼光谱、粉末X射线衍射、核磁共振、DFT和适当的合成方法研究不成功的MOF合成的溶液相和固态非MOF产物（目标3）。该奖项反映了NSF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。

NON-TECHNICAL SUMMARY:Metal-organic frameworks (MOFs) are a class of materials that have shown promise in several industrially and societally relevant applications including carbon capture, water purification, and catalysis. Except for select examples, the development of general and robust large-scale syntheses of MOFs has proven elusive, limiting broad implementation to the greater community. Current efforts to optimize MOF syntheses for scale-up often focus on trial-and-error type approaches that can be time-consuming and costly. With this project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, Prof. Douglas Genna and his research group at Youngstown State University combines the tools of synthesis, spectroscopy, and computational modeling to develop mechanistic models of both successful and unsuccessful MOF synthesis reactions. These mechanistic models will identify the necessary chemical species for success and elucidate the deleterious species that lead to failed synthesis attempts. This information can then be used by the practitioner to develop robust synthesis protocols for existing MOF materials and provide opportunity and guidance for the exploration of new chemical spaces while limiting guesswork. An online lecture series is being developed to increase scientific and chemical literacy in adults.TECHNICAL SUMMARY:MOFs are a class of materials that continue to show promise in areas such as catalysis, drug delivery, molecular separations, and energy storage, amongst others. While exceptional work has been performed on the mechanisms of MOF self-assembly this remains an under-studied area of research. This project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, focus on understanding the solution-phase mechanism of formation of metal-organic frameworks (MOFs). Specifically, MOFs composed of group 13 metals (Al, Ga, and In) are studied using the tools of synthesis, density functional theory (DFT), and in-situ Raman spectroscopy. The formation of In-derived infinite chains and cationic trimers (Objective 1) and anionic Ga-MOFs (Objective 2) is studied using DFT to identify potential molecular and polymer intermediate targets for synthesis. The presence of said intermediates in solution is interrogated using in-situ Raman spectroscopy. Solution-phase and solid-state non-MOF products of unsuccessful MOF syntheses (Objective 3) are studied using Raman spectroscopy, powder-X-ray diffraction, nuclear magnetic resonance, DFT, and synthesis when appropriate.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.