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

非技术概述：金属有机骨架(MOF)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。除了精选的例子外，事实证明，MOF的全面和强有力的大规模合成的发展是难以捉摸的，限制了更广泛的社区的广泛实施。目前为了扩大规模而优化MOF合成的努力往往集中在试错式方法上，这种方法可能既耗时又昂贵。在材料研究部固态和材料化学计划的支持下，杨斯敦州立大学的道格拉斯·杰纳教授和他的研究小组结合了合成、光谱和计算建模工具，开发了成功和不成功的MOF合成反应的机理模型。这些机械模型将确定成功所需的化学物种，并阐明导致合成尝试失败的有害物种。然后，从业人员可以利用这些信息为现有的MOF材料制定可靠的合成方案，并在限制猜测的同时为探索新的化学空间提供机会和指导。一个在线系列讲座正在开发中，以提高成年人的科学和化学素养。技术摘要：MOF是一类在催化、药物输送、分子分离和能量存储等领域继续展示前景的材料。虽然已经开展了关于MOF自组装机制的特殊工作，但这仍然是一个研究不足的领域。该项目得到材料研究部固态和材料化学计划的支持，重点是了解金属-有机骨架(MOF)形成的溶液相机理。具体地，利用合成、密度泛函理论(DFT)和原位拉曼光谱等手段研究了由13族金属(Al、Ga和In)组成的MOF。用密度泛函理论研究了In衍生无限链和阳离子三聚体(目标1)和阴离子Ga-MOF(目标2)的形成，以确定潜在的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、密度泛函和适当的合成方法研究了MOF合成失败(目标3)的溶液和固态非MOF产品。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。

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.