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

RUI：金属有机框架形成的机理阐明：光谱、合成和计算方法

• 批准号: 2305285
• 负责人: Douglas Genna
• 金额: $ 34.68万
• 依托单位: Youngstown State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-08-01 至 2026-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2305285&HistoricalAwards=false
• 关键词: RUI; Mechanistic; Elucidation; Formation; Metal

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.

非技术摘要：金属有机框架 (MOF) 是一类材料，在碳捕获、水净化和催化等多种工业和社会相关应用中显示出前景。除了选定的例子外，通用且稳健的 MOF 大规模合成的开发已被证明难以捉摸，限制了在更大社区的广泛实施。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，这种方法既耗时又昂贵。在该项目中，扬斯敦州立大学的 Douglas Genna 教授和他的研究小组在材料研究部固态和材料化学项目的支持下，结合了合成、光谱和计算建模工具，开发了两种成功的机理模型。以及不成功的MOF合成反应。这些机械模型将识别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为现有 MOF 材料开发可靠的合成方案，并为探索新的化学空间提供机会和指导，同时限制猜测。正在开发一个在线讲座系列，以提高成人的科学和化学素养。技术摘要：MOF 是一类材料，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。尽管人们在 MOF 自组装机制方面进行了出色的工作，但这仍然是一个尚未得到充分研究的研究领域。该项目由材料研究部固态和材料化学项目支持，重点了解金属有机框架（MOF）形成的溶液相机制。具体来说，使用合成、密度泛函理论 (DFT) 和原位拉曼光谱工具研究由第 13 族金属（Al、Ga 和 In）组成的 MOF。使用 DFT 研究 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合成目标。使用原位拉曼光谱来询问溶液中所述中间体的存在。使用拉曼光谱、粉末 X 射线衍射、核磁共振、DFT 和适当的合成来研究不成功的 MOF 合成（目标 3）的溶液相和固态非 MOF 产物。该奖项反映了 NSF 的法定使命和通过使用基金会的智力优点和更广泛的影响审查标准进行评估，该项目被认为值得支持。