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Collaborative Research: Porous Molecules as a Platform for Solid-State Organometallic Chemistry

合作研究：多孔分子作为固态有机金属化学的平台

基本信息

批准号：
2310682
负责人：
Eric Bloch
金额：
$ 9万
依托单位：
Indiana 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：
2023-01-15 至 2023-12-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2310682&HistoricalAwards=false
关键词：
Collaborative Research Porous Molecules Platform

项目摘要

With the support of the Chemical Synthesis program in the Division of Chemistry, Eric Bloch of the University of Delaware and David Powers of Texas A&M University will study new methods for the preparation of porous catalysts. Porous materials are widely used around the world for a wide variety of applications, including water filtration and/or softening, as desiccants, and in medicine. A subset of porous materials is used on a large scale in catalytic applications, including in the cracking of hydrocarbons. A key challenge in using porous materials as catalysts, however, is controlling and optimizing their reactivity where total surface area, structure type, and stability can play a role in determining their activity. The Bloch/Powers team is building on promising preliminary results to develop a new method for the synthesis of active porous catalysts by creating reactive salts. In this method, a charged nonporous reactive organometallic species will be combined with an oppositely-charged porous non-reactive ion to afford a new class of porous solids. It is envisioned that for porous materials so constructed catalytic activity will be finely tunable across a range of useful transformations including carbon-hydrogen bond functionalization and cross-coupling reactions. In addition to this, these studies will aid in the characterization of reactive species during catalytic transformations using the tools of in situ crystallography and spectroscopy. Drs. Bloch and Powers will continue to work to increase diversity in science by bringing excitement of synthetic chemistry research to a broad audience through local and regional educational experiences, including the development of an annual online school on X-ray powder diffraction for undergraduate and graduate students.This collaborative project is targeting the development of new porous materials for site-isolated and solid-state organometallic chemistry. While designer porous solids such as zeolites and metal-organic frameworks have shown incredible promise as heterogeneous catalysts, general platforms for the development of solid-state organometallic chemistry within confined spaces remain elusive. This work seeks to combine charged, permanently porous coordination cages with complementary-charged reactive organometallic fragments for the preparation of a new class of reactive catalysts, porous salts. During this funding period, Bloch and Powers will elucidate the general structure-function properties of porous salts where cage charge, geometry, and functional group presentation will be leveraged to tune salt structure and porosity. Subsequently, Bloch and Powers will use these salts as platforms to incorporate designer reactive ions into porous solids where small molecule binding and activation will be studied to assess salt activity. Reactions to be studied will include C-H bond functionalization and cross-coupling catalysis. Finally, the Bloch/Powers team will utilize straightforward layer-by-layer growth to prepare optically transparent, chemically addressable films which will be used for solid-state photochemical transformations.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.

在化学系化学合成项目的支持下，特拉华大学的Eric Bloch和德州农工大学的David Powers将研究制备多孔催化剂的新方法。多孔材料在世界范围内广泛应用于各种应用，包括水过滤和/或软化，作为干燥剂和医学。多孔材料的一个子集在催化应用中大规模使用，包括在碳氢化合物的裂解中。然而，使用多孔材料作为催化剂的一个关键挑战是控制和优化它们的反应性，其中总表面积、结构类型和稳定性可以决定它们的活性。布洛赫和鲍尔斯的研究小组正以有希望的初步结果为基础，开发一种通过制造活性盐来合成活性多孔催化剂的新方法。在这种方法中，带电的无孔反应性有机金属将与相反带电的多孔无反应性离子结合，以提供一类新的多孔固体。可以设想，对于多孔材料，这种结构的催化活性将在一系列有用的转化中精细调节，包括碳氢键功能化和交叉偶联反应。除此之外，这些研究将有助于在催化转化过程中使用原位晶体学和光谱学工具表征反应物质。Drs。布洛赫和鲍尔斯将继续努力，通过当地和区域的教育经验，将合成化学研究的兴奋带给广大受众，从而增加科学的多样性，包括为本科生和研究生开发一个关于x射线粉末衍射的年度在线学校。这个合作项目的目标是开发新的多孔材料，用于现场隔离和固态有机金属化学。虽然沸石和金属有机框架等多孔固体作为多相催化剂已经显示出令人难以置信的前景，但在有限空间内发展固态有机金属化学的通用平台仍然难以捉摸。这项工作旨在将带电的永久多孔配位笼与互补带电的活性有机金属碎片相结合，以制备一类新的活性催化剂——多孔盐。在此资助期间，Bloch和Powers将阐明多孔盐的一般结构-功能特性，其中笼状电荷、几何形状和官能团表示将被利用来调整盐的结构和孔隙度。随后，Bloch和Powers将使用这些盐作为平台，将设计活性离子结合到多孔固体中，在多孔固体中研究小分子的结合和活化，以评估盐的活性。研究的反应包括碳氢键功能化和交叉偶联催化。最后，布洛赫/鲍尔斯团队将利用直接的逐层生长来制备光学透明、化学可寻址的薄膜，这种薄膜将用于固态光化学转化。该奖项反映了美国国家科学基金会的法定使命，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。