Metal-Organometallic Frameworks Supporting Catalytically Active Moieties

支持催化活性部分的金属-有机金属框架

• 批准号: 1106266
• 负责人: Kevin Holman
• 金额: $ 40.5万
• 依托单位: Georgetown University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-06-15 至 2015-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1106266&HistoricalAwards=false
• 关键词: Metal; Organometallic; Frameworks; Supporting; Catalytically

TECHNICAL SUMMARY:This project is supported by the Solid State and Materials Chemistry (SSMC) program in the Division of Materials Research (DMR). Metal-organic frameworks (MOFs) have for some years now been at the forefront in the discovery of new materials with applications dependent upon the exhibition of porosity. The supported research of Professor K. Travis Holman and coworkers at Georgetown University is synergistic with, but atypical of, the extensive efforts in metal-organic framework (MOF) chemistry to date. The work aims to develop microporous metal-organometallic frameworks (MOMFs) possessing metallocyclopentadienyl or metalloarene substituents, ultimately for use in heterogeneous catalysis. The research will involve the development of new families of aryl carboxylate ligands to which are appended various organometallic moieties. In analogy to the exploitation of aryl carboxylate ligands to sustain microporosity in traditional MOF materials, a large number of metal-organometallic frameworks can be derived from the new organometallic arylcarboxylates. Preliminary data shows that the organometallic ligands are fully compatible with MOF syntheses, microporous MOMFs with large pore volumes can be achieved, and new and/or existing MOF architectures can sustain the organometallic moieties in question. The resulting MOMFs are and will thereby be engendered with organometallic moieties that are feasible chemical precursors to known organometallic catalysts. Efforts will be directed at the post-synthetic activation of these moieties for application as heterogeneous catalysis for a wide range of atom-economic organic transformations. Activation parameters and benchmark reactions will be studied. The proposal seeks to significantly broaden the range of available heterogeneous MOF-based catalysts and extend them to hitherto unstudied reactions in porous materialsNON-TECHNICAL SUMMARY:Microporous materials - that is, those that possess permanent, accessible channels on the size-scale of individual small molecules ( 2 nm) find a host of applications in industrial settings: ion-exchange, selective sorption, separations, important large and small scale chemical transformations, etc. They are integrated into the world economy on a large scale and new microporous materials with improved performance in a variety of traditional and emerging areas (e.g., fuel cell membrane technology, separations and fuel refinement technologies, CO2 sequestration, other forms of environmental remediation including nuclear waste remediation, gas/fuel storage, commodity and specialty chemicals) are continually being developed. Metal-organic frameworks (MOFs) have emerged in the past 15+ years as probably the most promising class of new microporous materials and, of the many rapidly emerging applications for MOFs, one of the most promising is in their use as heterogeneous catalysts - i.e. to facilitate new, commercially relevant chemical transformations. With support from the Solid-State and Materials Chemistry program in the Division of Materials Research, this project seeks to dramatically expand the scope of MOF materials through the development of a new family of analogous materials that can be described as metal-organometallic frameworks (MOMFs). MOMFs will integrate important known and emerging catalysts into microporous MOF architectures leading to enhanced chemical properties and greater industrial compatibility for these catalysts. The funds will support the education of five PhD student-years, several undergraduate students, and high school students. The project also seeks to broaden the impact of this materials-oriented work via educational outreach on multiple fronts. The proposed work attempts to significantly contribute to the NSF's mission to promote achievement and progress in science/engineering and its potential to contribute to the Nation by integrating educational development and basic research that is impactful to the nation's various chemical technologies.

该项目由材料研究部（DMR）的固态和材料化学（SSMC）计划支持。金属有机框架（MOFs）多年来一直处于发现新材料的最前沿，其应用取决于孔隙率的表现。K教授的支持研究。Travis Holman和他在乔治城大学的同事与迄今为止在金属有机框架（MOF）化学方面的广泛努力是协同的，但不是典型的。这项工作的目的是开发微孔金属-有机金属框架（MOMF）具有双环戊二烯或金属芳烃取代基，最终用于多相催化。该研究将涉及开发新的芳基羧酸酯配体家族，其附加有各种有机金属部分。类似于利用芳基羧酸酯配体来维持传统MOF材料中的微孔性，大量的金属-有机金属框架可以衍生自新的有机金属芳基羧酸酯。初步数据显示，有机金属配体与MOF合成完全相容，可以实现具有大孔体积的微孔M0 MF，并且新的和/或现有的M0 F结构可以维持所讨论的有机金属部分。所得的MOMF是并且将由此由有机金属部分产生，所述有机金属部分是已知有机金属催化剂的可行的化学前体。努力将针对这些部分的合成后活化的应用程序作为多相催化的原子经济的有机转化的范围很广。活化参数和基准反应将进行研究。该提案寻求显著拓宽可用的基于多相MOF的催化剂的范围，并将它们扩展到迄今为止未研究的多孔材料中的反应。非技术概述：微孔材料-即，在单个小分子的尺寸尺度（2nm）上具有永久的、可进入的通道的那些材料在工业环境中找到许多应用：离子交换、选择性吸附、分离、重要的大规模和小规模化学转化，它们大规模地融入世界经济，并且在各种传统和新兴领域（例如，燃料电池膜技术、分离和燃料精炼技术、CO2封存、其它形式的环境补救（包括核废料补救、气体/燃料储存、商品和专用化学品）正在不断发展。 金属有机框架（MOFs）在过去的15年中已经出现，可能是最有前途的一类新的微孔材料，并且在MOFs的许多快速出现的应用中，最有前途的应用之一是它们作为非均相催化剂的用途-即促进新的商业相关的化学转化。 在材料研究部门的固态和材料化学计划的支持下，该项目旨在通过开发一系列新的类似材料来大幅扩展MOF材料的范围，这些材料可以被描述为金属-有机金属框架（MOMF）。MOMF将重要的已知和新兴催化剂整合到微孔MOF架构中，从而增强这些催化剂的化学性质和更大的工业兼容性。 这些资金将支持五个博士生学年，几个本科生和高中生的教育。该项目还力求通过多方面的教育外联活动扩大这一注重材料的工作的影响。建议的工作试图通过整合教育发展和对国家各种化学技术有影响的基础研究，为NSF促进科学/工程成就和进步的使命及其为国家做出贡献的潜力做出重大贡献。