Metal-Organometallic Frameworks Supporting Catalytically Active Moieties

技术概述：该项目得到材料研究部(DMR)固体与材料化学(SSMC)计划的支持。多年来，金属有机骨架(MOF)一直处于发现新材料的前沿，其应用取决于孔隙率的显示。乔治城大学K·特拉维斯·霍尔曼教授和他的同事所支持的研究与迄今在金属有机框架(MOF)化学方面的广泛努力是协同的，但不是典型的。这项工作旨在开发具有金属环戊二烯或金属芳烃取代基的微孔金属-有机金属骨架(MOMF)，最终用于多相催化。这项研究将涉及开发新的芳基羧酸盐配体家族，这些配体上添加了各种有机金属部分。类似于利用芳基羧酸盐配体来维持传统MOF材料的微孔率，新的有机金属芳基羧酸盐可以衍生出大量的金属-有机金属骨架。初步数据表明，有机金属配体与MOF的合成是完全相容的，可以得到具有大孔容的微孔MOMF，新的和/或现有的MOF结构可以支持所讨论的有机金属部分。由此得到的有机金属基团是并将由此产生的有机金属部分是已知的有机金属催化剂的可行的化学前体。将致力于这些部分的合成后活化，以应用于广泛的原子经济有机转化的多相催化。将对活化参数和基准反应进行研究。该提案旨在显著拓宽现有的基于MOF的多相催化剂的范围，并将其扩展到迄今为止尚未研究过的多孔材料中的反应。非技术概述：微孔材料-即那些在单个小分子(2 Nm)的尺寸尺度上具有永久、可访问通道的材料在工业环境中找到大量应用：离子交换、选择性吸附、分离、重要的大小规模的化学转化等。它们大规模地融入世界经济，并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、二氧化碳封存、其他形式的环境补救，包括核废物补救、气体/燃料储存、商品和特种化学品)正在继续开发。金属有机骨架(MOF)在过去15多年里可能是最有前途的一类新型微孔材料，在许多迅速崛起的MOF应用中，最有前途的应用之一是用作多相催化剂-即促进新的、商业上相关的化学转化。在材料研究部固态和材料化学项目的支持下，该项目寻求通过开发可描述为金属-有机金属骨架(MOMF)的新的类似材料家族来极大地扩大MOF材料的范围。MOMFS将把重要的已知和新兴催化剂集成到微孔MOF结构中，从而提高这些催化剂的化学性质和工业兼容性。这笔资金将支持五个博士生年、几个本科生和高中生的教育。该项目还力求通过在多个方面进行教育宣传，扩大这项以材料为导向的工作的影响。这项拟议的工作试图为NSF促进科学/工程领域的成就和进步的使命做出重大贡献，并通过整合教育发展和对国家各种化学技术产生影响的基础研究来为国家做出贡献的潜力。

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.