Quantifying the Dynamic Response in Metal-Organic Frameworks (MOFs): A Platform for Tuning Chemical Space in Porous Materials

量化金属有机框架 (MOF) 的动态响应：调节多孔材料化学空间的平台

基本信息

批准号：
EP/T034068/1
负责人：
Lee Brammer
金额：
$ 63.87万
依托单位：
University of Sheffield
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2021
资助国家：
英国
起止时间：
2021 至无数据
项目状态：
未结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FT034068%2F1
关键词：
Quantifying Dynamic Response Metal Organic

项目摘要

Metal-organic frameworks (MOFs) are periodic crystalline materials with molecular-scale pores that are among the most widely studied classes of materials across a range of scientific and engineering disciplines. Their modular construction from metal-ion-containing nodes linked by organic ligands enables both spatial and chemical tuning to selectively trap molecules in the pore space. These features allow the performance of MOFs to be optimised for numerous applications including storage and separation of gases, detection of molecules, environmental remediation, catalysis and drug delivery. Their potential impact therefore spans the energy, transport, environmental and health care sectors.The periodic crystalline nature of MOFs makes them amenable to atomic-level characterisation by diffraction methods and extensive characterisation by a variety of spectroscopic techniques, which collectively provide far greater detail pertinent to materials design and optimisation than for non-crystalline competitor materials such as activated carbons. MOFs also present advantages over established crystalline porous materials such as zeolites and similar oxide materials as the modular construction of MOFs from metal ions and organic ligands and the opportunity for post-synthesis chemical modification enables almost limitless versatility in pore size, pore shape and spatial arrangement of chemical functionality. Some 10s of thousands of MOFs have been reported in the past 20 years. Most MOFs have fixed pore sizes and shape, but less than 1% are known to be flexible i.e. they change their pore space in response to an external stimulus. This allows the design of materials that can respond to a variety of such stimuli, including temperature, pressure, light and molecular guests, allowing finer control of molecular capture properties at the heart of applications of MOFs.This project builds on our recent discovery of a new flexible 'breathing' MOF Me2NH2[In(NH2BDC)2] (SHF-61) (NH2BDC = aminobenzenedicarboxylate), which exhibits a substantial guest-responsive pore opening and closing behaviour. The MOF exhibits excellent CO2/N2 and CO2/CH4 adsorption selectivity, indicating potential for industrially relevant gas separation, and has markedly different flexible responses to different small molecule guests, which suggests an underlying host-guest behaviour that can be exploited for many applications in separations, detection or catalysis. What further sets this MOF apart, even from most other flexible MOFs, is that it retains its integrity as single crystals during dynamic behaviour, providing an almost unprecedented opportunity for accurate and detailed structural characterisation by single-crystal X-ray diffraction. This project will exploit this extraordinary opportunity for insight into guest-responsive flexible behaviour as a platform for development of responsive materials. We will develop a new family of materials by chemical modification and reticular synthesis (pore-space expansion). These materials will be studied systematically to provide a broad range a fundamental knowledge applicable to the MOF field, and exploited in the short-term for selective molecular recognition including gas separation, but also to build a foundation for longer-term applications in catalysis and other areas. The research will be conducted by a multi-disciplinary team of chemists and chemical engineers. The Brammer-Düren-Fletcher-Oswald team provide extensive experience and the necessary expertise in synthesis, characterisation and computational modelling/simulation of MOFs and an established record of collaboration. Specialised expertise supported by excellent laboratory facilities and complemented by extensive engagement with national facilities will enable a systematic and quantitative investigation leading to development of a versatile family of MOF materials and a source of fundamental information for research worldwide on flexible MOFs.

金属有机框架（MOF）是带有分子规模毛孔的周期性晶体材料，是一系列科学和工程学科中最广泛研究的材料类别。它们从有机配体连接的含金属离子的节点的模块化结构使空间和化学调整可以选择性地将分子捕获到孔隙空间中。这些功能允许对MOF的性能进行优化，以针对多种应用，包括储存和分离，分子的检测，环境修复，催化和药物输送。因此，它们的潜在影响跨越了能量，运输，环境和医疗保健领域。MOF的周期性结晶性质使它们可以通过衍射方法来表征原子水平的特征，并通过各种光谱技术进行了广泛的特征，这些技术与非材料设计和优化相比，与非crystalline竞争者相比，这些技术统一提供了更大的详细信息。 MOF还具有与已建立的晶体多孔材料（例如沸石和类似的氧化物材料）相似的优势，例如金属离子和有机配体的MOF的模块化结构，以及合成后化学修饰的机会，使孔隙大小，毛孔形状和化学功能的空间布置几乎无限。在过去的20年中，已有大约10秒的MOF。大多数MOF具有固定的孔径和形状，但已知少于1％的孔具有柔韧性，即它们因外部刺激而改变孔隙空间。这允许设计可以响应各种此类刺激的材料，包括温度，压力，光和分子来宾，从而可以更好地控制MOF的应用中的分子捕获属性。该项目以我们最近发现的新型灵活的“呼吸” MOF ME2NH2 [（NH2BDC）[IN（NH2BDC）2]（nh2bdc）（nhf-f-61（nh 2b）（nh 2bd2）（nH2bd2）（nH2BD）（nH2BD）（nH2BD）（nH2BD）（nH2BD）（nh2bd2）氨基苯基辅助酯），它表现出很大的客人响应性孔隙开口和闭合行为。 MOF表现出出色的CO2/N2和CO2/CH4吸附选择性，表明可能具有工业相关的气体分离的潜力，并且对不同的小分子来宾具有明显不同的柔性响应，这表明可以在分离，检测或催化的许多应用中探索一种潜在的宿主 - 获得式行为。即使与大多数其他灵活的MOF相比，该MOF的进一步设置是在动态行为过程中保留其作为单晶的完整性，从而提供了几乎前所未有的机会，可以通过单晶体X射线衍射来准确，详细的结构表征。该项目将利用这个非凡的机会来深入了解客人响应的灵活行为，作为开发响应材料的平台。我们将通过化学修饰和网状合成（孔隙空间膨胀）开发新的材料家族。这些材料将被系统地研究，以提供广泛的范围，一种适用于MOF领域的基本知识，并在短期内探讨了选择性分子识别，包括气体分离，但也为在催化和其他领域的长期应用建立基础。该研究将由化学家和化学工程师的多学科团队进行。 Brammer-Düren-Fletcher-Oswald团队在MOF的合成，表征和计算建模/仿真以及既定的协作记录方面提供了丰富的经验和必要的专业知识。由优秀的实验室设施支持的专业知识并通过与国家设施的广泛互动完成的专业知识将实现系统性和定量的投资，从而开发多功能的MOF材料家族，并提供全球范围内有关灵活MOF研究的基本信息的来源。