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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）是具有分子尺度孔隙的周期性晶体材料，是一系列科学和工程学科中研究最广泛的材料类别之一。它们由有机配体连接的含金属离子节点组成的模块化结构使得空间和化学调谐能够选择性地将分子捕获在孔隙空间中。这些特性可以优化mof的性能，适用于多种应用，包括气体的储存和分离、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能源、运输、环境和保健部门。mof的周期性结晶特性使其能够通过衍射方法进行原子级表征，并通过各种光谱技术进行广泛表征，这些技术共同提供了与材料设计和优化相关的更多细节，而不是非晶体竞争材料，如活性炭。与沸石和类似的氧化物材料相比，mof也具有优势，因为mof由金属离子和有机配体组成的模块化结构，以及合成后化学修饰的机会，使得mof在孔径、孔形状和化学功能的空间排列方面几乎具有无限的通用性。在过去的20年里，大约有成千上万的MOFs被报道。大多数mof具有固定的孔隙大小和形状，但已知只有不到1%的mof具有柔性，即它们可以根据外部刺激改变孔隙空间。这使得设计出能够响应各种刺激的材料，包括温度、压力、光和分子客体，从而更好地控制分子捕获特性，这是mof应用的核心。该项目建立在我们最近发现的一种新的柔性“呼吸”MOF Me2NH2[In(NH2BDC)2] (SHF-61) （NH2BDC =氨基苯二羧酸盐）的基础上，该MOF表现出实质性的客体响应孔的打开和关闭行为。MOF表现出优异的CO2/N2和CO2/CH4吸附选择性，表明了工业相关气体分离的潜力，并且对不同的小分子客体具有明显不同的柔性响应，这表明潜在的主客体行为可以用于分离，检测或催化的许多应用。进一步使这种MOF与大多数其他柔性MOF不同的是，它在动态行为中保持了单晶的完整性，为单晶x射线衍射的精确和详细的结构表征提供了几乎前所未有的机会。该项目将利用这一难得的机会，深入了解客人反应灵活的行为，作为开发反应性材料的平台。我们将通过化学改性和网状合成（孔隙空间扩张）来开发一个新的材料家族。这些材料将被系统地研究，以提供广泛适用于MOF领域的基础知识，并在短期内用于选择性分子识别，包括气体分离，但也为在催化和其他领域的长期应用奠定基础。这项研究将由一个由化学家和化学工程师组成的多学科团队进行。brammer - d<e:1> ren- fletcher - oswald团队在mof的合成、表征和计算建模/模拟方面提供了丰富的经验和必要的专业知识，并建立了合作记录。在优秀实验室设施的支持下，加上与国家机构的广泛合作，专业知识将使系统和定量的调查成为可能，从而开发出多功能MOF材料家族，并为全球柔性MOF研究提供基础信息来源。