Exploration of Al-based metal-organic frameworks with multiple linkers and functionalities - microscopic structuring and proton conduction

具有多个连接体和功能的铝基金属有机框架的探索——微观结构和质子传导

• 批准号: 280984923
• 负责人: Professor Dr. Jürgen Senker
• 金额: --
• 依托单位: Physikalisch-Chemisches Institut
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/280984923?language=en
• 关键词: Exploration; Al; based; metal; organic

Metal-organic frameworks represent a versatile class of porous materials, whose properties can be controlled by varying the framework topology, the organic linker molecules and by introducing guest molecules. Aluminium, which combines low weight, easy availability and low toxicity together with a high thermal and chemical stability of the Al-MOFs, is one of the most appealing ions to build such materials. Its tendency to lead to microcrystalline materials, however, often hamper the determination of structure-property relationships. This project aims at exploring Al-based MOFs based on polycarboxylate linkers, their functionalised derivatives and mixtures thereof in both aqueous and non-aqueous synthesis conditions. In particular, by varying number and arrangement of carboxylic acid groups, we expect to encourage the formation of MOFs with new inorganic building units and frameworks. Special emphasis will be placed on introducing free, acidic proton bearing groups to create materials potentially prone to proton conduction. The incorporation of amphoteric guest molecules shall help to establish efficient proton conduction pathways. To develop a better understanding for the complex interplay between the proton donor density, the incorporated guest molecules and the influence of the particle size on the proton mobility and transport, dynamical processes of framework, guests and the protons themselves will be studied systematically within this project.To accomplish this, we brought together the research groups of N. Stock and J. Senker, adding their complementary skills in synthesis and characterisation of structural and dynamical properties of Al-MOFs. For a thorough and efficient synthetic screening of new MOF topologies, the Stock group will develop two high-throughput reactors allowing to work with temperature gradients and to carry out vapour phase crystallisation reactions. For selected systems, synthetic strategies towards Al-MOF nanoparticles with controlled particle sizes will be established. For the structure elucidation, including order parameters in isomorphous MOFs and host-guest connectivities, the Senker group will rely on NMR-crystallographic approaches combining solid-state NMR spectroscopy and powder diffraction. Furthermore, solid-state NMR spectroscopy will play an essential role for analysing local dynamical processes of linkers, guests and acidic protons over a broad temperature and frequency range. To discriminate between proton mobility at the outer vs. the inner particle surfaces of the MOF nanoparticles, hyperpolarisation techniques will be used. The NMR data shall be supported by temperature dependent impedance spectroscopic investigations which will be carried out in close cooperation with Profs. Janek, Papastavrou and Wark. For most materials we will rely on the behaviour of the DC conductivity and complement these data with simulations of the AC conductivity based on equivalent circuits for selected systems.

金属有机框架是一种多用途的多孔材料，其性能可以通过改变框架拓扑结构、有机连接分子和引入客体分子来控制。铝，结合了重量轻，易于获得和低毒性以及al - mof的高热稳定性和化学稳定性，是构建此类材料最具吸引力的离子之一。然而，它倾向于导致微晶材料，这往往阻碍了结构-性能关系的确定。本项目旨在探索基于聚羧酸酯连接剂、其功能化衍生物及其混合物的铝基mof在水和非水条件下的合成。特别是，通过改变羧酸基团的数量和排列，我们希望鼓励形成具有新的无机结构单元和框架的MOFs。将特别强调引入自由的酸性质子承载基团，以创造可能倾向于质子传导的材料。两性客体分子的结合将有助于建立有效的质子传导途径。为了更好地理解质子供体密度、结合客体分子之间的复杂相互作用以及粒子大小对质子迁移和输运的影响，本项目将系统地研究框架、客体和质子本身的动力学过程。为了实现这一目标，我们汇集了N. Stock和J. Senker的研究小组，增加了他们在al - mof的结构和动力学特性的合成和表征方面的互补技能。为了对新的MOF拓扑结构进行全面有效的合成筛选，Stock集团将开发两个高通量反应器，允许在温度梯度下工作并进行气相结晶反应。对于选定的体系，将建立具有控制粒径的Al-MOF纳米颗粒的合成策略。对于结构解析，包括同构mof的有序参数和主客体连接，Senker团队将依靠核磁共振晶体学方法结合固态核磁共振波谱和粉末衍射。此外，固体核磁共振波谱将在广泛的温度和频率范围内分析连接子、客体和酸性质子的局部动力学过程中发挥重要作用。为了区分MOF纳米颗粒的外表面和内表面的质子迁移率，将使用超极化技术。核磁共振数据将由温度相关阻抗谱调查支持，该调查将与教授密切合作进行。Janek， Papastavrou和Wark。对于大多数材料，我们将依赖于直流电导率的行为，并用基于选定系统等效电路的交流电导率模拟来补充这些数据。

项目成果

Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study.

• DOI: 10.1021/jacs.7b10148
• 发表时间: 2018-01
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: T. Wittmann;Arobendo Mondal;C. B. L. Tschense;J. J. Wittmann-J.;Ottokar Klimm;Renée Siegel;B. Corzilius;Birgit Weber;M. Kaupp;J. Senker

Structure property relationships affecting the proton conductivity in imidazole loaded Al-MOFs.

• DOI: 10.1039/c6dt03048c
• 发表时间: 2016-09
• 期刊: Dalton transactions
• 影响因子: 4
• 作者: T. Homburg;C. Hartwig;H. Reinsch;M. Wark;N. Stock

Selective host–guest interactions in metal–organic frameworks via multiple hydrogen bond donor–acceptor recognition sites

通过多个氢键供体受体识别位点在金属有机框架中选择性主客体相互作用

• DOI: 10.1039/c8ta12190g
• 发表时间: 2019
• 期刊: Journal of Materials Chemistry A
• 影响因子: 11.9
• 作者: T. Wittmann;C.B.L. Tschense;L. Zappe;C. Koschnick;R. Siegel;R. Stäglich;B.V. Lotsch;J. Senker
• 通讯作者: J. Senker

New group 13 MIL-53 derivates based on 2,5-thiophenedicarboxylic acid

• DOI: 10.1002/zaac.201700260
• 发表时间: 2017-10
• 期刊: Zeitschrift für anorganische und allgemeine Chemie
• 作者: C. B. L. Tschense;N. Reimer;Chin-Wen Hsu;H. Reinsch;Renée Siegel;Wu Chen;Chia‐Her Lin;A. Cadiau-A.-Cad

Design and Precursor-based Solid-State Synthesis of Mixed-Linker Zr-MIL-140A.

• DOI: 10.1021/acs.inorgchem.0c02221
• 发表时间: 2020-09
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: S. Leubner;Renée Siegel;Julia Franke;M. Wharmby;C. Krebs;H. Reinsch;J. Senker;N. Stock