Multivariate, flexible MOFs: The role of functionalized linkers, heterogeneity and defects

多元、灵活的 MOF：功能化连接体、异质性和缺陷的作用

• 批准号: 323219031
• 负责人: Professor Dr. Roland A. Fischer
• 金额: --
• 依托单位: Lehrstuhl für Anorganische und Metallorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/323219031?language=en
• 关键词: Multivariate; flexible; MOFs; role; functionalized

Based on the collaboratively obtained results in FOR 2433 during the 1st period, the project S1 will primarily focus on research questions related to materials functions, namely on QF2 the design, synthesis and characterization of switchable catalysts catG@MOF in the 2nd period of funding. The notation catG refers to a catalytically active guest, which includes structurally defined molecular catalyst (established from homogeneous catalysis) as well as surfactant stabilized metal nanoparticles. The underlying research question (QP3) is how defects, disorder and heterogeneity will influence the responsive behavior of the parent flexible MOFs. Therefore S1 will also study the more general effects of inclusion of defG, which denotes defect generating but catalytically inactive guests (for example, nanoscale polystyrene and silica beads etc.). Addressing QF2, however, requires flexible MOF candidates, which show a switching behavior under multicomponent conditions in the solid/liquid and as well in the solid/gas situation (QF1 which is based on the knowledge about QP4, specific vs. non specific adsorption/switching). These mixed adsorption phenomena will be studied on a selection of flexible MOFs made available by S1 and S2. A second, however related work package will deal with the elucidation of the mechanistic origin of the ultrahigh kinetic selectivity in light hydrocarbon adsorption at special polymorphs of the fu-MOF family, namely the honeycomb net structures [Zn2(fu-bdc)2(bipy)] system. This fu-MOF features a rigid framework and does not undergo a phase transition during guest uptake/release. However, in case of C3 functional alkylether side groups -OR (R: propyl, vinyl, propinyl) at the bdc backbone we observed spectacular selective adsorption of propene over propane and propyne. A combined time–resolved multicomponent gas/solid adsorption study (including break-through experiments with S2) and solid-state NMR study (using deuterated hydrocarbon guest molecules with P1) will be performed together with theoretical modeling (e.g. mobility and diffusion, T2).

基于在第一阶段合作获得的FOR 2433结果，项目S1将主要关注与材料功能相关的研究问题，即在第二阶段资助中，QF 2可切换催化剂catG@MOF的设计，合成和表征。符号catG是指催化活性客体，其包括结构上定义的分子催化剂（由均相催化建立）以及表面活性剂稳定的金属纳米颗粒。潜在的研究问题（QP 3）是缺陷、无序和异质性将如何影响母体柔性MOF的响应行为。因此，S1还将研究包含defG的更一般的影响，defG表示产生缺陷但无催化活性的客体（例如，纳米级聚苯乙烯和二氧化硅珠等）。然而，解决QF 2需要灵活的MOF候选者，其在固体/液体以及固体/气体情况下的多组分条件下显示出切换行为（QF 1，其基于关于QP 4的知识，特异性与非特异性吸附/切换）。这些混合的吸附现象将在S1和S2提供的一系列柔性MOFs上进行研究。第二，然而，相关的工作包将处理在特殊的多晶型物的fu-MOF家族，即蜂窝状网状结构[Zn 2（fu-bdc）2（bipy）]系统的轻烃吸附的吸附动力学选择性的机理起源的阐明。这种fu-MOF具有刚性框架，并且在客体吸收/释放期间不经历相变。然而，在bdc骨架处的C3官能烷基醚侧基-OR（R：丙基、乙烯基、丙炔基）的情况下，我们观察到丙烯相对于丙烷和丙炔的显著选择性吸附。将结合时间分辨多组分气体/固体吸附研究（包括S2的突破实验）和固态NMR研究（使用P1的氘代烃客体分子）以及理论建模（例如迁移率和扩散，T2）。