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Metal-Organic Frameworks Derived from Zero-Valent Metal Substrates: Mechanisms of Formation and Modulation of Properties

机译:零价金属基质衍生的金属有机骨架:形成机理和性能调控

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摘要

The replicative construction of metal-organic frameworks (MOFs) templated with solvent-insoluble solid substrates is of marked importance, as it allows for the assembly of 2D and 3D macro- and mesoscopic architectures with properties that are challenging to attain by the conventional solution-based synthesis approach. This work reports an in situ and direct construction of MOFs from zero-valent metal substrates via a green hydrothermal oxidation-MOF construction chemistry without the use of any additional metal source, chemical reagents, or acidification of solvent, and elucidates the zero-valent metal derived formation mechanisms of MOFs and their structure modulation to 1D nanofibers (NFs), 2D film, and 3D core-shell microstructures. Through modulation of the competing surface oxidation-dissolution and MOF crystallization kinetics, Al@MIL-53 core-shell microstructures and MIL-53 (Al) NFs are obtained that exhibit unique morphologies and marked properties superior to the conventional MIL-53 (Al) powders. The generality of zero-valent metal-templated synthesis of MOFs is demonstrated with formation of MIL-53 (Al), HKUST-1, and ZIF-7 polycrystalline films on Al, Cu, and Zn metal meshes, elucidating the significance of the approach utilizing solid metal substrate that can be easily processed into various shapes, architectures, and compositions.
机译:以溶剂不溶性固体底物为模板的金属有机骨架(MOF)的复制结构具有重要意义,因为它允许组装2D和3D宏观和介观结构,而这些特性对于传统解决方案来说很难实现:基于综合的方法。这项工作报告了通过绿色水热氧化-MOF构造化学方法从零价金属基质原位直接构建MOF的过程,而无需使用任何其他金属来源,化学试剂或溶剂酸化,并阐明了零价金属推导了MOF的形成机理及其对1D纳米纤维(NFs),2D薄膜和3D核-壳微结构的结构调节。通过调节竞争性的表面氧化溶解和MOF结晶动力学,获得了Al @ MIL-53核壳微结构和MIL-53(Al)NF,它们表现出独特的形态和明显的性能,优于传统的MIL-53(Al)粉末。通过在Al,Cu和Zn金属网上形成MIL-53(Al),HKUST-1和ZIF-7多晶膜证明了MOF的零价金属模板合成的普遍性,从而阐明了该方法的重要性利用可以很容易地加工成各种形状,结构和成分的固体金属基材。

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