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首页> 外文期刊>Crystal growth & design >Highly Porous Nanocrystalline UiO-66 Thin Films via Coordination Modulation Controlled Step-by-Step Liquid-Phase Growth
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Highly Porous Nanocrystalline UiO-66 Thin Films via Coordination Modulation Controlled Step-by-Step Liquid-Phase Growth

机译：高度多孔纳米晶UIO-66薄膜通过配位调节控制逐步液相生长

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摘要

Metal-organic frameworks (MOFs) possess exciting properties, which can be tailored by rational material design approaches. Integration of MOFs in functional nano- and mesoscale systems require selective crystallite positioning and thin-film growth techniques. Stepwise layer-by-layer liquid-phase epitaxy (LPE) emerged as one of the methods of choice to fabricate MOF@substrate systems. The layer-by-layer approach of LPE allows a precise control over the film thickness and crystallite orientation. However, these advantages were mostly observed in cases of tetra-connected dinuclear paddle-wheel MOFs and Hoffmann-type MOFs. Higher connected MOFs (consisting of nodes with 8-12 binding sites), such as the Zr-oxo cluster based families, are notoriously hard to deposit in an acceptable quality by the stepwise liquid-phase process. Herein, we report the use of coordination modulation (CM) to assist and enhance the LPE growth of UiO-66, Zr6O4(OH)(4)(bdc)(6) (bdc(2-) = 1,4-benzene-dicarboxylate) films. Highly porous and crystalline thin films were obtained with good control of the crystallite domain size and film thickness in the nanoscale regime. The crystallinity (by grazing incidence X-ray diffraction), morphology (by scanning electron microscopy, atomic form microscopy), elemental composition (by X-ray photoelectron spectroscopy), binding properties (by infrared spectroscopy), and adsorption capacity (by quartz crystal microbalance adsorption experiments) for volatile organic compounds (e.g. CH3OH) of the fabricated thin films were investigated. These results substantiate a proof-of-concept of CM-LPE of MOFs and could be the gateway to facilitate in general the deposition of chemically very robust and higher-connected MOF thin films with automatic process-controlled LPE techniques under mild synthetic conditions.
机译：金属 - 有机框架（MOFS）具有令人兴奋的特性，可通过合理的材料设计方法来定制。 MOF在功能纳米和MESCHE系统中的整合需要选择性微晶定位和薄膜生长技术。逐层逐层液相外延（LPE）作为制造MOF @衬底系统的选择方法之一。 LPE的层逐层方法允许精确控制膜厚度和微晶取向。然而，在Tetra连接的Dianclecle Paddle-Chabe Mof和Hoffmann型MOF的情况下，这些优点主要是观察到的。较高的连接MOF（由带有8-12个结合位点的节点组成），例如Zr-Oxo簇基的家族，逐步液相过程难以沉积可接受的质量。在此，我们报告使用配位调制（cm）来辅助和增强UIO-66，Zr6O4（OH）（4）（BDC）（6）（BDC（2-）= 1,4-苯的LPE生长二羧酸酯）薄膜。获得高度多孔和结晶的薄膜，并良好地控制纳米级制度中的微晶结构域尺寸和膜厚度。结晶度（通过放牧入射X射线衍射），形态（通过扫描电子显微镜，原子形式显微镜），元素组合物（通过X射线光电子能谱），结合性质（通过红外光谱）和吸附容量（通过石英晶体研究了用于制造的薄膜的挥发性有机化合物（例如CH 3 OH）的微量吸附试验。这些结果证实了MOF的CM-LPE的概念证据，并且可以是促进在轻度合成条件下具有自动过程控制的LPE技术的化学非常坚固且更高连接的MOF薄膜的通道。

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  • 来源
    《Crystal growth & design》 |2019年第3期|共10页
  • 作者

    Semrau A. Lisa; Wannapaiboon Suttipong; Pujari Sidharam P.; Vervoorts Pia; Albada Bauke; Zuilhof Han; Fischer Roland A.;

  • 作者单位

    Tech Univ Munich Dept Chem Lichtenbergstr 4 D-85748 Garching Germany;

    Tech Univ Munich Dept Chem Lichtenbergstr 4 D-85748 Garching Germany;

    Wageningen Univ Lab Organ Chem Stippeneng 4 NL-6708 WE Wageningen Netherlands;

    Tech Univ Munich Dept Chem Lichtenbergstr 4 D-85748 Garching Germany;

    Wageningen Univ Lab Organ Chem Stippeneng 4 NL-6708 WE Wageningen Netherlands;

    Wageningen Univ Lab Organ Chem Stippeneng 4 NL-6708 WE Wageningen Netherlands;

    Tech Univ Munich Dept Chem Lichtenbergstr 4 D-85748 Garching Germany;

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  • 中图分类 晶体学;
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