Defect Creation in Surface Mounted Metal-Organic Framework Thin Films.
Defect Creation in Surface Mounted Metal-Organic Framework Thin Films.
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DOI：
10.1021/acsami.9b18672
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发表时间：
2019-12
影响因子：
9.5
通讯作者：
Z. Wang;Sebastian Henke;M. Paulus;A. Welle;Zhiying Fan;Katia Rodewald;B. Rieger;R. Fischer
中科院分区：
文献类型：
--
作者：
Z. Wang;Sebastian Henke;M. Paulus;A. Welle;Zhiying Fan;Katia Rodewald;B. Rieger;R. Fischer
缺陷工程是一种用于定制金属有机框架（MOFs）性质的策略。大量的工作已经致力于研究的缺陷化学和结构的块体MOF，然而，报道的例子，缺陷工程表面安装的MOF（SURMOF）薄膜是罕见的。在这项工作中，通过使用缺陷产生链接器并利用液相逐步外延逐层生长（LBL），将缺陷引入到MOF薄膜中。提出了两种基于LBL的方法，即混合法和交替法，通过用一组产生缺陷的连接体H2 ip（苯甲酸）、H2OH-ip（5-羟基苯甲酸）和H2 pydc（3，5-吡啶二甲酸）部分取代母体H3 btc（苯-1，3，5-三羧酸），将缺陷引入到原型表面安装的MOF（SURMOF）HKUST-1中.通过X射线衍射、红外反射吸收光谱和拉曼光谱对所制备的“缺陷”SURMOFs的结晶性和相纯度进行了表征。的缺陷产生的连接器和类型的诱导缺陷的掺入，其特征在于通过紫外-可见光谱，飞行时间二次离子质谱，甲醇吸附，扫描电子显微镜和1H核磁共振光谱（样品消化后）。这两种方法提供了控制MOF薄膜中缺陷形成的途径。
Defect engineering is a strategy for tailoring the properties of metal-organic frameworks (MOFs). Plenty of efforts have been devoted to study the defect chemistry and structure of bulk MOFs, however, the reported example of defect-engineered surface mounted MOF (SURMOF) thin film is rare. In this work, defects were incorporated in MOF thin films by using defect generating linkers and taking advantage of the liquid-phase stepwise epitaxial layer-by-layer growth (LBL). Two methods based on the LBL, named mixing method and alternating method, are proposed for incorporating defects in the prototypical surface mounted MOF (SURMOF) HKUST-1 by partially substituting the parent H3btc (benzene-1,3,5-tricarboxylic acid) linker with a set of defect-generating linkers H2ip (isophthalic acid), H2OH-ip (5-hydroxyisophthalic acid) and H2pydc (3,5-pyridinedicarboxylic acid). The crystallinity and phase purity of the obtained "defected" SURMOFs were confirmed by X-ray diffraction, infrared reflection absorption spectroscopy and Raman spectroscopy. The incorporation of the defect generating linkers and the type of induced defects were characterized by ultraviolet-visible spectroscopy, time-of-flight secondary ion mass spectrometry, methanol adsorption, scanning electron microscopy and 1H nuclear magnetic resonance spectroscopy (after digestion of the samples). These two methods provide avenues for controlling the defects formation in MOF thin films.