Synthesis of hybrid metal-organic frameworks of {FexMyM1-x-y′}-MIL-88B and the use of anions to control their structural features
Synthesis of hybrid metal-organic frameworks of {FexMyM1-x-y′}-MIL-88B and the use of anions to control their structural features
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DOI：
10.1039/c6nr05463c
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发表时间：
2016-01-01
期刊：
影响因子：
6.7
通讯作者：
Oh, Moonhyun
中科院分区：
文献类型：
--
作者：
Choi, Sora;Cha, Wonhee;Oh, Moonhyun
具有合适组成和结构特征的金属有机骨架(MOF)或配位聚合物(CP)的受控形成是金属有机骨架研究的重要课题之一。特别是，可靠地制备含有两种以上不同金属离子或有机连接物的杂化MOF，以及全面了解MOF的结构灵活性，是生产具有所需性质的MOF的核心问题。我们报道了在每个粒子中含有两种或三种金属离子的微米级杂化MOF粒子[也称为配位聚合物粒子(CPP)]的合成：{FexMyM1-x-y‘}-MIL-88B(MIL代表材料拉瓦西耶，M和M’=Ga，Co，或Mn)。扫描电子显微镜图像显示形成了均匀的微米级六角棒，能量色散X射线光谱和元素图谱图像证实了两种或三种金属离子同时进入CPP中。有趣的是，由MIL-88B制成的CPP的结构特征是通过改变结构中涉及的阴离子来控制的。在结构中加入大的乙酰丙酮阴离子得到了封闭的MIL-88B结构，具有较小的晶胞体积。然而，当加入小的氯离子时，得到了具有较大晶胞体积的开放的MIL-88B结构。用硝酸根离子合成了中间体半开放的MIL-88B结构。通过粉末X射线衍射、全图拟合和热重分析，验证了MIL-88B的三种不同结构形式。
The controlled formation of metal-organic frameworks (MOFs) or coordination polymers (CPs) with suitable components and structural features is one of the most important themes in MOF research. In particular, the reliable preparation of hybrid MOFs containing more than two different kinds of metal ions or organic linkers and a comprehensive understanding of the structural flexibility of MOFs are the central issues for the production of MOFs with the desired properties. We report the synthesis of micro-sized hybrid MOF particles [also known as coordination polymer particles (CPPs)] containing two or three kinds of metal ions in each particle: {FexMyM1-x-y'}-MIL-88B (MIL stands for Materials of Institut Lavoisier, M and M' = Ga, Co, or Mn). Scanning electron microscopy images revealed the formation of well-defined uniform micro-sized hexagonal rods, and energy-dispersive X-ray spectroscopy and elemental mapping images verified the simultaneous incorporation of two or three kinds of metal ions within the CPPs. Interestingly, the structural features of CPPs made from MIL-88B were controlled by altering the anions involved in the structure. Incorporating large acetylacetonate anions within the structure resulted in the closed MIL-88B structure with a small cell volume. However, the open MIL-88B structure with a large cell volume was obtained when small chloride anions were incorporated. The intermediate semi-open MIL-88B structure was also prepared using nitrate anions. Three different structural forms of MIL-88B were verified by powder X-ray diffraction, whole pattern fitting, and thermogravimetric analysis.