Water Adsorption in Porous Metal-Organic Frameworks and Related Materials
Water Adsorption in Porous Metal-Organic Frameworks and Related Materials
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DOI：
10.1021/ja500330a
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发表时间：
2014-03-19
影响因子：
15
通讯作者：
Yaghi, Omar M.
中科院分区：
文献类型：
--
作者：
Furukawa, Hiroyasu;Gandara, Felipe;Yaghi, Omar M.
多孔材料中的水吸附对于许多应用（例如电池、热电池和偏远地区的饮用水输送）是重要的。在这项研究中，我们已经确定了三个标准，实现高性能的多孔材料的水吸附。这些标准涉及水在孔隙中的冷凝压力、吸收能力以及材料的可回收性和水稳定性。为了寻找一种性能优异的多孔材料，我们研究和比较了23种材料的吸水性能，其中20种是金属有机框架（MOFs）。在这些MOF中，有10种锆（IV）MOF，其中的一个子集MOF-801-SC（单晶形式）、-802、-805、-806、-808、-812和-841是首次报道的。M0 F-801-P（微晶粉末形式）较早被报道并且在此研究其吸水性质。M0 F-812仅被制备和结构表征，但没有检查水吸附，因为它是M0 F-841合成的副产物。所有新的锆MOFs都是由Zr 6 O 4（OH）（4）（-CO2）（n）二级结构单元（n = 6、8、10或12）和各种形状的羧基有机连接体制成的，以制成扩展的多孔框架。确认了所有23种材料的永久孔隙率，并测量了它们的吸水性，以揭示M0 F-801-P和M0 F-841是基于上述三个标准的最高性能者;它们是水稳定的，在五次吸附/解吸循环后不损失容量，并且在室温下容易再生。X射线单晶研究和粉末中子衍射研究揭示了MOF-801中的水吸附位点的位置，并突出了孔内吸附的水分子之间的分子间相互作用的重要性。
Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset of these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)(4)(-CO2)(n) secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.