A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability
A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability
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DOI：
10.1021/ja8057953
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发表时间：
2008-10-22
影响因子：
15
通讯作者：
Lillerud, Karl Petter
中科院分区：
文献类型：
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作者：
Cavka, Jasmina Hafizovic;Jakobsen, Soren;Lillerud, Karl Petter
多孔晶体在石油化学、催化、气体储存和选择性分离等领域具有重要的工业应用价值。其独特的性质是基于分子尺度的多孔性。然而，沸石和类似的基于氧化物的材料的主要限制是孔的相对小的尺寸，通常在中等尺寸分子的范围内，限制了它们在药物和精细化学应用中的使用。金属有机框架（MOFs）在这方面提供了一个突破。新的MOFs出现的速度越来越快，但新的，稳定的无机建筑砖的出现是罕见的。在这里，我们提出了一种新的锆基无机建筑砖，允许合成具有前所未有的稳定性的非常高的表面积的MOF。高稳定性是基于强Zr-O键和内部Zr-6-簇在除去或加入μ（3）-OH基团后可逆重排的能力的组合，而连接的羧酸盐没有任何变化。大多数MOFs的弱热、化学和机械稳定性可能是限制其在大规模工业应用中使用的最重要的性质。本研究中提出的Zr-MOFs具有工业应用所需的韧性;分解温度高于500摄氏度，耐大多数化学品，即使在暴露于10吨/厘米（2）的外部压力后，它们仍保持结晶状态。
Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr-6-cluster to rearrange reversibly upon removal or addition of mu(3)-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm(2) of external pressure.