Stability of UiO-66 under acidic treatment: Opportunities and limitations for post-synthetic modifications
Stability of UiO-66 under acidic treatment: Opportunities and limitations for post-synthetic modifications
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DOI：
10.1016/j.micromeso.2015.01.032
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发表时间：
2015-05-15
影响因子：
5.2
通讯作者：
Loebbecke, S.
中科院分区：
文献类型：
--
作者：
Piscopo, C. G.;Polyzoidis, A.;Loebbecke, S.
在金属有机框架（MOFs）的化学和功能改性中，由于这些材料对水分、化学和热处理的高度敏感性，保持其结构和拓扑结构是一个具有挑战性的目标。多孔材料UiO-66是最稳定的MOFs之一，在相对广泛的化学和物理条件下保持其性能。UiO-66的独特的鲁棒性来自于构成框架的12配位Zr-6-簇。然而，不同的合成途径可能导致不同的锆位配位，影响这种MOF在催化等应用中的稳定性和活性。本文综述了UiO-66在酸处理下的稳定性。多孔金属-有机框架已根据两种替代程序合成;这两种固体材料和市售的UiO-66样品已悬浮在几种含水酸中，并在浸渍试验后进行表征。这些结果导致更好地理解所选MOF的酸性稳定性问题，澄清是否可以通过选择专用合成路线来增强其稳定性，并提供必要的信息，以便进行大量的合成后修饰。在这些反应中，UiO-66的磺化，这是一个非常重要的例子，已被研究。已经证实了UiO-66相对于无机酸的稳定性;然而，该MOF不容许使用亲电阳离子物质。(C)2015 Elsevier Inc. All rights reserved.
In chemical and functional modification of Metal-organic frameworks (MOFs), preserving their structure and topology is a challenging goal, due to the high sensitivity of these materials to moisture, chemical and thermal treatments. The porous material UiO-66 is one of the most stable MOFs, retaining its properties under a relative wide range of chemical and physical conditions. The unique robustness of UiO-66 derives from the 12-coordinated Zr-6-clusters that constitute the framework. Nevertheless, variation on the synthetic pathways may lead to different coordination of the Zirconium sites, influencing the stability and activity of this MOF during applications such as catalysis.Herein a survey of the stability of UiO-66 under acidic treatment is presented. The porous metal-organic framework has been synthesized according to two alternative procedures; these two solid materials and a commercially available UiO-66 sample have been suspended in several aqueous acids and have been characterized after the impregnation tests. These results lead to a better understanding of the matter of acidic stability of the selected MOF, clarifying whether it is possible to enhance its stability by choosing a dedicated synthesis route and providing essential information in order to proceed with a large number of post-synthetic modifications. Among these reactions, the sulfonation of UiO-66, which is an example of outstanding importance, has been investigated. The stability of UiO-66 versus mineral acids has been confirmed; however this MOF does not tolerate the use of electrophilic cationic species. (C) 2015 Elsevier Inc. All rights reserved.