Nguyen Hue T T, Tu Thach N, Nguyen My V, Lo Tien H N, Furukawa Hiroyasu, Nguyen Ngoc N, Nguyen My D
Nguyen Tat Thanh University , 300A Nguyen Tat Thanh Street , District 4, Ho Chi Minh City 755414 , Vietnam.
Department of Chemistry , University of California , Berkeley , California 94720 , United States.
ACS Appl Mater Interfaces. 2018 Oct 17;10(41):35462-35468. doi: 10.1021/acsami.8b11037. Epub 2018 Oct 3.
A Zr(IV)-based metal-organic framework (MOF), termed reo-MOF-1 [ZrO(HO)(SNDC)], composed of 4-sulfonaphthalene-2,6-dicarboxylate (HSNDC) linkers and ZrO(HO)(CO) clusters was synthesized by solvothermal synthesis. Structural analysis revealed that reo-MOF-1 adopts the reo topology highlighted with large cuboctahedral cages (23 Å). This structure is similar to that found in DUT-52 (fcu topology), however, reo-MOF-1 lacks the body-centered packing of the 12-connected ZrO(OH)(CO) clusters, which is attributed to the subtle, but crucial influence in the bulkiness of functional groups on the linkers. The control experiments, where the ratio of HSNDC/naphthalene-2,6-dicarboxylate linkers was varied, also support our finding that the bulky functionalities play a key role for defect-controlled synthesis. The reo-MOF-1 framework was obtained by linker exchange to yield a chemically and thermally stable material despite its large pores. Remarkably, reo-MOF-1 exhibits permanent porosity (Brunauer-Emmett-Teller and Langmuir surface areas of 2104 and 2203 m g, respectively). Owing to these remarkable structural features, reo-MOF-1 significantly enhances the yield in Brønsted acid-catalyzed reactions.
通过溶剂热合成法合成了一种基于锆（IV）的金属有机框架（MOF），称为reo-MOF-1 [ZrO(HO)(SNDC)]，它由4-磺基萘-2,6-二羧酸酯（HSNDC）连接体和ZrO(HO)(CO)簇组成。结构分析表明，reo-MOF-1采用了以大立方八面体笼（23 Å）为特征的reo拓扑结构。这种结构与DUT-52（fcu拓扑结构）中的结构相似，然而，reo-MOF-1缺乏12连接的ZrO(OH)(CO)簇的体心堆积，这归因于连接体上官能团体积的细微但关键的影响。控制实验中改变了HSNDC/萘-2,6-二羧酸酯连接体的比例，这也支持了我们的发现，即庞大的官能团在缺陷控制合成中起关键作用。尽管reo-MOF-1具有大孔，但通过连接体交换获得了化学和热稳定的框架材料。值得注意的是，reo-MOF-1表现出永久孔隙率（Brunauer-Emmett-Teller和Langmuir表面积分别为2104和2203 m²/g）。由于这些显著的结构特征，reo-MOF-1显著提高了布朗斯特酸催化反应的产率。
