Evaluation of heterogeneous metal-organic framework organocatalysts prepared by postsynthetic modification.
Evaluation of heterogeneous metal-organic framework organocatalysts prepared by postsynthetic modification.
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DOI：
10.1021/ic1011549
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发表时间：
2010-09-06
影响因子：
4.6
通讯作者：
Cohen SM
中科院分区：
文献类型：
--
作者：
Garibay SJ;Wang Z;Cohen SM
一种以2 - 氨基- 1,4 - 苯二甲酸（NH₂ - BDC）为构建单元的金属 - 有机框架（MOF）可与一组环状酸酐发生化学修饰。通过多种方法，包括核磁共振（NMR）和电喷雾电离质谱（ESI - MS），证明了这些试剂对名为MIL - 53(Al) - NH₂（MIL = 拉瓦锡材料研究所）的铝基MOF的修饰，并且通过热重分析（TGA）、粉末X射线衍射（PXRD）和气体吸附分析证实了修饰后MOF的结构完整性。与这些环状酸酐反应生成的MOF在其孔隙内显示出羧酸官能团。此外，研究表明马来酸功能化的MIL - 53(Al) - AMMal可作为布朗斯特酸催化剂，促进几种小分子环氧化物的甲醇解反应。实验表明，MIL - 53(Al) - AMMal以非均相方式起作用，并且在至少三个催化循环中具有可重复使用性和稳定的活性。此处呈现的研究结果展示了MOF上共价后合成修饰（PSM）的几个重要特征，包括：1）使用简单的有机试剂（例如酸酐）轻松引入催化功能；2）利用和回收有机催化MOF的能力；3）通过选择官能团控制催化活性。这些研究结果清楚地表明，共价后合成修饰是获得用作有机催化材料的新型MOF化合物的一种有力手段。
A metal-organic framework (MOF) containing 2-amino-1,4-benzenedicarboxylate (NH2-BDC) as a building block is shown to undergo chemical modification with a set of cyclic anhydrides. The modification of the aluminum-based MOF known as MIL-53(Al)-NH2 (MIL = Matérial Institut Lavoisier) by these reagents is demonstrated by using a variety of methods, including NMR and ESI-MS, and the structural integrity of the modified MOFs has been confirmed by TGA, PXRD, and gas sorption analysis. Reaction with these cyclic anhydrides produces MOFs that display carboxylic acid functional groups within their pores. Furthermore, it is shown that maleic acid functionalized MIL-53(Al)-AMMal can act as a Brønsted acid catalyst and facilitate the methanolysis of several small epoxides. Experiments show that MIL-53(Al)-AMMal acts in a heterogeneous manner and is recyclable with consistent activity over at least three catalytic cycles. The findings presented here demonstrate several important features of covalent postsynthetic modification (PSM) on MOFs, including: 1) facile introduction of catalytic functionality using simple organic reagents (e.g. anhydrides); 2) the ability to utilize and recycle organocatalytic MOFs; 3) control of catalytic activity through choice of functional group. The findings clearly illustrate that covalent postsynthetic modification represents a powerful means to access new MOF compounds that serve as organocatalytic materials.
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