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通过改变活化方法调控二维pH稳定金属有机框架材料的催化效率

Variation in Catalytic Efficacies of a 2D pH-Stable MOF by Altering Activation Methods.

作者信息

Behera Janaki, Pal Arun, Sahoo Rupam, Das Madhab C

机构信息

Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721302, WB, India.

School of Science, Constructor University, Campus Ring 1, 28759, Bremen, Germany.

出版信息

Chemistry. 2024 Jun 17;30(34):e202400375. doi: 10.1002/chem.202400375. Epub 2024 May 17.

Abstract

Although it is well-known that the Lewis acidity of Metal-Organic Frameworks (MOFs) can effectively enhance their catalytic activity in organic transformations, access to these Lewis-acidic sites remains a key hurdle to widespread applications of Lewis-acidic catalysis by MOFs. Easy accessibility of strong Lewis acidic sites onto 2D MOFs by using proper activation methods can be a cornerstone in attaining desired catalytic performance. Herein, we report a new 2D chemically stable MOF, IITKGP-60, which displayed excellent framework robustness over a wide pH range (2-12). Benefiting from the abundant open metal sites (OMSs) and framework robustness, the catalytic activity of the developed material was explored in one-pot three-component Strecker reaction and Knoevenagel condensation reaction. Moreover, the developed catalyst is superior in catalyzing the reactions involving sterically hindered substrate (1-naphthaldehyde) with high turnover number. A comparative catalytic study was conducted using different activation methods (chloroform and methanol exchanged activated samples), highlighting the significant effect of activation methods on its catalytic performances. The sustainable synthetic pathway under solvent-free conditions for a broad scope of substrates using low catalyst loading and excellent recyclability made the developed pH-stable framework a promising heterogeneous catalyst.

摘要

尽管众所周知,金属有机框架(MOF)的路易斯酸性可以有效提高其在有机转化中的催化活性,但利用这些路易斯酸性位点仍然是MOF路易斯酸催化广泛应用的关键障碍。通过适当的活化方法使二维MOF易于获得强路易斯酸性位点可能是实现所需催化性能的基石。在此,我们报道了一种新型二维化学稳定的MOF,IITKGP-60,它在很宽的pH范围(2至12)内表现出优异的框架稳定性。得益于丰富的开放金属位点(OMS)和框架稳定性,我们在一锅三组分斯特雷克反应和克诺文格尔缩合反应中探索了所制备材料的催化活性。此外,所开发的催化剂在催化涉及空间位阻底物(1-萘甲醛)的反应时具有高周转数,表现优异。使用不同的活化方法(氯仿和甲醇交换活化样品)进行了比较催化研究,突出了活化方法对其催化性能的显著影响。在无溶剂条件下,使用低催化剂负载量和优异的可回收性,为广泛的底物提供可持续的合成途径,使得所开发的pH稳定框架成为一种有前景的多相催化剂。

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