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KIT-5 结构和织构随磺酸基功能化方法的不同而变化。

KIT-5 Structural and Textural Changes in Response to Different Methods of Functionalization with Sulfonic Groups.

机构信息

Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.

出版信息

Int J Mol Sci. 2023 Jan 21;24(3):2165. doi: 10.3390/ijms24032165.

Abstract

In this project, KIT-5 materials were effectively functionalized with sulfonic groups introduced by grafting or the co-condensation method and tested as heterogeneous solid acid catalyst. A co-condensation procedure leading to the stable, -SOH functionalized KIT-5 materials was successfully established. Moreover, the influence of both synthesis methods on the structural and textural parameters, as well as surface chemistry, morphology, and catalytic activity of -SOH/KIT-5 materials was thoroughly investigated. The syntheses with 3-mepkaptopropyltrimethoxysilane (MPTMS) acting as a modifying agent resulted in samples in which functional groups were introduced into the structure and/or onto the mesoporous silica surface. The oxidation stage of -SH to -SOH groups was carried out under mild conditions, using a "green" oxidant (HO). The application of different functionalization techniques and the introduction of different amounts of modifying agent allowed for an evaluation of the influence of these parameters on the ordering of the mesoporous structure of KIT-5 materials. The applied methods of assessment of the physicochemical parameters (XRD, low-temperature N sorption, TEM) showed that, especially when the co-condensation method was applied, as the number of functional groups increased, the ordering of structure characteristic of KIT-5 decreased. On the other hand, the samples modified by grafting had a stable structure, regardless of the amount of introduced MPTMS. Test reactions carried out on the basis of Friedel-Crafts alkylation process showed that the synthesized materials can be considered promising acid catalysts in heterogeneous catalysis reactions.

摘要

在这个项目中,通过接枝或共缩合方法将磺酸基团有效功能化 KIT-5 材料,并将其测试为非均相固体酸催化剂。成功建立了一种导致稳定的 -SOH 功能化 KIT-5 材料的共缩合程序。此外,还彻底研究了两种合成方法对 -SOH/KIT-5 材料的结构和结构参数、表面化学、形态和催化活性的影响。以 3-巯丙基三甲氧基硅烷(MPTMS)为改性剂的合成导致功能基团被引入到结构中以及/或者介孔硅表面上。-SH 基团氧化为 -SOH 基团是在温和条件下进行的,使用“绿色”氧化剂(HO)。不同功能化技术的应用和不同量改性剂的引入允许评估这些参数对 KIT-5 材料介孔结构有序性的影响。应用的物理化学参数评估方法(XRD、低温 N 吸附、TEM)表明,特别是当应用共缩合方法时,随着功能基团数量的增加,KIT-5 的结构有序性降低。另一方面,通过接枝改性的样品具有稳定的结构,无论引入的 MPTMS 量如何。基于傅里德-克拉夫茨烷基化反应进行的测试反应表明,所合成的材料可以被认为是多相催化反应中有前途的酸催化剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaaa/9917139/103aa203e9dd/ijms-24-02165-g001.jpg

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