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介孔二氧化硅干凝胶中限域的丁基-甲基-吡啶四氟硼酸盐:热行为及基质-模板相互作用

Butyl-Methyl-Pyridinium Tetrafluoroborate Confined in Mesoporous Silica Xerogels: Thermal Behaviour and Matrix-Template Interaction.

作者信息

Putz Ana-Maria, Almásy László, Horváth Zsolt Endre, Trif László

机构信息

"Coriolan Drăgulescu" Institute of Chemistry, Bv. Mihai Viteazul, No. 24, 300223 Timisoara, Romania.

Institute for Energy Security and Environmental Safety, Centre for Energy Research, Konkoly-Thege Miklós út 29-33, 1121 Budapest, Hungary.

出版信息

Materials (Basel). 2021 Aug 29;14(17):4918. doi: 10.3390/ma14174918.

Abstract

Organic-inorganic silica composites have been prepared via acid catalyzed sol-gel route using tetramethoxysilan (TMOS) and methyl-trimethoxysilane (MTMS) as silica precursors and -butyl-3-methylpyridinium tetrafluoroborate ([bmPy][BF]) as co-solvent and pore template, by varying the content of the ionic liquid (IL). Morphology of the xerogels prepared using the ionic liquid templating agent were investigated using scanning electron microscopy and small angle neutron scattering (SANS). Thermal analysis has been used in order to evaluate the thermal and structural stability of the materials, in both nitrogen and synthetic air atmosphere. In nitrogen atmosphere, the IL decomposition took place in one step starting above 150 °C and completed in the 150-460 °C temperature interval. In synthetic air atmosphere, the IL decomposition produced two-step mass loss, mainly in the 170-430 °C temperature interval. The decomposition mechanism of the IL inside the silica matrix was studied by mass spectrometric evolved gas analysis (MSEGA). The measurements showed that the degradation of the IL's longer side chain (butyl) starts at low temperature (above 150 °C) through a C-N bond cleavage, initiated by the nucleophilic attack of a fluorine ion.

摘要

通过酸催化溶胶 - 凝胶法,以四甲氧基硅烷(TMOS)和甲基三甲氧基硅烷(MTMS)作为硅源前驱体,以1 - 丁基 - 3 - 甲基吡啶四氟硼酸盐([bmPy][BF₄])作为共溶剂和孔模板,通过改变离子液体(IL)的含量制备了有机 - 无机二氧化硅复合材料。使用扫描电子显微镜和小角中子散射(SANS)研究了使用离子液体模板剂制备的干凝胶的形态。为了评估材料在氮气和合成空气气氛中的热稳定性和结构稳定性,进行了热分析。在氮气气氛中,离子液体的分解在150℃以上开始分一步进行,并在150 - 460℃的温度区间内完成。在合成空气气氛中,离子液体的分解产生两步质量损失,主要发生在170 - 430℃的温度区间内。通过质谱逸出气体分析(MSEGA)研究了二氧化硅基质中离子液体的分解机理。测量结果表明,离子液体较长侧链(丁基)的降解在低温(150℃以上)通过氟离子的亲核攻击引发的C - N键断裂开始。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7458/8433830/703161865331/materials-14-04918-g001.jpg

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