Synthesis and sorption properties of β-cyclodextrin-containing aerosilogel

L. Belyakova, D. Lyashenko
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Abstract

Aromatic organic acids are among the common environmental pollutants that enter the water with washouts from agricultural lands, wastewater from chemical and pharmaceutical industries. Taking into account the high toxicity of aromatic substances, the important task of water purification is the removal of their trace amounts. This problem can be solved by using chemically modified inorganic materials, such as silicas, which have high mechanical, chemical, hydrolytic, and radiation stability. Therefore, they do not lose their sorption capacity during long-term use and do not pollute water with sorbent degradation products. The purpose of this work is the synthesis of a sorption-active material for removal of toxic aromatic acids by chemical immobilization of β-cyclodextrin functional groups on an aerosilogel (highly dispersed type of amorphous silica). A β-cyclodextrin-containing aerosilogel was synthesized by two-stage liquid-phase chemical modification of hydroxylated silica surface. Using the methods of IR spectroscopy, spectrophotometry, thermogravimetry, pH metry, low-temperature adsorption-desorption of nitrogen, chemical and elemental analysis of the surface, the surface structure and its quantitative chemical composition, and also parameters of porous structure of initial and chemically modified aerosilogels were determined. Sorption of benzoic, salicylic and β-resorcylic acids on aerosilogels from aqueous buffer solutions with pH=1 was studied. The insignificant contribution of silanol and aminopropyl groups and complete participation of chemically fixed β-cyclodextrin in the sorption of aromatic acids were proved. The results obtained are analyzed using kinetic models for pseudo-first and pseudo-second order processes, as well as Langmuir and Freundlich models for equilibrium adsorption on homogeneous and heterogeneous surfaces. It has been found that the sorption kinetic processes are well described by a pseudo-first order equation (in the presence of one type of functional groups on the surface) and a pseudo-second order equation for bi- and trifunctional aerosilogels. Experimental results on the equilibrium sorption of aromatic acids on β-cyclodextrin-containing aerosilogel are in good agreement with the Langmuir adsorption equation. This is evidence of decisive contribution of grafted oligosaccharide groups to the sorption of organic acids. The proposed chemical approach to increasing the sorption activity of aerosilogel can be used to obtain specific chromatographic carriers, as well as inorganic sorbents for the effective removal of small amounts of highly toxic organic substances from water and aqueous solutions.
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含β-环糊精气凝胶的合成及其吸附性能
芳香族有机酸是常见的环境污染物之一,随着农业用地的冲刷、化学和制药工业的废水进入水中。考虑到芳香物质的高毒性,水净化的重要任务是去除其痕量。这个问题可以通过使用化学改性的无机材料来解决,如二氧化硅,它具有很高的机械、化学、水解和辐射稳定性。因此,它们在长期使用过程中不会失去吸附能力,也不会因吸附剂降解产物污染水体。本工作的目的是通过在气硅凝胶(高度分散的无定形二氧化硅)上化学固定β-环糊精官能团来合成一种吸附活性材料,用于去除有毒的芳香酸。对羟基化二氧化硅表面进行两段液相化学改性,合成了含β-环糊精气硅凝胶。采用红外光谱法、分光光度法、热重法、pH法、低温氮吸附-解吸法、表面化学分析、元素分析、表面结构、定量化学组成以及初始气相硅胶和化学改性气相硅胶的孔隙结构参数。研究了pH=1的缓冲水溶液中苯甲酸、水杨酸和β-间环酸在气相凝胶上的吸附。证明了硅醇和氨基丙基对芳香酸吸附的贡献不显著,化学固定β-环糊精完全参与了芳香酸的吸附。利用准一级和准二级过程动力学模型,以及均匀和非均匀表面平衡吸附的Langmuir和Freundlich模型对所得结果进行了分析。研究发现,双官能团和三官能团气凝胶的吸附动力学过程可以用伪一阶方程(表面存在一种官能团时)和伪二阶方程很好地描述。芳香酸在含β-环糊精气凝胶上的平衡吸附实验结果与Langmuir吸附方程吻合较好。这是接枝寡糖基团对有机酸吸附的决定性贡献的证据。所提出的提高气硅凝胶吸附活性的化学方法可用于获得特定的色谱载体,以及用于从水和水溶液中有效去除少量高毒性有机物质的无机吸附剂。
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