Surface Modification of Multiwalled Carbon Nanotubes to Impart Technological Properties

M. V. Buzaeva, I. A. Makarova, E. S. Vaganova, O. A. Davydova, Yu. I. Sud’in, V. A. Sergeev
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Abstract

The work considers the processes of modifying the surface of multiwalled carbon nanotubes with various polar groups: carboxyl, alcoholic hydroxyl, and quaternary ammonium salt. A procedure is developed using an oxidizing mixture of hydrogen peroxide, nitric acid, and sulfuric acid for the carboxylation of carbon nanotubes at a temperature of 70°C, which minimizes the formation of amorphous carbon and increases the concentration of carboxyl groups on the surface to 5.5 wt %. Tubes with a surface modified with a quaternary ammonium salt are obtained from carboxylated carbon nanotubes by reaction with triethanolamine. The modification of carbon nanotubes with ethyl hydroxyl groups is carried out with the participation of a free-radical initiator in an ethanol medium. The initial defects of nanotubes determine the number and nature of the defects at which chemical bonding occurs during functionalization, regardless of the method of nanocarbon material processing. The thermal–oxidative stability of the initial and modified carbon nanotubes in air is explored. The initial nanotubes are the most stable; they maintain their properties even when heated up to 520°C in air. For modified nanotubes, the thermal stability decreases in the series multiwalled nanotubes with carboxyl groups on the surface, multiwalled nanotubes with alcoholic hydroxyl groups, and multiwalled nanotubes modified with a quaternary ammonium salt, the oxidation of which begins at 400°C. The grafting of alcohol hydroxyl groups onto the surface of multiwalled carbon nanotubes is of considerable interest for obtaining an adsorption material with a developed surface, capable of covalently binding metal ions due to hydroxyl groups, similarly to complexing agents such as ethylene glycol or pyrocatechol. Carbon nanomaterials modified with polar groups exhibit good adsorption properties with respect to heavy metal ions. The degree of extraction of zinc and copper ions in the case of carboxylated nanotubes reaches 98%.

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多壁碳纳米管表面改性赋予其工艺性能
摘要本文研究了用羧基、醇羟基和季铵盐等不同极性基团修饰多壁碳纳米管表面的过程。在70℃的温度下,利用过氧化氢、硝酸和硫酸的氧化混合物对碳纳米管进行羧基化,使无定形碳的形成最小化,并将表面羧基的浓度提高到5.5 wt %。以羧化碳纳米管为原料,与三乙醇胺反应得到了表面经季铵盐修饰的碳纳米管。在乙醇介质中,在自由基引发剂的参与下,用乙基羟基修饰碳纳米管。无论纳米碳材料的加工方法如何,纳米管的初始缺陷决定了功能化过程中化学键形成缺陷的数量和性质。研究了初始碳纳米管和改性碳纳米管在空气中的热氧化稳定性。初始纳米管是最稳定的;即使在空气中加热到520°C,它们也能保持其性能。对于改性的纳米管,表面有羧基的多壁纳米管、有醇羟基的多壁纳米管和有季铵盐修饰的多壁纳米管的热稳定性降低,这些纳米管的氧化开始于400℃。将醇羟基接枝到多壁碳纳米管的表面上,对于获得具有发达表面的吸附材料具有相当大的兴趣,这种材料由于羟基而能够共价结合金属离子,类似于乙二醇或邻苯二酚等络合剂。极性基团修饰的碳纳米材料对重金属离子具有良好的吸附性能。羧基化纳米管对锌、铜离子的萃取率达到98%。
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