苦杏仁苷十四酸酯为模板合成一维纳米无机材料
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摘要
模板法因其结构规整、操作方便、易于控制等优点已成为合成一维纳米材料的首选方法。在模板法中,水凝胶作为合成无机纳米材料的模板已得到广泛研究和应用,但仍存在着机理不明确、价格高昂、合成复杂等诸多缺陷。而水凝胶因子因其优良的可控性、生物相容性而备受关注,并有可能避免上述缺陷。本文以酶催化合成的苦杏仁苷十四酸酯凝胶因子为模板,合成了铁氧化物纳米线以及二氧化硅纳米管两种无机材料。主要工作和结果如下:
(1)通过酶催化法合成了苦杏仁苷十四酸酯凝胶因子,采用红外光谱(IR)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)以及质谱(MS)对其进行了结构表征及确证。其凝胶性能结果表明,该凝胶因子可以凝胶中等极性及芳香性溶剂。对该凝胶因子在盐、高分子、不同pH条件下的凝胶行为进行了研究。
(2)凝胶因子对非均相对正己烷-水体系的凝胶性能研究表明正己烷-水体系的凝胶温度随着正己烷含量的增加,其凝胶温度下降,且通过扫描电子显微镜(SEM)发现其微观形貌也发生了相应变化。模板法合成铁氧化物一般通过将铁离子还原或沉淀到模板中,本文采用将分散在正己烷中的四氧化三铁纳米粒进行排列的方式合成出直径为10 nm的铁氧化物纳米线,通过SEM对其微观形貌进行了表征,并通过热重分析(TGA/DTA)对合成的纳米线组分进行了判断,初步推断该纳米线为三氧化二铁纳米线。
(3)经过实验条件的优化,以酸性的凝胶因子苦杏仁苷十四酸酯为模板,γ-氨丙基三乙氧基硅烷( Aminopropyltriethoxysilane , APS )作为助结构导向剂(Co-Structure-Directing Agent,CSDA),四乙氧基硅烷(Tetraethylorthosilicate,TEOS)为硅源,在水环境中合成了二氧化硅纳米管。SEM和透射电子显微镜(TEM)结果显示该纳米管直径为200-300 nm,管壁厚50 nm,长度可达12μm。
At present, template method has become the first choice for the preparations of nano-materials, due to its easiness, convenience and the regular structures of products. However, there are some disadvantages, such as unclear mechanism, expensiveness, and complicated steps, which would limit the applications. In this method, hydrogel has been widely used as the template to prepare the inorganic nano-materials. Thus, extensive attention has been focused on hydrogelator in the wide ranges of applications. In this study, two inorganic nano-materials: iron oxide nanowires and silica nanotubes have been synthesized by using amygdalin myristic esters as template. The main results are as followed:
(1) The amygdalin myristic esters were synthesized through enzyme catalysis method. Its structure was characterized by IR, 1H NMR, 13C NMR and MS. The results of its gellation ability showed that medium polarity and aromatic solvents could be gelated by the gelator. Besides, its gel behaviors in salt solutions, polymer solutions and at different pH solutions were studied respectively.
(2) The relationship between the gel temperature and the content in the n-hexane - water system was studied. The gel temperature decreased with the increasing of n-hexane content. Besides, we found that the content of n-hexane could change the shape and the surface appearance of the system using SEM. Generally, the iron ions were reduced or precipitated to the template to prepare the iron oxide nanowires in the template method. However, in our method, iron oxide nanowires were synthesized by arranging iron oxide nanoparticles dispersed in hexane. The morphology was characterized by SEM. The components were analyzed by TGA / DTA, which presumed to be ferric oxide.
(3) Silica nanotubes were prepared successfully using acidic gelator amygdalin myristic esters as the template, APS as the CSDA and the TEOS as silica source in water environment. Moreover, the parameters of the synthesis were explored and discussed.
(1)通过酶催化法合成了苦杏仁苷十四酸酯凝胶因子,采用红外光谱(IR)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)以及质谱(MS)对其进行了结构表征及确证。其凝胶性能结果表明,该凝胶因子可以凝胶中等极性及芳香性溶剂。对该凝胶因子在盐、高分子、不同pH条件下的凝胶行为进行了研究。
(2)凝胶因子对非均相对正己烷-水体系的凝胶性能研究表明正己烷-水体系的凝胶温度随着正己烷含量的增加,其凝胶温度下降,且通过扫描电子显微镜(SEM)发现其微观形貌也发生了相应变化。模板法合成铁氧化物一般通过将铁离子还原或沉淀到模板中,本文采用将分散在正己烷中的四氧化三铁纳米粒进行排列的方式合成出直径为10 nm的铁氧化物纳米线,通过SEM对其微观形貌进行了表征,并通过热重分析(TGA/DTA)对合成的纳米线组分进行了判断,初步推断该纳米线为三氧化二铁纳米线。
(3)经过实验条件的优化,以酸性的凝胶因子苦杏仁苷十四酸酯为模板,γ-氨丙基三乙氧基硅烷( Aminopropyltriethoxysilane , APS )作为助结构导向剂(Co-Structure-Directing Agent,CSDA),四乙氧基硅烷(Tetraethylorthosilicate,TEOS)为硅源,在水环境中合成了二氧化硅纳米管。SEM和透射电子显微镜(TEM)结果显示该纳米管直径为200-300 nm,管壁厚50 nm,长度可达12μm。
At present, template method has become the first choice for the preparations of nano-materials, due to its easiness, convenience and the regular structures of products. However, there are some disadvantages, such as unclear mechanism, expensiveness, and complicated steps, which would limit the applications. In this method, hydrogel has been widely used as the template to prepare the inorganic nano-materials. Thus, extensive attention has been focused on hydrogelator in the wide ranges of applications. In this study, two inorganic nano-materials: iron oxide nanowires and silica nanotubes have been synthesized by using amygdalin myristic esters as template. The main results are as followed:
(1) The amygdalin myristic esters were synthesized through enzyme catalysis method. Its structure was characterized by IR, 1H NMR, 13C NMR and MS. The results of its gellation ability showed that medium polarity and aromatic solvents could be gelated by the gelator. Besides, its gel behaviors in salt solutions, polymer solutions and at different pH solutions were studied respectively.
(2) The relationship between the gel temperature and the content in the n-hexane - water system was studied. The gel temperature decreased with the increasing of n-hexane content. Besides, we found that the content of n-hexane could change the shape and the surface appearance of the system using SEM. Generally, the iron ions were reduced or precipitated to the template to prepare the iron oxide nanowires in the template method. However, in our method, iron oxide nanowires were synthesized by arranging iron oxide nanoparticles dispersed in hexane. The morphology was characterized by SEM. The components were analyzed by TGA / DTA, which presumed to be ferric oxide.
(3) Silica nanotubes were prepared successfully using acidic gelator amygdalin myristic esters as the template, APS as the CSDA and the TEOS as silica source in water environment. Moreover, the parameters of the synthesis were explored and discussed.
引文
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[2]许仲梓金陆.纳米材料模板合成技术研究.材料导报, 2007, 21(F11): 143-147
[3]王秀丽.模板法合成纳米结构材料.化学通报, 2005, 68(10): 723-730
[4] Losic D. Microstructured surfaces engineered using biological templates: a facile approach for the fabrication of superhydrophobic surfaces. J Serb Chem Soc, 2008, 73(11): 1123-1135
[5] Yamauchi Y, Kuroda K. Rational design of mesoporous metals and related nanomaterials by a soft-template approach. Chemistry-an Asian Journal, 2008, 3(4): 664-676
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