多孔SiO_2微球的制备与表征
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摘要
多孔SiO_2微球是一类具有特殊形貌的多孔材料,在吸附与分离、催化剂载体、药物可控释放等领域有广泛的应用前景。实验结合模板法和溶胶-凝胶法,在两个水硅比不同的正硅酸乙酯-乙醇-氨水-水体系中分别制备了普通和中空多孔SiO_2微球,采用扫描电镜、透射电镜、氮气等温吸附、(小角)X射线衍射、红外光谱、差热-热重分析等手段研究各组份含量对多孔微球的形成及所得微球的结构与性能的影响,对微球的形成机理进行了初步探讨,测试并分析了不同结构与孔特性的多孔微球对山梨酸的吸附行为。
实验在高水硅比体系引入烷基链长不同的阳离子表面活性剂十二、十四和十六烷基三甲基溴化铵为多孔模板,制得表面活性剂/SiO_2复合微球,煅烧去除表面活性剂,得到纳米孔SiO_2微球。研究发现,随表面活性剂烷基链的增长,孔径增大,孔的有序性增强。表面活性剂用量增多,孔容和比表面积也增大。十六烷基三甲基溴化铵用量为0.3mol时所制得微球形貌最好,孔的有序性最高,其比表面积、孔容、孔径分别为909 m2/g、0.5749 ml/g、2.02nm。在低水硅比体系中制备的微球具有纳米微孔,微球表面积、孔容很小;随氨水用量增大,微球的团聚程度减轻;在该体系中引入十六烷基三甲基溴化铵,制得同时具有微孔与介孔的SiO_2微球,但孔是无序的。
在高水硅比体系中,采用聚苯乙烯(PS)微球和不同阳离子表面活性剂分别为中空部分和纳米孔的模板,先制得PS/表面活性剂/SiO_2复合微球,煅烧去除模板后得到壳上具有介孔的中空SiO_2微球。结果发现,随表面活性剂烷基链长增加,所制中空微球壳厚增加,并且壳上介孔的孔径增大,有序性增强。多次包覆SiO_2可进一步增大中空微球的球壳厚度。在低水硅比体系中,采用PS微球为中空模板,不用任何表面活性剂可制备壳上具有无序纳米微孔的中空SiO_2微球。研究发现,只有氨水用量小于4.5mol时,才能形成中空微球。提高聚苯乙烯微球用量,可增加样品中形成的中空球的数量,增加正硅酸乙酯时,微球破碎减少,表面变粗糙,颗粒间空隙减少。
研究多孔微球对山梨酸吸附行为发现,微球对山梨酸的吸附能力取决于其孔容与孔径的大小,孔容、孔径越大其吸附能力越强。此外,中空比非中空SiO_2微球的吸附能力显著增大。
Porous silica microspheres are porous materials with special morphology, having great potential applications in many fields, such as catalyst carrier, adsorption and separation, controlled drug delivery and release etc. In this work, normal and hollow porous SiO_2 microspheres were prepared by a combined template route with sol-gel process in two tetraethyl orthosilicate-ethanol-ammonia-water media with distinct water/silica ratios. Factors influencing the formation, structure and properties of the obtained porous SiO_2 microspheres were studied by SEM, TEM, small angle XRD, IR, TG-DTA, etc. The formation mechanism of the porous microspheres is discussed. The adsorption capabilities of sorbic acid of the porous SiO_2 microspheres with different microstructures and pore characteristics were tested and compared.
In the medium with a high H2O/TEOS ratio, surfactants, including dodecy-, tetradecyl- and cetyl-trimethylammonium bromide were added. Surfactant-silica composite microspheres were prepared and porous SiO_2 microspheres were obtained after the removal of surfactants by calcination. It is shown that the pore size increases and the nanopores become more ordered with increasing alkyl chain length of the surfactants. The pore volume and specific surface area also increases with the amount of surfactants. The microspheres prepared with 0.3mol cetyl-trimethylammonium bromide have the highest ordering and largest specific surface area, pore volume and pore diameter of 909 m2/g, 0.5749 ml/g and 2.02nm, respectively. In the medium with a low H2O/TEOS ratio, microporous silica microspheres with small surface areas and pore volumes were obtained. The aggregation of product is reduced with the increase in addition of ammonia solution. With addition of cetyl-trimethylammonium bromide in this medium, microspheres with combined mesoporous and microporous were prepared, however, the pores are not ordered.
Hollow mesoporous SiO_2 microspheres were synthesized using polystyrene (PS) beads as core template and dodecy-, tetradecyl- and cetyl-trimethylammonium bromide as porogens. PS-surfactant-silica composite microspheres were formed. Hollow mesoporous SiO_2 microspheres were obtained after the removal of PS and surfactants by calcination. It is found that the thickness of shells and pore diameter increase with increasing the alkyl chain length and amount of surfactants. The thickness of the hollow SiO_2 shells could also be increased by repeated silica coatings. In the medium with a low H2O/TEOS ratio, hollow microporous SiO_2 microspheres were prepared without addition of surfactant via PS templating. Hollows were only templated when the amount of ammonia solution was less than 4.5mol. Increasing the amount of PS can increase hollow spheres among the product. With the increase in amount of TEOS, less hollow microspheres are found broken. The surface of hollow microspheres is more coarse and interparticle voids decrease.
Tests on adsorption of sorbic acid of the prepared porous silica microspheres show that the adsorption behavior of porous microspheres mainly depends on their pore volumes and pore diameters. The larger the pore volume and pore diameter the microspheres have, the higher the adsorption capability. In addition, hollow porous microspheres exhibit much higher adsorption of sorbic acid than non-hollow ones.
实验在高水硅比体系引入烷基链长不同的阳离子表面活性剂十二、十四和十六烷基三甲基溴化铵为多孔模板,制得表面活性剂/SiO_2复合微球,煅烧去除表面活性剂,得到纳米孔SiO_2微球。研究发现,随表面活性剂烷基链的增长,孔径增大,孔的有序性增强。表面活性剂用量增多,孔容和比表面积也增大。十六烷基三甲基溴化铵用量为0.3mol时所制得微球形貌最好,孔的有序性最高,其比表面积、孔容、孔径分别为909 m2/g、0.5749 ml/g、2.02nm。在低水硅比体系中制备的微球具有纳米微孔,微球表面积、孔容很小;随氨水用量增大,微球的团聚程度减轻;在该体系中引入十六烷基三甲基溴化铵,制得同时具有微孔与介孔的SiO_2微球,但孔是无序的。
在高水硅比体系中,采用聚苯乙烯(PS)微球和不同阳离子表面活性剂分别为中空部分和纳米孔的模板,先制得PS/表面活性剂/SiO_2复合微球,煅烧去除模板后得到壳上具有介孔的中空SiO_2微球。结果发现,随表面活性剂烷基链长增加,所制中空微球壳厚增加,并且壳上介孔的孔径增大,有序性增强。多次包覆SiO_2可进一步增大中空微球的球壳厚度。在低水硅比体系中,采用PS微球为中空模板,不用任何表面活性剂可制备壳上具有无序纳米微孔的中空SiO_2微球。研究发现,只有氨水用量小于4.5mol时,才能形成中空微球。提高聚苯乙烯微球用量,可增加样品中形成的中空球的数量,增加正硅酸乙酯时,微球破碎减少,表面变粗糙,颗粒间空隙减少。
研究多孔微球对山梨酸吸附行为发现,微球对山梨酸的吸附能力取决于其孔容与孔径的大小,孔容、孔径越大其吸附能力越强。此外,中空比非中空SiO_2微球的吸附能力显著增大。
Porous silica microspheres are porous materials with special morphology, having great potential applications in many fields, such as catalyst carrier, adsorption and separation, controlled drug delivery and release etc. In this work, normal and hollow porous SiO_2 microspheres were prepared by a combined template route with sol-gel process in two tetraethyl orthosilicate-ethanol-ammonia-water media with distinct water/silica ratios. Factors influencing the formation, structure and properties of the obtained porous SiO_2 microspheres were studied by SEM, TEM, small angle XRD, IR, TG-DTA, etc. The formation mechanism of the porous microspheres is discussed. The adsorption capabilities of sorbic acid of the porous SiO_2 microspheres with different microstructures and pore characteristics were tested and compared.
In the medium with a high H2O/TEOS ratio, surfactants, including dodecy-, tetradecyl- and cetyl-trimethylammonium bromide were added. Surfactant-silica composite microspheres were prepared and porous SiO_2 microspheres were obtained after the removal of surfactants by calcination. It is shown that the pore size increases and the nanopores become more ordered with increasing alkyl chain length of the surfactants. The pore volume and specific surface area also increases with the amount of surfactants. The microspheres prepared with 0.3mol cetyl-trimethylammonium bromide have the highest ordering and largest specific surface area, pore volume and pore diameter of 909 m2/g, 0.5749 ml/g and 2.02nm, respectively. In the medium with a low H2O/TEOS ratio, microporous silica microspheres with small surface areas and pore volumes were obtained. The aggregation of product is reduced with the increase in addition of ammonia solution. With addition of cetyl-trimethylammonium bromide in this medium, microspheres with combined mesoporous and microporous were prepared, however, the pores are not ordered.
Hollow mesoporous SiO_2 microspheres were synthesized using polystyrene (PS) beads as core template and dodecy-, tetradecyl- and cetyl-trimethylammonium bromide as porogens. PS-surfactant-silica composite microspheres were formed. Hollow mesoporous SiO_2 microspheres were obtained after the removal of PS and surfactants by calcination. It is found that the thickness of shells and pore diameter increase with increasing the alkyl chain length and amount of surfactants. The thickness of the hollow SiO_2 shells could also be increased by repeated silica coatings. In the medium with a low H2O/TEOS ratio, hollow microporous SiO_2 microspheres were prepared without addition of surfactant via PS templating. Hollows were only templated when the amount of ammonia solution was less than 4.5mol. Increasing the amount of PS can increase hollow spheres among the product. With the increase in amount of TEOS, less hollow microspheres are found broken. The surface of hollow microspheres is more coarse and interparticle voids decrease.
Tests on adsorption of sorbic acid of the prepared porous silica microspheres show that the adsorption behavior of porous microspheres mainly depends on their pore volumes and pore diameters. The larger the pore volume and pore diameter the microspheres have, the higher the adsorption capability. In addition, hollow porous microspheres exhibit much higher adsorption of sorbic acid than non-hollow ones.
引文
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