| 自组装和共缩聚法制备磺酸基修饰的硅柱磷酸锆 |
| Preparation of Sulfonic Acid-Functionalized Silica-Pillared Zirconium Phosphate with the Self-Assembly Method and Cocondensation |
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| 摘要: 以十六胺插层磷酸锆为原料, 利用十二烷基二甲基苄基氯化铵为导向模板剂, 通过正硅酸乙酯和巯丙基三甲氧基硅烷的层间共水解缩聚, 并结合双氧水对巯丙基的熏蒸氧化, 制备了磺酸基修饰的硅柱磷酸锆材料。通过XRD、SEM、N2吸附-脱附和FT-IR等方法对柱撑材料进行了结构表征。结果表明, 通过调变预撑剂和模板剂中的碳链长度可以优化材料的柱撑结构和孔结构, 磺酸基修饰的材料孔径分布在2.17 nm左右, 比表面积可达163 m2·g-1, 且保留有规整有序的柱撑磷酸锆层板结构。磺酸基的修饰则成功调变了材料的酸位性质, Brönsted酸量最高可达2.71 mmol·g-1, 总酸量可达5.20 mmol·g-1。利用柠檬酸与正丁醇的酯化反应为探针反应, 由于磺酸基修饰的硅柱磷酸锆材料具有独特的空间反应效应和较为丰富的Brönsted酸位, 酯化反应转化率最高可达95.74%。 |
| 关键词: 巯基修饰的 磺酸基修饰的 柱撑 共缩合 氧化 酯化 |
| 基金项目: 国家自然科学基金(No.21101017/B0107)资助项目。 |
| Abstract: A series of sulfonic acid-functionalized silica-pillared zirconium phosphate materials with ordered layer structure were synthesized using the hexadecylamine (HDA) intercalated α-ZrP as raw material, dodecyl dimethyl benzyl ammonium chloride (DDBAC) as templet agent, tetraethyl orthosilicate (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) as the mixed silicon source, hydrogen peroxide as oxidant. The structure of the sulfonic acid-functionalized materials were characterized by XRD, SEM, N2 adsorption-desorption and FTIR. Pillared layered structure and pore structure were optimized by adjusting the length of long chain in organic amine and templet. Meanwhile, the specific surface area and pore diameter of the resulting materials are about 163 m2·g-1 and 2.17 nm, and the materials have ordered layer structure and pillared structure. The acid site property was adjusted, and the number of sulfonic acid groups and the total acid value respectively increase to 2.71 mmol·g-1 and 5.20 mmol·g-1. Due to the special steric effect and abundant Brönsted acid sites, the material shows excellent performance with 95.74% conversion in the esterification of citric acid with n-butanol. |
| Keywords: thiol-functionalized sulfonic acid-functionalized pillared cocondensation oxidation esterification |
| 投稿时间：2014-09-12 修订日期：2014-11-17 |
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| 花益香,刘文晋,王红宁,陈若愚.自组装和共缩聚法制备磺酸基修饰的硅柱磷酸锆[J].无机化学学报,2015,31(3):493-500. |
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