高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (3): 731.

• 研究论文 • 上一篇    下一篇

苯磺酸修饰的层柱磷酸锆的制备及催化应用

李颖,刘可,华伟明,乐英红,高滋   

  1. 复旦大学化学系, 上海市分子催化和功能材料重点实验室, 上海 200433
  • 收稿日期:2010-10-11 修回日期:2010-11-28 出版日期:2011-03-10 发布日期:2011-02-23
  • 通讯作者: 乐英红 E-mail:yhyue@fudan.edu.cn
  • 基金资助:

    国家“九七三”计划项目(批准号: 2006CB806103)、国家自然科学基金(批准号: 20633030, 20773027, 20773028)和上海市科学技术委员会基金(批准号: 08DZ2270500)资助.

Phenylsulfonic Acid Functionalized Porous Phosphate Heterostructure Materials as Strong Solid Acids

LI Ying, LIU Ke, HUA Wei-Ming, YUE Ying-Hong*, GAO Zi   

  1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, China
  • Received:2010-10-11 Revised:2010-11-28 Online:2011-03-10 Published:2011-02-23
  • Contact: YUE Ying-Hong E-mail:yhyue@fudan.edu.cn
  • Supported by:

    国家“九七三”计划项目(批准号: 2006CB806103)、国家自然科学基金(批准号: 20633030, 20773027, 20773028)和上海市科学技术委员会基金(批准号: 08DZ2270500)资助.

摘要: 以共缩合方法制备了一系列苯磺酸修饰的层柱磷酸锆材料,利用N2吸附、Si核磁共振、红外光谱和热重分析等方法对其结构进行了表征. 将其应用于对苯二酚与叔丁醇烷基化反应中,结果发现催化剂合成时的投料比对其催化性能有较大的影响,催化剂ZrP-0.4-2-10%-PhSO3H的催化性能最佳,反应4 h对苯二酚的转化率为85.4%,2-叔丁基对苯二酚得率达到58.5%. 酸性表征结果显示,催化剂活性与其表面可接触酸性位的数目密切有关. 该催化剂还具有较好的重复利用性能,反应3次后产物得率仅下降10%. 催化剂失活是由于磺酸基团的脱落或活性位被积碳覆盖所引起.

关键词: 层状磷酸锆, 苯磺酸, 烷基化, 可接触酸性位

Abstract: A series of phenylsulfonic acid functionalized porous phosphate heterostructure (PPH) materials were prepared by co-condensation method and characterized by SEM, FT-IR, 29Si MAS NMR, TG and N2 adsorption. Their catalytic behavior for alkylation of hydroquinone with tert-butanol was compared. ZrP-0.4-2-10%-PhSO3H is a more active catalyst for the reaction in comparison to others. The conversion of hydroquinone and yield of 2-tert-butylhydroquinone on the catalyst reach 85.4% and 58.5% at 150 oC. The activity correlates well with the amount of the accessible acid sites on its surface. The catalyst is stable and reusable, and the product yield is only reduced by 10% after four runs. The reduction in activity is probably caused by leaching of phenylsulfonic group or deposition of coke on the active sites.

Key words: Zirconium phosphate, phenylsulfonic acid, alkylation, accessible acid sites

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