应用化学

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介孔分子筛Ti-AlKIT-1的制备、表征与催化性能

李惠云*,刘院英,黄东枫,吕倍红   

  1. (安阳师范学院化学化工学院 安阳 455002)
  • 收稿日期:2011-08-18 修回日期:2011-11-10 出版日期:2012-07-10 发布日期:2012-07-10
  • 通讯作者: 李惠云,教授; Tel/Fax:0372-2900040; E-mail:hyli739@sina.com; 研究方向:催化化学
  • 基金资助:
    河南省应用化学重点学科资助课题(教高2008776),安阳市科技攻关项目(2009064)

Synthesis, Characterization and Catalytical Properties of Ti-AlKIT-1 Mesostructured Molecular Sieves

LI Huiyun*, LIU Yuanying, HUANG Dongfeng, LV Beihong   

  1. (Chemistry & Chemical Industry School,Anyang Normal University,Anyang 455002,China)
  • Received:2011-08-18 Revised:2011-11-10 Published:2012-07-10 Online:2012-07-10
  • Contact: LI Hui-Yun

摘要: 分别采用直接(ds)和后合成法(ps)合成含铝的介孔分子筛Al(ds or ps)KIT-1。 以钛酸四丁酯Ti(OEt)4为钛源,将钛嫁接在AlKIT-1表面制备出Ti-AlKIT-1样品。 用傅里叶变换红外光谱、X射线粉末衍射、固体核磁共振(MAS NMR)、固体紫外可见漫反射光谱(DRS)、能谱(EDS)和N2吸附-脱附对样品进行了表征,并以双氧水氧化环己醇为探针考察了样品的催化活性。 实验结果表明,分子筛Ti-AlKIT-1具有规整的介孔孔道结构,钛进入介孔分子筛骨架而成为四配位的骨架钛,铝的存在形式与样品AlKIT-1的预处理有关,经铵溶液洗涤的Al(ds)KIT-1中没有非骨架铝。 Ti-AlKIT-1在催化双氧水氧化环己醇反应中铝和钛存在明显的协同作用。 样品Ti-Al(ds)KIT-1表现出更高的催化作用,这与其具有较高的比表面积、较大的孔容和较高钛铝比有关,80 ℃反应48 h,重复使用3次后,环己醇的转化率降低至51.3%,仅下降4.31%。

关键词: 介孔分子筛Ti-AlKIT-1, 钛-铝, 协同作用, 环己醇氧化

Abstract: The mixed mesoporous sieves Ti-AlKIT-1 materials were prepared through Ti grafting on AlKIT-1 obtained either directly or by post-synthesis using relatively inexpensive aluminium and titanium precursors, and characterized by FT-IR, XRD, MAS NMR, DRS, EDS and physical adsorption-desorption of nitrogen and used as catalysts toward the oxidation of cyclohexanol in 30% H2O2. XRD and N2 adsorption-desorption showed that the original mesoporous structure of the Ti-AlKIT-1 was retained with a lower BET surface area, pore volume and smaller pore size. Based on the combined FT-IR and DRS studies, it was concluded that the infrared spectroscopy can result a powerful tool to verify the Ti(Ⅳ) incorporation into the framework of AlKIT-1. 27Al MAS NMR spectra indicated that the ammonium-washed samples present only tetracoordinated aluminium. All Ti-AlKIT-1 catalysts showed significant activity in the oxidation of cyclohexanol due to the cooperative action of Ti and Al. Ti-Al(ds)KIT-1 with higher Ti/Al molar ratio and BET surface area and pore volume showed better catalytic activity than Ti-Al(ps)KIT-1. The as-prepared catalyst is stable and reusable. The conversion of cyclohexanol was 51.3% after three runs, only decreased by 4.31% after 48 h catalytic reaction at 80 ℃.

Key words: mesoporous sieves Ti-AlKIT-1, titanium-aluminium, cooperative action, oxidation of cyclohexanol

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