双过渡金属杂原子介观催化材料的制备及在有机合成中的应用  

Preparation of mesoscale catalysis materials with bitransition metal heteroatoms and its application in organic synthesis

作　　者：王广健[1,2] 刘广卿[2] 杨振兴[2] 徐明霞[1] 陈士夫[2] 吕莹[2] 

机构地区：[1]天津大学材料科学与工程学院,天津300072 [2]安徽淮北煤炭师范学院化学系,安徽淮北235000

出　　处：《功能材料》2007年第A07期2510-2513,共4页Journal of Functional Materials

基　　金：安徽省教育厅科研基金资助项目（2006kj288）;国家自然科学基金资助项目（20673042）

摘　　要：以煅烧偏高岭土为硅源，Na2MoO4为钼源，ZrO2为锆源，十六烷基三甲基溴化铵（CTAMB）为结构导向剂，利用水热法合成了规则六方结构的Zr-Mo-MCM-41介观催化材料。红外（FTIR）分析表明，799cm^-1处出现的伸缩振动峰可能为Zr-O键和Mo-O键的重叠峰。扫描电镜分析表明，合成的Zr-Mo-MCM-41催化材料的分散性能好，平均粒径在400nm左右且其颗粒为球形，这与X射线衍射（XRD）和激光粒度分析结果相一致．N2吸附脱附曲线研究表明，催化材料具有明显的介孔结构特征，孔径分布窄，在3．3nm左右。以H2O2为氧化剂，环戊烯环氧化反应作为探针反应，结果表明高有序介观催化材料Mo-Zr-MCM-41，与单一的杂原子Mo-MCM-41和Zr-MCM-41催化剂相比，在催化性能、水热稳定性、循环使用次数等方面得到明显改善，体现了双金属的催化协同效应。Mesoscale catalysis materials MCM-41 modified by single （Mo） or bimetal （Mo-Zr） ions with ordered hexagonal arrangement were prepared by direct synthesis under hydrothermal conditions using metakaolinite, sodium molybdate（IV）, zirconium oxide and cetyltrimethylammonium bromide （CTAB） surfactant as silicon source, molybdenum source, zirconium source and structure-directing template, respectively. Characterizations with FT-IR showed that overlap peak of Zr-O and Mo-O bonds maybe responsible for stretching vibration modes at 799 cm^-1. Scanning electron microscopy images indicated that Mo-Zr-MCM-41 was of well dispersion with size ca. 400 nm and sphericity, in agreement with that of X-ray diffraction and laser light-scattering analysis. N2 adsorption-desorption curves revealed that Mo-Zr-MCM-41 was of a typical hexagonal arrangement of mesoporous structure with narrow pore size dispersion （ca. 3.3nm）. The results showed that highly ordered mesoscale catalysis materials Mo-Zr-MCM-41 greatly improved in catalysis performance, hydrothermal stability, circular use index et al in comparison with that of single-heteroatom Mo-MCM-41 and Zr-MCM-41 using H2O2 and cyclopentene epoxidation as oxidant and probe reaction, respectively. This was attribute to bi-transition metals synergistic catalysis effect.

关 键 词：Zr-Mo-MCM-41 偏高岭土 烯烃环氧化 协同催化 

分 类 号：TB383[一般工业技术—材料科学与工程] TQ426.8[化学工程]