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用于甲醇选择性氧化制二甲氧基甲烷的介孔VO(x)-TiO2复合氧化物的制备与表征

Preparation and characterization of mesoporous VO(x)-TiO2 complex oxides for the selective oxidation of methanol to dimethoxymethane.

作者信息

Liu Jingwei, Sun Qing, Fu Yuchuan, Shen Jianyi

机构信息

Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.

出版信息

J Colloid Interface Sci. 2009 Jul 15;335(2):216-21. doi: 10.1016/j.jcis.2009.03.027. Epub 2009 Apr 2.

Abstract

Mesoporous VO(x)-TiO(2) with high surface areas were prepared using the procedure of evaporation-induced self-assembly combined with ammonia posttreatment. The samples were characterized by X-ray diffraction (XRD), laser Raman spectroscopy (LRS), transmission electron microscopy (TEM), N(2) adsorption, temperature-programmed reduction (H(2)-TPR), microcalorimetry for the adsorption of NH(3), and isopropanol probe reaction. Their catalytic activities were evaluated for the reaction of selective oxidation of methanol to dimethoxymethane (DMM). It was found that the VO(x)-TiO(2) materials exhibited high surface areas with pore diameters of 4 nm. The vanadia species were highly dispersed in the VO(x)-TiO(2) within 30 wt% VO(x) content, evidenced by the results of XRD and LRS. The VO(x)-TiO(2) samples exhibited both surface acidic and redox properties. The surface acidity was further enhanced on the addition of SO(4)2-. The catalyst SO(4)2-/30VO(x)-TiO(2) exhibited good performance for the selective oxidation of methanol (57% conversion) to DMM (83% selectivity) at 423 K.

摘要

采用蒸发诱导自组装结合氨后处理的方法制备了具有高比表面积的介孔VO(x)-TiO(2)。通过X射线衍射(XRD)、激光拉曼光谱(LRS)、透射电子显微镜(TEM)、N(2)吸附、程序升温还原(H(2)-TPR)、NH(3)吸附微量热法和异丙醇探针反应对样品进行了表征。评估了它们对甲醇选择性氧化制二甲氧基甲烷(DMM)反应的催化活性。结果发现,VO(x)-TiO(2)材料具有高比表面积,孔径为4nm。通过XRD和LRS结果证明,在VO(x)含量为30wt%时,钒物种在VO(x)-TiO(2)中高度分散。VO(x)-TiO(2)样品兼具表面酸性和氧化还原性质。添加SO(4)2-后表面酸性进一步增强。催化剂SO(4)2-/30VO(x)-TiO(2)在423K下对甲醇选择性氧化制DMM表现出良好的性能(转化率57%,选择性83%)。

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