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直接合成具有高锰含量的有序且反应活性异常的MnSBA - 15介孔分子筛。

Direct synthesis of well-ordered and unusually reactive MnSBA-15 mesoporous molecular sieves with high manganese content.

作者信息

Selvaraj M, Lee T G

机构信息

Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore - 119260.

出版信息

J Phys Chem B. 2006 Nov 2;110(43):21793-802. doi: 10.1021/jp063957i.

Abstract

The mesoporous MnSBA-15 materials with different n(Si)/n(Mn) ratios of 4, 8, 20, and 50 have been synthesized, for the first time, using manganese nitrate tetrahydrate and Pluronic 123 triblock polymer [(EO)20(PO)70(EO)20] by simply adjusting the molar ratio of water to hydrochloric acid (n(H2O)/n(HCl)) under direct hydrothermal conditions. For the effect of structural and textural properties with incorporation of manganese, the MnSBA-15 has been synthesized with different synthesis temperatures at the fixed molar ratios of n(Si)/n(Mn) = 4 and n(H2O)/n(HCl) = 295 in the synthesis gel. The hydrothermal and thermal stabilities of MnSBA-15 have also been investigated. The calcined MnSBA-15 materials prepared have been characterized by ICP-AES, XRD, N2 adsorption, ESR, FE-SEM, and TEM. The ICP-AES studies show a higher amount of manganese incorporation on the silica pore walls, as MnSBA-15 with a n(Si)/n(Mn) ratio up to 2.2 can be successfully prepared at a fixed n(H2O)/n(HCl) molar ratio of 295 by adjusting the ratios of n(Si)/n(Mn) in the synthesis gel. The structural and textural properties of calcined MnSBA-15 prepared can be found by the results of XRD and N2 adsorption. The investigation of ESR results clearly describe the effect of structure and Mn species coordination on the SBA-15 silica pore walls while the uniform pore diameter and rope-like hexagonal mesoporous structure of MnSBA-15 can be identified by TEM and FE-SEM images. With increasing synthesis temperature, an increase the unit cell parameter, pore size, and pore volume and a decrease the specific surface area and pore wall thickness of MnSBA-15 can be obviously noted by the results of XRD and N2 adsorption. The hexagonal MnSBA-15 materials prepared could be tested as catalysts in epoxidation of trans-stilbene to produce trans-stilbene oxide under various optimal conditions while their catalytic properties could also be compared to the results of MnMCM-41 and ZrMnMCM-41.

摘要

首次通过在直接水热条件下简单调节水与盐酸的摩尔比(n(H₂O)/n(HCl)),使用四水合硝酸锰和普朗尼克123三嵌段聚合物[(EO)₂₀(PO)₇₀(EO)₂₀]合成了n(Si)/n(Mn)比分别为4、8、20和50的介孔MnSBA - 15材料。为了研究锰掺入对结构和织构性质的影响,在合成凝胶中固定n(Si)/n(Mn) = 4和n(H₂O)/n(HCl) = 295的摩尔比下,以不同的合成温度合成了MnSBA - 15。还研究了MnSBA - 15的水热稳定性和热稳定性。通过ICP - AES、XRD、N₂吸附、ESR、FE - SEM和TEM对制备的煅烧MnSBA - 15材料进行了表征。ICP - AES研究表明,在二氧化硅孔壁上有较高的锰掺入量,因为在固定的n(H₂O)/n(HCl)摩尔比为295的情况下,通过调节合成凝胶中的n(Si)/n(Mn)比,可以成功制备n(Si)/n(Mn)比高达2.2的MnSBA - 15。通过XRD和N₂吸附结果可以了解制备的煅烧MnSBA - 15的结构和织构性质。ESR结果的研究清楚地描述了结构和锰物种配位对SBA - 15二氧化硅孔壁的影响,而MnSBA - 15的均匀孔径和绳状六方介孔结构可以通过TEM和FE - SEM图像识别。XRD和N₂吸附结果表明,随着合成温度的升高,MnSBA - 15的晶胞参数、孔径和孔体积增加,比表面积和孔壁厚度减小。制备的六方MnSBA - 15材料可以在各种最佳条件下作为反式二苯乙烯环氧化制备反式氧化二苯乙烯的催化剂进行测试,同时其催化性能也可以与MnMCM - 41和ZrMnMCM - 41的结果进行比较。

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