MFI沸石前驱体和硅酸钠共组装制备水热稳定的管状介孔分子筛

化学学报 ›› 2004, Vol. 62 ›› Issue (14): 1357-1361. 上一篇下一篇

MFI沸石前驱体和硅酸钠共组装制备水热稳定的管状介孔分子筛

郑均林, 张晔, 吴东, 孙予罕

中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 太原, 030001

投稿日期:2003-04-21 修回日期:2004-03-31 发布日期:2014-02-17
通讯作者: 孙予罕,E-mail:yhsun@sxicc.ac.cn E-mail:yhsun@sxicc.ac.cn
基金资助:
国家重点基础研究专项经费(No.G2000048001)、国家重点自然科学基金(No.29973057)和山西省自然科学基金(No.991023)资助项目.

Synthesis of Hydrothermally Stable Mesoporous Aluminosilicates with Tubular Morphology from MFI Zeolitic Precursors and Sodium Silicates

ZHENG Jun-Lin, ZHANG Ye, WU Dong, SUN Yu-Han

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001

Received:2003-04-21 Revised:2004-03-31 Published:2014-02-17

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摘要/Abstract

在CTAB模板剂的作用下,硅酸钠、铝酸钠和含有MFI纳米簇的沸石前躯体溶液通过S⁺I^-路线共组装得到了高水热稳定的管状形貌介孔分子筛.XRD结果显示样品具有类似MGM-41的规则排列六方孔道结构.在沸水中处理150 h后,介孔特征仍然保留,显示出很好的水热稳定性.综合SEM和TEM的观察结果,此介孔分子筛具有中空的管状形貌,平均管长2.0μm,平均直径为0.30 μm.含有MFI纳米簇的沸石前躯体作为硅源的一部分加入体系中,MFI纳米簇伴随来自于硅酸钠的可溶性硅物种共同进入分子筛骨架,在提高水热稳定性的同时,没有降低六方纳米孔道的规整度,也没有对分子筛形貌调变带来不利影响.MFI纳米簇中,硅氧四面体和铝氧四面体的紧密联结方式在进入分子筛骨架时得以保留是水热稳定性提高的主要原因.作为硅源的另一部分加入的硅酸钠,使合成体系pH值足够高(pH＞13),加入H₂SO₄调节体系pH值到10,管状形貌的介孔分子筛在逐步中和过程中形成.通过这种特殊的共组装方法合成介孔分子筛,在获得中空的管状形貌的同时显著提高水热稳定性,为这种管状形貌介孔分子筛的应用奠定了基础.

关键词: 介孔分子筛, 水热稳定性, 形貌控制, 管状, 沸石前躯体

Hydrothermally stable mesoporous aluminosilicates with hollow tubular morphology and hexagonal nanochannels were prepared through co-assembly of sodium silicates, sodium aluminates and MFI aluminosilicate precursors.The XRD results indicated that the synthesized materials were well-ordered hexagonal mesostructures of MCM-41 type.The highly regular hexagonal mesostructures could survive 150 h age in boiling water, exhibiting good hydrothermal stability.Combining the SEM and TEM investigations, the as-made materials showed hollow tubular morphology with mean diameter of 0.30 μm and average length of 2.0 μm.MFI aluminosilicate precursors as precursor (I) enhanced the hydrothermal stability without compromising the ability to tailor the second-order structure.Sodium silicates donating soluble silica species as precursor (II) made the assembly system strongly alkaline, and hollow tubular morphology of mesoporous aluminosilicates evolved after the pH value of the mixture was adjusted to 10 by adding proper amount of H₂SO₄.Under the direction of CTAB template, these two different precursors cooperated with each other and condensed together in the assembly process.Combining the properties of good hydrothermal stability, tubular morphology and high surface areas, these mesostructured materials can find potential applications in catalysis, separation and optic electronics.

Key words: mesoporous aluminosilicate, hydrothermal stability, morphology tailoring, tubule, protozeolitic nanoclusters

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郑均林, 张晔, 吴东, 孙予罕. MFI沸石前驱体和硅酸钠共组装制备水热稳定的管状介孔分子筛[J]. 化学学报, 2004, 62(14): 1357-1361.

ZHENG Jun-Lin, ZHANG Ye, WU Dong, SUN Yu-Han. Synthesis of Hydrothermally Stable Mesoporous Aluminosilicates with Tubular Morphology from MFI Zeolitic Precursors and Sodium Silicates[J]. Acta Chimica Sinica, 2004, 62(14): 1357-1361.

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