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基于ZSM-5纳米晶种的有序介孔铝硅酸盐的高温合成及其酸性性能的改善

High-Temperature Synthesis of Ordered Mesoporous Aluminosilicates from ZSM-5 Nanoseeds with Improved Acidic Properties.

作者信息

Vu Xuan Hoan, Eckelt Reinhard, Armbruster Udo, Martin Andreas

机构信息

Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059 Rostock, Germany.

出版信息

Nanomaterials (Basel). 2014 Aug 18;4(3):712-725. doi: 10.3390/nano4030712.

Abstract

Ordered mesoporous SBA-15 analogs with different Si/Al ratios were successfully prepared in a two-step process from self-assembly of ZSM-5 nanoseeds at high temperature in mildly acidic media (473 K, pH 3.5). The obtained products were characterized as SAXS, XRD, N₂ sorption, FTIR, TEM, NH₃-TPD, AAS and ICP. The results show that the initial Si/Al molar ratio of ZSM-5 precursors strongly affects the final materials' properties. A highly condensed, well-ordered mesoporous SBA-15 analog with improved hydrothermal stability and acidic properties can be prepared from low aluminum containing ZSM-5 precursors (Si/Al ≥ 20). Reducing the initial Si/Al molar ratio to 10, however, leads to the formation of a disordered mesoporous SBA-15 type material accompanied by degraded textural and acidic properties. The gas phase cracking of cumene, carried out as probe reaction to evaluate Brønsted acidity, reveals that an increased density of Brønsted acid sites has been achieved over the SBA-15 analogs compared to conventional Al-SBA-15 due to the preservation of zeolite building units in the mesopore walls of the SBA-15 analogs.

摘要

通过两步法,在温和酸性介质(473 K,pH 3.5)中,由ZSM-5纳米晶种在高温下自组装成功制备了具有不同Si/Al比的有序介孔SBA-15类似物。采用小角X射线散射(SAXS)、X射线衍射(XRD)、N₂吸附、傅里叶变换红外光谱(FTIR)、透射电子显微镜(TEM)、氨程序升温脱附(NH₃-TPD)、原子吸收光谱(AAS)和电感耦合等离子体发射光谱(ICP)对所得产物进行了表征。结果表明,ZSM-5前驱体的初始Si/Al摩尔比对最终材料的性能有很大影响。由低铝含量的ZSM-5前驱体(Si/Al≥20)可以制备出具有高度缩合、有序介孔结构、水热稳定性和酸性均得到改善的SBA-15类似物。然而,将初始Si/Al摩尔比降至10时,会导致形成无序的介孔SBA-15型材料,同时其结构和酸性性能也会下降。以异丙苯的气相裂解作为探针反应来评估布朗斯特酸度,结果表明,与传统的Al-SBA-15相比,由于SBA-15类似物的介孔壁中保留了沸石结构单元,其布朗斯特酸位密度有所增加。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c13f/5304696/1c1ce11698c3/nanomaterials-04-00712-g001.jpg

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