铝在β沸石中的状态及酸性或碱性介质的影响

Chun Yang, Qinhua Xuaf
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引用次数: 71

摘要

用傅立叶红外光谱对铝在沸石β中的状态进行了详细的研究。在去模板沸石β中检测到三种铝——框架铝、非框架铝和瞬态铝。我们样品中铝的状态强烈依赖于补偿阳离子的性质,这与brougate - lami等人的结论一致。对铝的种类进行了新的分配,并对铝的状态及其转变提出了新的看法。实验结果表明,由于β沸石的骨架是可变形的,当具有高电子亲和性的质子位于阳离子位置时,沸石晶格会发生畸变和张力,导致Al-O键断裂和铝的去除。因此,β沸石在酸性介质中受到脱铝作用。另一方面,当H+被其他阳离子(如Na+)取代时,沸石的高变形性也会导致沸石结构的松弛,从而使瞬态铝甚至非骨架铝回到骨架中。由于离子交换作用,阳离子非框架铝进入溶液;在碱性介质中羟基化后也可重新插入骨架中。
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States of aluminum in zeolite β and influence of acidic or basic medium

The states of aluminum in zeolites β were investigated in detail with FTIR spectroscopy. Three kinds of aluminum—framework, nonframework, and transient-state aluminum—were detected in template-removed zeolite β. The states of aluminum in our samples intensely depends on the nature of compensating cation, consistent with the conclusion of Brougeat-Lami et al. But some new assignments of aluminum species and new opinions about the states of aluminum and their transformation are proposed. From the experimental results, we suggest that, because the framework of zeolite β is deformable, the distortion and the tension of zeolite lattice occur when protons, which possess high electron affinity, are located at cationic sites, leading to the breakage of Al-O bond and the removal of aluminum. Therefore, zeolite β is subjected to dealumination in acidic medium. On the other hand, the high deformability also results in the relaxation of zeolite structure when H+ is replaced by other cations (e.g., Na+) so that transient-state aluminum and even nonframework aluminum can go back into the framework. Owing to ion-exchange, the cationic nonframework aluminum species enter the solution; moreover, it can also reinsert into the framework after hydroxylation in basic medium.

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Metal-organic Frameworks for Catalysis 19th International Zeolite Conference(IZC’19)参加報告 19th International Zeolite Conference(IZC’19)参加報告 実験化学,計算機化学,データサイエンスの融合による設計的ゼオライト合成 古典的なASFモデルを打破するジェット燃料直接合成用Co/Ymeso-La触媒
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