State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences , P.O. Box 165, Taiyuan, Shanxi 030001, PR China.
University of Chinese Academy of Sciences , Beijing 100049, PR China.
ACS Appl Mater Interfaces. 2017 May 3;9(17):14899-14910. doi: 10.1021/acsami.7b02738. Epub 2017 Apr 18.
Chainlike zeolites are advantageous to various applications as a catalyst or an adsorbent with specific selectivity; however, it is often very difficult to get desired morphology due to the complexity of zeolite synthesis process. In this work, appropriate parameters for the synthesis of perfect chainlike ZSM-5 zeolites were well determined, which illustrates that the chain length can be controlled by the composition of synthesis mixture, the amount of residual alcohol in the synthesis system, and the crystallization time. Moreover, the mechanism of chainlike crystal growth was investigated by analyzing the surface species during the synthesis process, with the help of density functional theory (DFT) calculation. The results indicate that the formation of disk crystals with proper dimension and flat surface having abundant hydroxyl groups is crucial to the growth of chainlike ZSM-5 crystals; the condensation of Si-OH groups on the (010) facet is energetically more favorable than that on other facets, leading to the growth of MFI crystals along the b-orientation. Through finely tuning the multifarious synthesis parameters, chainlike ZSM-5 zeolites with controllable length in b-orientation are obtained without using any other extra organic additives except the necessary template agent such as tetrapropylammonium hydroxide (TPAOH). Owing to the increased tortuosity of pore channels in the chainlike ZSM-5, the difference between p-xylene and o/m-xylenes in their adsorption behavior and diffusivity is greatly enhanced. These results help to clarify the formation mechanism of zeolites with chainlike morphology and then bring forward an effective approach to get zeolite materials with specific properties in adsorption and catalysis.
链状沸石作为一种具有特定选择性的催化剂或吸附剂具有许多优势,然而,由于沸石合成过程的复杂性,往往很难获得所需的形态。在这项工作中,我们确定了合成完美链状 ZSM-5 沸石的合适参数,这表明链长可以通过合成混合物的组成、合成体系中残留醇的量和结晶时间来控制。此外,通过分析合成过程中的表面物种,并借助密度泛函理论(DFT)计算,研究了链状晶体生长的机理。结果表明,形成具有适当尺寸和丰富羟基的平坦表面的圆盘晶体对于链状 ZSM-5 晶体的生长至关重要;Si-OH 基团在(010)面上的缩合在能量上比在其他面上更有利,导致 MFI 晶体沿着 b 方向生长。通过精细调整各种合成参数,在不使用任何其他额外有机添加剂(除了必要的模板剂如四丙基氢氧化铵(TPAOH)的情况下,得到了具有可控长度的沿 b 方向生长的链状 ZSM-5 沸石。由于链状 ZSM-5 中孔道的迂曲度增加,p-二甲苯和邻/间二甲苯在吸附行为和扩散性方面的差异大大增强。这些结果有助于阐明具有链状形态的沸石的形成机制,从而提出了一种获得具有特定吸附和催化性能的沸石材料的有效方法。