Seed-induced synthesis of functional MFI zeolite materials: Method development, crystallization mechanisms, and catalytic properties

doi:10.1007/s11705-019-1852-x

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (2) : 143-158 https://doi.org/10.1007/s11705-019-1852-x

REVIEW ARTICLE

Seed-induced synthesis of functional MFI zeolite materials: Method development, crystallization mechanisms, and catalytic properties

Zhaoqi Ye¹, Hongbin Zhang²(

), Yahong Zhang¹, Yi Tang¹(

)

¹. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, and Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai 200433, China
². Institute for Preservation of Chinese Ancient Books, Fudan University Library, Fudan University, Shanghai 200433, China

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Abstract

As an important zeolite material, MFI zeolites, as well as their controllable synthesis, are of great interest in both basic and applied science. Among the developed synthetic approaches, the seed-induced method has gradually evolved into a facile, low-cost, and even green alternative to give zeolites the desirable physicochemical properties. In this review, we briefly summarize the development of seed-induced syntheses of diverse functional MFI zeolites, where the “living” seed crystals not only direct the formation of zeolitic framework but also function as special “templates” or “units” to fine-tune the zeolite materials with diverse sizes, shapes, compositions, morphologies and pore structures. Moreover, on the basis of their structural features and crystallization behaviors in seed-induced synthesis, we reveal the roles of seeds and discuss the related crystallization mechanisms including both classical and non-classical pathways. We also want to guide readers to investigate the structure-performance relationships between these functional MFI zeolite catalysts and suitable catalytic reactions.

Keywords seed-induced synthesis MFI zeolite synthesis mechanism catalytic property

Corresponding Author(s): Hongbin Zhang,Yi Tang

Just Accepted Date: 15 October 2019 Online First Date: 29 November 2019 Issue Date: 24 March 2020

Cite this article:

Zhaoqi Ye,Hongbin Zhang,Yahong Zhang, et al. Seed-induced synthesis of functional MFI zeolite materials: Method development, crystallization mechanisms, and catalytic properties[J]. Front. Chem. Sci. Eng., 2020, 14(2): 143-158.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1852-x
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I2/143

Fig.1 Schematic illustration of microstructure control by crystal-shape design, deposition, and growth using different crystal-shape modifiers to construct monolithic membranes with zig-zag channels (right) and straight channels (middle) along its short dimension, or be equiaxed (left) (reprinted by permission from [¹⁶], copyright Wiley, 2007).

Fig.2 Scenarios of the construction of hollow (a) and guest encapsulated (b) zeolite capsules and the corresponding transmission electron microscope (TEM) images of hollow (c) and Fe₂O₃-filled zeolite capsules (d) (adapted with permission from [¹⁹], copyright American Chemistry Society, 2002).

Fig.3 A seed surface crystallization approach for rapid synthesis of single-crystal single-particle ZSM-5 zeolite (a), the scanning electron microscope (SEM) image of the typical product with the corresponding TEM image (b inset, c and d) and selected area electron diffraction (SAED) pattern (c inset), and TEM images of the sample after alkaline treatment (e) (reproduced with permission from Elsevier [¹²]).

Fig.4 Proposed pathway for the fabrication of hierarchical zeolites from silanized seeds (a) and TEM image of products prepared with typical organosilanes such as (3-aminopropyl)trimethoxysilane (b and c) and n-octadecyltrimethoxysilane (d and e) (adapted with permission from the Royal Society of Chemistry [²¹]).

Fig.5 TEM images of the ZSM-5 mesocrystals synthesized with different KF/Si (= x), TPABr/Si (= y), and H₂O/Si (= z) ratios and types of organic templates (EA, HDA, and TEA denote ethylamine, hexamethylenediamine, and trimethylamine, respectively). The results are adapted with permission from [²²], copyright Wiley 2016.

Fig.6 Field emission SEM (a) and TEM image (b, c) of crystal bundle-like MFI mesocrystal and the corresponding SAED image (c inset); high resolution TEM image (d, e) of nanorods and corresponding FFT image (e inset); high-angle annular dark field scanning transmission electron microscopy image of an individual particle (f) with the Si (g) and Al (h) mapping results at the same area. Scale bars are 400 (a, b), 250 (c, f–h), 10 (d), and 5 nm (e). Reprinted with permission from the American Chemistry Society [²³].

Fig.7 Schematic illustration showing different routes for the seed-induced synthesis of functional zeolite materials. Reproduced with modification from [²²], copyright Wiley 2016.

Fig.8 Possible pathways of zeolite crystallization. Reprinted with permission from the American Chemistry Society [²⁷].

Fig.9 SEM image of silicalite-1 seed used in initial gels (a) with a sketch of an aggregated structure (b), and the result of the secondary growth of a monocrystalline particle (c) and a polycrystalline aggregate (d) exemplified by TEM images respectively. The results are adapted with permission from [¹¹], copyright the American Chemistry Society 2009.

Fig.10 (A) Evolution of precursor particles and their distinctive attachment modes on the seed during the non-classical crystallization to construct diverse mesocrystals; (B) morphology of the as-synthesized MFI-BZM (a), their distinctive core-shell-shell mesoscopic structure (silicalite-1@nanocrystal ZSM-5@nanorod ZSM-5) (b), and the detail of the seed-induced dynamic particle-attached mechanism (c). Reproduced with permission from the American Chemical Society [²³].

Tab.1 Si/Al ratio and acid properties of typical seed-directed MFI zeolites

Fig.11 Conversion and selectivity for the tandem reaction of Pt@HSM, Broken-Pt@HSM and commercial Pt-SiO₂ (a), and the corresponding schematic illustrations of the whole process of the reactions on Pt@HSM and Broken-Pt@HSM (b). Reproduced with permission from the Royal Society of Chemistry [¹⁰³].

Fig.12 Conversion of methanol over conventional ZSM-5, NS-Z5 with/without the introduction of the boron (a), and glycerol conversion over ZSM-5 with different porosity (b). The results are adapted in part with permission from [²⁸] and [³¹].

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[1]	Baoyu Liu, Qiaowen Mu, Jiajin Huang, Wei Tan, Jing Xiao. Fabrication of titanosilicate pillared MFI zeolites with tailored catalytic activity[J]. Front. Chem. Sci. Eng., 2020, 14(5): 772-782.

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