Research Progress on Hierarchically Porous Zeolites: Structural Control, Synthesis and Catalytic Applications

doi:10.15541/jim20170255

Abstract

Abstract:

Zeolite has an excellent ion-exchange property, rich acid sites and good structure and catalysis stability. Therefore, it has been widely used in many fields, i.e., industrial catalysis, separation and adsorption, etc. However, the application of zeolite is greatly limited in many catalytic reactions involved in the large molecules due to its smaller micropore size (< 1.5 nm). The introduction of hierarchically porous structure into conventional zeolite crystals not only keeps their crystalline framework, acidic active sites and high thermal and hydrothermal stability, but also accelerates the diffusion/transfer of larger molecules and greatly decreases the formation of carbon residue, thus prolonging the catalyst life, which enables them more popular applications in the catalytic field. Herein, the recent research progresses of the control of pore structural, the synthesis strategy and mechanism of some typical kinds of hierarchically porous zeolites, including disordered mesoporous/macroporous structure, ordered mesoporous/macroporous structure, dual mesopore structure with certain orientation, hollow structure and macroporous-mesoporous-microporous structure, etc, are concluded. In addition, the application progresses of these hierarchically porous zeolites in catalytic fields are summarized. Compared with the conventional zeolites and amorphous mesopore materials, the novel hierarchically porous zeolites show more excellent catalytic performance due to the crystalline framework and the introduce of hierarchically pore structure. Finally, an outlook for the hierarchically porous zeolite promising development in the future is put forward.

Key words: hierarchically porous, zeolite, structure control, macropore/mesopore/micropore, catalysis, review

CLC Number:

TQ174

CHEN Hang-Rong, ZHOU Xiao-Xia, SHI Jian-Lin. Research Progress on Hierarchically Porous Zeolites: Structural Control, Synthesis and Catalytic Applications[J]. Journal of Inorganic Materials, 2018, 33(2): 113-128.

Figures/Tables 17

Fig. 1 Schematic representation of the influence of Al content on the desilication treatment of MFI zeolites in NaOH solution[22]

Fig. 2 (a) Schematic illustration of hierarchical microporous- mesoporous zeolite crystals ZSM-5 in the presence of an carbon template, typical SEM (b) and TEM (c) images of the templated zeolites, including the electron diffraction pattern[2]

Fig. 3 (a) Schematic synthetic process of hierarchically porous zeolite ZSM-5; (b) FE-SEM image and SAED pattern of the hierarchically porous zeolite ZSM-5; (c) Time dependence of the anisole conversion over different catalysts for Friedel-Crafts acylation of anisole and acetyl chloride[32]

Fig. 4 Schematic illustration of mesoporous zeolite Beta by using cationic polymers, N2 adsorption/desorption isotherms and the corresponding pore-size distribution curve and TEM image of mesoporous zeolite Beta[36,38]

Fig. 5 (a) Formation of ordered mesoporous materials between primary units and CTAB; (b) Amorphous mesophase or a mixture of the mesophse and pure zeolite crystals formed by the assembly between oligomers/nanoparticles and CTAB during room temperature aging; (c) The synthesis of hierarchical mesoporous zeolites (HMZ) by using zeolite subnanocrystal precursor to assemble with CTAB; (d) The formation of nanozeolite aggregates due to size-mismatch between nanocrystals and CTAB[41]

Fig. 6 SEM (a, b), TEM (c), and HR-TEM (d) images of hierarchical mesoporous ZSM-5 zeolites through co-templating of CTAB and F127, and (e) is the corresponding SAED pattern taken from the whole particle in image (c)[41]

Fig. 7 SEM and TEM images and the proposed structure model of the MFI zeolite nanosheets[34]

Fig. 8 (a) Single quaternary ammoniums in the template molecules are located in the straight channel and serve as a template to direct the formation of SCZN; (b) SEM images of as-made samples by using different hydrophobic carbon chain, BCPh-n-6-6; (c) High-resolution transmission electron microscopy (HRTEM) images of as-made SCZN-2 templated by BCPh-6-6-6; (d) Pore properties of calcined SCZN-2[43]

Fig. 9 (A) Schematic drawing of the formation mechanism of sample ZSM-5-ODM; (B) N2 adsorption/desorption isotherms and corresponding BJH pore diameter distribution curves of the sample ZSM-5-ODM; (C) Low and high-magnification FE-SEM images of ZSM-5-ODM with an inset in (e) showing high-resolution image on particular sections; (f)Typical HR-TEM image of ZSM-5-ODM and the corresponding selected area electron diffraction (SAED) pattern (inset)[44]

Fig. 10 Chemical reaction illustration for the condensation of benzaldehyde with ethanol and the effect of reaction time on the conversion of benzaldehyde over the different samples[44]

Fig. 11 (a-e) TEM images of HMZS at different magnifications and its electron diffraction pattern; (f) XRD patterns, (g-h) N2 sorption isotherms and pore size distributions of MZS (●), HMZS (▲) and conventional ZSM-5 zeolite (■). Isotherms of MZS and HMZS are offset by 100 and 200 cm3/g[46]

Fig. 12 Adsorption isotherms of MB and (b) adsorption curves of BHb in PBS by using conventional ZSM-5 zeolite, MZS and HMZS[46]

Fig. 13 Schematic drawing of the suggested formation process of the mesoporous zeolite with a hollow capsular structure (MZ-HCS)[47]

Fig. 14 SEM (a), TEM (b, c) and HR-TEM (d) images of MZ-HCS. Inset in (a) is a deliberately selected capsule with a broken shell; the HR-TEM image was taken from the area in the black square of (c); (e-f) 27Al and 29Si MAS NMR spectra of (A) AAS and (B) MZ-HCS[47]

Fig. 15 SEM images with different magnifications of (a-c) calcined conventional zeolite X and (d-f) hierarchical zeolite X[48]

Fig. 16 Schematic representation of the synthesis of hierarchically micro-meso-macroprous aluminosilicates (left), and TEM investigation of the formation of micro-meso-macroporous aluminosilicate (right)[51]

Table 1 Catalytic activity for cracking of 1,3,5-triisopropylbenzene and the structural parameters for various samples[a][51]

	Conv /%	Contact time /ms	BET surface area /(m²•g^-1)	Si/Al	Product distribution/%
	Conv /%	Contact time /ms	BET surface area /(m²•g^-1)	Si/Al	P1	P2	P3	P4	P5	P6
MMM(2)	28.59	12	562	80	25.29	3.30	7.59	63.80	—	—
	44.46	18	—	—	25.91	3.01	6.57	62.86	—	1.64
	88.63	24	—	—	37.14	13.37	4.73	4.44	12.42	27.87
ZSM-5	17.25	12	302	75	40.75	16.98	25.51	16.75	—	—
	23.26	18	—	—	49.22	25.92	18.57	6.32	—	—
	23.97	24	—	—	24.48	26.41	16.85	5.59	—	—
Al-MCM-41	—	24	996	82	—	—	—	—	—	—
MCM-41	—	24	1075	∞	—	—	—	—	—	—

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