Mesoporous Zeolite ZSM-5 Synthesized via Gel Conversion with Polyethyleneglycol as Template and Its Catalytic Performance

doi:10.15541/jim20150180

Abstract

Abstract:

A simple strategy for synthesizing mesoporous zeolite ZSM-5 via gel conversion was successfully developed with polyethyleneglycol as mesopore directing agent. It is revealed that the gel obtained after 9-15 h evaporation of solvents could be transferred into mesoporous ZSM-5 zeolite after treatment at 160℃ for 24 h. However, pure ZSM-5 zeolite or mesoporous silica was achieved with too short or too long evaporation periods. The results indicate that the gelation process through solvent evaporation controls the hierarchical structure formation kinetically, which not only provides an appropriate amount of water for zeolite crystallization, but also prevents the phase-separation between zeolite and amorphous phases. Due to the introduction of the mesoporosity of several tens of nanometers in size, this hierarchical micro/mesostructured zeolite exhibits enhanced catalytic activities in the large molecules involved reactions, including aldol condensation of benzaldehyde with n-butyl alcohol and Pechmann reaction of resorcinol with ethylacetoacetate.

Key words: mesoporous zeolite, polyethyleneglycol, gel conversion, one-pot

CLC Number:

O611

AN Jian-Guo, GAO Xiang, JIN Jun-Jiang, GU Jin-Lou, LI Liang, LI Yong-Sheng, SHI Jian-Lin. Mesoporous Zeolite ZSM-5 Synthesized via Gel Conversion with Polyethyleneglycol as Template and Its Catalytic Performance[J]. Journal of Inorganic Materials, 2015, 30(11): 1148-1154.

Figures/Tables 11

Fig. 1 XRD patterns of conventional ZSM-5 and MZ-X samples

Fig. 2 (a) N2 adsorption-desorption isotherms of MZ-X samples and (b) N2 adsorption-desorption isotherms of conventional ZSM-5 and MZ-9 with the pore-size distribution curve of MZ-9 (inset)

Table 1 Textural properties of the samples

Sample	Gel weight loss /%	S_BET /(m²·g^-1)	S_external /(m²·g^-1)	V_total /(cm³·g^-1)	V_micro /(cm³·g^-1)	V_external /(cm³·g^-1)	Pore size /nm
MZ-0	95	385	85	0.18	0.12	0.06	-
MZ-9	87	441	172	0.30	0.11	0.19	10-50
MZ-15	82	469	365	0.60	0.06	0.54	10-40
MZ-21	64	603	603	1.36	0	1.36	5-15
Conventional ZSM-5	-	395	98	0.18	0.11	0.07	-

Fig. 3 SEM images of MZ-0 (a), MZ-9 (b, c), MZ-15 (d) and MZ-21 (e, f)

Fig. 4 TEM images of MZ-9 at different magnifications (a, b) and HR-TEM images from the area marked by a white square in b (c), as well as selected area electron diffraction (SAED) corresponded to c (d)

Fig. 5 29Si (a) and 27Al (b) MAS NMR spectra of MZ-9

Fig. 6 Thermogravimetric analysis (TGA) curves of conventional ZSM-5 and MZ-9

Fig. 7 Proposed synthesis procedure of mesoporous ZSM-5 templated by PEG

Fig. 8 NH3-TPD profiles of conventional H-ZSM-5 and MZ-9

Fig. 9 Aldol condensation of benzaldehyde and n-butyl alcohol (a) and Pechmann reaction of resorcinol with ethyl acetoacetate (b)

Table 2 Catalytic properties of MZ-9 and conventional ZSM-5[a]

Reactions	MZ-9 (Si/Al=25)	Con ZSM-5 (Si/Al=25)
Benzaldehyde + n-butyl alcohol	43.3	19.1
Resorcinol+ethylacetoacetate	40.0	17.5

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