Postsynthesis of hierarchical core/shell ZSM-5 as an efficient catalyst in ketalation and acetalization reactions

doi:10.1007/s11705-019-1878-0

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (2) : 258-266 https://doi.org/10.1007/s11705-019-1878-0

RESEARCH ARTICLE

Postsynthesis of hierarchical core/shell ZSM-5 as an efficient catalyst in ketalation and acetalization reactions

Peng Luo, Yejun Guan, Hao Xu(

), Mingyuan He, Peng Wu(

)

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China

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Abstract

Hierarchical core/shell Zeolite Socony Mobil-five (ZSM-5) zeolite was hydrothermally postsythesized in the solution of NaOH and diammonium surfactant via a dissolution-reassembly strategy. The silica and alumina species were firstly dissolved partially from the bulky ZSM-5 crystals and then were in situ reassembled into the MFI-type nanosheets with the structure-directing effect of diammonium surfactant, attaching to the out-surface of ZSM-5 core crystals. The mesopores thus were generated in both the core and shell part, giving rise to a micropore/mesopore composite material. The micropore volume and the acidity of the resultant hybrid were well-preserved during this in situ recrystallization process. Possessing the multiple mesopores and enlarged external surface area, the core/shell ZSM-5 zeolite exhibited higher activity in the ketalation and acetalization reactions involving bulky molecules in comparison to the pristine ZSM-5.

Keywords core/shell ZSM-5 in situ recrystallization mesopore ketalation and acetalization reactions

Corresponding Author(s): Hao Xu,Peng Wu

Online First Date: 15 January 2020 Issue Date: 24 March 2020

Cite this article:

Peng Luo,Yejun Guan,Hao Xu, et al. Postsynthesis of hierarchical core/shell ZSM-5 as an efficient catalyst in ketalation and acetalization reactions[J]. Front. Chem. Sci. Eng., 2020, 14(2): 258-266.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1878-0
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I2/258

Fig.1 XRD patterns (A) and corresponding product yield and Si/Al ratio (B) of pristine ZSM-5 zeolite and the samples treated by NaOH solutions with different concentrations in the presence of diammonium surfactant. Pristine ZSM-5 (a), Re-ZSM-5-0.20 (b), Re-ZSM-5-0.25 (c), Re-ZSM-5-0.30 (d), Re-ZSM-5-0.40 (e). Treatment condition: ZSM-5 : 0.13 C_18-6-Pr : x NaOH : 55 H₂O, 423 K, 5 days.

Fig.2 SEM images of pristine ZSM-5 (a and b), Re-ZSM-5-0.20 (c and d), Re-ZSM-5-0.25 (e and f), Re-ZSM-5-0.30 (g and h), and Re-ZSM-5-0.40 (i and j).

Fig.3 TEM images of Re-ZSM-5-0.25. A whole view under low magnification (a) and high-resolved image of the shell part (b).

Fig.4 EDX analyzed element results of pristine ZSM-5 (a) and Re-ZSM-5-0.25 (b and c).

Fig.5 (A) N₂ sorption isotherms of pristine ZSM-5 (a), Re-ZSM-5-0.25 (b) and Re-ZSM-5-0.30 (c); (B) pore size distribution of pristine ZSM-5 (a), Re-ZSM-5-0.25 (b) and Re-ZSM-5-0.30 (c).

Tab.1 Textural properties of pristine ZSM-5 and Re-ZSM-5 zeolites

Fig.6 FT-IR spectra in the hydroxyl stretching vibration region for pristine ZSM-5 (a) and Re-ZSM-5-0.25 (b).

Fig.7 FT-IR spectra of pyridine desorption on pristine ZSM-5 (A) and Re-ZSM-5-0.25 (B) at different temperatures of 298 K (a), 323 K (b), 373 K (c), 423 K (d) and 473 K (e). (C) FT-IR spectra of pyridine desorption on pristine ZSM-5 (a) and Re-ZSM-5-0.25 (b) at the same temperature of 423 K and (D) NH₃-TPD profiles of pristine ZSM-5 (a) and Re-ZSM-5-0.25 (b).

Fig.8 Catalytic performance of the pristine ZSM-5 and Re-ZSM-5-0.25 in the ketalation of cyclohexanone (a) and the acetalization of benzaldehyde with pentaerythritol (b). Reaction condition: benzaldehyde or cyclohexanone (20 mmol); pentaerythritol (10 mmol); toluene (8 mL); cat., 50 mg; temp., 393 K; reaction time, 2 h for reaction (a) and 2 or 4.5 h for reaction (b).

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