The effect of hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios on its pore structure and catalytic performance

doi:10.1007/s11705-020-1948-3

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (2) : 269-278 https://doi.org/10.1007/s11705-020-1948-3

RESEARCH ARTICLE

The effect of hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios on its pore structure and catalytic performance

Yuexin Hou¹, Xiaoyun Li², Minghui Sun^1,³, Chaofan Li^1,⁴, Syed ul Hasnain Bakhtiar¹, Kunhao Lei¹, Shen Yu¹, Zhao Wang¹, Zhiyi Hu^1,⁴, Lihua Chen¹(

), Bao-Lian Su^1,^3,⁵(

)

¹. Laboratory of Living Materials at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
². State Key Laboratory of Silicate Material for Architectures, Wuhan University of Technology, Wuhan 430070, China
³. Laboratory of Inorganic Materials Chemistry (CMI), University of Namur, B-5000 Namur, Belgium
⁴. Nanostructure Research Centre (NRC), Wuhan University of Technology, Wuhan 430070, China
⁵. Clare Hall, University of Cambridge, Cambridge, CB3 9AL, UK

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Abstract

Hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios (Hier-ZSM-5-x, where x = 50, 100, 150 and 200) were synthesized using an ordered mesoporous carbon-silica composite as hard template. Hier-ZSM-5-x exhibits improved mass transport properties, excellent mechanical and hydrothermal stability, and higher catalytic activity than commercial bulk zeolites in the benzyl alcohol self-etherification reaction. Results show that a decrease in the Si/Al ratio in hierarchical single-crystal ZSM-5 zeolites leads to a significant increase in the acidity and the density of micropores, which increases the final catalytic conversion. The effect of porous hierarchy on the diffusion of active sites and the final catalytic activity was also studied by comparing the catalytic conversion after selectively designed poisoned acid sites. These poisoned Hier-ZSM-5-x shows much higher catalytic conversion than the poisoned commercial ZSM-5 zeolite, which indicates that the numerous intracrystalline mesopores significantly reduce the diffusion path of the reactant, leading to the faster diffusion inside the zeolite to contact with the acid sites in the micropores predominating in ZSM-5 zeolites. This study can be extended to develop a series of hierarchical single-crystal zeolites with expected catalytic performance.

Keywords hierarchical zeolites single crystalline interconnected pores improved diffusion performance benzyl alcohol self-etherification reaction

Corresponding Author(s): Lihua Chen,Bao-Lian Su

Just Accepted Date: 22 April 2020 Online First Date: 13 July 2020 Issue Date: 10 March 2021

Cite this article:

Yuexin Hou,Xiaoyun Li,Minghui Sun, et al. The effect of hierarchical single-crystal ZSM-5 zeolites with different Si/Al ratios on its pore structure and catalytic performance[J]. Front. Chem. Sci. Eng., 2021, 15(2): 269-278.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1948-3
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I2/269

Fig.1 (a) XRD patterns; (b) nitrogen adsorption-desorption isotherms; (c) micropore size distributions; (d) mesopore size distributions of Hier-ZSM-5-x.

Fig.2 (a,b) SEM images of Hier-ZSM-5-50; (c,d) SEM images of Hier-ZSM-5-100; (e,f) SEM images of Hier-ZSM-5-150; (g,h) SEM images of Hier-ZSM-5-200.

Fig.3 (b) TEM image of the Hier-ZSM-5-100 sample; (a,c) SAED patterns of the area indicated by the red and yellow dashed circles in panel (b), respectively; (d,e) HRTEM images of the area indicated by the green and blue boxes in panel (b), respectively; (f) FFT patterns of the area indicated by the white boxes in panel (d) and (e).

Fig.4 (a) ²⁹Si MAS NMR spectra; (b) ²⁷Al MAS NMR spectra; (c) NH₃-TPD profiles of Hier-ZSM-5-x.

Tab.1 Chemical and textural properties for samples and catalytic performance of ZSM-5 zeolite in BA self-etherification reaction

Fig.5 (a) XRD patterns; (b) nitrogen adsorption-desorption isotherms; and (c) SEM images of Hier-ZSM-5-100 with different stability tests: (I) crushed with a pressure of 50 MPa; (II) heated at 120 °C for 2 d in Teflon-lined stainless-steel autoclave; (III) treated with steam at 700 °C for 2 h.

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