Fabrication of MIL-100(Fe)@SiO2@Fe3O4 core-shell microspheres as a magnetically recyclable solid acidic catalyst for the acetalization of benzaldehyde and glycol

doi:10.1007/s11705-016-1596-9

Front. Chem. Sci. Eng.

2016, Vol. 10

Issue (4) : 534-541 https://doi.org/10.1007/s11705-016-1596-9

RESEARCH ARTICLE

Fabrication of MIL-100(Fe)@SiO₂@Fe₃O₄ core-shell microspheres as a magnetically recyclable solid acidic catalyst for the acetalization of benzaldehyde and glycol

Yinlong Hu,Shuang Zheng,Fumin Zhang(

)

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China

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Abstract

Heterogeneous catalysts with convenient recyclability and reusability are vitally important to reduce the cost of catalysts as well as to avoid complex separation and recovery operations. In this regard, magnetic MIL-100(Fe)@SiO₂@Fe₃O₄ microspheres with a novel core-shell structure were fabricated by the in-situ self-assembly of a metal-organic MIL-100(Fe) framework around pre-synthesized magnetic SiO₂@Fe₃O₄ particles under relatively mild and environmentally benign conditions. The catalytic activity of the MIL-100(Fe)@SiO₂@Fe₃O₄ catalyst was tested for the liquid-phase acetalization of benzaldehyde and glycol. The MIL-100(Fe)@SiO₂@Fe₃O₄ catalyst has a significant amount of accessible Lewis acid sites and therefore exhibited good acetalization catalytic activity. Moreover, due to its superparamagnetism properties, the heterogeneous MIL-100(Fe)@SiO₂@Fe₃O₄ catalyst can be easily isolated from the reaction system within a few seconds by simply using an external magnet. The catalyst could then be reused at least eight times without significant loss in catalytic efficiency.

Keywords metal-organic frameworks heterogeneous catalysis magnetically recoverable catalysts core-shell structure acetalization

Corresponding Author(s): Fumin Zhang

Online First Date: 09 November 2016 Issue Date: 29 November 2016

Cite this article:

Yinlong Hu,Shuang Zheng,Fumin Zhang. Fabrication of MIL-100(Fe)@SiO₂@Fe₃O₄ core-shell microspheres as a magnetically recyclable solid acidic catalyst for the acetalization of benzaldehyde and glycol[J]. Front. Chem. Sci. Eng., 2016, 10(4): 534-541.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1596-9
https://academic.hep.com.cn/fcse/EN/Y2016/V10/I4/534

Fig.1 Scheme 1Schematic illustration of the preparation of MIL-100(Fe)@SiO₂@Fe₃O₄ microsphere. TEOS: tetraethoxysilane; APTES: 3-aminopropyltriethoxysilane; H₃BTC: 1,3,5-benzenetricarboxylic acid

Fig.2 SEM images of (A) Fe₃O₄, (B) SiO₂@Fe₃O₄ and TEM images of (C) Fe₃O₄, (D) SiO₂@Fe₃O₄ and (E) MIL-100(Fe)@SiO₂@Fe₃O₄

Fig.3 XRD patterns of simulated Fe₃O₄ obtained from crystal structure data, simulated MIl-100(Fe) obtained from crystal structure data, Fe₃O₄, SiO₂@Fe₃O₄ and MIL-100(Fe)@SiO₂@Fe₃O₄

Fig.4 (A) N₂ adsorption isotherms at ?196 °C and (B) pore size distributions based on the density functional theory of MIL-100(Fe) and MIL-100(Fe)@SiO₂@Fe₃O₄

Tab.1 Physicochemical properties of various catalysts

Fig.5 FTIR spectra of Fe₃O₄, SiO₂@Fe₃O₄, MIL-100(Fe) and MIL-100(Fe)@SiO₂@Fe₃O₄

Fig.6 The magnetic hysteresis loops of Fe₃O₄ and the MIL-100(Fe)@SiO₂@Fe₃O₄ core-shell magnetic catalyst. The photograph in the inset shows the convenient separation process of the catalyst by a magnet

Fig.7 Acetalization of benzaldehyde and glycol in the presence of MIL-100(Fe)@SiO₂@Fe₃O₄ and SiO₂@Fe₃O₄as a function of reaction time. Reaction conditions: 0.06 g of catalyst, 35 mmol of benzaldehyde, 64 mmol of glycol and 10 mL of cyclohexane used as the water removal agent at 80 °C

Fig.8 Activity comparison of different catalysts in the acetalization of benzaldehyde with glycol. (a) blank; (b) MIL-100(Fe)@SiO₂@Fe₃O₄; (c) MIL-100(Fe); (d) USY; (e) H-Beta; (f) Amberlyst-15. Reaction conditions: 0.06 g of catalyst, 35 mmol of benzaldehyde, 64 mmol of glycol and 10 mL of cyclohexane used as the water removal agent at 80 °C for 120 min

Fig.9 Reusability of (A) MIL-100(Fe)@SiO₂@Fe₃O₄ and (B) Amberlyst-15 in the catalytic acetalization of aldehyde with glycol. Reaction conditions: 0.06 g of catalyst, 35 mmol of benzaldehyde, 64 mmol of glycol and 10 mL of cyclohexane used as the water removal agent at 80 °C for 120 min. (a) recovered catalyst with no fresh catalyst added and (b) fresh catalyst added to maintain a constant amount (0.06 g) of catalyst

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