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

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.

Graphical abstract

Keywords

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

References

[1] Sartori G, Ballini R, Bigi F, Bosica G, Maggi R, Righi P. Protection (and deprotection) of functional groups in organic synthesis by heterogeneous catalysis. Chemical Reviews, 2004, 104(1): 199–250

[2] Miao J, Wan H, Shao Y, Guan G, Xu B. Acetalization of carbonyl compounds catalyzed by acidic ionic liquid immobilized on silica gel. Journal of Molecular Catalysis A Chemical, 2011, 348(1-2): 77–82

[3] Wang Y, Gong X, Wang Z, Dai L. SO3H-functionalized ionic liquids as efficient and recyclable catalysts for the synthesis of pentaerythritol diacetals and diketals. Journal of Molecular Catalysis A: Chemical, 2010, 322(1-2): 7–16

[4] Iwamoto M, Tanaka Y, Sawamura N, Namba S. Remarkable effect of pore size on the catalytic activity of mesoporous silica for the acetalization of cyclohexanone with methanol. Journal of the American Chemical Society, 2003, 125(43): 13032–13033

[5] Climent M J, Corma A, Iborra S, Navarro M C, Primo J. Use of mesoporous MCM-41 aluminosilicates as catalysts in the production of fine chemicals: Preparation of dimethylacetals. Journal of Catalysis, 1996, 161(2): 783–789

[6] Parangi T F, Wani B N, Chudasama U V. Acetalization of carbonyl compounds with pentaerythritol catalyzed by metal(iv) phosphates as solid acid catalysts. Industrial & Engineering Chemistry Research, 2013, 52(26): 8969–8977

[7] Dhakshinamoorthy A, Alvaro M, Garcia H. Metal organic frameworks as solid acid catalysts for acetalization of aldehydes with methanol. Advanced Synthesis & Catalysis, 2010, 352(17): 3022–3030

[8] Jin Y, Shi J, Zhang F, Zhong Y, Zhu W. Synthesis of sulfonic acid-functionalized MIL-101 for acetalization of aldehydes with diols. Journal of Molecular Catalysis A Chemical, 2014, 383-384: 167–171

[9] Corma A, García H, Llabrés i Xamena F X. Engineering metal organic frameworks for heterogeneous catalysis. Chemical Reviews, 2010, 110(8): 4606–4655

[10] Gascon J, Corma A, Kapteijn F, Llabrés i Xamena F X. Metal organic framework catalysis: Quo vadis? ACS Catalysis, 2014, 4(2): 361–378

[11] Al-Janabi N, Alfutimie A, Siperstein F R, Fan X. Underlying mechanism of the hydrothermal instability of Cu₃(BTC)₂ metal-organic framework. Frontiers of Chemical Science and Engineering, 2015: 1–5

[12] Dhakshinamoorthy A, Asiri A M, Garcia H. Catalysis by metal-organic frameworks in water. Chemical Communications, 2014, 50(85): 12800–12814

[13] Horcajada P, Surblé S, Serre C, Hong D Y, Seo Y K, Chang J S, Grenèche J M, Margiolaki I, Férey G. Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores. Chemical Communications, 2007, 27(27): 2820–2822

[14] Yoon J W, Seo Y K, Hwang Y K, Chang J S, Leclerc H, Wuttke S, Bazin P, Vimont A, Daturi M, Bloch E, Llewellyn P L, Serre C, Horcajada P, Grenèche J M, Rodrigues A E, Férey G. Controlled reducibility of a metal-organic framework with coordinatively unsaturated sites for preferential gas sorption. Angewandte Chemie International Edition, 2010, 49(34): 5949–5952

[15] Dhakshinamoorthy A, Alvaro M, Chevreau H, Horcajada P, Devic T, Serre C, Garcia H. Iron(iii) metal-organic frameworks as solid Lewis acids for the isomerization of a-pinene oxide. Catalysis Science & Technology, 2012, 2(2): 324–330

[16] Zhang F, Jin Y, Shi J, Zhong Y, Zhu W, El-Shall M S. Polyoxometalates confined in the mesoporous cages of metal-organic framework MIL-100(Fe): Efficient heterogeneous catalysts for esterification and acetalization reactions. Chemical Engineering Journal, 2015, 269: 236–244

[17] Zhang F, Shi J, Jin Y, Fu Y, Zhong Y, Zhu W. Facile synthesis of MIL-100(Fe) under HF-free conditions and its application in the acetalization of aldehydes with diols. Chemical Engineering Journal, 2015, 259: 183–190

[18] Lukosi M, Zhu H, Dai S. Recent advances in gold-metal oxide core-shell nanoparticles: Synthesis, characterization, and their application for heterogeneous catalysis. Frontiers of Chemical Science and Engineering, 2016, 10(1): 39–56

[19] Govan J, Gun’ko Y K. Recent advances in the application of magnetic nanoparticles as a support for homogeneous catalysts. Nanomaterials (Basel, Switzerland), 2014, 4(2): 222–241

[20] Zhang T, Zhang X, Yan X, Kong L, Zhang G, Liu H, Qiu J, Yeung K L. Synthesis of Fe₃O₄@ZIF-8 magnetic core-shell microspheres and their potential application in a capillary microreactor. Chemical Engineering Journal, 2013, 228: 398–404

[21] Zhang H J, Qi S D, Niu X Y, Hu J, Ren C L, Chen H L, Chen X G. Metallic nanoparticles immobilized in magnetic metal-organic frameworks: Preparation and application as highly active, magnetically isolable and reusable catalysts. Catalysis Science & Technology, 2014, 4(9): 3013–3024

[22] Deng Y, Qi D, Deng C, Zhang X, Zhao D. Superparamagnetic high-magnetization microspheres with an Fe3O4@SiO2 core and perpendicularly aligned mesoporous SiO2 shell for removal of microcystins. Journal of the American Chemical Society, 2008, 130(1): 28–29

[23] Ding H L, Zhang Y X, Wang S, Xu J M, Xu S C, Li G H. Fe₃O₄@SiO₂ core/shell nanoparticles: The silica coating regulations with a single core for different core sizes and shell thicknesses. Chemistry of Materials, 2012, 24(23): 4572–4580

[24] Zhang C F, Qiu L G, Ke F, Zhu Y J, Yuan Y P, Xu G S, Jiang X. A novel magnetic recyclable photocatalyst based on a core-shell metal-organic framework Fe₃O₄@MIL-100(Fe) for the decolorization of methylene blue dye. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(45): 14329–14334

[25] Yu S, Wan J, Chen K. A facile synthesis of superparamagnetic Fe₃O₄ supraparticles@MIL-100(Fe) core-shell nanostructures: Preparation, characterization and biocompatibility. Journal of Colloid and Interface Science, 2016, 461: 173–178

[26] Ke F, Qiu L G, Zhu J. Fe₃O₄@MOF core-shell magnetic microspheres as excellent catalysts for the Claisen-Schmidt condensation reaction. Nanoscale, 2014, 6(3): 1596–1601

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Higher Education Press and Springer-Verlag Berlin Heidelberg