Schiff base functionalized Fe3O4@Boehmite Core-Shell Nano-Particles to Support MoO2(acac)2 for Catalytic Epoxidation of Alkenes

Document Type : Research Paper


1 Department of Chemistry, Shahrood university of technology, shahrood, Iran

2 Department of chemistry, Shahrood university of technology, shahrood, Iran


Fe3O4 nanoparticles were prepared solvothermally and then covered with boehmite shell via hydrothermal assisted sol-gel processing of aluminum 2-propoxide. Then the hydroxyl covered outer surface of the boehmite shell was covalently functionalized with 3-(tri-methoxysilyl) propylamine and the terminal amine groups converted to imine by refluxing with 2-hydroxybenzaldehyde. Then it was used to support bis-acetylacetonato-di-oxo-molybdenum (VI). The supported catalyst was characterized by Fourier transform Infrared spectroscopy, elemental analysis, inductive coupled plasma and transmission electron microscopy analysis and it was applied in the epoxidation of cis-cyclooctene. The catalytic procedure was optimized for different parameters such as solvent, oxidant, and temperature. The reaction progress was investigated by gas-liquid chromatography analysis. The used catalyst was simply recovered from the solution by applying a magnet and recycling experiments revealed that this heterogeneous nano-catalyst could be repeatedly applied for the epoxidation of cis-cyclooctene. The optimized conditions were also used for the epoxidation of some other alkenes successfully.


Main Subjects

[1] Y. Zhu, L.P. Stubbs, F. Ho, R. Liu, C.P. Ship, J.A. Maguire, N. S. Hosmane, “Magnetic Nanocomposites: A New Perspective in Catalysis”, ChemCatChem, Vol. 2, 2010, pp. 365-374.
[2] Á. Molnár, A. Papp, “Catalyst recycling-A survey of recent progress and current status”, Coord. Chem. Rev., Vol. 349, 2017, pp. 1-65.
[3] M.S. Kwon, I.S. Park, J.S. Jang, J.S. Lee, J. Park, “Magnetically separable Pd catalyst for
highly selective epoxide hydrogenolysis under mild conditions”, Org. Lett., Vol. 9, 2007, pp. 3417-3419.
[4] M. Mirzaee, B. Bahramian, A. Amoli, “Schiff base-functionalized boehmite nanoparticle-supported molybdenum and vanadium complexes: efficient catalysts for the epoxidation of alkenes”, Appl. Organometal. Chem., Vol. 29, 2015, pp. 593-600.
[5] M. Mirzaee, B. Bahramian, M. Mirebrahimi, “Amine‐functionalized boehmite nanoparticle‐supported molybdenum and vanadium complexes: Efficient catalysts for epoxidation of alkenes”, Chin. J. Catal., Vol. 637, 2016, pp. 1263-1274.
[6] M. Mirzaee, B. Bahramian, J. Gholizadeh, A. Feizi, R. Gholami, “Acetylacetonate complexes of vanadium and molybdenum supported on functionalized boehmite nano-particles for the catalytic epoxidation of alkenes”, Chem. Eng. J., Vol. 308, 2017, pp. 160-168.
[7] M. Mirzaee, B. Bahramian, A. Ashrafian, A. Amoli, “Boehmite nano‐particles functionalized with silylpropylamine‐supported Keggin‐type heteropolyacids: Catalysts for epoxidation of alkenes”, Appl. Organometal. Chem., Vol. 32, 2018, e4011, pp. 1-9.
[8] Y. Zheng, S. Ji, H. Liu, M. Li, H. Yang, “Synthesis of mesoporous γ-AlOOH@Fe3O4 magnetic nanomicrospheres”, Particuology, Vol. 10, 2012, pp. 751-758.
[9] M. M. Amini, M. Mirzaee, “Effect of solution chemistry on preparation of boehmite by hydrothermal assisted sol-gel processing of aluminum alkoxides”, J. Sol-Gel Sci. Technol., Vol. 36, 2005, pp. 19-23.
[10] S.T. Oyama, Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis, Elsevier, Hungary, 2008, p. 43.
[11] D.C. Bradley, R.C. Mehrotra, I.P. Rothwell, A. Singh, Alkoxo and Aryloxo Derivatives of Metals, Academic Press, London, 2001, p. 276.
[12] Y. Zhang, J.Y. Liu, S. Ma, Y.J. Zhang, X. Zhao, X. D. Zhang, Z.D. Zhang, “Synthesis of PVP-coated ultra-small Fe3O4 nanoparticles as a MRI contrast agent”, J. Mater. Sci. Mater. Med., Vol. 10, 2010, pp. 1205-1210.
[13] M. Mirzaee, M.M. Amini, M. Sadeghi, F. Yeganeh Mosavi, M. Sharbatdaran, “Preparation and characterization of boehmite, CuO, TiO2 and Nb2O5 by hydrothermal assisted sol-gel processing of metal alkoxides” Ceramics-Silikáty Vol. 49, 2005, pp. 52-59.
[14] B. Cornils, W.A. Hermann, Applied Homogeneous Catalysis with Organometallic Compounds, Wiley, Weinheim, 1996, p. 68.
[15] M. Mohammadikish, M. Masteri-Farahani, S. Mahdavi, “Immobilized molybdenum-thiosemicarbazide Schiff base complex on the surface of magnetite nanoparticles as a new nanocatalyst for the epoxidation of olefins”, J. Magn. Magn. Mater., Vol. 354, 2014, pp. 317-323.