Synthesis and Characterization of Monodisperse Magnetite Hollow Microspheres


Monodisperse hollow magnetite microspheres were successfully synthesized by an one-step process through a tem-plate-free hydrothermal approach employing simultaneously a mixture of FeCl3.6H2O and ferrocene as precursor and a propylene glycol-isopropanol mixture as solvent. The morphologies and properties of the magnetite microspheres were characterized by X-ray diffraction (XRD), Raman and infrared spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), adsorption of nitrogen (BET method) and SQUID magnetometry. The results show that the microspheres consist of a single crystalline phase of magnetite. On the other hand, the size and the internal hollow of the microspheres depend on the temperature of growth and can be tuned by modifying the synthesis conditions.

Share and Cite:

F. Márquez, T. Campo, M. Cotto, R. Polanco, R. Roque, P. Fierro, J. Sanz, E. Elizalde and C. Morant, "Synthesis and Characterization of Monodisperse Magnetite Hollow Microspheres," Soft Nanoscience Letters, Vol. 1 No. 2, 2011, pp. 25-32. doi: 10.4236/snl.2011.12005.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] J. Liu and D. F. Xue, “Thermal Oxidation Strategy towards Porous Metal Oxide Hollow Architectures,” Advanced Materials, Vol. 20, No. 13, 2008, pp. 2622-2627. doi:10.1002/adma.200800208
[2] Q. X. Guo, Y. S. Zhao, W. L. Mao, Z. W. Wang, Y. J. Xiong and Y. N. Xia, “Cubic to Tetragonal Phase Transformation in Cold-Compressed Pd Nanocubes,” Nano Letters, Vol. 8, No. 3, 2008, pp. 972-975. doi:10.1021/nl0731217
[3] C. L. Yang and D. F. Xue, “Formation of Nb2O5 Nanotube Arrays through Phase Transformation,” Advanced Materials, Vol. 20, No. 5, 2008, pp. 1055-1058.
[4] H. Colfen and S. Mann, “Higher-Order Organization by Mesoscale Self-Assembly and Transformation of Hybrid Nanostructures,” Angewandte Chemie International Edition, Vol. 42, No. 21, 2003, pp. 2350-2365. doi:10.1002/anie.200200562
[5] D. Yu, X. Sun, J. Zou, Z. Wang, F. Wang and K. Tang, “Oriented Assembly of Fe3O4 Nanoparticles into Monodisperse Hollow Single-Crystal Microspheres,” Journal of Physical Chemistry B, Vol. 110, No. 43, 2006, pp. 21667-21671. doi:10.1021/jp0646933
[6] H. Deng, X. Li, Q. Peng, X. Wang, J. Chen and Y. Li, “Monodisperse Magnetic Single-Crystal Ferrite Microspheres,” Angewandte Chemie International Edition, Vol. 117, No. 18, 2005, pp. 2782-2785. doi:10.1002/anie.200462551
[7] A. H. Lu, E. L. Salabas and F. Schuth, “Magnetic Nanoparticles: Synthesis, Protection, Functionalization, and Application,” Angewandte Chemie International Edition, Vol. 46, No. 8, 2007, pp.1222-1244. doi:10.1002/anie.200602866
[8] J. Ge, Y. Hu, M. Biasini, W. P. Beyermann and Y. Yin, “Superparamagnetic Magnetite Colloidal Nanocrystal Clusters,” Angewandte Chemie International Edition, Vol. 46, No. 23, 2007, pp. 4342-4345. doi:10.1002/anie.200700197
[9] D. Hogemann, V. Ntziachristos, L. Josephson and R. Weissleder, “High Throughput Magnetic Resonance Imaging for Evaluating Targeted Nanoparticle Probes,” Bioconjugate Chemistry, Vol. 13, No. 1, 2002, pp. 116-121. doi:10.1021/bc015549h
[10] L. Gao, J. Wu, S. Lyle, K. Zehr, L. Cao and D. Gao, “Magnetite Nanoparticle-Linked Immunosorbent Assay,” Jour- nal of Physical Chemistry C, Vol. 112, No. 44, 2008, pp. 17357- 17361. doi:10.1021/jp805994h
[11] G. P. Escobar, A. Q. Beroy, M. P. P. Iritia and J. H. Huerta, “Kinetic Study of the Combustion of Methyl-Ethyl Ketone over Α-Hematite Catalyst,” Chemical Engineering Journal, Vol. 102, No. 2, 2004, pp. 107-117.
[12] W. Werner and R. Wolfgang, “Surface Chemistry and Catalysis on Well-Defined Epitaxial Iron-Oxide Layers,” Progress in Surface Science, Vol. 70, No. 1-3, 2002, pp. 1-151.
[13] C. T. Black, C. B. Murray, R. L. Sandstrom, S. Sun, “Spin-Dependent Tunneling in Self-Assembled Cobalt- Nano-crystal Superlattices,” Science, Vol 290, No. 5494, 2000, pp. 1131-1134. doi:10.1126/science.290.5494.1131
[14] M. T. López-López, J. G. D. Durán, A. V. Delgado, F. J. González-Caballero, “Stability and Magnetic Characterization of Oleate-Covered Magnetite Ferrofluids in Different Nonpolar Carriers,” Journal of Colloid and Interface Science, Vol. 291, No. 1, 2005, pp. 144-151.
[15] H. Zeng, J. Li, J. P. Liu, Z. L. Wang, S. H. Sun, “Exchange-Coupled Nanocomposite Magnets by Nanoparticle Self-Assembly,” Nature, Vol. 420, No. 6914, 2002, pp. 395-398. doi:10.1038/nature01208
[16] S. Tiwari, R. J. Choudhary and D. M. Phase, “Effect of Growth Temperature on the Structural and Transport Properties of Magnetite Thin Films Prepared by Pulse Laser Deposition on Single Crystal Si Substrate,” Thin Solid Films, Vol. 517, No. 11, 2009, pp. 3253-3256. doi:10.1016/j.tsf.2008.11.074
[17] M. S. Martina, J. P. Fortin, C. Menager, O. Clement, G. Barratt, C. Grabielle-Madelmont, F. Gazeau, V. Cabuil and S. Lesieur, “Generation of Superparamagnetic Liposomes Revealed as Highly Efficient MRI Contrast Agents for in Vivo Imaging,” Journal of the American Chemical Society, Vol. 127, No. 30, 2005, pp. 10676-10685. doi:10.1021/ja0516460
[18] N. A. Frey, S. Peng, K. Cheng and S. Sun, “Magnetic Nanoparticles: Synthesis, Functionalization, and Applications in Bioimaging and Magnetic Energy Storage,” Chemistry Society Reviews, Vol. 38, No. 9, 2009, pp. 2532-2542. doi:10.1039/b815548h
[19] J. Dobson, “Magnetic Nanoparticles for Drug Delivery,” Drugs Development Research, Vol. 67, No. 1, 2006, pp. 55-60. doi:10.1002/ddr.20067
[20] A. Schlachter, M. E. Gruner, M. Spasova, M. Farle and P. Entel, “Preparation and Properties of Nanostructured Magnetic Hollow Microspheres: Experiment and Simulation,” Phase Transitions, Vol. 78, No. 9&11, 2005, pp. 741-750. doi:10.1080/01411590500288809
[21] H. Itoh and T. Sugimoto, “Systematic Control of Size, Shape, Structure, and Magnetic Properties of Uniform Magnetite and Maghemite Particles,” Journal of Colloid and Interface Science, Vol. 265, No. 2, 2003, pp. 283-295. doi:10.1016/S0021-9797(03)00511-3
[22] S. H. Gee, Y. K. Hong, D. W. Erickson and M. H. Park, “Synthesis and Aging Effect of Spherical Magnetite (Fe3O4) Nanoparticles for Biosensor Applications,” Journal of Applied Physics, Vol. 93, No. 10, 2003, pp. 7560-7562. doi:10.1063/1.1540177
[23] L. A. Harris, J. D. Goff, A. Y. Carmichael, J. S. Riffle, J. J. Harburn, T. G. St. Pierre and M. Saunders, “Magnetite Nanoparticle Dispersions Stabilized with Triblock Copolymers,” Chemistry of Materials, Vol. 15, No. 6, 2003, pp. 1367-1377. doi:10.1021/cm020994n
[24] F. Márquez, C. Morant, J. M. Sanz and E. Elizalde, “Attachment of Magnetite Nanoparticles on Carbon Nanotubes Bundles and Their Response to Magnetic Fields,” Journal of Nanoscience and Nanotechnology, Vol. 9, 2009, pp. 3810-3814. doi:10.1166/jnn.2009.NS72
[25] F. Márquez, C. Morant, J. M. Sanz and E. Elizalde, “Post-Synthesis Alignment of Chemically Modified Carbon Nanotubes in Magnetic Fields,” Journal of Nano- science and Nanotechnology, Vol. 9, 2009, pp. 6127- 6131.
[26] J. L. Lyon, D. A. Fleming, M. B. Stone, P. Schiffer and M. E. Williams, “Synthesis of Fe Oxide Core/Au Shell Nano-particles by Iterative Hydroxylamine Seeding,” Nano Letters, Vol. 4, No. 4, 2004, pp. 719-723. doi:10.1021/nl035253f
[27] S. Peng and S. Sun, “Synthesis and Characterization of Hollow Fe3O4 Nanoparticles,” Angewandte Chemie International Edition, Vol. 46, No. 22, 2007, pp. 4155-4157. doi:10.1002/anie.200700677
[28] B. P. Jia and L. Gao, “Morphological Transformation of Fe3O4 Spherical Aggregates from Solid to Hollow and Their Self-Assembly under an External Magnetic Field,” Journal of Physical Chemistry C, Vol. 112, No. 3, 2008, pp. 666-671. doi:10.1021/jp0763477
[29] H. J. Fan, U. G?sele and M. Zacharias, “Formation of Nanotubes and Hollow Nanoparticles Based on Kirkendall and Diffusion Processes: A Review,” Small, Vol. 3, No. 10, 2007, pp. 1660-1671. doi:10.1002/smll.200700382
[30] D. Kim, J. Park, K. An, N. K. Yang, J. G. Park and T. Hyeon, “Synthesis of Hollow Iron Nanoframes,” Journal of the American Chemical Society, Vol. 129, No. 18, 2007, pp. 5812- 5813. doi:10.1021/ja070667m
[31] P. Hu, L. Yu, A. Zuo, C. Guo and F. Yuan, “Fabrication of Monodisperse Magnetite Hollow Spheres,” Journal of Physical Chemistry C, Vol. 113, No. 3, 2009, pp. 900-906. doi:10.1021/jp806406c
[32] X. Wang, F. L. Yuan, P. Hu, L. J. Yu and L. Bai, “Self-Assembled Growth of Hollow Spheres with Octahedron-like Co Nanocrystals via One-Pot Solution Fabrication,” Journal of Physical Chemistry C, Vol. 112, No. 24, 2008, pp. 8773- 8778. doi:10.1021/jp0775404
[33] D. B. Yu, X. Q. Sun, J. W. Zou, Z. R. Wang, F. Wang and K. Tang, “Oriented Assembly of Fe3O4 Nanoparticles into Monodisperse Hollow Single-Crystal Microspheres,” Journal of Physical Chemistry B, Vol. 110, No. 43, 2006, pp. 21667-21671.doi:10.1021/jp0646933
[34] D. Lee, R. E. Cohen and M. F. Rubner, “Heterostructured Magnetic Nanotubes,” Langmuir, Vol. 23, No. 1, 2007, pp. 123-129. doi:10.1021/la0612926
[35] Q. L. Ye, Y. Kozuka, H. Yoshikawa, K. Awaga, S. Bandow and S. Iijima, “Effects of The Unique Shape of Submicron Magnetite Hollow Spheres on Magnetic Properties and Domain States,” Physical Review B, Vol. 75, No. 22, 2007, pp. 224404-224408. doi:10.1103/PhysRevB.75.224404
[36] M. Ohnish, Y. Kozuka, Q. L. Ye, H. Yoshikawa, K. Awaga, R. Matsuno, M. Kobayashi, A. Takahara, T. Yokoyama, S. Bandow and S. Iijima, “Phase Selective Preparations and Surface Modifications of Spherical Hollow Nanomagnets,” Journal of Material Chemistry, Vol. 16, No. 31, 2006, pp. 3215-3220. doi:10.1039/b605472b
[37] H. P. Liang, H. M. Zhang, J. S. Hu, Y. G. Guo, L. J. Wan and C. L. Bai, “Pt Hollow Nanospheres: Facile Synthesis and Enhanced Electrocatalysts,” Angewandte Chemie International Edition, Vol. 43, No. 12, 2004, pp. 1540-1543. doi:10.1002/anie.200352956
[38] J. C. Bao, Y. Y. Liang, Z. Xu and L. Si, “Facile Synthesis of Hollow Nickel Submicrometer Spheres,” Advanced Materials, Vol. 15, No. 21, 2003, pp. 1832-1835. doi:10.1002/adma.200305315
[39] L. T. Lu, L. D. Tung, J. Long, D. G. Fernig and N. T. K. Thanh, “Facile Synthesis of Stable, Water-Soluble Magnetic Copt Hollow Nanostructures Assisted by Multi- hiol Ligands,” Journal of Material Chemistry, Vol. 19, No. 33, 2009, pp. 6023- 6028. doi:10.1039/b906839b
[40] A. Saito and H.C. Foley, “Curvature and Parametric Sensitivity in Models for Adsorption in Micropores,” AIChE Journal, Vol. 37, No. 3, 1991, pp. 429-437. doi:10.1002/aic.690370312
[41] L. Y. Wang, J. Luo, Q. Fan, M. Suzuki, M. H. Engelhard, Y. Lin, N. Kim, J. Q. Wang and C. Zhong, “Monodispersed Core?Shell Fe3O4@Au Nanoparticles,” Journal of Physical Chemistry B, Vol. 109, No. 46, 2005, pp. 21593-21601. doi:10.1021/jp0543429
[42] X. Teng, D. Black, N. Watkins, Y. Gao and H. Yang, “Platinum-Maghemite Core?Shell Nanoparticles Using a Sequential Synthesis,” Nano Letters, Vol. 3, No. 2, 2003, pp. 261-264. doi:10.1021/nl025918y
[43] R. M. Cornell and U. Schwertmann, “The Iron Oxides,” VCH, New York, 1996.
[44] O. N. Shebanova and P. J. Lazor, “Raman spectroscopic study of magnetite (FeFe2O4): a new assignment for the vibrational spectrum,” Journal of Solid State Chemistry, Vol. 174, No. 2, 2003, pp. 424-430. doi:10.1016/S0022-4596(03)00294-9
[45] D. L. A. De Faria and S. Venancio Silva, M. T. De Oliveira, “Raman Microspectroscopy of Some Iron Oxides and Oxyhydroxides,” Journal of Raman Spectroscopy, Vol. 28, No. 11, 1997, pp. 873-878. doi:10.1002/(SICI)1097-4555(199711)28:11<873::AID-JRS177>3.3.CO;2-2
[46] O. N. Shebanova and P. J. Lazor, “Raman Study of Magnetite (Fe3O4): Laser-Induced Thermal Effects and Oxidation,” Journal of Raman Spectroscopy, Vol. 34, No. 11, 2003, pp. 845- 852. doi:10.1002/jrs.1056
[47] X. Gao, K. M. K. Yu, K. Y. Tam and S. C. Tsang, “Colloidal Stable Silica Encapsulated Nano-Magnetic Composite as a Novel Bio-Catalyst Carrier,” Chemical Communications, No. 24, 2003, pp. 2998-2999. doi:10.1039/b310435d

Copyright © 2022 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.