Communications
Materials Science decomposition of organometallic and coordination com-
pounds.[1, 9, 14, 18, 20–27] However, most of these approaches were
Monodisperse Magnetic Single-Crystal Ferrite focused on the synthesis of ferrite particles limited to
Microspheres** diameters below 30 nm. There are no reports on the synthesis
of well-crystallized ferrite nanoparticles with sizes similar to
protein molecules. The development of a facile and economic
Hong Deng, Xiaolin Li, Qing Peng, Xun Wang,
synthetic strategy for the synthesis of hydrophilic, biocom-
Jinping Chen, and Yadong Li*
patible magnetite nanoparticles would benefit their technical
use in biomedical fields, especially for applications in vivo.
It has been thought that many novel properties and potential Herein we report a general approach for the fabrication of
applications would emerge from monodisperse materials with monodisperse, hydrophilic, and single-crystalline ferrite
small dimensions. Therefore, the synthesis of monodisperse microspheres by a solvothermal reduction method. To the
nanoparticles has been intensively pursued for their techno- best of our knowledge, this is the first report on the synthesis
logical and fundamental scientific importance.[1–7] The syn- of single-crystalline magnetic microspheres. The ferrite
thesis of nanostructured magnetic materials has become a spheres had monodisperse diameters that were tunable in
particularly important area of research and is attracting a the range of 200–800 nm. This work resulted in an important
growing interest because of the potential applications such method for obtaining various monodisperse, magnetic, and
materials have in ferrofluids, advanced magnetic materials, single-crystalline microspheres, and provided an opportunity
catalysts, colored pigments, high-density magnetic recording to further apply these promising materials.
media, and medical diagnostics.[8–13] Spinel ferrites (MFe2O4 ; Typical syntheses of Fe3O4 and ferrite microspheres were
M = Fe, Mn, Zn, or Co) are among the most important carried out in a solvothermal system by modified reduction
magnetic materials and have been widely used in electronic reactions between FeCl3 and ethylene glycol. We confirmed
devices, information storage, magnetic resonance imaging the production of Fe3O4 by conducting controlled oxidation
(MRI), and drug-delivery technology.[8, 9, 14] Magnetite (Fe3O4) reactions in which a- and g-Fe2O3 were produced (Supporting
has recently been considered an ideal candidate for biological Information).[1b, 28–29] The crystalline structures of MFe2O4
applications, both as a tag for sensing and imaging, and as an were characterized by XRD. As shown in Figure 1, the
activity agent for antitumor therapy.[15–17] For high perfor-
mance in function-specific biological applications, magnetic
particles must be spherical and have smooth surfaces, narrow
size distributions, large surface areas (for maximal protein or
enzyme binding), high magnetic saturation (ss) to provide
maximum signal, and good dispersion in liquid media.[6, 18, 19]
After Sugimoto and Matijević reported the preparation of
magnetite particles with a narrow size distribution in the early
1980s,[20] monodisperse ferrite has been fabricated by various
chemistry-based synthetic methods, including coprecipitation,
the reverse micelle method, microwave plasma synthesis, sol-
gel techniques, freeze drying, ultrasound irradiation, hydro-
thermal methods, laser pyrolysis techniques, and thermal
Figure 1. XRD patterns of Fe3O4, trace a; MnFe2O4, trace b; ZnFe2O4,
[*] Dr. H. Deng, X. Li, Q. Peng, X. Wang, Prof. Y. Li trace c; and CoFe2O4, trace d.
Department of Chemistry and the Key Laboratory of Atomic &
Molecular Nanosciences
(Ministry of Education, China)
patterns can be easily indexed to Fe3O4 (JCPDS 75-1609),
Tsinghua University, Beijing, 100084 (P.R. China)
and MnFe2O4 (JCPDS 74-2403), ZnFe2O4 (JCPDS 22-1012), and
National Center for Nanoscience and Nanotechnology CoFe2O4 (JCPDS 22-1068). The Fe3O4 sample was deter-
Beijing, 100084 (P.R. China) mined by X-ray photoelectron spectroscopy (Supporting
Fax: (+ 86) 10-6278-8765 Information).
E-mail:
[email protected] The size and shape of the products were examined by
Prof. J. Chen TEM and scanning electron microscopy (SEM). Figure 2
Department of Physics shows representative images of the spinel ferrite compounds,
Peking University, Beijing, 100084 (P.R. China)
which are spherical and have very narrow diameter distribu-
[**] This work was supported by the NSFC (90 406 003, 20 401 010,
tions. The standard deviation for Fe3O4 particle diameters is
50 372 030, 20 025 102, 20 131 030), the Foundation for the Author of
National Excellent Doctoral Dissertation of the P.R. China, and the 5 %, excluding agglomerate particles (for diameter-distri-
state key project of fundamental research for nanomaterials and bution histograms of the MFe2O4 microspheres, see Support-
nanostructures (2003CB716901). ing Information). Furthermore, the shape and size of the a-
Supporting information for this article is available on the WWW Fe2O3 and g-Fe2O3 products remained unchanged from those
under http://www.angewandte.org or from the author. of the Fe3O4 precursor. In a typical solvothermal process, the
2782 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/anie.200462551 Angew. Chem. Int. Ed. 2005, 44, 2782 –2785
Angewandte
Chemie
CoFe2O4 (Supporting Information). The atomic ratio Fe/O for
Fe3O4 was 3:4, and an analogous M/Fe/O ratio of 1:2:4 was
observed for each of the other MFe2O4 products (M = Mn,
Zn, Co), in agreement with the expected stoichiometry in
each case.
High-resolution TEM (HRTEM) analysis provided more
detailed structural information on the microspheres. A
representative TEM image of the Fe3O4 microspheres is
shown in Figure 3 a, in which the HRTEM image (boxed area)
further supports the single-crystalline nature of the particles
(Supporting Information). The interlayer distance was calcu-
lated to be 0.48 nm, which agrees well with the separation
between the (101) lattice planes.
Figure 3. a) Representative TEM image of a Fe3O4 microsphere
(diameter 200 nm); b) HRTEM image of the boxed region of part (a)
and the electron-diffraction pattern of the individual Fe3O4
microsphere (inset).
Figure 2. Representative TEM images (a, c, e, and g) and SEM images Both the literature[6, 7] and our own experimental evidence
(b, d, f, and h) of microspheres of Fe3O4, (a and b); MnFe2O4, (c and have led us to believe that ethylene glycol plays an important
d); ZnFe2O4, (e and f); and CoFe2O4, (g and h). Microsphere diameter role in ferrite formation. Ethylene glycol is a strong reducing
is 800 nm in the SEM images, and 200 nm in the TEM images, in agent with a relatively high boiling point,[7] and has been
which the insets show the corresponding electron diffraction patterns. widely used in the polyol process to provide monodisperse
fine metal or metal oxide nanoparticles. However, magnetic
spinel ferrite particles have a strong tendency to agglomerate
during their formation in the liquid-phase process. To obtain
diameters of the MFe2O4 ferrite microspheres were influ- monodisperse Fe3O4 particles, we designed a modified
enced by reaction time and the concentration of starting synthetic route in which three added features were found to
material. With precursor concentration (0.13 m) and temper- be critical. First, NaAc was added for electrostatic stabiliza-
ature (200 8C) held constant, microsphere diameters were tion to prevent particle agglomeration. Such benefits of NaAc
observed to be 200 nm at a reaction time of 8 h (Figures 2 a, were found in similar syntheses with Ru, Pt, and Rh
c, e, and g), 400 nm at 48 h, and 800 nm at 72 h particles.[30, 31] In our system, NaAc was even more important,
(Figures 2 b, d, f, and h). Likewise, microsphere diameters as its addition seems to assist in the ethylene glycol mediated
increased with an increase in precursor concentration. How- reduction of FeCl3 to Fe3O4. Control experiments showed that
ever, the complex nature of the growth process makes it Fe3+ could not be reduced by ethylene glycol alone under the
difficult to obtain a straightforward correlation between same reaction conditions. Second, polyethylene glycol was
particle diameter and changes in reaction time or precursor added as a surfactant and as an additional preventative
concentration. Electron-diffraction patterns taken from indi- measure against particle agglomeration. The third feature is
vidual MFe2O4 microspheres revealed the single-crystalline the increased reaction temperature of 200 8C, which is
nature of these samples. Energy-dispersive X-ray analysis necessary for the production of Fe3O4.
(EDAX) was also measured to determine the chemical The magnetic properties of the ferrite microspheres were
composition of the ferrite samples. Results from EDAX investigated with a vibrating sample magnetometer. Figure 4
spectra from individual ferrite microspheres showed that shows the magnetization curves measured at 300 K for
samples contain only Fe and O for Fe3O4 ; Mn, Fe, and O for MFe2O4 microspheres with diameters of 200 nm. The
MnFe2O4 ; Zn, Fe, and O for ZnFe2O4 ; and Co, Fe, and O for magnetic saturation values are 81.9 emu g 1 for Fe3O4,
Angew. Chem. Int. Ed. 2005, 44, 2782 –2785 www.angewandte.org 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2783
Communications
Experimental Section
Fe3O4 microsphere synthesis:[32] FeCl3·6 H2O (1.35 g, 5 mmol) was
dissolved in ethylene glycol (40 mL) to form a clear solution, followed
by the addition of NaAc (3.6 g) and polyethylene glycol (1.0 g). The
mixture was stirred vigorously for 30 min and then sealed in a teflon-
lined stainless-steel autoclave (50 mL capacity). The autoclave was
heated to and maintained at 200 8C for 8–72 h, and allowed to cool to
room temperature. The black products were washed several times
with ethanol and dried at 60 8C for 6 h.
The above process can be can be extended to the synthesis of
MFe2O4 (M = Co, Mn, Zn) microspheres by coprecipitation of MII
and FeIII chlorides (M2+/Fe3+ = 0.5).[32] For example, a mixture of
MnCl2·4 H2O (0.50 g, 2.5 mmol) and FeCl3·6 H2O (1.35 g, 5 mmol)
Figure 4. Room-temperature magnetization curves of ferrite
under the same reaction conditions as used for the synthesis of Fe3O4
microspheres (diameter 200 nm): Fe3O4, trace a; g-Fe2O3, trace b;
microspheres, produced microspheres of MnFe2O4.
a-Fe2O3, trace c; MnFe2O4, trace d; ZnFe2O4, trace e; and CoFe2O4,
All samples were characterized on a Bruker D8 Advance powder
trace f.
X-ray diffractometer with CuKa radiation (l = 1.5418 ). The TEM
and HRTEM images were generated with a Hitachi H-800 trans-
mission electron microscope and with a JEOL JEM-2010F high-
53.2 emu g 1 for MnFe2O4, 60.0 emu g 1 for ZnFe2O4, and resolution transmission electron microscope. SEM images were taken
with a NORAN LDO 1530 apparatus. Magnetic studies were carried
61.6 emu g 1 for CoFe2O4. More detailed investigations of the
out on a Quantum Design SQUID magnetometer.
magnetic properties of these products are still in progress. The
product of Fe3O4 oxidation in HNO3 gave a ss value of Received: November 9, 2004
72 emu g 1 (Figure 4), which is close to the value of 74 emu g 1 Published online: March 30, 2005
determined from the analysis of commercial g-Fe2O3 powder
(Aldrich, 48-1-066-5), supporting the formation of g-Fe2O3
under these conditions. After the Fe3O4 sample was oxidized
in air at 400 8C for 3 h, the ss value of the product was
.Keywords: colloids · crystal growth · iron · magnetic properties ·
reduction
negligible (Figure 4), which indicates that under these con-
ditions Fe3O4 is transformed into a-Fe2O3.
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