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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 38:212–216, 2008
Copyright # 2008 Taylor & Francis Group, LLC
ISSN: 1553-3174 print/1553-3182 online
DOI: 10.1080/15533170801926465

Synthesis and Characterization of a-Fe2O3 Nanoparticles of

Different Shapes
P. S. Chowdhury, P. R. Arya, and K. Raha
Pyro Division, High Energy Materials Research Laboratory, Pune, India

Control of nanocrystal shape is important in various applications,

Interest in developing a nano-oxidizer matrix for reaction with such as catalysis,[5] solar cells,[6] biological labeling,[7] and
nano Al for energetic applications led to the development of nano- energetic materials.[8] The simultaneous control of size,
metric Fe2O3. We have reported a synthetic procedure for nano- morphology, and size distribution of colloidal nanocrystals is a
iron oxide using starch as the capping agent. Here, aqueous
solution of ferric chloride was added into starch solution and challenging task. Narrow size distribution and homogeneity,
after stirring it was basified by triethyl amine to get colloidal pre- the main goals of preparative approaches can be achieved by
cipitate of ferric hydroxide. This precipitate after centrifuging careful control of all synthetic parameters.
and heating yielded nanoparticles of iron oxide. The method is Although many techniques for the synthesis of nanocrystalline
suitable for scaling up due to its reproducible nature and eco metal oxides have been reported, it is rather difficult to produce
friendliness. This nano-iron oxide was fully characterized by
chemical analysis, XRD, SEM, and TEM. The experimental them in large quantities. The morphology and composition of
results show that with increasing calcination temperature, obtained particles strongly depend on a large number of synthesis
particle size as well as morphology changes. parameters such as pH, concentration of the reactants, tempera-
ture, and method of mixing, rate of heating, concentration of pas-
Keywords a-Fe2O3, monodispersed, nanotube, annealing tempera- sivating agent and rate of oxidation.[9] The nature and
ture, delaminate concentration of anions such as chloride, phosphate, nitrate or
sulfate have a strong influence on particle size and shape.[10,11]
Thus, the sensitive nature of the preparation method complicates
both the reproducibility and the scale of the synthesis. Sub-micro-
metric iron oxide particles are very useful in magnetic, catalytic,
INTRODUCTION
pigment and biological imaging applications. In energetic
Colloidal inorganic nanocrystals are of great interest for both
material studies, nano-size oxidizers and fuels play a very import-
fundamental research and technical applications due to their
ant role by increasing heat output and faster reaction rates when
strong size and shape dependent properties and excellent
mixed in stoichiometric proportions. Kinetically controlled
chemical processibility.[1 – 4] In most cases, these advantages
ignition is achieved by the oxidizer particles with high surface
can be exploited only with relatively monodisperse samples.
area. There has been an increased interest in the use of nano alu-
Aiming at advanced materials, much effort has been focused on
minium in energetics.[12] A typical nanoenergetic material
the development of new strategies for the synthesis of monodis-
consists of nano-fuel and nano-oxidizer, which liberates huge
persed nanoparticles in the region of 1–100 nanometers. In this
amount of energy according to the thermite reaction:
size regime, the physicochemical properties do not depend on
the chemical composition only, but on the shape and size of the 3 1 3
Al þ MO ¼ Al2 O3 þ M þ DH
nanoparticles. New developmental methods for the preparation 2 2 2
of nanomaterials as well as the modification of their size,
shape, porosity, morphology has been pursued not only for Where M is metal (such as Mo, Cr, W, Sn, Fe) and H is the heat
basic scientific interest, but also for technological applications. output of the reaction. In the solution phase, synthesis of iron
oxide nanopowders and colloids, several methods such as sol-
gel method, hydrothermal method, forced hydrolysis, electrode-
Received 6 July 2007; accepted 16 October 2007. position method, plasma arc method, microwave heating, etc.
The authors thank Dr. A. Subhananda Rao, Director HEMRL for have been reported. Haematite (a-Fe2O3), the most stable iron
constant encouragement. oxide in nature, is of technological as well as scientific interest
Address correspondence to P. S. Chowdhury, Pyro Division,
because of its use as catalyst, pigment, sensor, burning rate
High Energy Materials Research Laboratory, Pune, India. E-mail:
paramita_15@[Link] or [Link]@[Link] enhancer, oxidizer in energetics, etc. Several methods have

212
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a-Fe2O3 NANOPARTICLES OF DIFFERENT SHAPES 213

been tried so far for synthesis of iron oxide nano-structures. Scanning Electron Microscopic (SEM) Study
Zhang et al. have synthesized nanowires of iron oxides,[13] Figures 2(a), (b) and (c) shows the SEM data of samples
Woo et al. synthesized a-Fe2O3 nanorods by a sol gel calcined at 4508C, 6508C, and 8508C, respectively. The
method,[14] Wang et al. used solid-gas reaction process under sample prepared at 4508C shows uniform spherical particles
700 and 8008C to synthesize a-Fe2O3 nanobelts.[15] of approximately 20 nm size. From the SEM data, it was
Here, we have presented a simple method to produce gram evident that with increase in temperature, particles tend to
size of iron oxide nanopowders via polymer matrix encapsula- become tubular in nature. The SEM data revealed that at
tion. The best part of this method is its eco-friendly nature due 6508C heated sample (Figure 2b) the particles tend to form
to its one pot green synthetic procedure. The polymer used here channel like structures in between two spherical particles.
is starch, a biopolymer abundant in nature. We have studied the When the particles are heated at 8508C, they became nanotubes
change in particle morphology with increased calcination (Figure 2c). The particles have a narrow size distribution and
temperature. almost exclusively consist of monodispersed Fe2O3
nanoparticles.

RESULTS AND DISCUSSION Transmission Electron Microscopic (TEM) Study

Nanoscopic a-Fe2O3 was synthesized by treating appro- Figure 3 displays the TEM images of the Fe2O3 nanocrystals
priate amount of hydrated ferric chloride embedded in starch heated at 4508C, 6508C, and 8508C. The size calculated from
solution with equivalent amount of base, Triethyl amine TEM closely agrees with that calculated from XRD analysis.
(TEA), and finally calcining the product at three different It is clear from TEM that an increased calcination temperature
temperatures, such as 4508C, 6508C, and 8508C, respectively. mainly leads to the elongation of particles along the C axis. The
Chemical analysis data shows that all the particles were 99.7% HRTEM image of the 8508C heated sample (Figure 3d) shows
pure in nature. the spacing of 0.37 nm between adjacent lattice planes. This
data is in full agreement with the two (012) crystal planes of
a-Fe2O3, which clearly indicates that the direction perpendicu-
X-Ray Diffraction Study lar to (012) plane is the preferred growth direction of the single
Figure 1 shows the XRD pattern of nanocrystals of iron crystalline nanotubes.
oxide. The XRD pattern of the nanocrystal is considerably The selected area electron diffraction pattern (Figure 4)
broadened due to the very small size of the crystallites. The applied on the whole particle shows that this particle
XRD spectrum indicates that the final product is highly crystal- behaves as a single crystal. These observations confirm that
lized a-Fe2O3 and almost all the peaks can be indexed to the the small particles behave as small single crystals in a per-
orthorhombic structure of haematite (JCPDS ref. no. 01-084- fectly aligned manner and the particle resultantly appears as
0306), except the one at 308, which may be caused by a quasi single crystal. The HRTEM data of 6508C and
another phase of Fe2O3 produced under high temperature treat- 8508C heated samples clearly showed the formation of
ment. The symmetry of the lattice is m3m. From the XRD nanotubes.
analysis it was evident that the nanocrystal is pure. The crystal- These temperature-dependent morphology results suggest
lite sizes were calculated from Scherer equation and the that the formation process of the nanotubes occur via dissol-
average crystallite sizes were found to be 20 nm, 30 nm, and ution of iron oxide nanospheres, and this is due to a high pro-
43 nm for the 4508C, 6508C, and 8508C calcined samples. portion of structural defects being produced in the iron oxide
nanocrystals, as reported by Scott et al.[16] There is a strong
possibility of oriented attachment parallel to the C axis. The
observed lattice plane in this image is the 012, which lie per-
pendicular to the C axis, respectively. The longest extension
of the aggregates is manifested in the direction of the c axis.
When base was added the Fe3þ ions were converted to
Fe(OH)3 and dangling bonds on the surface react more with
the hydroxide ions to form sheet like structures.[17] As the
annealing temperature increases, the particles start coalescing
with each other and finally start delaminating. The sheets get
separated from each other and start rolling to form tube like
structures (Scheme 1).
Finally, the presence of starch is very important for the for-
mation of nanotubes material. The nanotubes can be attributed
to the starch acting as a capping agent and initiating the growth
FIG. 1. XRD pattern of nano-iron oxide. along C axis.
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214 P. S. CHOWDHURY ET AL.

FIG. 2. SEM data of nano-iron oxide heated at (a) 4508C, (b) 6508C and (c) 8508C.

FIG. 3. TEM data of nano-iron oxide heated at (a) 4508C, (b) 6508C, (c) 8508C, (d) a single nanotube heated at 8508C, and (e) lattice fringes of nanotube
obtained by HRTEM.
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a-Fe2O3 NANOPARTICLES OF DIFFERENT SHAPES 215

diffractometer (Cu Ka source of 1.5418A radiation). Crystal-

lite sizes (D) of the powders were calculated by the X-ray
line broadening technique performed on the direction of
lattice using computer software (APD 1800, Philips Research
Laboratories) based on Hall equation and Scherer formula:
0:94l
D¼ Cos u
b
Where l is the X-ray wavelength, u the Bragg’s angle and b is
the pure full width of the diffraction line at half of the
maximum intensity.[18]
The size of the particles was also determined from TEM
images obtained using a JEOL-TEM-2010 transmission
electron microscope with operating voltage of 200 kV.
FIG. 4. SAED pattern of nano iron oxide.
Samples for TEM were prepared by making a clear dispersion
of the nanocrystals in acetone and placing a drop of the solution
EXPERIMENTAL SECTION on a carbon coated copper grid. The solution was allowed to
evaporate leaving behind the nanocrystals on the carbon grid.
Materials and Synthesis SEM analysis was obtained with a JEOL-6500 FEG SEM at
All the reactants and solvents were of analytical grade and 5-kV operating voltage and a working distance of 7.6 mm.
used without further purification. In a typical procedure, an
appropriate amount of FeCl3, 6H2O and starch (molar ratio, CONCLUSION
1:2) were added to double distilled water and stirred for half Single crystalline hematite particles of different shapes with
an hour. To this solution, triethyl amine was added dropwise a narrow size distribution were synthesized in good yield using
to maintain the pH in the range 8– 9 and brown colloidal an iron (III) precursor. With this approach, a novel and comfor-
precipitate of ferric hydroxide was obtained. The precipitate table route to iron oxide colloids is available in addition to the
was collected by centrifuging at a speed of 5000 rpm and well-known complex formation routes. Because of its easy syn-
washed by acetone and ethanol. Finally, it was dried in air thesis and storage stability (no agglomeration when stored in
oven at 708C the dried sample was calcined at three different air), this route provides an advantageous and cheap access to
temperatures, namely 4508C, 6508C, 8508C, in a furnace for iron oxide colloids in gram quantities. The batch size
5 hours. Chocolate brown iron oxide nanopowders were prepared here is around 50 g. Only using starch as the
obtained. This iron oxide is of haematite nature, i.e., of a-type. polymer, the formation of the colloidal material is highly regu-
lated, leading to monodispersed particles with a well-defined
morphology. This is probably due to the structure-directing
Characterization
effect of the starch matrix, which due to its polyol (-OH)
Chemical analysis of all the three samples was carried out to
groups, encapsulates the ferric hydroxide colloids in a cage
determine the purity. X-ray powder diffraction patterns were
like structure. We believe that oxide nanoparticles are very
taken at room temperature using a model of Philips
suitable for the oriented attachment mechanism as the correctly
attached particles lead to a gain in lattice free energy, as well as
it helps in relieving the strain within the molecules. In
summary, we have described in this paper the shape controlled
synthesis of haematite (a-iron oxide) nanostructures only by
changing their calcination temperature. Further studies are
under way to investigate the effect of other reaction parameters
on the crystallite morphology.

REFERENCES
1. E. Matijevic, Preparation and Properties of Uniform Size
Colloids, Chem. Mater., 1993, 5, 412– 426.
2. J.H. Fendler, Self Assembled Nanostructured Materials, Chem.
Mater., 1996, 8, 1616– 1624.
3. E. Matijevic, Annu. Rev. Mater. Sci., 1985, 15, 483.
4. E. Matijevic, Uniform Inorganic Colloid Dispersions: Achieve-
SCH. 1. Schemetic diagram of nanotube formation. ments and Challenges, Langmuir, 1994, 10, 8 –16.
Downloaded from [Link]
[Link] [Link]

216 P. S. CHOWDHURY ET AL.

5. T. Ruhle, O. Timpe, N. Pfänder, and R. Schlögl, Tribochemical 11. J. Livage, M. Henry, and C. Sanchez, Sol Gel Chemistry of Tran-
Activation of Iron Oxide for the Reduction of NO with CO: sition Metal Oxides, Prog. Solid State Chem., 1988, 18, 259– 341.
How Lattice Defects Can Influence the Catalytic Activity, 12. H. Ritter and S. Braun, High Explosives Containing Ultrafine Alu-
Angew. Chem. Int. Ed., 2000, 39, 4379– 4382. minium ALEX, Propellants. Explos. Pyrotech., 2001, 26, 311–314.
6. J.A. Navio, G. Colon, M.I. Litter, and G.N. Bianco, Synthesis, 13. Y.Y. Fu, R.M. Wang, J. Xu, J. Chen, Y. Yan, A.V. Narlikar, and
Characterization and Photo Catalytic Properties of Iron-doped H. Zhang, Synthesis of Large Arrays of Aligned a-Fe2O3 Nano-
Titania Semiconductors Prepared from TiO2 and Iron(III) Acety- wires, Chem. Phys. Lett., 2003, 379, 373– 379.
lacetonate, J. Mol. J. Mol. Catal. A: Chem., 1996, 106, 267– 276. 14. K. Woo, H.J. Lee, J.P. Ahn, and Y.S. Park, Sol-gel Mediated Syn-
7. C. Feldmann, Preparation of Nanoscale Pigment Particles, Adv. thesis of Fe2O3 Nanorods, Adv. Mater., 2003, 15, 1761– 1764.
Mater., 2001, 13, 1301– 1306. 15. X.G. Wen, S.H. Wang, Y. Ding, Z.L. Wang, and S.H. Yang, Con-
8. A.E. Gash, T.M. Tillotson, J.H. Satcher, J.F. Poco, L.W. Hrubesh, trolled Synthesis and Growth Mechanism of Nanobelts and Nano-
and R.L. Simpson, Use of Epoxides in the Sol Gel Synthesis of wires, J. Phys. Chem. B, 2005, 109, 215– 220.
Porous Iron (III) Oxide Monoliths from Fe(III) Salts. Chem. 16. J.K. Bailey, C.J. Brinker, and M.L. Mecartney, Growth Mechan-
Mater., 2001, 13, 999– 1007. isms of Iron Oxide Particles of Differing Morphologies from the
9. C. Domingo, R. Rodriguez-Clemente, and M. Blesa, Morphologi- Forced Hydrolysis of Ferric Chloride Solutions, J. Colloid Inter-
cal Properties of a-FeOOH, g-FeOOH and Fe3O4 Obtained by face Sci., 1993, 157, 1 –13.
Oxidation of Aqueous Fe(II) Solutions, J. Colloid. Interface 17. Q. Chen, W. Zhou, G. Du, and L.-M. Peng, Trititanate Nanotubes
Sci., 1994, 165, 244– 252. Made via Single Alkali Treatment, Adv. Mater., 2002, 14,
10. N.J. Reeves and S. Mann, Influence of Inorganic and Organic 1208– 1211.
Additives on the Tailored Synthesis of Iron Oxides, J. Chem. 18. P. Klug and L.E. Alexander, Direction Procedures for Poly-
Soc. Faraday Trans., 1991, 87, 3875– 3880. crystalline, Amorphous Materials, 1954, Wiley, New York.