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Materials Letters 65 (2011) 32983300

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

A facile route to synthesize nano-hematite colloid


Ren-bo Cao, Xiao-quan Chen , Wen-hao Shen, Zhou Long
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510641, PR China

a r t i c l e

i n f o

Article history:
Received 5 August 2010
Accepted 2 March 2011
Available online 9 March 2011
Keywords:
Nanomaterials
Hematite colloid
Synthesis
Optical properties

a b s t r a c t
Monodispersed nano-hematite colloid with an average diameter of 50 nm has been successfully synthesized
through solid transformation of ferrihydrite at boiling temperature in aqueous solution. Low-cost ferric sulphate
and ammonia were used as raw materials. The effects of the boiling and washing pretreatments of starting
materials solutions and ferrihydrite on the formation of stable monodispersed nano-hematite colloid were
studied. The obtained nano-hematite colloid was stable for more than 15 days and showed a strong absorption in
the UV region. The resulting nano-hematite particles displayed various shapes such as pseudocube, nanoplatelet
and irregular polyhedral. This colloid could potentially be useful for printing and painting applications.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Nanoparticles of iron oxide, in different phases, are being currently
explored for their diverse range of applications such as magnetic storage
media, environment protection, sensors, catalysis, pigments, clinical
diagnosis and treatment etc. Particularly in the painting and printing
industries, stable nano-hematite colloid is suitable for the coloration of
plastic bottles and lms for food packaging and the manufacture of
wood protection coatings owing to its high UV absorption [1]. Because of
these signicant practical applications, in recent years many pathways
have been reported for the fabrication of nano-hematite. Although these
ways possess their own advantages, most of them used relatively
expensive FeCl3 [24], Fe(NO3)3 [5,6] or organic iron [7] as iron sources
and consumed large amounts of energy because of their high reaction
temperature and long reaction time [2,5,7]. Moreover, it was always
difcult for the nano-hematite particles obtained from these methods to
be well dispersed in solvent, one of the vital requirements for the
painting and printing application [8].
In order to alleviate the drawbacks of the mentioned methods, herein,
we reported a facile route to synthesis stable monodispersed nanohematite colloid by phase transformation of ferrihydrite at boiling
temperature, using cheap ferric sulphate and ammonia as raw materials
and ferrous chloride as catalyst [6]. The stability, characteristic and optical
properties of nano-hematite colloid were also discussed in this paper.

and 10 ml ammonia were dissolved in 100 ml distilled water and


heated to boil under magnetic stirring (300 rpm), respectively. Then
the as-prepared boiling ammonia solution was gradually added to
ferric sulphate solution under vigorous stirring (1000 rpm) in 5 min
to get the precursor (ferrihydrite, Fe(OH)3). After washing with
distilled water for seven times (250 ml distilled water each time), the
precursors were redispersed in 200 ml distilled water. Then the pH of
the solution was adjusted to 5.0 by hydrochloride solution (0.1 mol/L)
and 0.2 g ferrous chloride was added into this system. At last the
suspension was heated to boil and kept reuxing for 5 h under
magnetic stirring (300 rpm).
2.2. Characterization of nano-hematite colloid
The obtained products were characterized by X-ray Diffraction
(Bruker D8 ADVANCE diffractometer with Cu-K radiation,
Germany), UVvis absorption spectra (Scinco S-3150, Korea), Dynamic Light Scattering (Malvern Zetasizer Nano, England), Transmission Electron Microscope (JEM-100CXII, Japan), Fourier Transform
Infrared Spectroscopy (Bruker Vector 33, Germany), and Zeta
potential (Malvern Zetasizer Nano, England).

3. Results and discussion

2. Experimental

3.1. The stability of nano-hematite colloid

2.1. Preparation of nano-hematite colloid

In our experiments, it was found that the preparation conditions of


precursor exerted signicantly effects on the formation of nanohematite colloid, which were schematized in Table 1. From Table 1, it
can be noticed that sample 1, which was transformed from the
washed precursors prepared by mixing boiling ammonia and ferric
sulphate solutions, exhibited good colloidal stability and narrow size
distribution. During the period of our observation (N15 days) no

All chemicals were of analytical grade and used without further


purication. In a typical experimental procedure, 4.0 g ferric sulphate
Corresponding author. Tel.: +86 20 87110961; fax: +86 20 87110961.
E-mail addresses: 279169804@qq.com (R. Cao), xqchencn@scut.edu.cn (X. Chen).
0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.03.006

R. Cao et al. / Materials Letters 65 (2011) 32983300

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Table 1
The preparation conditions of precursors, the stability and particles size of nanohematite colloid obtained from different precursors.
Sample Treatments

1
2
3

Solutions

Precursor

Boiling
Room
temperature
Boiling

Washed
Washed

Colloid Size
(d nm)

Stability
(days)

Y
Y

N 15
b5

Unwashed N

50
Peak1 = 43 Peak2 = 194
Peak3 = 492
3000

Key: Solutions = ammonia and ferric sulphate solutions, Y = yes, N = no.

noticeable precipitation was noted, which is a highly desirable property for printing and painting applications. This phenomenon may
due to its high Zeta potential (nearly 81 mV), which can increase the
barrier of potential that prevents particles in suspension from contacting with each other and thus reduces agglomeration (Fig. 1). In
contrast, samples 2 and 3 which were fabricated from the precursors
without being washed or boiled were not colloid or stable colloid. This
may be ascribed to the following reasons: rst, the boiling treatment
was helpful to the sudden formation of homogeneous ferrihydrite
crystal nucleuses in large scale, which is crucial for the preparation of
nearly uniform hematite particles [6]; besides, the washing procedure
can greatly reduce sulfate ions, which can be readily absorbed on the
surfaces of hematite crystals to form coordinating bonds and thus can
cause the agglomeration of hematite particles [9].
3.2. Characterization of -Fe2O3 samples
Fig. 2a shows the XRD patterns of as-prepared precursors and
products. The XRD patterns of the precursor samples agree well with
that of 2-line ferrihydrite revealing amorphous structures [8]. After
reuxing, the nal products exhibited structural characteristic with
pure rhombohedral symmetry of -Fe2O3 (JCPDS card no. 33-0664)
indicating the crystalline hematite phase and absence of other
impurity phase. It was interesting to note that the obtained hematite
displays a preferential orientation of (110) peak. The orientations
of (110) in -Fe2O3 structures were benecial for the photocatalytic
application due to the good conductivity for fast electron transfer [11].
Fig. 3 illustrates the size distribution of nano-hematite and the
morphologies of nano-particles. Fig. 3a displays that the hematite
particles present various shapes (pseudocube, nanoplatelet and
irregular polyhedral) with a size distribution ranging from 20 nm
to 60 nm (Fig. 3b). The formation of these diverse morphologies is
mainly attributed to the selective adsorption of sulfate ions on

Fig. 2. XRD pattern (a) and FT-IR spectra (b) of the precursor and hematite.

ferrihydrite and hematite surfaces. The FT-IR (Fig. 2b) absorption


bands between 900 cm 1 and 1200 cm 1 indicate that, though the
precursors had been washed several times, few sulfate ions were still
absorbed on the precursor [11]. So in the following reaction process,
sulfate ions were most strongly adsorbed to the faces of the newly
formed hematite parallel to the c-axis such as {110} and {100}, or on
{012} or on (001) through bridging-bidentate and monodentate adsorption [12], leading to the retarded growth in the direction normal
to the c-axis, which induced the appearances of the pseudocube, nanoplatelet and irregular polyhedral structures [13].
3.3. Optical properties
Fig. 4a shows that nano-hematite colloid had strong absorption in
the UV region (200400 nm) and weakly absorption in the visible
regions (400800 nm). The mechanisms of this optical absorption can
mainly be attributed to two types of electronic transitions: (1) indirect
charge transition of Fe3+ 3d 3d corresponding to absorption in the
visible region and (2) the direct charge transition of O2 2p Fe3+ 3d
contributing to absorption in the UV region [8,10]. The relationship of
absorption coefcient and the incident photon energy of semiconductors can be experimentally obtained using Tauc's formula:

n
h = A hEg

Fig. 1. Zeta potential along time for the nano-hematite colloid (particle charge was
positive).

where is the absorption coefcient, A is a constant, and n is equal to


0.5 for allowed direct transitions and 2 for allowed indirect transitions

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R. Cao et al. / Materials Letters 65 (2011) 32983300

Fig. 4. a) The UVvis absorbance spectrum of nano-hematite colloid. Tauc plot analysis
of optical ban gap of b) direct transition and c) indirect transition for nano-hematite
particles.

ferrihydrite. The determination results revealed that the obtained


colloid was stable for more than 15 days, and the nanocrystalline Fe2O3 presented various shapes. The UVvis absorbance spectrum
showed that the nano-hematite colloid owned a strong absorbing
ability within the UV region.
Acknowledgement
This study was nancially supported by the Grand Science and
Technology Special Plan Projects of Guangdong Province of PR China
(no. 2008A090300016).
References
Fig. 3. The TEM image a) and size distribution b) of nano-hematite colloid, Concentration = 1% (w/w).

[14]. In Fig. 4b and c, (h)1/n is plotted against h, the indirect and


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respectively. The indirect transition band gap agrees well with the
previously reported results [15]. While the direct transition band gap
shows a little blue shift. Such a blue shift can be ascribed to quantum
connement [16].
4. Conclusions
In summary, stable monodispersed nano-hematite colloid was
prepared by a facile route, the modied solid phase transformation of

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