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Materials Letters 62 (2008) 504 506


www.elsevier.com/locate/matlet

A novel method to prepare Cr2O3 nanoparticles


Zhenzhao Pei a,b,, Yi Zhang a
a

Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100080, PR China
b
Graduate School of Chinese Academy of Sciences, Beijing 100039, PR China
Received 11 February 2007; accepted 29 May 2007
Available online 2 June 2007

Abstract
By the reaction system of CrO3 and HCHO in aqueous solution, Cr2O3 nanoparticles were first prepared via hydrothermal synthesis. The
process can be easily scaled up. The reaction time was only 1 h and the reaction temperature was 170 C. The products were loosely agglomerated
Cr2O3 particles of 5070 nm in average particle size calculated from the Scherrer's formula, whose microstructure and that of the precursor were
investigated by SEM. And IR, TG and BET were other characterization methods to study the process. The findings showed that the higher
calcination temperature and the higher total concentration were factors to result in the larger average particle size.
2007 Elsevier B.V. All rights reserved.
Keywords: Hydrothermal synthesis; Cr2O3; Characterization methods; Microstructure

1. Introduction
For nanoparticles of Cr2O3 to be widely used in fields such as
catalyst [1], wear resistance [2], H2 absorption material [3] and
so on, it is significant to develop some economical processes to
prepare them.
There have been some ways to obtain Cr2O3 nanoparticles,
including microwave plasma [4], decomposition of chromium
(III) nitrate solution [5], laser-induced deposition [6], sonochemical reaction [7], gas condensation [8] and so on. But
since either these processes are complex or their reaction apparatus are expensive, most of them have difficulties in being
industrialized. Some new methods of preparation should be
explored.
Hydrothermal synthesis is a typical way to prepare nanoparticles, but no literature has reported that Cr2O3 nanoparticles have
been successfully obtained in this way. Haitao Xu et al. [9] used a
hydrothermal technique to produce Cr2O3 particles, but the

Corresponding author. Beiertiao 1, Zhongguancun, Beijing 100080, PR


China. Tel.: +86 10 82610244; fax: +86 10 62561822.
E-mail address: zzpei@home.ipe.ac.cn (Z. Pei).
0167-577X/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.05.073

sizes of the products were about 500 nm, not in the range of
nanometers. In this research, nanoparticles of Cr2O3 were obtained successfully via hydrothermal technique by the reaction
system of CrO3 and HCHO in aqueous solution. The reaction time
was only 1 h, much shorter than that in Haitao Xu's experiment,
12 h. The prospect of the process is promising.
2. Experimental procedure
CrO3 (99%, AR) was used as chromium source and oxidant
and HCHO aqueous solution (13.55 mol/l) used as reducing
agent. Deionized water was prepared from Milli-Q system
(Millipore, France).
5 g CrO3 and 3.5 ml HCHO aqueous solution were added
into a 200 ml Teflon-lined cylindrical bomb previously filled
with 120 g deionized water, and magnetically stirred for several
minutes until they became a homogeneous solution. Then the
sealed bomb was heated at 170 C for 1 h in an oven. After that,
it was cooled to room temperature and the solution was filtered.
The filter cake was washed for 3 times. Then the cake was dried
at 100 C for 5 h. The obtained particles were black, with size in
the grade of m to mm, which were called Material 1. Material 1
was calcinated in electric oven at different temperatures for 1 h.
The obtained powders were black when calcinated at 500 C but

Z. Pei, Y. Zhang / Materials Letters 62 (2008) 504506

Fig. 1. IR spectra of Material 1.

green at 700 C. They were called Material 2. Experiments


under different reaction conditions were done as above.
3. Analysis
Thermalgravimetric analyzer (STA 449C, NETZSCH) and
FT-IR spectrometer (SPECTRUM GX II, Perkin-Elmer, Powers
were diluted in KBr) were used to investigate Material 1. X-ray
powder diffraction (X' Pert PRO MPD, PANalytical, the
Netherlands) using Cu K radiation ( = 1.5408) was performed
to verify Material 2. Morphology of products was analyzed by
field-emission scanning electron microscopy (JSM-6700F,
Electron Company, Japan) and specific surface areas of particles
were obtained by BrunauerEmmettTeller area measurement
(BET, ASIMP, Quantachrome).
4. Results and discussion

505

Fig. 3. XRD patterns of the precursor and chromium oxide calcinated at different
temperatures: (a) the precursor; (b) Cr2O3 calcinated at 500 C (5gCrO3:3.3 ml
HCHO).

values of their formulae. And Fig. 2 is the thermogravimetric curve for


the decomposition of Material 1. According to it, the total mass loss of
Material 1 is 37.2%. Through figuration, x is 5, which is different from
the x value of the precursor in the literature [10]. Then the formula of
the precursor is Cr2O35H2O. It is amorphous, as Fig. 3 (a) shows.
In Fig. 3, XRD patterns of the precursor and chromium oxide after
calcination at different temperatures are shown. Fig. 3 (b) reveals that
Material 2 is Cr2O3. Its average particle size was calculated through the
Scherrer's formula D = 0.89 / Bcos. D, , B and were the average
particle size, the X-ray wavelength, the angular line width of halfmaximum intensity and the Bragg's angle respectively. And the results
were listed in Table 1.
So the possible mechanism was concluded as follows:
CrO3 H2 OH2 CrO4
H2 CrO4 2H CrO2
4

4.1. Verification of Material 1 and Material 2


Fig. 1 is the IR spectra of Material 1. It shows that the five peaks are
respectively 3416, 1566, 1363, 923, and 530 cm- 1, which indicates that
the formula of the precursor is Cr2O3xH2O, as reported in the literature
[10]. But these peaks show a few shifts from those of the precursor in
the literature [10]. They are 3370, 1620, 1430, 850 and 530 cm- 1
respectively. It should be due to different intramolecular interactions in
these two precursors, which derive from the differences between the x

8H 4CrO2
4 3HCHO 3H2 O2Cr2 O35H2 O 3CO2
Cr2 O35H2 OCr2 O3 5H2 O

4.2. Morphology and size distribution of the precursor and Cr2O3


nanoparticles
Fig. 4 shows the FE-SEM photographs of Material 1 and Cr2O3
nanoparticles obtained at different reaction conditions and calcination

Table 1
Effects of reactant concentrations and calcination temperatures on the specific
surface area and average particle size
CrO3 (g)

Fig. 2. Thermogravimetric curve for the decomposition of Material 1.

5.0
5.0
7.5

Volume of HCHO
solution (ml)

Calcination
temperature
(C)

Specific surface
area (m2/g)

Average
particle size
(nm)

3.30
3.30
4.95

500
700
500

36
23.02
35.37

50.78
70.36
63.82

506

Z. Pei, Y. Zhang / Materials Letters 62 (2008) 504506

Cr2O3 nanoparticles in an approximately round shape, as image (b) and


(c) showed. And higher calcination temperature could weaken the
agglomeration of nanoparticles, as the comparison of image (b) with (c).
It was in agreement with the literature [11].
Table 1 shows the influences of different factors on specific surface
area and average particle size. And average particle size changed with
the concentration of reactants and the calcination temperature of the
precursor. Table 1 revealed a law: When the ratio of reactants was the
same, the average particle size became larger with the increase of the
total concentration. For example, the average size of the products when
the reactants were 7.5 g CrO3 and 4.95 ml HCHO solution was larger
than that when the reactants were 5 g CrO3 and 3.3 ml HCHO solution.
And when other parameters were the same, higher calcination
temperature could lead to larger average particle size. And the change
of the average particle size had the opposite trend to that of the specific
surface area.

5. Conclusion
Nanoparticles of Cr2O3 with narrow size distribution were
firstly prepared via hydrothermal synthesis and appeared loosely
agglomerated. The process needs no surfactant or stirrer. And
higher calcination temperature and higher total concentration
could result in larger average particle size. The process was
easily controlled and the reaction time only needed 1 h. For the
advantages of it, this process has the potential to be applied into
the industry.
Acknowledgement
The research was supported by the Key Program Project of
the National Natural Science Foundation of China (Grant No.
0303011134).
References

Fig. 4. FE-SEM photographs: (a) Material 1, (b) chromium oxide particles


(calcinated at 500 C, 5gCrO3:3.3 ml HCHO), (c) chromium oxide particles
(calcinated at 700 C, 5 g CrO3:3.3 ml HCHO).

temperatures. Fig. 4 (a) is the image of the precursor and Fig. 4 (b) and (c)
is that of the Cr2O3 nanoparticles. And image (a) reveals that the precursor
is in irregular shape with the size distribution between 20 and 900 m.
But after calcination, the precursor decomposed to loosely agglomerated

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