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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
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
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).
8H 4CrO2
4 3HCHO 3H2 O2Cr2 O35H2 O 3CO2
Cr2 O35H2 OCr2 O3 5H2 O
Table 1
Effects of reactant concentrations and calcination temperatures on the specific
surface area and average particle size
CrO3 (g)
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
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
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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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