Materials Letters 58 (2004) 387 – 389

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Mechanochemical synthesis of cobalt oxide nanoparticles

Huaming Yang *, Yuehua Hu, Xiangchao Zhang, Guanzhou Qiu
Department of Inorganic Materials, School of Resources Processing and Bioengineering, Central South University, Changsha 410083, PR China
Received 31 March 2003; accepted 10 June 2003

Abstract

Cobalt oxide (Co3O4) nanoparticle was synthesized by thermal treatment of the precursor obtained via mechanochemical reaction of
Co(NO3)2
6H2O with NH4HCO3. Calcination of the precursor at 300 jC resulted in the formation of Co3O4 nanoparticles of 13 nm in crystal
size. The precursor was examined by simultaneous differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The Co3O4
nanoparticles were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Effect of calcination temperature
on Co3O4 crystal size was discussed. The activation energy (E) of Co3O4 nanoparticle formation during thermal treatment was calculated to
be 15.9 kJ/mol.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Cobalt oxide (Co3O4); Nanomaterials; Mechanochemical synthesis; X-ray technique

1. Introduction processing, including ZnS, CdS, ZrO2, LiMn2O4, SiO2,

Cobalt oxide (Co3O4) powder has a wide range of
applications in various fields of industry including anode
materials for rechargeable Li-ion battery, catalyst, gas sensor
and magnetic materials [1 –4]. The properties of Co3O4 in
above applications are highly related to the particle size. It
has been indicated that nanocrystalline Co3O4 is especially
good for the property promotion [5]. Much effort has been
made to prepare Co3O4 nanoparticles, including pulsed laser
deposition [6], sol – gel route [7], reduction –oxidation route
[8], gel hydrothermal oxidation [5], homogeneous precipi-
tation [9], staged oxidation process [10] and cobalt salt
decomposition [11 –13], but through all of the above meth-
ods, nanocrystalline Co3O4 is more difficult and inconve-
nient to obtain.
Mechanochemical processing is a novel method involv-
ing the mechanical activation of solid-state displacement
chemical reactions, either during milling or during follow-
ing heat treatment [14]. Recently, a wide variety of nano-
particles have been synthesized by mechanochemical
* Corresponding author. Tel.: +86-731-8830549; fax: 86-731-8710804.
E-mail address: hmyang@mail.csu.edu.cn (H. Yang).
CeO2, et al. [15 –18]. Mechanochemical synthesis is partic-
ularly suitable for large-scale production because of its
simple process and low cost [19]. However, there is few
report on the mechanochemical preparation of nanosized
Co3O4. In this paper, the synthesis of Co3O4 nanoparticles
by mechanochemical processing is investigated.
2. Experimental
The starting materials were AR-grade Co(NO3)2
6H2O
and NH4HCO3. Five grams of starting materials were put in
an agate mortar with Co(NO3)2
6H2O to NH4HCO3 molar
ratio of 2:5. The starting materials were mixed and milled at
room temperature until the color of the as-milled powder
kept unchanged, then the as-milled powder was thoroughly
washed with distilled water and dried at 100 jC in air to
obtain the nanoparticle precursor. The precursor was cal-
cined at 300 jC in air in a porcelain crucible for 2 h to
prepare the Co3O4 nanoparticles.
The precursor was examined by simultaneous TGA –
DTA techniques (TA, SDT2960) at a heating rate of 20 jC/
min. The Co3O4 nanoparticles were characterized by XRD
(Rigaku, D/max-gA, Cu-Ka radiation) and TEM (JEOL,
JEM-200CX). The average crystal size (D) of the nano-

0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0167-577X(03)00507-X
388 H. Yang et al. / Materials Letters 58 (2004) 387–389

Fig. 1. XRD patterns of the as-milled powders: (a) amorphous precursor, (b)
after heat treatment at 300 jC for 2 h.
Fig. 3. XRD patterns of the Co3O4 nanoparticles synthesized at different
particle was calculated from diffraction peak half-widths calcination temperatures.
using the Scherrer formula.

3. Results and discussion

The stoichiometric mixture of the starting powders was

milled, corresponding to the following reaction equation:

2CoðNO3 Þ2
6H2 O þ 5NH4 HCO3

¼ Co2 ðOHÞ2 CO3 þ 4NH4 NO3 þ NH3 þ 4CO2 þ 14H2 O
ð1Þ

The reaction was observed to be very fast; the color of the

mixture changed frequently and remained grey finally.
Ammonia gas can be obviously smelt during the milling.
Fig. 1 shows the XRD patterns of the as-milled powders.
After about 30 min milling of the mixture, no other peak
is evident, which indicates that the reaction Co(NO3)2
Fig. 4. Variation of XRD crystal size (D) with heat treatment temperature.
6H2O + NH4HCO3 was complete and that the product was
amorphous precursor. From the XRD profile, it can be
deduced that the crystallization of Co3O4 is initiated in
the amorphous mixture of the starting materials. Conse-

Fig. 2. TGA – DTA curves of the nanoparticle precursor. Fig. 5. TEM micrograph of the Co3O4 nanoparticles.
 H. Yang et al. / Materials Letters 58 (2004) 387–389
Fig. 6. Plot of lnD as a function of calcination temperature for the
nanoparticle precursor.
quently, the solid-phase diffusion is accelerated by the
milling. Calcination of the precursor at 300 jC for 2
h resulted in the formation of the nanocrystalline Co3O4,
and the calculated value of the crystal size of Co3O4
nanoparticle was about 13 nm.
Fig. 2 shows the TGA – DTA curves of the nanoparticle
precursor. In the DTA curve, a distinct exothermic peak at
150 jC – 250 jC was evident, which results from dehydra-
tion and decomposition of the precursor. TGA curve indi-
cated a weight loss of 35.6% occurred from ambient to 250
jC. This value agrees well with the theoretical mass loss of
36.8% corresponding to the following reaction. No change
in the TGA –DTA curves can be observed after 250 jC:
3Co2 ðOHÞ2 CO3 þ O2 ¼ 2Co3 O4 þ 3H2 O þ 3CO2 :
The XRD patterns of the Co3O4 nanoparticles after
calcined at different temperatures are shown in Fig. 3. The
intensity and definition of the diffraction peaks associated
with Co3O4 increase with increasing heat-treated tempera-
ture. Fig. 4 shows the variation of XRD crystal size (D) of
Co3O4 nanoparticles prepared by the thermal treatment of
precursor at different temperatures. It can be indicated that
the crystal size rapidly increases from approximately 13 nm
at 300 jC to ~38 nm at 600 jC.
The TEM image of the Co3O4 nanoparticles in Fig. 5
shows monodisperse and ultrafine particles with uniform
size, which coincides with the XRD crystal size. The
individual particles are found to be mostly single crystal.
A straight line of lnD versus 1/T (Fig. 6) is plotted
according to the Scott [20] equation given below under the
condition of homogeneous growth of nanocrystallite, which
approximately describes the growth rate of nanocrystallite
from thermal treatment of amorphous compounds:
D ¼ CexpðE=RT Þ
where D is the average nanocrystallite size, C is the
constant, E is the activation energy, R is the ideal gas
constant and T is the absolute temperature.
389
There exists a good linear relationship. E value could be
calculated from the slope of the straight line as E = 15.9 kJ/
mol. It shows that the growth of Co3O4 nanocrystallite is
easily affected by the calcination temperature, which can be
observed from Fig. 4.
4. Conclusions
Mechanochemical processing of Co(NO3)2
6H2O and
NH4HCO3 resulted in the formation of amorphous precur-
sor during milling, which was then oxidized to nanocrystal-
line Co3O4 after thermal treatment at 300 jC in air. The
XRD crystal size of the Co3O4 nanoparticle rapidly in-
creased with increasing heat-treated temperature of the
precursor, crystal size varying from 13 to 38 nm at 300
jC – 600 jC. The activation energy(E) of Co3O4 nano-
crystallite formation during thermal treatment was calculat-
ed to be 15.9 kJ/mol. The calcination temperature has a
prominent effect on the nanocrystallite growth. The Co3O4
nanoparticle is promising for high-performance functional
materials.
Acknowledgements
This work was supported by the National Science
Foundation for Distinguished Young Scholar of China (no.
59925412) and the Excellent Doctoral Dissertation Founda-
tion of Hunan Province (no. 200114).
ð2Þ
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