Colloids and Surfaces A: Physicochem. Eng.

Aspects 226 (2003) 35–44

Preparation of ZnO particles by precipitation transformation

method and its inherent formation mechanisms
S.C. Zhang∗ , X.G. Li
State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering,
Peking University, P.O. Box 171, Beijing 100871, PR China

Received 10 December 2002; accepted 1 July 2003

Abstract

The ZnO particles were prepared by implementing the precipitation transformation method from Zn5 (CO3 )2 (OH)6 in an
aqueous solution at a low temperature (room temperature to 70 ◦ C). The phase transformation process was detected by using a
pH-meter and an X-ray diffraction (XRD). With an increase of temperature and concentration and quantity of NaOH solution, the
ZnO phase became easier to form, otherwise, the ε-Zn(OH)2 phase would need to be formed. The morphology of ZnO particles
and its formation mechanism were investigated. Through controlling the reaction conditions and the post-treatment, the ZnO
nanoparticles can be obtained.
© 2003 Elsevier B.V. All rights reserved.

Keywords: ZnO; Particles; Chemical synthesis; Precipitation transformation; Growth habit

1. Introduction In order to obtain high quality zinc oxide powders

ZnO is an interesting material from several points
of view. Zinc oxide is a large band gap (3.3–3.6 eV)
n-type semiconductor [1] and shows both photocon-
ductivity and photocatalytic activity. ZnO nanopar-
ticles also show size-dependent electronic and op-
tical properties, which are known as quantum-size
effects. Furthermore, ZnO is a technologically impor-
tant material. For these reasons, ZnO nanoparticles
have been widely used in pigments, rubber additives,
gas sensors, varistors [2], transducers, transparent
UV-protection films, UV light-emitting devices, and
chemical sensors.
∗ Corresponding author. Fax: +86-10-62765930.
E-mail address: s.c.zhang@263.net (S.C. Zhang).
with a fine particle size, a narrow size distribution and
a special morphology, various preparation techniques
have been used to synthesize zinc oxide nanoparticles,
including precipitation [3], sol–gel [4–6], microemul-
sion [7–9], spray pyrolysis [10–12], hydrothermal
method [13,14], laser vaporization condensation [15],
flow injection synthesis [16]. Of these, the precipita-
tion method has been most widely used industrially.
Commonly, the precipitation technique needs heat
processing of the precipitation precursor, which con-
sumes more energy. During the heat processing, the
particles are subjected to agglomerate, which leads to
a broader particle size distribution. Colloid solutions
of ZnO with particle sizes smaller than 10 nm can
be gained by sol–gel technique [17], but the organic
solvent must be used in this method. In this paper,

0927-7757/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0927-7757(03)00383-2
36 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44
we describe a new technique, the precipitation trans-
formation method, to prepare the ZnO particles, by
which the precipitation is directly transformed into
ZnO in an aqueous solution, and no further heat pro-
cessing and organic solvents were needed. The effects
of the reaction conditions on the phase transforma-
tion and morphologies of particles were investigated
in detail, and the formation mechanisms of particles
were also considered.
2. Experimental
The synthetic procedures for the ZnO particles
by precipitation transformation method are briefly
summarized in Scheme 1. To 50 ml of a solution of
ZnSO4 50 ml of a solution of Na2 CO3 of the same
concentration was added while being vigorously
stirred, thereafter a solution of NaOH also of the
same concentration was added. All chemicals used in
the experiments were of analytical reagents AR grade
and the water was de-ionized. The concentration of
ZnSO4 , Na2 CO3 , and NaOH aqueous solution were
varied in the range of 1, 0.5, 0.1, and 0.02 mol l−1 . The
reaction was performed at different temperatures: 25,
40, 55, and 70 ◦ C. ZnO nanoparticles were obtained
after the slurry was washed, filtered, and dried.
The pH values of the reaction solution were in-
spected on-line through a pH-meter. The structure
and morphology of basic zinc carbonate and ultimate
products were investigated using X-ray diffraction
(XRD) (Rigaku D/MAX-RA diffractometer with
Cu K␣ radiation), transmission election microscopy
(JEM 200CX TEM), and Fourier transform infrared
spectrophotometer (Shimadzu FTIR-8400).
Na2CO3
solution
Dropping
ZnSO4 Zn5(CO3)2(OH)6
solution gel
Precipitation
transformation
Scheme 1.
3. Results and discussions
3.1. Phase transformation
The phase transformation process can be detected
on-line by a pH-meter combined with X-ray diffrac-
tion measurements. Fig. 1 shows the pH value curves
of ZnSO4 solutions with the addition of Na2 CO3 or
NaOH solution at different reaction temperatures: 25,
40, 55, and 70 ◦ C.
During the stage of adding the Na2 CO3 solution,
the reactions in the solution can be shown below:
5Zn2+ + 5CO3 2− + 3H2 O
Zn5 (OH)6 (CO3 )2 (s)
+ 3CO2 (g) (1)
Zn2+ + H2 O
ZnOH+ + H+ (2)
CO3 2− + H2 O
HCO3 − + OH− (3)
The main reaction is Eq. (1). Eq. (2) and (3) give
more effects on the initial stage and the last stage of
adding the Na2 CO3 solution. At the initial stage, the
concentration of the Zn2+ ions is rather high, so the
Eq. (2) give big contribute to the solution, and make
the pH value rather low. At the last stage of adding the
Na2 CO3 solution, the concentration of the Zn2+ ions
is rather low, and the equilibrium constant of Eq. (2) is
10−7.841 , is smaller than that of Eq. (3), 10−3.666 (the
equilibrium constants at 25 ◦ C were calculate by using
SUPCRT92 [18]), so the Eq. (3) is easier to perform
and make the pH value jump (see Fig. 1). The X-ray
diffraction and the FTIR results both confirmed that
all the intermediate products were Zn5 (CO3 )2 (OH)6 .
Fig. 2 shows the FTIR spectra of the intermediate
products under different reaction temperatures. The
NaOH
solution
Dropping
ZnO ZnO
slurry particles
Filtering
Precipitation
Washing
Drying
 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44 37

Zone ΙΙ for 40 ºC
Zone Ι for 40 ºC
Zone ΙΙ Zone ΙΙΙ
Zone Ι for 55 ºC for 55 ºC for 55 ºC

Zone Ι for 70 ºC Zone ΙΙ for 70 ºC Zone ΙΙΙ for 70 ºC

13

12

11

10

8
pH

3
0 10 20 30 40 50

Q (mL)

Fig. 1. The pH value curves of ZnSO4 solutions with the adding of Na2 CO3 or NaOH at the conditions of ZnSO4 1 mol l−1 , the mol
ratio of ZnSO4 :Na2 CO3 :NaOH = 1:1:1, and different reaction temperature: 25 ◦ C (䉬, 䉫); 40 ◦ C (䉱, ); 55 ◦ C (䊉, 䊊); and 70 ◦ C
(䊏, 䊐). Solid symbols represent the curves of ZnSO4 solutions with the adding Na2 CO3 , and open symbols represent that with adding
NaOH.

main features of the spectra correspond to basic
zinc carbonate [19]. This spectrum clearly indicates
the presence of carbonate groups. The split v3 fre-
quency with the bands at 1510 and 1385 cm−1 was
recorded. The IR bands corresponding to v1 fre-
quency located at 1046 cm−1 , v2 at 833 cm−1 and
v4 at 710 cm−1 were also visible. With the increase
of reaction temperature, the fine structure of FTIR
spectrum can be found for the better crystallization
of Zn5 (CO3 )2 (OH)6 [19]. The IR bands at 517 and
469 cm−1 are visible. These IR bands can be assigned
to ZnO [19]. But the ZnO is too little to detect by
XRD.
The pH value curves are different when adding a
NaOH solution. At temperatures of 55, and 70 ◦ C, the
pH value curves show one initial increase in pH, zone
I, that corresponds to the increase of concentration of
OH− . Subsequently, a decrease in pH value, zone II,
indicates the existence of an OH− consuming process
according to Eq. (4) or Eq. (5):
Zn5 (OH)6 (CO3 )2 (s) + 4OH−

5ZnO(s) + 2CO3 2− + 5H2 O (4)
Zn5 (OH)6 (CO3 )2 (s) + 4OH−

5ε − Zn(OH)2 (s) + 2CO3 2− (5)
The second increase in pH, zone III, occurs after the
decrease, indicates the process of phase transforma-
tion is completed. The zones II and III occur earlier
at a temperature of 70 ◦ C rather than that of 55 ◦ C,
which indicates with the increase of temperature the
phase transformation is becoming easier. The whole
process can be confirmed by X-ray diffraction mea-
surements (Fig. 3). The phase transformation from
Zn5 (OH)6 (CO3 )2 to ZnO occurs at the beginning of
zone II (Fig. 3b), and is completed at the beginning of
zone III (Fig. 3c).
38 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44

d
1556

a
738 699

1046 954 517469

710
833
1510 1385

1800 1600 1400 1200 1000 800 600 400

Wavenumber (1/cm)

Fig. 2. FIRT spectra of the mediate precipitates with conditions of ZnSO4 1 mol l−1 , the mol ratio of ZnSO4 :Na2 CO3 = 1:1, and different
reaction temperature: (a) 25 ◦ C; (b) 40 ◦ C; (c) 55 ◦ C; (d) 70 ◦ C.

At a temperature of 40 ◦ C, there are only zones I and perature of 25 ◦ C, there is only zone I and no phase
II, the phase transformations from Zn5 (OH)6 (CO3 )2 transformation occurs (Fig. 4a).
to ZnO and ε-Zn(OH)2 both exist (Fig. 4b). The prod- From Fig. 3, it also can be found that the quan-
uct is a mixture of ZnO and ε-Zn(OH)2 . At a tem- tity of NaOH is another important factor for phase

Zn 5(OH) 6(CO3)2
ZnO
Intensity (arb. units)

10 20 30 40 50 60 70 80
2θ (degree)

Fig. 3. X-ray diffraction patterns of the samples with conditions of ZnSO4 1 mol l−1 , the mol ratio of ZnSO4 :Na2 CO3 = 1:1, reaction
temperature of 55 ◦ C and different mol ratio of NaOH:ZnSO4 : (a) 0; (b) 0.56; (c) 0.92; (d) 1 and stirring further 5 min.
 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44 39

Zn 5(OH) 6(CO3)2
ZnO
-Zn(OH)2
Intensity (arb. units)

10 20 30 40 50 60 70 80
2θ (degree)

Fig. 4. X-ray diffraction patterns of the samples with conditions of ZnSO4 1 mol l−1 , the mol ratio of ZnSO4 :Na2 CO3 :NaOH = 1:1:1, and
different reaction temperature: (a) 25 ◦ C; (b) 40 ◦ C; (c) 55 ◦ C; (d) 70 ◦ C.

transformation. For further confirmation, the experi-
ment was conducted at a low temperature (25 ◦ C) and
with a large quantity of NaOH. When a double amount
of NaOH was used, the Zn5 (OH)6 (CO3 )2 phase was
transformed to ZnO completely (Fig. 5).
The concentration of ZnSO4 solutions also has an
effect on the phase transformation. Fig. 6 shows XRD
patterns of products from ZnSO4 solutions with differ-
ent concentrations. With the decrease of the concen-
tration of ZnSO4 solutions, Zn5 (OH)6 (CO3 )2 phase is

Zn 5(OH) 6(CO3)2
ZnO
Intensity (arb. units)

b
a

10 20 30 40 50 60 70 80
2θ (degree)

Fig. 5. X-ray diffraction patterns of the samples with conditions of ZnSO4 1 mol l−1 , the mol ratio of ZnSO4 :Na2 CO3 = 1:1, reaction
temperature of 55 ◦ C and different mol ratio of NaOH:ZnSO4 : (a) 0; (b) 1; (c) 2; (d) 2 and stirring further 2 h.
40 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44

Zn 5(OH)6(CO3)2
ZnO
ε -Zn(OH)2

d
Intensity (arb. units)

10 20 30 40 50 60 70 80
2θ (degree)

Fig. 6. X-ray diffraction patterns of the samples with conditions of the mol ratio of ZnSO4 :Na2 CO3 :NaOH = 1:1:2, reaction temperature
of 25 ◦ C, and different concentration of ZnSO4 (a) 1 mol l−1 ; (b) 0.5 mol l−1 ; (c) 0.1 mol l−1 ; (e) 0.02 mol l−1 .

more easy to transform to ε-Zn(OH)2 and the ZnO
cannot be obtained. In our experiments, the pure ZnO
phase was obtained from 1 mol l−1 ZnSO4 solutions,
and the nearly pure ε-Zn(OH)2 phase was obtained
from 0.02 mol l−1 ZnSO4 solutions, although there
was a small Zn5 (OH)6 (CO3 )2 phase.
Based on the above results, and combined with the
previous work of Zhong and co-workers [20], we can
decompose the Eqs. (4) and (5) into the following
reactions:
Zn5 (OH)6 (CO3 )2 (s)
5Zn
Zn2+ + 2OH−
Zn(OH)2
Zn(OH)2 + 2OH−
Zn(OH)4 2−
Zn(OH)4 2− + Zn(OH)4 2−
Zn2 O(OH)6 4− + H2 O
Znx Oy (OH)z (z+2y−2x)− + Zn(OH)4 2−

Znx+1 Oy+1 (OH)z+2 (z+2y−2x+2)− + H2 O
In these equations, the subscript “x, y, z” repre-
sents the numbers of “Zn2+ , O2− , OH− ” within
the respective crystal. When the critical size of the
(z+2y−2x)−
cluster Znx Oy (OH)z reaches the values re-
quired for the formation of ZnO powder, the cluster
(z+2y−2x)−
Znx Oy (OH)z is precipitated as ZnO [20]. If
the amount and concentration of OH− ion are not big
enough, ZnO cannot be obtained, and the ε-Zn(OH)2
phase forms, or no phase transformation process is
performed. The temperature may affect the activity
energy of the reactions.
3.2. Morphology
−
2+
+ 2CO3 2−
+ 6OH
The morphologies of ZnO particles obtained by
(6) the precipitation transformation method are shown
(7) in Fig. 7. From the electron diffraction pattern of
a particle (Fig. 7a), one can find that the particle
(8) is comprised of several single crystals aggregated
along certain directions. The shape of a single crys-
tal is a pyramid-prism or elongated pyramid-prism
(9) (Fig. 7a–f). Beautiful patterns with symmetric struc-
tures, extended triangle (Fig. 7a) and hexagonal
(Fig. 7b), are formed by aggregating single crystals.
(10) The morphologies of ZnO particles can be interpreted
from the point of view of the formation mechanism.
The growth habit of single crystals is related to
the relative growth rate of various faces bounding the
crystal. The difference between the growth rates of
 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44 41

Fig. 7. Morphologies of ZnO particles prepared by precipitation transformation method at 55 ◦ C (a, b, and c) and 70 ◦ C (d, e, and f).

various crystal faces results in different growth habits
[20]. In the precipitation transformation process, the
viscosity of the solution is lower, the diffusion of ions
(including complex) is not the main factor affecting
the growth rate, so the growth rate of various crystal
faces is mainly related to their interface structure.
The ZnO crystal obtained by precipitation trans-
formation method belongs to the hexagonal crystal
system (from XRD patterns shown in Figs. 3–5). In
the coordination structure of ZnO, each Zn2+ ion is
surrounded by four O2− ions. All the tetrahedrons are
connected together by corner sharing. According to the
new rule on crystal growth mechanism put forward by
Zhong and his co-workers, the growth rate in [0 0 0 1]
direction is the fastest, and the velocities of crystal
growth in the different directions obey the follow-
ing relationship: V0 0 0 1 > V0 1 1̄ 1̄ > V0 1 1̄ 0 >
V0 1 1̄ 1 > V0 0 0 1̄ . The growth habits of ZnO crystal
42 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44

[0001]

[0001] [0001]

Fig. 9. Sketch map of ZnO particle aggregated from single crystals.

can be shown in Fig. 8 [20], which are similar to the

Fig. 8. Growth habits of ZnO single crystal (from [20]).
experimental results (Fig. 7a–f).
During the growth of ZnO crystal, the single crys-
tals aggregate together under the driving forces of sur-
face energy, electrostatic force, and so on. Accord-
ing to Eq. (6)–(10), the growth units of ZnO crystal
are the complex Zn(OH)4 2− with a tetrahedron form.
The complex Zn(OH)4 2− is connected with the clus-
(z+2y−2x)−
ter Znx Oy (OH)z by corner sharing. Along
the [0 0 0 1] direction, the growth rate of crystal is the
fastest, i.e. the complex Zn(OH)4 2− is easiest to be
connected with the interface (0 0 0 1). So, the electron
charge on the surface of ZnO crystal is not balanced,
and becoming more negative along the [0 0 0 1] direc-
tion. And then, the single crystals aggregate with the
[0 0 0 1] direction directing outside (Figs. 7 and 9). At
the same time, the coordinate directions of ZnO maybe
have an effect on the aggregating direction of differ-

Fig. 10. Formation processes of ZnO particles by precipitation transformation method.

 S.C. Zhang, X.G. Li / Colloids and Surfaces A: Physicochem. Eng. Aspects 226 (2003) 35–44
Fig. 11. Morphology of ZnO nanoparticles prepared by precipita-
tion transformation method.
ent single crystals, just like the aggregation of SrTiO3
crystals [21], i.e. the aggregating direction of single
crystals along the coordinate direction (Fig. 7d–f).
For further study of the formation mechanics of
ZnO singles crystals, a sample was taken from the re-
action slurry during the phase transformation process
after the ZnO phase was formed, detected by TEM.
From the TEM results (Fig. 10), one can find that
there are some soft aggregations with the shape sim-
ilar to the single crystal. An electron diffraction pat-
tern (Fig. 10b) shows that the small particles in the
aggregation are amorphous ZnO. During the further
reaction and post-treatment, the soft aggregation can
transform into single crystal. For further confirmation,
the post-treatment condition was controlled strictly,
such as washing with ethanol more than three times,
and drying at a low temperature, and then the smaller
particle was obtained, with a particle size of ∼100 nm
(Fig. 11).
4. Conclusions
The ZnO particles can be prepared by a precipita-
tion transformation method from Zn5 (CO3 )2 (OH)6 in
aqueous solution at a low temperature. The reaction
temperature and concentration and quantity of NaOH
solution have great effects on the phase transformation
process. With the increase of temperature and con-
centration and quantity of NaOH solution, the ZnO
phase is becoming easier to be formed, otherwise, the
ε-Zn(OH)2 phase will need to be formed.
43
The ZnO particles were formed by aggregating
several single crystals along a certain direction. The
morphology of ZnO particles and the growth habit
of single crystals are greatly relative to the crystal
structure. ZnO crystal is a polar crystal, which be-
longs to the hexagonal crystal system. So, the growth
habit of a single crystal is pyramid-prism or elon-
gated pyramid-prism. The ZnO single crystal was
also formed by aggregating small amorphous ZnO
particles and subsequently crystallizing into a single
crystal. Through controlling the reaction conditions
and the post-treatment, the ZnO nanoparticles can be
obtained.
Acknowledgements
This work was supported by National Natural Sci-
ence Foundation of China (Grant No. 20025103 and
20171002), Ministry of Science and Technology of
China (Grant No. 2001CB610503), and China Post-
doctoral Science Foundation.
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