Available online at www.sciencedirect.

com

Materials Letters 62 (2008) 1339 – 1341

www.elsevier.com/locate/matlet

A different chemical route to synthesize ZnO nanoparticles

Chunlei Wang, Qiuyu Li, Baodong Mao, Enbo Wang ⁎, Chungui Tian
Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University,
Ren Min Street No. 5268, Changchun, Jinlin 130024, PR China

Received 11 June 2007; accepted 16 August 2007

Available online 22 August 2007

Abstract

A new reaction was developed to synthesize ZnO nanoparticles with nearly uniform, spherical morphology ranging from 25 to 50 nm via
directly oxidizing zinc powders with iodine in ethanol. Iodine plays key roles in the nucleation of ZnO nanoparticles and it is favorable for the
growth of ZnO nanoparticles gradually and avoids the agglomeration to some extent. Moreover, this process is well repeatable and easy controlled.
The morphology evolution of the ZnO nanoparticles at different reaction time was monitored through transmission electron microscope (TEM).
The room temperature photoluminescence (PL) spectrum displays strong ultraviolet emission peaks and relative weak near band-edge free
excitonic emission peak.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Semiconductors; Nanomaterials

1. Introduction nanoparticles with uniform morphology and size [6,7]. Among

Zinc oxide (ZnO), an important II–VI semiconductor with a
direct wide band gap (3.37 eV) and a large exciton binding energy
(60 meV), is currently attracting worldwide intense interests
because of its importance in fundamental studies and its numerous
applications especially as optoelectronic materials [1]. Recent
researches show that ZnO nanomaterials can be used as promising
piezoelectric nanogenerators, which trigger a wide range of
subsequent research in searching for new synthetic methods to
synthesize ZnO nanomaterials [2]. Among various ZnO nanos-
tructures, ZnO nanoparticles are the most frequently studied [3]
because of their interest in fundamental study and also their
applied aspects such as in solar energy conversion, photocatalysis,
light-emitting materials [4], transparent UV protection films and
chemical sensors [5]. Hitherto, searching new methodology to
synthesize uniform ZnO nanoparticles is still of great importance
for both fundamental study and application of ZnO nanomaterials.
Various methods have been developed for the syntheses of ZnO
⁎ Corresponding author. Tel.: +86 431 85098787; fax: +86 431 85098787.
E-mail addresses: wangeb889@nenu.edu.cn, wangenbo@public.cc.jl.cn
(E. Wang).
0167-577X/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.08.044
these synthetic routes, solution chemical methods provide a
promising way for low cost and large-scale production, which do
not need expensive raw materials and complicated equipments
[8,9]. However, most solution methods use zinc salts as the
starting material and the reactions are generally carried out in
water or alcohol by the hydrolysis of zinc salts in the presence of a
base [10,11]. It is has been demonstrated that the anion of the zinc
salts and the cation of the base have great effect on the formation
of the ZnO nanocrystals [12,13]. Moreover, most methods exploit
surface modification or protecting reagents to prevent agglom-
eration and control the morphology development of ZnO
nanocrystals. There are still few reports about synthesizing ZnO
nanoparticles at mild condition that do not need any protecting
reagents and complicated process control.
In present work, a new reaction was employed to synthesize
nearly uniform spherical ZnO nanoparticles with no agglomer-
ation. The growth process and morphology evolution of the ZnO
nanoparticles are investigated in series of experiments. The
experimental results indicated that the morphology evolution
depends on the reaction time. Iodine plays key roles in the
nucleation and growth of the ZnO nanoparticles and the possible
formation mechanism was also discussed.
1340 C. Wang et al. / Materials Letters 62 (2008) 1339–1341

2. Experimental section

All chemicals (analytical grade reagents) were purchased

from Beijing Chemicals Co. Ltd. and used as received without
further purification. 1 g of iodine (I2) was dissolved in 40 mL of
absolute ethanol under constant magnetic stirring. Then 0.6 g of
solid zinc powders was added and the reddish purple solution
became clear gradually. After keeping vigorous magnetic
stirring for about several minutes, the solution became slightly
turbid, which indicated the nucleation of ZnO at room
temperature. When the reaction time exceeded 2 h, the solution
became clear and white sediments formed. The mixtures were
filtrated, and distilled water was added into the flask to further
ultrasonication wash. Then appropriate ultrasonical intensity
was chose to disperse the ZnO products in the solution and
remain residual zinc powders on the bottom of the flask. The
process remained about 10 min and the residual zinc powders
on the bottom of the flask were separated from the system. The
above layer was redispersed in ethanol, washed with distilled
water and absolute ethanol for several times to remove
impurities. Finally, the precipitate was dried under vacuum at
60 °C for 4 h and the as-prepared ZnO nanoparticles were
obtained. X-ray diffraction (XRD) patterns were measured Fig. 2. TEM images of as-synthesized ZnO nanoparticles under different
reaction time (a) 5 min, (b) 30 min, (c) 2 h, and (d) 2 h in high magnifications.
using a Rigaku D/max-IIB X-ray diffractometer at a scanning
rate of 4° per min with 2θ ranging from 10° to 80°, using Cu Kα
radiation (λ = 1.5418 Å). The size and morphology of the ZnO The obtained ZnO samples are of wurtzite structure (hexagonal phase,
nanoparticles were characterized with transmission electron space group P63mc). The results indicate that the products consist of
microscope (TEM, JEM-2010) at an acceleration voltage of pure phase and no characteristic peaks were observed for other
200 kV. The samples were dispersed in absolute ethanol and impurities. The sharp peaks indicate that the products were well
crystallized.
ultrasonicated before TEM observation. The room temperature
The size and morphology evolution of ZnO nanoparticles were
photoluminescence (PL) spectrum was performed on a JY-
characterized with TEM. Typical TEM images of the as-prepared ZnO
Labram spectrometer with a He–Cd laser as the excitation nanoparticles under different reaction time are shown in Fig. 2. Fig. 2a
source at 325 nm. exhibits whisker-like nanoparticles with average diameter of about 30–
50 nm at the earlier stage of the nanoparticles growth (5 min). As the
3. Results and discussions reaction time prolonged (30 min), the nanoparticles become spherical
like as shown in Fig. 2b. Fig. 2c and d shows the nanoparticles
Fig. 1 shows typical XRD pattern of the as-obtained nanoparticles. synthesized in aqueous solution reacting for 2 h with the diameter of
All the diffraction peaks can be well indexed to the hexagonal phase about 25–50 nm. It can be seen that the sample are nearly uniform
ZnO reported in JCPDS card (No. 36-1451, a = 3.249 Å, c = 5.206 Å). spherical nanoparticles free from agglomeration. The corresponding
size distribution histograms of the samples shown in Fig. 2(a)–(d) were
shown in the electronic supplementary information.
To investigate the details of the reaction process, several factors
were taken into account. In the early stage of the reaction, the dissolved
I2 in ethanol reacted with Zn to produce ZnI2, the reddish purple
solution become clear. As the reaction time prolonged, the solution

Fig. 1. XRD pattern of as-synthesized ZnO nanoparticles. Scheme 1.

 C. Wang et al. / Materials Letters 62 (2008) 1339–1341
Fig. 3. PL spectra of the as-prepared ZnO nanoparticles at room temperature.
became turbid gradually. Because there are still residual zinc powders
in the system, the solution looks gray. Furthermore, several other
controlled experiments were carried out. Firstly the experiment was
carried out in the deaerated ethanol solution of I2 in an Ar-saturated
flask (50 mL). With the absence of the O2, the white sediment was not
obtained under the same condition. When the system was exposed to
air, the white sediment was obtained immediately, indicating the
nucleation of the ZnO nanoparticles. This result shows that the oxygen
atom in ZnO comes from O2 in the air. This is interesting to the
synthesis of ZnO nanoparticles and different from other reported
synthesis routes for ZnO nanoparticles [10,11]. This experiment results
also show that the H2O was also coming from humidity in the air.
When the reaction completed, a drop of the above clear solution in the
flask was took out and added to AgNO3 aqueous solution. The AgNO3
solution became turbid immediately, which implied the presence of I− in
the final solution. Based on the above discussion, a possible formation
procedure of the nanoparticles was proposed as shown in Scheme 1: In
the reaction, I2 plays an important role in the formation of the ZnO
nanoparticles. I2 was the reactant in Eq. (1) and also was the product of the
Eq. (2), so the amount of Zn is superfluous compared with I2 making sure
the completion of the growth of ZnO nanoparticles. Due to the oxidation
of I− to I2, the Zn powders transformed to zinc cation (Eq. (1)). On other
hand, OH− was easy to be obtained in the system due to the reduction of
O2 (Eq. (2)) [14].
The formation speed of Zn(OH)2 in the current reaction is slower
than those in reactions through the hydrolysis of zinc salts to obtain Zn
(OH)2, probably because of the participation of I2. As a result, it is
favorable for the nucleation and growth of the ZnO nanoparticles
gradually and avoids the agglomeration to some extent [12,13].
Moreover, the quantity of H2O in this reaction is small because the H2O
comes from humidity in the air. This is also one reason that the
formation of ZnO particles is slow.
So it is easy to be seen from the TEM images (Fig. 2) that the
obtained ZnO nanoparticles are with nearly uniform shape and size.
1341
Besides ethanol, deionized water could also be used as solvent.
However, TEM results showed the nanoparticles were not as uniform
and spherical as that obtained in ethanol solution.
The PL spectrum in Fig. 3 shows that the obtained ZnO
nanoparticles display strong ultraviolet emission peaks centered at
(∼) 388 nm, which comes from recombination of excitonic centers. The
emission peaks centered at 512 nm, which come from nanoparticles,
referred to the near band-edge free excitonic emission and the deep
level or trap state emission. Both of these peaks are generally attributed
to the special structure of the prepared nanocrystals, especially single
ionized oxygen vacancies from the surface of the nanostructures.
4. Conclusions
In summary, a novel reaction was developed for the synthesis
of ZnO nanoparticles with nearly uniform spherical morphol-
ogy by directly oxidizing zinc powders with iodine in ethanol.
This process is well repeatable and easy controlled, which may
offer an attractive strategy for the fabrication of other oxide
nanoparticles.
Acknowledgment
The authors thank the National Natural Science Foundation
of China for the financial support (20371011).
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.matlet.2007.08.044.
References
[1] C. Pacholski, A. Kornowski, H. Weller, Angew. Chem., Int. Ed. Engl. 43
(2004) 4774.
[2] Z.L. Wang, J. Song, Science 312 (2006) 242.
[3] R. Turgeman, S. Tirosh, A. Gedanken, Chem. Eur. J. 10 (2004) 1845.
[4] G.R. Gattorno, P.S. Jacinto, L.R. Va'zquez, J. Phys. Chem., B 107 (2003)
12597.
[5] E. Meulenkamp, J. Phys. Chem., B 102 (1998) 5566.
[6] L. Spanhel, M.A. Anderson, J. Am. Chem. Soc. 113 (1991) 2826.
[7] E. Wong, J. Bonevich, P. Searson, J. Phys. Chem., B. 102 (1998) 7770.
[8] Q. Tang, W. Zhou, J. Shen, W. Zhang, Y. Qian, Chem. Commun. (2004)
712.
[9] C. Wang, E. Shen, E. Wang, L. Gao, Z. Kang, C. Tian, Mater. Lett. 59
(2005) 867.
[10] Z.R. Tian, J.A. Voigt, B. Mckenzie, J. Am. Chem. Soc. 124 (2002) 12954.
[11] C. Wang, E. Wang, E. Shen, L. Gao, Mater. Res. Bull. 41 (2006) 2298.
[12] H. Du, F. Yuan, S. Huang, J. Li, Y. Zhu, Chem. Lett. 33 (2004) 770.
[13] E. Hosono, S. Fujihara, T. Kimura, Electrochem. Solid State Lett. 7 (2004)
C49.
[14] X. Cao, X. Wang, Inorganic Chemistry, Higher Education Press, China,
1994, p. 526.