Journal of Alloys and Compounds 459 (2008) 537542

Synthesis and characterization of CuO ower-nanostructure

processing by a domestic hydrothermal microwave
D.P. Volanti
a
, D. Keyson
b
, L.S. Cavalcante
c,
, A.Z. Sim oes
a
,
M.R. Joya
d
, E. Longo
a
, J.A. Varela
a
,
P.S. Pizani
d
, A.G. Souza
b
a
Laborat orio Interdisciplinar em Cer amica, Departamento de Fsico-Qumica, Instituto de Qumica,
Universidade Estadual Paulista, P.O. Box 355, 14801-907 Araraquara, SP, Brazil
b
Laborat orio de Ensino de Ci encias e Laborat orio de Combustveis e Materiais, Departamento de Qumica,
Universidade Federal da Paraba, 58051-900 Jo ao Pessoa, PB, Brazil
c
Laborat orio Interdisciplinar de Eletroqumica e Cer amica, Departamento de Qumica,
Universidade Federal de S ao Carlos, P.O. Box 676, 13565-905 S ao Carlos, SP, Brazil
d
Departamento de Fsica, Universidade Federal de S ao Carlos, P.O. Box 676, 13565-905 S ao Carlos, SP, Brazil
Received 27 March 2007; received in revised form 7 May 2007; accepted 8 May 2007
Available online 22 May 2007
Abstract
The synthesis and characterization of CuOower-nanostructure processed in domestic hydrothermal microwave oven was presented. Phase anal-
ysis was carried out using X-ray diffraction (XRD) and micro-Raman scattering (MRS) and the results conrmed the CuOower-nanostructure as a
single-phase. The eld-emission scanning electron microscopy (FEG-SEM) was used to estimate the average spheres diameter while transmission
electron microscope (TEM) to observe the thorn of the ower-nanostructures. The mechanism of CuO ower-nanostructures formation is proposed
and explained.
2007 Elsevier B.V. All rights reserved.
Keywords: Nanostructured materials; Oxide materials; Nanofabrications; Microstructure; Scanning electron microscopy
1. Introduction
In past times, the chemical synthesis of inorganic materials
with unusual and novel morphologies has attracted considerable
attention because of their potential applications in various elds
such as catalysts, medicine, electronics, ceramics, pigments,
and cosmetics [14]. In particular, the hierarchical structure
is one of the important forms among various morphologies
[5,6]. Recently, copper oxide-nanostructured materials, such as:
nanorods [7], nanowires [8], nanoribbons [9] and nanobelts [10],
have attracted considerable attention due to their fundamental
importance and potential future applications.
This material presents several applications and many efforts
have been made to synthesize cupric oxide nanoparticles. For

Corresponding author. Tel.: +55 16 3361 5215; fax: +55 16 3351 8350.
E-mail address: laeciosc@bol.com.br (L.S. Cavalcante).
example, Brookshier et al. [11] prepared CuO nanoparticles by
spin coating technique controlling SiO
2
size. Huang and Mati-
jeric [12] reported copper-II-oxide sols of denite size and shape
inaqueous solutions. ClayandCohen[13] synthesizedCuOnan-
oclusters within lms of diblock copolymers. Lisiecki and Pileni
[14] produced Cu and CuO nanomaterials from inverse micelle
solutions. Recently, CuOinpolypyrole synthesizedbythe metal-
organic decomposition(MOD) technique was alsoreported[15].
Inparticular, a varietyof CuOnanostructures have beenprepared
by high-temperature approaches [16]. Hydrothermal method has
gained space as a versatile method for preparation of copper
oxide in temperatures ranging from 373 to 473 K for different
times [1720].
In this paper, we report the preparation of CuO ower-
nanostructures by hydrothermal microwave and its characteri-
zation by X-ray diffraction (XRD) and micro-Raman scattering
(MRS). The morphology of microspheres CuOwas observed by
0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2007.05.023
538 D.P. Volanti et al. / Journal of Alloys and Compounds 459 (2008) 537542
eld-emission scanning electron microscopy (FEG-SEM) and
transmission electron microscope (TEM).
2. Experimental details
2.1. Synthesis of CuO ower-nanostructures
CuO ower-nanostructures were synthesized by a hydrothermal microwave
method in the presence of polyethylene glycol (PEG). The experimental details
were the following. 5 10
3
mol/Lof CuCO
3
Cu (OH)
2
(99%purity Aldrich),
0.1 g of PEG (Mw 400) (99.9% purity Acros Organics), were added to 100 mL
of deionized H
2
O. The solution was stirred for 15 min and later 5 mL of NH
4
OH
(30% in NH
3
Acros Organics) was added under constant stirring, producing a
intense blue precipitate of [Cu(NH
3
)
4
]
2+
. The resulted solution was transferred
into a sealed Teon autoclave and placed in a domestic microwave. Finally, the
reactional system was heat treated at 393 K for 1 h. CuO ower-nanostructures
were collected and washed with deionized water several times and then dried at
353 K in a hot plate.
2.2. Characterizations
The obtained powder were characterized by X-ray powder diffraction
(XRD) using a (Rigaku-DMax/2500PC, Japan) with Cu K radiation
( = 1.5406

A) in the 2 range from 20

to 75

with 0.02

/min. The
micro-Raman measurements were performed at room temperature using the
514.5 nm line of an argon ion laser as the excitation source. The power was
kept at 10 mW and a 100 m lens was used. The spectra were recorded using
a T-64000 Jobin-Yvon triple monochromator coupled to a CCD detector. The
morphology of as-prepared samples was observed using a high resolution
eld-emission gun scanning electron microscopy FEG-SEM (Supra 35-VP,
Carl Zeiss, Germany). The transmission electron microscopy (TEM) images of
the powders was made in a Philips CM 200.
3. Results and discussion
Fig. 1 shows the XRD pattern of the CuO powder prepared
by domestic microwave hydrothermal method.
All diffraction peaks can be indexed in the CuO mono-
clinic phase. The lattice parameters were calculated using the
least square renement from the UNITCELL-97 program [21].
The obtained parameters were (a = 4.692

A, b = 3.428

A, and
c = 5.136

A with volume cell of 81.52

A
3
). These values are
consistent with the one reported in the literature and with the
respective JCPDS (Joint Committee on Powder Diffraction
Standards) card No. 45-0937 [22].
Fig. 2 illustrates micro-Raman scattering spectra of CuO
powder processed in domestic microwave hydrothermal.
CuO belongs to the C
6
2h
space group with two molecules
per primitive cell. One can nd the zone center Raman active
normal modes
RA
= 4Au +5Bu +Ag +2Bg. There are three
Fig. 1. XRD patterns of CuO powder prepared by the microwave hydrothermal
at 120

Cfor 1 h. The (|) vertical lines indicate the position and relative intensity
of 45-0937 JCPDS card le diffraction peaks for the monoclinic phase.
Fig. 2. Micro-Raman scattering spectra of CuO powder prepared by the domes-
tic microwave hydrothermal at 393 K for 1 h.
acoustic modes (Au +2Bu), six infrared active modes (3Au +
3Bg), andthree Ramanactive modes (Ag +2Bg). Three Raman-
active optical phonons have been identied and comparable to
that reported in the literature by other methods (Table 1).
Table 1
Identied Raman normal modes in crystalline CuO synthesized obtained by different methods
Method Temperature (K) Time (h) (Ag +2Bg) (cm
1
) Reference
Hydrothermal 373453 10 289.3/338.5/622.7 [18]
Hydrothermal 373453 10 295.2/342.7/633.5 [23]
Flux 950 20 296/346/636 [24]
Precipitation 473773 277.5/329.9/610.8 [25]
Vapoursolid reaction 663703 2472 298.4/347.9/633.7 [26]
Solid state reaction 1073 2 282/332/618 [27]
Hydrothermal microwave 393 1 283.8/333.5/622.5 This work
D.P. Volanti et al. / Journal of Alloys and Compounds 459 (2008) 537542 539
Fig. 3. FEG-SEM micrographies: (a) several CuO ower-nanostructures, (b) FEG-SEM micrography of an agglomerated of CuO ower-nanostructures, (c) FEG-
SEM micrography of an individual CuO microsphere, (d) inset of (c) shows the zoom of thorns of CuO ower-nanostructures and (e) TEM micrographies of thorns
of CuO ower-nanostructures obtained in the domestic hydrothermal microwave method.
A single phase CuO ower-nanostructures with a mono-
clinic structure was obtained. No Cu
2
O modes [28] are present,
demonstrating a single CuO ower-nanostructures phase. The
Raman peaks position are dependent on the preparation method,
geometry and crystal structure. It is evidenced the forma-
tion of only phase by micro-Raman in a reduced temperature
and time compared with other methods reported for copper
oxide.
Fig. 3(ad) illustrates the morphology obtained by FEG-
SEM of CuO ower-nanostructure processing in a domestic
hydrothermal microwave while the thorns were investigated by
TEM (Fig. 3(e)).
A large number of CuO ower nanostructures agglomer-
ates are shown in Fig. 3(a). A small set of agglomerates is
detached and presented in Fig. 3(b). An individual ower-
nanostructures with a diameter of approach 1.7 m0.72 is
shows in Fig. 3(c). A zoom in Fig. 3(c) shows one thorn
of CuO ower nanostructures (see Fig. 3(d)). A individual
thorn is shown in detail in Fig. 3(e) by TEM analysis with
a diameter of approach 13.28 nm0.44. The attainment of
ower-nanostructures is affected by variable processing as tem-
perature, pressure, PEG orientation and microwave absorbers.
This occurs because copper oxide, which is a component of the
precursor, is a strong microwave absorber at 2.45 GHz [29]. The
combination of domestic microwave and hydrothermal cell to
study other materials beyond CuO is most important due the
facilities such as reduction of synthesis time and electric energy
costs.
Table 2 illustrates a comparative CuOnanostructure obtained
by different methods and several experimental conditions.
Comparing the data of CuO ower-nanostructures obtained
by different methods, we can see that the hydrothermal
Table 2
Data obtained for CuO ower-nanostructures synthesized for different methods
Method Temperature (K) Time (h) PEG/EG assisted Diameter (m) Reference
Interfacial precipitation 1073 1 No 2.72.8 [30]
Hydrothermal conventional 368453 24 Yes [31]
Hydrothermal conventional 383 12 No 1020 [32]
Hydrothermal conventional 393 3 No [33]
Hydrothermal conventional 473 20 Yes [34]
Hydrothermal conventional 373453 224 No 48 [35]
Hydrothermal conventional 333453 110 No 46 [36]
Hydrothermal microwave 393 1 Yes 0.71.9 This work
540 D.P. Volanti et al. / Journal of Alloys and Compounds 459 (2008) 537542
microwave leads to small diameter at short annealing time.
This is an interesting result indicating that this method provides
low sintering temperatures, minimize the electric energy costs,
which cannot be reached using conventional methods.
From the data presented in Table 2, we can make a com-
parison with the presented methods in literature. Similar CuO
nanostructures were prepared for He [30] from interfacial pre-
cipitation. However, the temperature required was very high
and the average diameter was superior than ours CuO ower-
nanostructures. Yan and Xue [31] prepared several metal oxides
by a novel spontaneous ion replacement methodology includ-
ing CuO microspheres, but the time and temperature employed
were much higher compared with the hydrothermal microwave
method. CuO microspheres were obtained for Xu and Xue [32]
utilizing the hydrothermal conventional in the same tempera-
ture, but with annealing time and average diameter superior to
our work. Li et al. [33] reported the preparation of CuO nanos-
tructures as a function of synthesis temperature, concentration
and pH value. The authors obtained CuO microspheres at pH 4,
temperature of 473 Kand time of 20 h. In our work, we obtained
the CuO ower-nanostructures at pH 12 due the addition of
NH
4
OH, temperature of 393 K and time of 1 h. In the follow-
ing article [34] is addressed that quantities of PEG superior
than 20 mL can be the main reason for the ower-like nanos-
tructures. In our work, we believe that PEG acts as a template
for the formation of CuO ower-nanostructures. The inuence
of template can be observe by the homogeneous distribution
in particle diameter that is caused by the orientation that the
promotes template during the formation of CuO microsphere.
Therefore, the PEG addition and temperature are important for
the formation of CuO ower-nanostructures. The microwave
energy allows to reduce the preparation time and accelerates the
formation of CuO particle. Therefore, is possible to obtain a
CuO ower-nanostructures in a much small time by hydrother-
mal conventional. Liu and Zeng [35] reported the formation
of self-organized CuO crystallites after thermal treatment for
224 h at temperatures ranging from 373 to 753 K. The CuO
microspheres obtained are similar to spherical assemblies or
dandelions with a puffy appearance and diameters ranging
from 4 to 8 m. However, the authors didnt use templates to
obtain the CuO nanostructures, and its microspheres were pre-
pared in a superior time and temperature compared to our work.
Xu et al. [36] has obtained CuO pricky microspheres by a sim-
ple solution method, processed in hydrothermal microwave. The
microspheres no present a circular formhomogeneous much and
with average diameter, annealing time and temperature superior
to hydrothermal microwave. However, those larger diameters are
inappropriate for nanocatalysis applications. Ours CuO ower-
nanostructures obtained by the hydrothermal microwave method
requires thermal treatment for 1 h at 393 K, with diameters of
ranging from 0.7 to 1.9 m. These CuO microspheres can be a
future candidate for potential application in nanocatalysis that
requires low cost, temperature and preparation time.
Fig. 4(a) illustrates an average of CuOmicrospheres obtained
by counting 106 microspheres (Fig. 3(a)). The CuO micro-
spheres synthesized by the hydrothermal microwave method
present an average diameter of 1.3 m in a 25.47% percentage.
Fig. 4. (a) Graphical in pizza form for medium percentage of CuO micro-
spheres and (b) graphical of average diameter distribution with error bar for
CuO microspheres obtained for domestic hydrothermal microwave method.
Few deviation was noted in the average particle diameter distri-
bution. The biggest deviation of the average diameter is found
for the smallest CuO microspheres. A well homogeneous and
organized particles with larger size was evident. This is caused
by the microwave energy which accelerates the particle reaction
leading to an uniform coalescence process.
The formation of CuO ower-nanostructure is discussed
according to the mechanism illustrated in Fig. 5.
In the suggested mechanism, PEG acts as a template for the
CuO ower-nanostructures formation. In the (I) initial stage,
the aqueous solution of Cu
2+
plus PEG and NH
3
leads to the
rst nucleation seeds which act as an initial nucleus along the
particle growth. When the particle reaches a critical dimension,
PEG absorbs the small particles by the ended OH bonds acting
as a template for the formation of CuO ower-nanostructures.
This can be observed in a (II) intermediated growth. The micro-
graphies showed a CuO particle after 30 min of heat treatment.
Annealing for 1 h at 393 K leads to a ower-nanostructures
(see nal stage (III)). The CuO microspheres obtained by a
novel hydrothermal microwave method are homogeneous in
size and form much similar to an ower with thorns found in
nature.
D.P. Volanti et al. / Journal of Alloys and Compounds 459 (2008) 537542 541
Fig. 5. Mechanism of the CuO ower-nanostructures formation in comparison to an ower with thorns.
4. Conclusions
We have synthesized CuOower-nanostructures by a domes-
tic hydrothermal microwave method after thermal treatment at
393 K for 1 h. The CuO ower-nanostructures with single phase
was identied by XRDand micro-Raman techniques and present
monoclinic lattice. The average diameter is of

=1.3 m and the

fast formation of CuO ower-nanostructures is caused by the
microwave irradiationinthe presence of PEGandNH
4
OH. TEM
micrographies showed that the thorn present a average diame-
ter of

=13.28 nm. The obtained CuO ower-nanostructures is a

promising candidate for potential application in catalysis.
Acknowledgements
The authors thank the nancial support of the Brazilian
research nancing institutions: CAPES, FAPESP and CNPq. To
the Tec. Rorivaldo Camargo and Daniel Wiedemann by photo-
graph of the ower.
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