Copyright © 2010 American Scientific Publishers Nanoscience and

All rights reserved Nanotechnology Letters

Printed in the United States of America Vol. 2, 35–40, 2010

Self-Assembled Synthesis and Characterization of

Dandelion-Like and Flower-Like Cupric
Oxide Nanostructures
Li Cao1
†
∗ , Zhengtao Deng2 , Feifei Wang1 , Pengju G. Luo3 , Guling Zhang4 ,
Fangqiong Tang2 , and Bingsuo Zou1
5
∗
1
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics,
Chinese Academy of Sciences, Beijing 100080, China
2
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100101, China
3
Department of Biological Sciences, Clemson University, Clemson, SC 29634, USA and
Delivered
Department of Basic Sciences, by College,
Sherman IngentaSpartanburg,
to: SC 29304, USA
4
College of Science, Minzu Guest User
University of China, Beijing 100081, China
5
School of MSE, BeijingIPInstitute of Technology, Beijing 100081, China
: 202.58.86.15
Wed, 25 Aug 2010 02:42:42
Dandelion-like and flower-like cupric oxide (CuO) nanostructures were prepared at low tempera-
ture using self-assembled synthesis through hydrothermal and solvothermal reactions. The only
difference of these two methods is that water or ethanol was applied in the respective reaction
as reaction solvent. To our best knowledge it is the first time these complex CuO nanostructures
could be synthesized using an almost identical synthetic route with simply changing the reaction
solvent. Compared with the other synthesis methods that have been reported in the literatures,
this self-assembled synthesis provided easier route to form diverse complex CuO nanostructures.
The obtained CuO nanostructures were characterized with scanning electron microscopy, energy-
dispersive X-ray spectra, X-ray Diffraction, and Raman spectra. Possible formation mechanisms of
these CuO nanoscale structures are also discussed.
Keywords: CuO, Dandelion-Like Nanostructure, Flower-Like Nanostructure.

Cupric oxide (CuO), as a narrow band-gap p-type semi-
conductor oxide, has been widely studied as heterogeneous
catalysis, magnetic storage media, solar-energy transfor-
mation, gas sensor and varistors.1–5 Specifically, as one
of the transition metal oxides (TMOs), CuO has been
extensively studied after the discovery of its unusually
high-Tc superconductors (cuprates). With the decrease in
crystal size, nanoscale cupric oxides exhibit unique prop-
erties which are significantly different from those of their
bulk counterparts, such as large interfacial areas, homo-
geneity, highly reactive surfaces, and unusual optical,
electrical and catalytic properties. For example, CuO nano-
materials have more interesting photothermal and photo-
conductive properties than their bulk materials.6
Because the morphology of nanostructures also plays
important role to their properties and applications,
∗
Authors to whom correspondence should be addressed.
†
Now Working at the Department of Chemistry, Clemson University,
Clemson, SC 29634, USA.
investigation of different morphological CuO nano-
structures, especially different patterns made of CuO
nanocrystals, will provide exciting perspectives for their
applications. In the past few years, a series of wet chemi-
cal methods have been reported to synthesize simple CuO
nanocrystals, nanowires, nanorods and nanoribbons.7–9
Besides these simple CuO nanocomposites, some complex
CuO morphological structures have also been reported
in the literatures, such as dandelion-like10
11 and flower-
like12
13 nanostructures.
Several different synthetic methods for the prepara-
tion of complex nanostructures have been investigated.10–17
For instance, Liu et al. synthesized dandelion-like CuO
nanostructures by means of solvothermal reaction;10 and
Vaseem et al. reported flower-like CuO nanocomposite
using hydrothermal process.13 Among these methods, Hex-
amethylenetetramine (HMTA; C6 H12 N4 , as a weak alkali,
were usually used in the synthesis of various different
complex CuO structures, such as shuttle-like, sphere-like
and flower-like nanostructures.13
16
17 Most of these studies

Nanosci. Nanotechnol. Lett. 2010, Vol. 2, No. 1 1941-4900/2010/2/035/006 doi:10.1166/nnl.2010.1056 35

Self-Assembled Synthesis and Characterization of Dandelion-Like and Flower-Like Cupric Oxide Nanostructures
also required other alkalis to adjust pH value in the reac-
tion. One example in point is that sodium hydroxide
(NaOH) was utilized in the preparation of flower-like CuO
nanostructure.13
17
In this paper, we report the synthetic preparation of
dandelion-like and flower-like CuO nanostructures at low
temperature using hydrothermal and solvothermal reac-
tions respectively. HMTA and cupric nitrate (Cu(NO)2 
were applied. Though the synthesis of dandelion-like and
flower-like CuO nanostructures have been reported in the
literatures, to our best knowledge it is the first time these
complex CuO nanostructures could be synthesized using
an almost identical synthetic route with simply changing
the reaction solvent: water for hydrothermaol reaction and
ethanol for solvothermal reaction. The obtained dandelion-
like and flower-like CuO nanostructures were studied using
different characterization methods including scanning elec-
tron microscopy (SEM), energy-dispersive X-ray spectra
(EDS), X-ray Diffraction (XRD), and Raman Delivered
spectra. Theby Ingenta
possible mechanisms for the formation of these complex
Guest User
CuO nanostructures are also discussed in this paper.
IP : 202.58.86.15
Dandelion-like and flower-like CuO were synthesized
Wed, 25 Aug 2010 02:42:42
using hydrothermal and solvothermal reactions respec-
tively. Water and ethanol were chosen for these reactions
because they are two of the most widely used solvents
in chemical synthesis. These two solvents are cheap, non-
toxic, and environmental friendly. Specifically, these two
solvents have different boiling points: one is over 90  C
(100  C for water); and the other is below 90  C (78.5  C
for ethanol). For CuO nanostructures synthesis at low tem-
perature in solution phase, 90  C is the suitable tempera-
ture to be applied.11
16 It would be interesting to see the
chemistry reactions when 90  C is used in the synthetic
processes with these two solvents.
A typical hydrothermal synthesis of dandelion-like CuO
was carried out as followed. Cu(NO)2 aqueous solution
(0.01 M, 20 mL) was mixed with HMTA aqueous solu-
tion (0.01 M, 20 mL) in a 100 mL beaker. The mixture
solution was vigorously stirred using a magnetic stirring
apparatus. After 20 minutes stirring, the mixture solution
was transferred into a Teflon reaction autoclave (30 mL)
which was pre-cleaned with de-ionized water and dried at
room temperature. The reaction autoclave was then sealed
and heated at 90  C for 24 hours. In the end of the reac-
tion, the solution part was taken out and kept in a sepa-
rate beaker for further study. The precipitates in the Teflon
autoclaves were washed five times using de-ionized water.
Small amounts of precipitates were dropped on Indium tin
oxide (ITO)-coated glasses and then air dried five hours
at room temperature. The prepared samples on ITO-coated
glasses were examined later using various characterization
methods.
For the solvothermal synthesis process, the synthesis
route was similar as that of the hydrothermal reaction
except that ethanol was used as the primary solvent.
36
Cao et al.
The same post-treatment process and sample preparation
were also applied for the precipitate as in hydrothermal
reaction.
After the precipitates were dried on ITO-coated glasses,
the electron microscopy images and Energy Disper-
sive X-ray Spectroscopies were taken using a field
emission scanning electron microscope (Hitachi S-5200)
at an accelerating voltage of 10 kV. The two reac-
tion precipitates were further examined using a Brucker
D/MAX 2500 X-ray diffractometer with Cu K radiation
( = 154056 Å). The operation voltage and current were
maintained at 40 kV and 250 mA during the examination.
The Raman spectra of the reaction precipitates were
measured with microscopic confocal Raman spectrome-
ter (Renishaw, RM2000, U.K.) at room temperature at
514.5 nm with Ar+ laser. The laser spot was focused about
1 m and the resolution of the spectra was 1 cm−1 .
The precipitates of hydrothermal and solvothermal reac-
tions wereto:examined under SEM. For hydrothermal reac-
tion
precipitates, the shape and configuration of them
appeared
like a dandelion (dandelion-like), which was
composed
of bundles of CuO nanoscale needles (Fig. 1(a)).
For solvothermal reaction precipitate under SEM, it looked
like a beautiful rose (flower-like). A close look of the
flower-like structure showed that it was well-oriented in
perfect assembly with bundles of nano-sized rose petals
(Fig. 1(b)). The diameter of dandelion-like CuO structure
ranged between 1.5 and 3 m; and the diameter of flower-
like CuO structure was around 0.5–1 m (Fig. 1).
The energy-dispersive X-ray spectra (Fig. 2(a)) of the
dandelion-like and flower-like CuO samples showed the
presence of only Cu and O in these structures. Further con-
firmation with X-ray diffraction demonstrated that these
two types of structures were of crystalline nature (mono-
clinic phase) of CuO (Fig. 2(b)).
To determine whether these crystalline structures were
in nanoscale size range, XRD and Raman spectra were
examined. The well-known Debye-Scherrer formula was
used to calculate the average crystal size. From plane
(002) in XRD (Fig. 2(b)), the size of the crystals for the
formed needle-like CuO structure was ∼12 nm. The size
of the crystals for formed petal-like CuO structure was
∼15 nm.
Raman spectra of the dandelion-like and flower-like
CuO structures were measured at room temperature. As
it is well known, CuO belongs to the C62h space group
with two molecules per primitive cell. Thus the normal
vibration modes of CuO, including three acoustic modes
(Au + 2Bu), six infrared active modes (3Au + 3Bu) and
three Raman active modes (Ag + 2Bg), can be found
at the zone center. The three Raman active modes of
the dandelion-like and flower-like CuO structures were
observed in the Raman spectra (Fig. 3). For the dandelion-
like CuO nanostructure, the three Raman scattering peaks
were 272 cm−1 , 320 cm−1 and 609 cm−1 . In comparison
Nanosci. Nanotechnol. Lett. 2, 35–40, 2010
Cao et al. Self-Assembled Synthesis and Characterization of Dandelion-Like and Flower-Like Cupric Oxide Nanostructures

(a)
(a)
Dandelion-like CuO

Intensity (a.u.)
0.80 1.60 2.40 3.20 4.00 4.80 5.60 6.40 7.20 8.00

Flower-like CuO

0.80 1.60 2.40 3.20 4.00 4.80 5.60 6.40 7.20 8.00
Energy (keV)

(b)

(111)
(002)
(b) a: Dandelion-like CuO
1600
b: Flower-like CuO

(111)
(200)
Delivered by Ingenta to:

Relative intensity (a.u.)

(110)
Guest User1200

(020)
IP : 202.58.86.15

(202)
Wed, 25 Aug 2010 02:42:42 (a)
800

400
(b)

0
30 40 50 60 70
2 theta/degree

Fig. 2. EDS (a) and XRD (b) of dandelion-like and flower-like CuO
Fig. 1. SEM images of (a) dandelion-like and (b) flower-like CuO nano- nanostructures.
structures. The insets are enlarged images of respective patterns.

with the vibrational spectra of a CuO single crystal,18 the
peak at 272 cm−1 could be assigned to the Ag mode, and
the peaks at 320, and 609 cm−1 to the Bg modes. The
corresponding full-width at half maximum (FWHM) of
the Raman peaks were 42 cm−1 , 35 cm−1 and 104 cm−1
respectively.
For the flower-like CuO nanostructure, the three Raman
scattering peaks were 274 cm−1 (Ag), 324 cm−1 (Bg),
611 cm−1 (Bg) and the corresponding FWHM were
39 cm−1 , 30 cm−1 and 74 cm−1 . Comparing these Raman
data of the two nanostructures, it is clear that the Raman
peaks of the dandelion-like CuO shifted slightly to the
lower frequencies and their corresponding FWHM was
broader relative to those of the flower-like CuO. Obvi-
ously, the Raman experimental data confirmed the XRD
results. That is to say, the red shift and broadening of the
Raman spectra increased with the decrease in CuO nano-
crystal size, which had already been discussed by Xu et al.
in the literature.19
As calculated from the XRD results (Fig. 2(b)), the
nanocrystals that formed in hydrothermal reaction (water
solution) were small (∼12 nm) while the nanocrystals
formed in solvothermal reaction (ethanol solution) were
larger (about 15 nm). It is well known that the boil-
ing point of water is 100  C, and 78.5  C for ethanol.
Boiling point determines the speed of evaporation of the
solvent, which is important for mass transportation. The
reaction temperatures were 90  C in this study for both
hydrothermal and solvothermal reactions. This temperature
is well above the boiling point of ethanol but below that
of water. At 90  C, there would be more mass transporta-
tion for copper(II) ion and CuO small nuclear-like clusters
in ethanol solution than in water solution. Thus, it is rea-
sonable to deduce that the nanocrystals formed in ethanol
would be larger than that formed in water.
Before the formation of the CuO dandelions and CuO
flowers, the CuO nanocrystals aged and continued to
develop into the nanoneedles and nanopetals through the
Ostwald ripening process, which has been believed to
assist the growth process through oriented attachment.20–23
During an Ostwald ripening process, larger nanocrystals
generally grow at the expense of small ones.24
25 In

Nanosci. Nanotechnol. Lett. 2, 35–40, 2010 37

Self-Assembled Synthesis and Characterization of Dandelion-Like and Flower-Like Cupric Oxide Nanostructures Cao et al.

Ag (a)
Dandelion-like CuO
Flower-like CuO

Bg Bg
Intensity (a.u.)

200 300 400 500 600 700 800

Wavenumber (cm–1)

Fig. 3. Raman scattering spectra of dandelion-like (black) and flower-

(b)
like (red) CuO nanostructures.

a solution-based fabrication of nanostructures, Delivered

Ostwald’sby Ingenta to:
ripening usually leads to the inhomogeneous crystal sizes Guest User
and morphologies. 25
26 IP : 202.58.86.15
In order to confirm that the dandelion-like and flower- 2010 02:42:42
Wed, 25 Aug
like CuO nanostructures were formed from the CuO
nanoneedles and nanopetals, the reaction solutions after
hydrothermal and solvothermal reactions were also inves-
tigated under SEM. For the solution part of hydrothermal
reaction, SEM image showed no dandelion-like CuO nano-
structures but plenty of nanoscale CuO needles (Fig. 4(a)).
These needles were ∼100 nm in length and their aspect
ratio (length by central width) was more than 10. The nee-
dles were aligned via one main crystallographic axe, as Fig. 4. Shape evolution of dandelion-like and flower-like CuO nano-
elucidated in Figure 4(a). It is possible that these nanoscale structures. (a) and (b) show the nanoscale needle-like and petal-like CuO,
CuO needles would ultimately form highly ordered and respectively.
well-oriented dandelions if reaction time was sufficient.
Similarly, petal-like CuO (Fig. 4(b)) in the solution part of Cu2+ + 2OH−1 → CuOH2
solvothermal reaction might finally assemble into flower-
like CuO nanostructures if enough reaction time was given. CuOH2 → CuO + H2 O
A time-dependant analysis of the reaction mixture would
Second, HMTA is also an effective morphology-
provide more information on how the nanoneedles and
directing agent and helps to control the formation of the
nanopetals precursors assemble into their ordered struc-
nanostructures.13
28 In our experiments, HMTA might have
tures. Such time-dependant analysis would also help deter-
helped not only control the shapes of CuO nanocrystal
mine the optimal time for the self-assembly, as have
configurations, but also form complex three-dimensional
done by Vaseem et al.13 These studies are currently under
nanostructures of dandelion-like and flower-like CuO.
investigations.
There are still some other possible mechanisms that
Possible growth mechanisms of the dandelion-like and
might have impact on the growth of CuO morphologies
flower-like CuO nanostructures in our experiments are
in our experiments. Firstly, because water and ethanol has
schematically illustrated in Figure 5. HMTA is believed to
different polarities (ethanol is much less polar than water),
have played an important role during the reactions. First,
the effect of the solvent polarity difference should be con-
HMTA could be hydrolyzed in the aqueous solution and
sidered as a factor for the formation of initial CuO crystal
then generate OH−1 ions,27 which is necessary for the pro-
size and shape, as well as the final formation of three-
duction of Cu(OH)2 and CuO:
dimensional nanoscale CuO structures. This possibility is
in line as in the literature discussion that solvating actions
C6 H12 N4 + 6H2 O → 6HCHO + 4NH3
of water and hydrogen bond play a great role on the forma-
NH3 + H2 O → NH4+ + OH− tion flower-like nanostructures.12 Systematic studies using

38 Nanosci. Nanotechnol. Lett. 2, 35–40, 2010

Cao et al. Self-Assembled Synthesis and Characterization of Dandelion-Like and Flower-Like Cupric Oxide Nanostructures

in water
Cu2+ + HMTA

Route 1 Small CuO nanocrystals CuO needles CuO dandelions

in ethanol
2+
Cu + HMTA

Route 2 Big CuO nanocrystals CuO petals CuO flowers

Fig. 5. Possible growth mechanism for the formation of CuO dandelions and CuO flowers in water (1) and in ethanol (2), respectively: Route 1:
Small CuO nanocrystals formed in water at first, then the nanocrystals aggregated into CuO needles; finally the needles organized into CuO dandelions;
Route 2: large nanocrystals formed in ethanol at first, then the nanocrystals aggregated into CuO petals, in the end the petals organized into CuO
flowers.

more solvents of different polarities will contribute to the
Delivered
understanding of the role of polarity in structure formation.by Ingenta
Secondly, the reaction temperature that we used inGuest our User
IP : 202.58.86.15
study might as well be a possible cause for the morpho-
Wed, that
logical difference variations, as aforementioned 25 Aug
the 2010
size of CuO nanocrystals might be affected by the reac-
tion temperature. During the self-assembled synthesis in
the synthetic reactions, the temperature also played a role
on the morphology formation of dandelion-like and flower-
like CuO nanostructures.
Though several possibilities on the growth of dandelion-
like and flower-like CuO nanostructures have been dis-
cussed, the exact mechanism of these nanostructures is still
not very clear. More research efforts should be devoted to
explore the growth mechanism of different morphologies
of CuO nanostructures. For examples, (1) Time-dependant
analysis of the reaction mixture might be helpful to under-
stand the growth mechanism of dandelion-like and flower-
like CuO nanostructures; (2) CuO nanostructures might
be affected if different ratio of water and ethanol were
applied. A more systematic study on the synthesis of com-
plex CuO nanostructures using different ratio of ethanol
and water will be investigated in the future.
In summary, it is the first time that complex nano-
structures such as dandelion-like and flower-like CuO
could be synthesized at low temperature using an almost
identical self-assembled synthetic route. This synthetic
route simply involved changing the reaction solvent: Water
solvent for hydrothermal reaction and ethanol solvent for
solvothermal reaction. The detailed structural characteriza-
tions exhibited that the dandelion-like and flower-like CuO
nanostructures grew from nanoscale needle-like and petal-
like CuO. XRD demonstrated that the size of the nano-
crystals that formed flower-like CuO was larger than that
of the ones of dandelion-like CuO, which is confirmed by
Raman spectra. Finally, both HMTA and the different boil-
ing points and polarities of solvents might contribute to
morphology formation of these two types of the dandelion-
like and to:
flower-like CuO.
Acknowledgment: We would like to thank National
Natural
Science Foundation of China (Grant numbers:
02:42:42
90606001, 20873039, and 20173073) and Talent Project
of Chinese Academy of Science of China for the financial
supports.
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Received: 13 March 2010. Accepted: 10 May 2010.

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40 Nanosci. Nanotechnol. Lett. 2, 35–40, 2010