Journal of Alloys and Compounds 704 (2017) 624e630

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Spontaneous growth of CuO nanoflakes and microflowers on copper

in alkaline solutions
Jinhang Fan, Dingding Tang, Dihua Wang*
School of Resource and Environmental Sciences, Wuhan University, Wuhan 430072, PR China

a r t i c l e i n f o a b s t r a c t

Article history: CuO with different nano-architectures was synthesized by spontaneous corrosion of copper in alkaline
Received 30 July 2016 aqueous solutions without any additives. CuO nanoflakes were obtained by simply immersing a copper
Received in revised form foil in NaOH solution, while flower-like architectures constructed with nanopetals were produced in
3 February 2017
Na2CO3 solution, indicating the pH value and the anions have a significant impact on the morphology and
Accepted 8 February 2017
structure of CuO. The growth rate slowed down with the decrease of the alkalinity of the solution. In a
Available online 10 February 2017
more concentrated NaOH solution (1 M), polyhedron-like Cu2O was observed at the early stage before
transforming into CuO nanoflakes. Based on these findings, massive production of nano-structured CuO
Keywords:
CuO
powders was successfully realized by using copper powder as the precursor. The growing mechanism of
Synthesis flower-like CuO could be explained by the oriented attachment. The extensive sources of feedstock, the
Corrosion simple synthetic method and the uniform architecture of the products enable CuO to be utilized in a
Oxide large scale.
Nanomaterial © 2017 Elsevier B.V. All rights reserved.
Microstructure

1. Introduction Cu foil via a solution process at room temperature [17]. Flower-like

CuO has attracted considerable interest in various fields,
including gas sensors and field emission emitters [1e3], lithium ion
batteries and solar cells [4e6], heterogeneous catalysis for CO
oxidation [7] and supercapacitors, photodetectors as well as pol-
lutants absorbents [8e10]. The performance of CuO is strongly
dependent on its morphologies and structures [11]. There are a
variety of different dimensional and morphological CuO reported
synthesized by different process. Gao et al. reported the synthesis
of CuO nanorods by hydrothermal method and the influence of
temperature on the structure of CuO [12]. CuO nanoribbon was
obtained by heat treatment of Cu(OH)2 formed in alkaline solution
using CuCl2 or Cu(NO3)2 as feeding material [13,14]. Liu et al. [15]
obtained CuO with different morphologies such as flower-like
and spherical architectures by oxidizing Cu foil in low concentra-
tion of alkaline solution (NaOH and NH3$H2O) at 60
C for 20 h.
Preparation of platelet-like and chrysanthemum-like nano-
structured CuO was also reported by immersing Cu into NaOH
aqueous solution with (NH4)2S2O8 at room temperature [16].
Furthermore, hierarchical microcabbage of CuO was fabricated on
CuO was synthesized on Cu plate in KOH solution [18]. These in-
vestigations suggest that the alkalinity of solution, concentration of
oxidant, surfactant in the solution and temperature has an impor-
tant effect on the morphology of the CuO product.
For massive production of CuO in a more environmentally
friendly way, a process using air as oxidant at room temperature
without any surfactant is more preferential. Based on the E-pH
diagram of copper, spontaneous oxidation/corrosion of Cu will take
place in alkaline solution in air. The alkalinity as well as the ions in
the solution could affect the corrosion process, thereby affect the
morphology of the corrosion product. To the best of our knowledge,
there is rare report in literature on the morphology investigation of
CuO formed over a wide range of alkalinity under air atmosphere.
In this paper, the effect of the concentration of NaOH and Na2CO3
on the morphology and structure of CuO growing on copper foil
was systematically investigated at room temperature. Based on the
optimized growing condition, massive production of nano-
structured CuO powder was synthesized using copper powder as
feeding stock.
2. Experimental

* Corresponding author. All chemicals were of analytical grade and purchased from
E-mail address: wangdh@whu.edu.cn (D. Wang). Sinopharm Chemical Reagent, Shanghai, China. The solutions of

http://dx.doi.org/10.1016/j.jallcom.2017.02.078
0925-8388/© 2017 Elsevier B.V. All rights reserved.
 J. Fan et al. / Journal of Alloys and Compounds 704 (2017) 624e630 625

sodium hydroxide and sodium carbonate were prepared by dis-

solving NaOH and Na2CO3 in deionized water, respectively. Copper
foil, powder with >99.5% purity was used as received. A piece of
fresh copper foil or several grams of copper powder was immersed
in the NaOH or Na2CO3 aqueous solution at room temperature for
different time. And then the samples were taken out of the solution
and washed with water and dried in a vacuum oven at 80
C for 4 h.
The detailed synthesis conditions are summarized in Table 1.
The obtained products were characterized by a Shimadzu XRD-
7000 X-ray diffraction analyzer (XRD). The size and morphology of
the samples were observed by FEI sirion field emission scanning
electron microscope (SEM). Their chemical composition was
analyzed on KRA TOSXSAM800 with Al Ka ionization source and
Confocal Raman Microspectroscopy (Renishaw, RMd1000) at an
excitation wave-length of 514.5 nm.

3. Results and discussions

3.1. Synthesis of nanostructured CuO on Cu foil

3.1.1. CuO growth in NaOH solution

A piece of copper foil was immersed into NaOH aqueous solu-
tion with different concentration. No oxide film formed on the
copper surface in the solution of pH < 10, consistent with previous
report [19] at which additional oxidant was added. When the
concentration of NaOH was higher than 0.1 M, a black film on
copper was observed after certain reaction time (inserted photos in
Fig. 1). The solution remained colorless, demonstrating no detect-
able copper ions in the solution. SEM image showed that the black
film consists of uniform nanoflakes (Fig. 1a) of CuO as evidenced by
the XRD patterns of the film (Fig. 1c). The morphology of CuO ob-
tained in 0.3 M solution was similar to the product obtained at
0.1 M, but the size of the nanoflakes grew larger (Fig. 1b and c). The
specific weight of CuO to CuO@Cu was 6.982 mg/g after 48 h of
immersion in 0.1 M aqueous NaOH solution, 8.307 mg/g in 0.3 M
aqueous NaOH solution.
Surprisingly, different phenomena were observed when copper Fig. 1. SEM images of CuO on copper foil prepared in NaOH solution under different
concentrations and duration: (a) 0.1 M (b, c) 0.3 M; (d) 1 M (6 h); (e) 1 M (48 h); (f) 1 M
foil was immersed into more concentrated NaOH solution (1 M).
(72 h); (g, h) 1 M (6 days).
The metallic luster of Cu foil disappeared within 6 h, different from
that in the diluted NaOH solution in which copper surface remained
almost unchanged in a short time. A gray-blue film precipitated on width formed on the surface of the polyhedron. As the immersion
the Cu surface. As shown in Fig. 1d, the gray-blue layer consisted of prolonged to 72 h, the copper foil was completely covered with
polyhedron shape particles with an anomalous size distribution. black spots and more petals with increased length (~2 mm) were
With prolonging immersion time (48 h), the surface color turned observed (Fig. 1f). The black spots were ascribed to CuO crystals as
into purple gray and some black spots were observed (Fig. 1e). The evidenced of two characteristic peaks at 35
and 40
in the XRD
diffraction peaks of Cu2O were observed in the XRD patterns of the pattern of the sample as shown in Fig. 2b. After immersion for 6
sample (Fig. 2a), demonstrating that the polyhedron was Cu2O. The days, the foil surface turned into black completely and large scale of
morphology of Cu2O (Fig. 1e) shows that the average size of the micro-flowers that composed of nano-flakes were observed
polyhedron particles with irregular shape decreases comparatively. (Fig. 1g). No Cu2O peak but CuO was monitored in the XRD pattern
Interestingly, some petals with 0.5e1 mm in length and 500 nm in

Table 1
The experimental parameters and the features of the products synthesized under different conditions.

Substrate Alkaline solutions Concentration (mol L1) Time (h) Product morphology

copper foil NaOH 0.1e0.3 144 nanoflakes

copper foil NaOH 1 6e48 polyhedron-like
copper foil NaOH 1 72 polyhedron-like/needle-like
copper foil NaOH 1 144 ultrathin flakes-based microflowers
copper foil Na2CO3 0.1 48 sheets-based microflowers
copper foil Na2CO3 0.2 12 sheets
copper foil Na2CO3 0.2 24 sheets/microflowers
copper foil Na2CO3 0.2 48e96 sheets-based microflowers
copper foil Na2CO3 0.5e0.8 48 sheets
copper powder NaOH 0.05e1 144 ultrathin sheets-based microflowers
copper powder Na2CO3 0.2 144 sheets-based microflowers
626 J. Fan et al. / Journal of Alloys and Compounds 704 (2017) 624e630

Fig. 2. XRD patterns of CuxO on copper foil prepared in 1 M NaOH solution under
different immersion time: (a) 48 h; (b) 72 h; (c) 6 days.

(Fig. 2c), suggesting that the polyhedral-like Cu2O was transformed

into flake-like CuO.
The results demonstrate that the concentration of NaOH has
strong effect on the growth of CuO. When the concentration of OH
is lower than 0.3 M, CuO nanoflakes form spontaneous by the
corrosion of copper foil in air atmosphere. In the higher concen-
tration of NaOH solution, flake-like CuO was obtained after several
days with polyhedron-like Cu2O as intermediate product. The fea-
tures of the corrosion products of copper foil in aqueous NaOH
solution under different experimental conditions are schematically
shown in Fig. 3 and summarized in Table 1.

3.1.2. CuO growth in Na2CO3 solution

Besides the alkalinity of solution, the anions in solution would
also affect the reaction rate and the morphology of corrosion
product of copper. The alkalinity of Na2CO3 is weaker than NaOH
but the carbonate anion might participate in the corrosion reaction.
Fig. 4aeh presents the SEM and optical images of the solid products
of copper foil in Na2CO3 aqueous solution under different condi-
tions. As can be seen, just a thin and incomplete black film formed
on the substrate in 0.1 M Na2CO3 solution, indicating a much slower
oxidation rate in Na2CO3 solution. The morphology of the film
possesses flowerlike structure in a size ranging from 300 nm to
Fig. 3. Schematic diagram of the corrosion of copper foil in aqueous NaOH solution at
different concentration and duration.
Fig. 4. SEM images of CuO on copper foil prepared in Na2CO3 solution under different
concentrations for 2 days: (a, b) 0.1 M (c, d) 0.2 M; (e, f) 0.5 M; (g, h) 0.8 M.
1 mm (Fig. 4a and b). The microflowers are made up of nanopetals
which are ~80 nm in width and dozens of nanometers in thickness.
By increasing the concentration of Na2CO3 to 0.2 M, the film
became thicker and covered the substrate more compactly (Fig. 4c
and d). However, when its concentration was higher than 0.5 M,
less solid corrosion products formed and less flower-like structure
was observed (Fig. 4e and g). The composition of the thin layer
products cannot be detected by XRD test under this condition.
Therefore, Raman Spectroscopy was applied to identify the
composition of the thin film. Three peaks located at 297, 345 and
625 cm1 were observed (Fig. 5), which were ascribed to CuO
nanocrystals [20].
The surface morphology of copper foil was monitored by SEM
during the immersing experiment in 0.2 M Na2CO3 solution (Fig. 6).
For immersion of 12 h, some petals in a width of 100e200 nm
stretched out from the copper surface (Fig. 6a). As the immersion
time prolonged to 24 h, the petals grew larger and more (Fig. 6b).
Further increasing the reaction time (48 h) led to the formation of
microflowers which were spontaneously assembled from the
nanopetals (Fig. 6c). The morphology then kept almost unchanged
within 4 days (Fig. 6d). It tends to form microflower structure in
Na2CO3 aqueous solution, no matter what the concentration it is.
However, the reaction rate is much slower than that in NaOH so-
lution. Fig. 7 and Table 1 qualitatively describe the main chemical
species and CuO structures on the copper foil formed in aqueous
 J. Fan et al. / Journal of Alloys and Compounds 704 (2017) 624e630
Fig. 5. Raman spectra of CuO on Cu foil obtained in 0.2 M Na2CO3 solution for 2 days.
Fig. 6. SEM images of CuO on copper foil prepared in 0.2 M Na2CO3 solution under
different immersion time: (a) 12 h (b) 24 h (c) 48 h (d) 96 h.
Na2CO3 solution under different experimental conditions.
3.2. Synthesis of CuO nanostructures on copper powders
Copper powder has much larger surface area and the mass
transfer of O2 is more efficient at a spherical fine particle/solution
interface than at a plane surface. It would be more promising to
prepare CuO with flower-like structures in a large scale by using
copper powders as precursors. It was found that copper powders
were firstly sprinkled on the surface of the NaOH or Na2CO3
aqueous solution at room temperature without any surfactant or
additive. After a given reaction time (72 h), the copper powders
sank to the bottom of the container due to the surface oxidation.
Fig. 8 shows the optical and SEM images of the samples obtained
via the NaOH route. The red brown copper powders turned into
black (Fig. 8a). SEM images further revealed that the copper par-
ticles (Fig. 8b) were transformed into hedgehog-like particles with
uniform morphologies (Fig. 8c). Fig. 8d displays the magnified
image of the detailed structure of an individual particle. Interest-
ingly, the image reveals an urchin-like morphology which is very
different from the previous reports [18,21,22]. The size of the flower
is in the range of 3e5 mm. Each flower composes of numerous flakes
627
Fig. 7. Schematic diagram of the corrosion of copper foil in aqueous Na2CO3 solution at
different concentration and duration.
Fig. 8. Optical images (a) and SEM images of copper powders before (b) and after (c, d)
the reaction in 0.05 M NaOH solution for 6 days.
which have an average width of 100 nm. XRD pattern was recorded
to characterize the final products and the results are shown in
Fig. 9. CuO phase was confirmed and no other crystalline com-
pounds such as Cu(OH)2 and Cu2O were observed.
Fig. 10a and b shows the XPS spectra of Cu 2p and O 1s of the
product, respectively. The peaks at 933.9 and 954 eV corresponded
to the binding energy of Cu 2P3/2 and 2p1/2, which is consistent with
CuO as reported by Hsieh et al. [23]. Furthermore, two shake up
satellite peaks of Cu 2p3/2 and Cu 2p1/2 were also observed at 943
and 964 eV, respectively, confirming the formation of Cu2þ. As
shown in Fig. 10b, the O 1s peak ranging from 527 eV to 536 eV was
broad and asymmetric, suggesting the existence of different species
of oxygen. After the curve-fitting procedure, two O 1s peaks
marked as i and ii emerged. The binding energy at 529.5 eV was
ascribed to O2 in CuO, while peak ii, was in agreement with ox-
ygen adsorbed on the surface of flower-like CuO. No other atom was
detected in the XPS spectra, demonstrating that the samples were
composed of only CuO.
Fig. 11aef exhibit the morphology of CuO obtained in NaOH
solution with different concentration. The flower-like structure
staid almost unchanged but curving at the edge of the flakes was
observed clearly, demonstrating that the thickness of the
628 J. Fan et al. / Journal of Alloys and Compounds 704 (2017) 624e630

Fig. 9. XRD patterns of flower like CuO on copper powders prepared in 0.05 M NaOH
solution for 6 days.

Fig. 11. SEM images of flower like CuO on copper powders prepared in NaOH solution
under different concentrations: (a, b) 0.1 M; (c, d) 0.4 M; (e, f) 1 M.

copper powder was also oxidized to black. Fig. 12aeb shows the
images of the products prepared by sprinkling the copper powders
on the surface of the aqueous Na2CO3 solution. The XRD peaks
matched those of CuO (inserted Figure in Fig. 12a). The specific
weight of CuO to CuO@Cu was 235.4 mg/g. Compared with the
products via the NaOH route, the particles still possessed the
flower-like structure but the morphology was more compact and
the flakes were much thicker, these were possibly due to the
weaker oxidization of copper in Na2CO3 aqueous solution.

3.3. Growth mechanism

Thermodynamically Cu is not stable in air under humid condi-

tion, which results in corrosion of copper and the formation of thin
oxide/compound film on its surface. The corrosion rate of copper
will be accelerated when the copper is immersed into NaOH or
Na2CO3 aqueous solution. In fact, the corrosion rate and corrosion
product will be affected by the concentration of oxygen, pH of the
solution and anions and oxidants in the solution as well as tem-
perature and impurities. Generally, the corrosion of copper in

Fig. 10. X-ray photoelectron spectrum of (a) Cu 2p and (b) O 1s of the CuO powders
prepared in 0.05 M NaOH solution for 6 days.

nanoflakes became smaller with increasing the concentration of

NaOH solution. The specific weight of CuO to CuO@Cu was
382.3 mg/g under the condition of 0.05 M aqueous NaOH solution
(144 h) and 508.7 mg/g in 0.1 M aqueous NaOH solution (144 h),
respectively. The growth rate was much faster when copper pow-
der was used as the precursor. Fig. 12. XRD patterns and SEM images of flower like CuO on copper powders prepared
When NaOH was replaced by Na2CO3 (0.2 M), the red brown in 0.2 M Na2CO3 solution for 6 days.
 J. Fan et al. / Journal of Alloys and Compounds 704 (2017) 624e630
alkaline solution is a spontaneous electrochemical process and can
be represented as following equations.
Anode reactions
Cu  2e/Cu2þ
Cu þ 2OH  2e/CuðOHÞ2
Cu þ 4OH  2e/CuðOHÞ2
4 (1b)
2Cu þ 2OH  2e/Cu2 O þ H2 O
2Cu þ 2OH þ CO2
3  4e/Cu2 ðOHÞ2 CO3
Cathode reaction
O2 þ 4e þ 2H2 O/4OH
Secondary reactions
Cu2þ þ 4OH /CuðOHÞ2
4 Although the exact mechanism for the synthesis of the flower-
Cu2þ þ 2OH /CuðOHÞ2
Cu þ Cu2þ þ 2OH /Cu2 O þ H2 O
2Cu2 O þ O2 þ 4H2 O þ 8OH /4CuðOHÞ2
4 (5)
2Cu2þ þ 2OH  þ CO2
3 /Cu2 ðOHÞ2 CO3

CuðOHÞ2
4 /CuO þ H2 O þ 2OH
Cu2 ðOHÞ2 CO3 þ 2OH /2CuO þ 2H2 O þ CO2
3 (8)
The main driving force for corrosion is the oxygen reduction
reaction (reaction (2)), and the coupled anodic reaction leads to the
oxidation of copper (reaction (1) to (1d)), and a series of chemical
transformation reaction at the metal/electrolyte interface might
take place (reaction (3) to (8)), which generates corrosion products
with different composition and morphology. Obviously, all these
reactions are affected by the electrolyte composition.
In this work, when the concentration of NaOH is lower than
0.3 M, CuO nanoflakes were obtained. The reactions involved can be
represented by reaction (1), (3) or (1b) followed by reaction (7).
Initially, the decomposition of Cu(OH)2 or Cu(OH)2 4 formed the
CuO nuclei on the substrate, and then the newly formed CuO
growing at the edge of the nuclei with liquid transportation of
Cu(OH)2 4 so that nanoflakes formed. According to the foregoing
description, the SEM images show that the nanoflakes obtained at
the OHconcentration of 0.3 M have the same structure as the
products at 0.1 M of OH, but the size grows bigger. This is mainly
because that the higher concentration of OH will accelerate the
formation of nuclei and increase the concentration of growth units,
resulting in larger nanoflakes.
When the concentration of NaOH is higher than 0.3 M, Cu foil
was firstly oxidized to Cu2O and then transformed into CuO. The
formation of Cu2O probably due to the reduction of Cu2þ by Cu in
the presence of high concentration of OH according to reaction (1)
and (4). Similar result was reported by Gao et al. [24]. In their
investigation, Cu2O film was obtained by immersing Cu foil into
CuSO4 solution through the in situ redox reaction. As the reaction
proceeds, the pH value would decrease because of the consumption
629
of OH. However, Cu2O is not stable under the lower concentration
of OH and the formed polyhedron-like Cu2O can be further
oxidized to flower-like CuO through the dissolution-deposition
process according to reaction (5) and (7). When the concentration
(1) of OH is much higher (1e5 M), Cu2O would finally be obtained
after 3 days immersion through reaction (1c) and (4). Under this
(1a) situation, the consumption of OH by the reactions would not
change the pH too much. Furthermore, the reactions would pro-
ceeds very slowly due to the formation of Cu2O. Once the compact
film of Cu2O formed, the oxidation of Cu would cease.
When NaOH was replaced by Na2CO3, the reactions might follow
(1c) reaction (1), (6) or (1d) and (8). The growth process of flower-like
CuO is illustrated in Fig. 6. At the early growth stage, CuO nano-
petals formed very quickly, followed by the modification and
(1d)
adjustment of the intermediate products. Finally, a flower-like CuO
was obtained. The size of the subunits was similar to the crystals at
the early growth stage. These features revealed that the final 3D
(2) architectures were assembled by the original small precursors.
Thus, it could be determined that the growth process of 3D flower-
like CuO in Na2CO3 solution is via an imperfectly oriented
attachment.
(3)
like and nanoflake CuO should be studied in more detail, it seems
(3a) that nanopetals rather than nanoflakes preferably grew in Na2CO3
solution at the initial growth stage. The two disparate growth
processes are strongly related to the pH value and the formation of
(4)
the intermediate product of Cu2(OH)2CO3. Although many experi-
mental parameters, such as temperature and surfactant can affect
the microstructure of the crystals, pH value is thought to be a more
important factor influencing the structure of product [25e27]. Due
to the participation of OH in the corrosion reactions, its concen-
(6)
tration has a significant influence on the nucleation and growth
behaviors. It should be noted here that the saturated pH value of
(7) Na2CO3was no more than 12, which is much lower than the critical
condition for the formation of the CuO nanoflakes in NaOH solu-
tion. This is due to the involvement of carbonate ions in the
corrosion reaction by coordinating with Cu2þ. Consequently, the
formed Cu2(OH)2CO3 acts as a precursor that transports Cu2þ to the
growing seed crystal tips with OH ligands attached. Zhang et al.
reported that the Cu2(OH)2CO3 rod arrays were successfully fabri-
cated by using NaHCO3 and (NH4)2S2O8 [19]. In their experiment,
the pH value was set between 8 and 8.5 and a blue film was ob-
tained on the surface of copper. Cu2(OH)2CO3 could dissolve in
Na2CO3 under this situation. When the concentration of the Na2CO3
was low, it only existed temporarily and quickly transformed into
Cu(OH)24 , and subsequently dehydrated into CuO. Therefore, no
Cu2(OH)2CO3 except for the black CuO was detected in the final
product. The formation of Cu2(OH)2CO3 may serve as the template
during the ensuing hydrolytic processes which proceeded much
more slowly than the Cu(OH)2 4 in NaOH solution. Thus, the
anisotropic growth was favored and resulted in the fabrication of
nanopetals. As the nanopetals growing, they attached to each other
and assembled into flower-like structure. If the concentration of
Na2CO3 was high enough, the transformation of Cu2(OH)2CO3 to
CuO would be suppressed and Cu2(OH)2CO3 would directly dissolve
in Na2CO3 without formation of CuO, which was evidenced by the
solution color which was gradually turned into blue.
4. Conclusions
Nanostructured CuO was successfully synthesized by simply
immersing copper into alkaline (NaOH and Na2CO3) solution under
air atmosphere without any additives at room temperature. Flake-
like CuO was obtained in NaOH solution while flower-like CuO was
synthesized in Na2CO3 aqueous solution. The oxidation process of
630 J. Fan et al. / Journal of Alloys and Compounds 704 (2017) 624e630
Cu foil in NaOH is significantly affected by its concentration.
Nanoflake-like CuO formed in low concentration solution (0.3 M).
When the concentration of NaOH was between 0.3 M and 1 M, the
process proceeded from Cu to Cu2O, and the Cu2O was further
oxidized to CuO with nanoflake structure. In Na2CO3 aqueous so-
lution, nanopetals formed initially, and then self-assembled to
flower-like CuO. Furthermore, large-scale nanostructured CuO
production was realized by using copper powder as the feedstock
with a more rapid growth rate. The controllable corrosion process
of metal in alkaline medium could be applied to the synthesis of
other metal oxides.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (51325102).
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