j m a t e r r e s t e c h n o l .

2 0 2 0;9(1):994–1004

Available online at www.sciencedirect.com

www.jmrt.com.br

Original Article

A facile method for synthesis of nanostructured

copper (II) oxide by coprecipitation

Wellington Marques Rangel ∗ , Rozineide A. Antunes Boca Santa,

Humberto Gracher Riella
Chemical Engineering Graduate Program (PósENQ), Department of Chemical and Food Engineering (EQA), Laboratory of Materials and
Corrosion (LabMAC), Federal University of Santa Catarina (UFSC), Florianópolis, SC 88040-900, Brazil

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

Article history: Due to their versatility e wide range of physical and chemical properties, transition metal
Received 18 February 2019 oxides are very promising as nanostructured materials. Copper oxides are indicated for
Accepted 15 November 2019 applications in increasingly wider areas as gas sensing, catalysts, solar cells, electrochromic
Available online 9 December 2019 devices, and antimicrobial materials. In this study, copper (II) oxide nanoparticles were syn-
thesized by the coprecipitation method from two precursors: copper sulfate and copper
Keywords: chloride. The evaluated precursor concentrations were 0.1 M and 0.2 M and temperatures
Nanoparticles were 50 ◦ C and 75 ◦ C. Different results were found, according to synthesis parameters and
Copper (II) oxide precursor used. Using copper sulfate as a precursor, a single phase of polycrystalline CuO
Coprecipitation could be obtained, and only a mixture of crystalline phases of CuO and cllinoatacamite
(Cu2 (OH)3 Cl) were found using copper chloride as the precursor. A known polymorphism
phenomenon was observed in clinoatacamite according to synthesis reaction parameters,
and all three polymorphs were found mixed with CuO nanoparticles. Crystallite sizes of
about 10 nm were found in this study, with leaf and rod-like nanostructured particles with
dimensions range from 190 to 700 nm, and very good thermal stability. Under the synthe-
sis conditions selected in this study, nanostructured materials made with copper sulfate
precursor exhibited smaller crystallite sizes and better thermal stability. The coprecipita-
tion method used was considered adequate to obtain nanostructured materials, with the
advantages of being simple, fast and inexpensive.
© 2019 The Authors. Published by Elsevier B.V. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

However, their size and morphology control is still in develop-

1. Introduction ment [1]. And, depends on the reaction conditions and several
interdependent parameters such as temperature, electrostatic
The broad properties spectrum of nanostructured transition
interactions and sterical confinements [2].
metal oxides has received great attention from researchers.
Copper Oxide (CuO) due to its excellent physical and
chemical properties [3] has numerous potential applica-
tions, including research fields as catalysis [4,28] and gas
∗
Corresponding author. sensors [5,31]. More advanced applications as solar cells,
E-mails: wellington@ifsc.edu.br, wellington.ifsc@gmail.com light-emitting diodes, photocatalyst, electrochemical, elec-
(W.M. Rangel).
https://doi.org/10.1016/j.jmrt.2019.11.039
2238-7854/© 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004
trochromic devices are possible research fields for copper
oxide nanostructured materials [6]. Furthermore, nanostruc-
tured CuO is used for several applications in the removal of
inorganic pollutants and could be used as potential compo-
nents for the fabrication of nanodevices [7]. Nanoparticles
specially designed for antimicrobial applications in biotech-
nology and pharmaceuticals have great demand and its
market was valued at US$ 17.5 billion in 2011 [8].
Copper is widely used as a potent biocidal for centuries
and both gram-positive and gram-negative bacteria are killed
when exposed to high copper concentrations [32]. The same
biocidal effect is reported in the literature for copper oxide
nanoparticles as a promising material to prepare antimi-
crobial textiles, with very effective results in cotton fabrics
[9]. Recent developments have also reported the antimicro-
bial properties of copper oxide nanoparticles in textiles for
biomedical applications [10]. The copper oxide impregnated
into cotton or polyester fabrics has shown good biocidal
results against various microorganisms and viruses. The low
risk of causing unfavorable effects on the skin is an advantage
of copper oxide nanoparticles application [11].
Nanostructured materials have a high antimicrobial effect
due to its high surface area to volume ratio and the depen-
dence of its cytotoxicity to particle size is reported in the
literature. It was also observed higher levels of cytotoxicity in
copper oxide nanoparticles than other transition metal oxides
such as iron oxide, titanium dioxide, and zinc oxide [12,29].
Their promising properties and low cost compared to other
metal oxides have increased the interest in the development
of nanostructured materials of copper (II) oxide. Its structure
is considered more efficient and stable for antimicrobial appli-
cations than copper (I) oxide at room temperature [3].
Many synthesis routes were reported to prepare nanostruc-
tured CuO particles, each one with advantages and drawbacks,
including sol-gel [13], hydrothermal [14], thermal decomposi-
tion [15,16], microwave irradiation [17], alcothermal [18] and
sonochemical processes [19,30]. In this context, this study pro-
posed the synthesis and characterization of copper (II) oxide
nanoparticles using two different precursors. The coprecipita-
tion synthesis method was chosen for its simplicity, reaction
rates at low temperatures and low cost.
Copper oxide nanoparticles were produced in two reaction
conditions, in an alkaline medium using sodium hydroxide
(NaOH). The precursors were copper sulfate (CuSO4 .5H2 O) and
copper chloride (CuCl2 .2H2 O). The synthesis was conducted
at temperatures of 50 ◦ C and 75 ◦ C and the concentrations of
metal salts were 0.1 M and 0.2 M. After preparing, copper (II)
nanoparticles made with copper sulfate as precursor showed
better results (minor crystallite sizes). The coprecipitation
method was considered suitable for obtaining nanostructured
materials, with the advantages of being simple, fast and inex-
pensive.
2. Experimental
2.1. Materials
Two copper salts were used to prepare CuO nanostructured
particles, copper sulfate (CuSO4 .5H2 O) 98 % PA (SYNTH) and
995
Table 1 – Experiments prepared for CuO nanoparticles
synthesis.
samples precursors Temperatures (◦ C) Concentration (M)
A CuSO4 .5H2 O 50 0.1
B CuSO4 .5H2 O 50 0.2
C CuSO4 .5H2 O 75 0.1
D CuSO4 .5H2 O 75 0.2
E CuCl2 .2H2 O 50 0.1
F CuCl2 .2H2 O 50 0.2
G CuCl2 .2H2 O 75 0.1
H CuCl2 .2H2 O 75 0.2
copper chloride (CuCl2 .2H2 O) 99 % PA (VETEC); sodium hydrox-
ide (NaOH) 97 % PA (NAFAN) was used as an alkaline reagent.
All reagents were used without purification and solutions pre-
pared with distilled and deionized water.
2.2. Synthesis method
Copper oxide nanoparticles were prepared using a chemi-
cal coprecipitation method and NaOH as an alkaline reagent.
First, 100 mL precursor solutions were prepared using dis-
tilled and deionized water (0.1 and 0.2 M) and kept in constant
magnetic stirring in a rounded bottom three-neck flask. The
temperature was raised and maintained at 50 or 75 ◦ C as sum-
marized in Table 1.
After, an alkali (NaOH 1,0 M) solution previously prepared,
was added drop-wise using a burette, until a volume ratio of 1:1
was obtained. Constant stirring (500 rpm) was maintained in
the whole experiment and alkali solution was added at a flow
rate of 5 ml/min obtaining a pH 14 at the end of alkali addition.
The solution color gradually changed from blue to black, and
a considerable amount of black precipitate was formed. The
reaction conditions were maintained for an additional 30 min
at the same temperature and constant stirring. The precipi-
tates obtained were filtered under vacuum and washed with
deionized water at room temperature. After washing, the pow-
der was dried in a vacuum drying oven for 5 h at 80 ◦ C, and
characterization was performed.
2.3. Characterization of CuO nanoparticles
The samples were characterized by X-ray diffraction (XRD)
analysis to evaluate the existing crystalline phases. The equip-
ment used was a Philips diffractometer X’pert model with
copper K␣ radiation (␭ = 1.5418 Å), 40 kV and 30 mA, 2␪ ranging
from 5 to 110 and an angular step of 0.05◦ .
Thermogravimetric analysis was applied (TGA) for mea-
suring the mass variation according to temperature. The
exothermic and endothermic peaks were also analyzed by dif-
ferential scanning calorimetry techniques (DSC). A thermal
analyzer Netzsch Simultaneous Thermal Analyzer STA 449 F3
was used and samples were evaluated in the range 22−1000 ◦ C
at a heating rate of 10 ◦ C / min, platinum sample holder and
with flowing nitrogen atmosphere of 20 mL/min.
The morphology of the material was analyzed at the
Electronic Microscopy Laboratory (LCME) at UFSC, through
scanning electron microscopy techniques (SEM) and trans-
mission electron microscopy (TEM). For SEM a JEOL model
996 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004
Fig. 1 – XRD patterns of the samples prepared with the
precursor CuSO4 .5H2 O: A - 50 ◦ C / 0.1 M; B - 50 ◦ C / 0.2 M; C -
75 ◦ C / 0.1 M and D - 75 ◦ C / 0.2 M.
JSM-6390LV was used, coupled to EDX (Energy Dispersive X-
ray Spectroscopy), which was used for qualitative elemental
analysis. Samples were pre-coated with gold and the images
were obtained at 15 kV accelerating voltage. The TEM anal-
yses were performed in a transmission electron microscope
JEOL JEM-1011 model, with 100 kV voltage.
3. Results and discussion
3.1. X-ray diffraction of nanoparticles synthesized
from copper sulfate
The XRD patterns of prepared precipitates with copper sulfate
as a precursor are presented in Fig. 1. The characteristic peaks
in the XRD patterns are shown 2␪ = 35,6◦ ; 2␪ = 38.7◦ e 2␪ = 48,9◦ ;
corresponding to planes (002) and (−111); (200) and (111); and
(−202) of CuO. With monoclinic crystal system, space group
C2/c and lattice parameters: a = 4.668 Å, b = 3.423 Å, c = 5.132 Å,
␣ = ␥ = 90◦ and ␤ = 99.54◦ [20]. Similar results were found by
Lange et al. [33], using the coprecipitation method with a
0.02 M solution of copper acetate as a precursor. Comparable
XRD results were found using copper sulfate as a precursor
and the coprecipitation method for coating cotton fibers [9];
and using coprecipitation method with subsequent applica-
tion of ultrasound [21].
In sample C, additional peaks observed are due to
the formation of brochantite (Cu4 (SO4 )(OH)6 ) e de posnjakite
(Cu4 (SO4 )(OH)6 .H2 O), confirmed by the XRD patterns pre-
sented in Fig. 2. In the work of Darezereshki and Bakhtiari [22]
similar results were obtained using CuSO4 as precursor salt.
According to Frost [23], in highly alkaline medium, copper
(II) oxide is the most stable form and brochantite becomes the
more stable phase in case of pH in 4–6 range.
All samples exhibited similar diffraction patterns with
small variations in intensity and width of the peaks. Only
when prepared at 75 ◦ C and at 0.1 M CuSO4 the pres-
ence of compounds like brochantite and posnjakite were
Fig. 2 – XRD patterns of the samples prepared with the
precursor CuCl2.2H2O, under the conditions: E - 50 ◦ C /
0.1 M; F - 50 ◦ C / 0.2 M; G - 75 ◦ C / 0.1 M; H – 75 ◦ C / 0.2 M.
detected indicating that the increase in temperature and
the use of lower concentrations difficult the removal of
sulfate ions (SO4)2- during the formation of CuO crystals.
The absence of impurity peaks, like Cu(OH)2 and Cu2 O,
demonstrated the high purity of the nanostructured material
produced.
3.2. X-ray diffraction of nanoparticles synthesized
from copper chloride
In the diffraction data obtained for the precursor copper chlo-
ride, there was the formation of different crystalline phases
(Fig. 2). Copper oxide characteristic peaks were found at
2␪ = 35,5◦ ; 2␪ = 38,7◦ and 2␪ = 48,9◦ , confirming the formation
of copper oxide in the nanostructured particles.
However, other peaks were found, suggesting a mix-
ture of crystalline phases. Peaks at: 2␪ = 16,3◦ ; 2␪ = 32,5◦ ; and
2␪ = 39,7◦ e 2␪ = 53,8◦ ; indicated the formation of chlorinated
compounds such as clinoatacamite (Cu2 (OH)3 Cl) and its poly-
morphs.
According to Frost [23], the mineral clinoatacamite (mono-
clinic) has polymorphism and also is shown in the form of
botallackite (monoclinic) and atacamite (orthorhombic). The sta-
bility order for these phases is clinoatacamite > atacamite >
botallackite and, according to the Ostwald rule in a chemical
reaction where different products are formed, the first being
formed is preferably the lowest Gibbs free energy chemical
compound, botallackite, in this case.
It was observed in the results, that increasing tempera-
ture or the precursor salt concentration favored the formation
of chlorinated compounds. Under the synthesis conditions in
this study, the formation of a single phase of copper oxide was
not observed.
As prepared, CuO nanostructured particles made with cop-
per sulfate precursor demonstrated better purity and could be
used in applications like antimicrobial textile materials with-
out further purification. Using copper chloride as precursor
salt, chlorinated impurities were found.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004 997

Table 2 – Average Crystallite size (nm) of CuO, calculated by the Scherrer equation, according to the type of precursor and
reaction conditions.
Precursor Temperature (◦ C) Concentration (M) Cryst. Size (nm)

0.1 10.7
50
0.2 10.0
CuSO4.5H2O
0.1 13.8
75
0.2 14.1
0.1 14.5
50
0.2 12.0
CuCl2.2H2O
0.1 14.5
75
0.2 13.2

Fig. 3 – Nanoparticles obtained with CuSO4 .5H2 O, 0.1 M concentration and temperature 50 ◦ C: a) and b) bright field image; c)
diffraction pattern; d) crystallite details.

3.3. Average crystallite size
The crystallite size, D, was estimated according to the Scher-
rer equation (Eq. 1), using as reference the highest intensity
peak at 2␪ = 35.6◦ . The angle parameter () and full width at
half maximum (FWHM) were calculated using the OriginPro
8 software, ␭ is the copper K␣ wavelength 1.5418 Å) and the
results are shown in Table 2.
0.9 
D=
FWHM .cos
Smaller nanoparticles were obtained using CuSO4 as pre-
cursor salt. The reaction temperature and concentration of
precursor salt also influenced the crystallite size, where an
increase of temperature generates an increase of crystallite
size, and for most cases, an increase of salt concentration
causes a decrease of crystallite size.
Rodriguez and Fernandez-Garcia [24] reported crystallite
sizes considerably smaller in the range of 7−9 nm for copper
(II) oxide. The crystallite size of the CuO nanoparticles depends
on the preparation method used. According to Aparna et al.
[25], the average particle diameter is: (i) about 10 nm when pre-
pared by sonochemical; (ii) 1–10 nm by the sol-gel method; (iii)
3–9 nm in the decomposition of copper acetate; (iv) 15–20 nm
in solid-state reactions; and (v) 4 nm when using the electro-
chemical method.
(1)
It is observed that any material which contains particles
or agglomerates of smaller sizes than 100 nm, or films, and
filaments of this range are considered nanostructured materi-
als [26]. For Rodriguez and Fernandez-Garcia [24] nanoparticle
sizes definition includes the range from 1 to 1000 nm, which
can be amorphous, fully crystalline or small aggregates of crys-
998 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004
Fig. 4 – Nanoparticles obtained with CuSO4 .5H2 O, concentration 0.2 M and temperature 50 ◦ C: a) and b) bright field images; c)
detail of the formed particle; d) dark field image.
tallites. A nanocrystal is formed by only one crystalline phase
and should have dimensions in the nanometric order, but for
nanoparticles, a crystalline phase is not strictly necessary.
3.4. Transmission electron microscopy (TEM),
nanoparticles prepared with copper sulfate
In Figs. 3 and 4, TEM microphotographs for nanoparticles
obtained from CuSO4 .5H2 O precursor are presented. The
nanostructured particles synthesized at 50 ◦ C at both con-
centrations have shown the same morphology. Agglomerates
were built with an average crystallite size between 10 and
11 nm. The rod-like crystals formed agglomerates with 190 nm
width in the center and thinner on the ends. Larger star-like
agglomerates formed three-dimensional clusters with diam-
eters ranging from 400 to 700 nm. In Fig. 3c, the image was
carried out by electron diffraction and indicated a nanostruc-
tured and polycrystalline material.
With temperature increasing to 75 ◦ C (Figs. 5 and 6), larger
crystallites with an average size of 14.5 nm were formed
(0.2 M precursor concentration). The sample prepared with
0.1 M precursor (Fig. 5) showed irregular structure, probably
caused by the presence of those chemical species: brochantite
(Cu4 (SO4 )(OH)6 ) and posnjakite (Cu4 (SO4 )(OH)6 .H2 O), detected
in XRD analysis.
The rods formed in sample D (Fig. 6) had an average width
of 220 nm and an average length of 800 nm, forming larger
structures than the synthesis carried out at 50 ◦ C.
The reaction temperature also has influenced on the
preferred orientation of crystal growth. At 50 ◦ C, the crystal-
lites agglomerated and built a three-dimensional structure
with 6 edges, and at 75 ◦ C, the crystal growth followed
a linear direction, forming small particles similar to a
rod.
3.5. Transmission electron microscopy (TEM),
nanoparticles prepared with copper chloride
Sample E was selected for TEM analysis and results obtained
with the precursor CuCl2 .2H2 O, are shown in Fig. 7. Agglom-
erates were visualized in this sample also, and crystallite
size was greater than those obtained with copper sulfate
as a precursor (considering the same conditions: 50 ◦ C and
0.1 M). In this case, the crystallites obtained had an aver-
age size of 21 nm and formed rod-like structures with an
average size of 220 nm width and 830 nm in length, with
subsequent cluster formation in three-dimensional struc-
tures.
The crystallite size calculated from TEM micrographs
and the values obtained by the Scherrer method revealed
good correlation as presented in Table 3. The major dif-
ferences observed in samples C (Fig. 5) and E (Fig. 7)
represents synthesis conditions where the nanoparticles
were a mixture of copper oxide and different contami-
nants.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004 999

Fig. 5 – Nanoparticles obtained with CuSO4 .5H2 O, concentration 0.1 M and temperature 75 ◦ C: a) and b) bright field images of
formed particles; c) and d) bright and dark field images of a nanostructured particle.

Fig. 6 – Nanoparticles obtained with CuSO4 .5H2 O, concentration 0.2 M and temperature 75 ◦ C: a) bright field image; b) and d)
bright and dark field images of a nanostructured particle prepared; c) crystallite details.
1000 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004

Fig. 7 – Nanoparticles obtained with CuCl2 .2H2 O, concentration 0.1 M and temperature 50 ◦ C: a) and b) bright field image of
particles; c) and d) bright and dark field image of one nanostructured particle prepared.

by XRD results. The same peaks of carbon and gold are also
Table 3 – Average crystallite size (nm) obtained by the
Scherrer method and TEM microphotographs. observed because of experimental conditions.

Precursor Sample Scherrer (nm) TEM (nm)

A 10.7 10.7 3.7. Thermal analysis (TGA and DSC)

B 10.0 10.9
CuSO4 .5H2 O
C 13.8 36.9
Thermogravimetric analysis (TGA) and differential scanning
D 14.1 14.6
CuCl2 .2H2 O E 14.5 20.8 calorimetry (DSC) was performed on samples synthesized at
50 ◦ C and with 0.2 M of precursor salt concentration (Samples
B and F) and the results are exhibited, respectively, in Fig. 13a
and b.
3.6. Scanning electron microscopy (SEM) and energy According to Patnaik [27], the heating when the tempera-
dispersive spectroscopy (EDX) ture is above 800 ◦ C converts the copper (II) oxide into copper (I)
oxide. Above this temperature, copper (I) oxide becomes the
3.6.1. Copper sulfate as a precursor more stable phase. For this reason, the samples were tested
Samples A, B, C and D (CuSO4 precursor) are presented in until 1000 ◦ C to observe the thermal stability of the obtained
Figs. 8, 9, 10, and 11, respectively. The results of analysis by CuO samples.
energy dispersive spectroscopy indicate the presence of only Sample B (Fig. 13a) produced with the precursor copper sul-
copper and oxygen in the samples developed with this precur- fate, showed a weight loss of about 3.4 %; in the temperature
sor. The other two peaks appearing in Figs. 8 (b), 9 (b), 10 (b) range between 25 and 136 ◦ C, probably due to the vaporiza-
and 11 (b) correspond to the presence of carbon and gold used, tion of water contained in the sample. There is a small signal
respectively, in the carrier tape and covering the samples. at 283 ◦ C associated with a weight loss of 1.15 % due to crys-
tallization water removal; these events are summarized in
3.6.2. Copper chloride as a precursor Table 4 (peaks values estimated in OriginPro 8).
Sample E (Fig. 12a) prepared with precursor copper chloride Sample B exhibited very good thermal stability, losing only
(CuCl2 ) was selected for this analysis (synthesis conditions: 5.6 % of its mass until the decomposition of CuO started at
50 ◦ C and 0.1 M). In EDX results, Fig. 12b, a presence of the about 900 ◦ C. The difference in CuO decomposition temper-
atom Chlorine is confirmed. This is due to the formation of ature, when compared with the literature, was probably an
clinoatacamite and its polymorphs in the sample, as confirmed effect of the resolution used (10 ◦ C / min).
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004 1001

Fig. 8 – CuO nanoparticles obtained with the precursor CuSO4 , conc. 0.1 M and temperature 50 ◦ C: a) micrograph; b)
elemental analysis by EDX.

Fig. 9 – CuO nanoparticles obtained with the precursor CuSO4 , conc. 0.2 M and temperature 50 ◦ C: a) micrograph; b)
elemental analysis by EDX.

Fig. 10 – CuO nanoparticles obtained with the precursor CuSO4 , conc. 0.1 M and temperature 75 ◦ C: a) micrograph; b)
elemental analysis by EDX.

Fig. 11 – CuO nanoparticles obtained with the precursor CuSO4 , conc. 0.2 M and temperature 75 ◦ C: a) micrograph; b)
elemental analysis by EDX.
1002 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004

Fig. 12 – CuO nanoparticles obtained with the precursor CuCl2 , conc. 0.1 M and temperature 50 ◦ C: a) micrograph; b)
elemental analysis by EDX.

Fig. 13 – Thermal analysis (TGA and DSC) of CuO nanostructured particles: a) sample B, precursor CuSO4 ; b) sample F,
precursor CuCl2 . Synthesis conditions: temperature 50 ◦ C and precursor salt concentration 0.2 M.

Table 4 – Results obtained experimentally in the thermal Table 5 – Results obtained experimentally in the thermal
analysis of sample B: precursor CuSO4 . Synthesis analysis of sample F: precursor CuCl2 . Synthesis
conditions: temperature 50 ◦ C and precursor salt conditions: temperature 50 ◦ C and precursor salt
concentration 0.2 M. concentration 0.2 M.
Event Temp. Range (o C) Central Peak (◦ C) Weight loss (%) Event Temp. Range (o C) Central Peak (◦ C) Weight loss (%)

1 25.6–136.4 58.2 3.38 1 25.9–107.3 66.1 15.84

2 230.8–349.0 283.1 1.15 2 141.4–154.1 147.8 0.63
3 909.2–995.6 943.8 5.98 3 201.3–252.0 218.5 3.25
4 782.7–800.1 796.1 0.36
5 943.7–985.7 970.8 11.20
The thermal behavior of sample F (Fig. 13b) which is a
mixture of copper (II) oxide and chlorinated compounds of
and copper chloride (CuCl2 .2H2 O) using concentra-
chemical formula Cu2 (OH)3 Cl, showed less thermal stability
tions of 0.1 M and 0.2 M; and temperatures of 50 ◦ C and
and larger weight loss in the temperature range observed. The
75 ◦ C.
different weight loss results observed in Figs. 13a and b are
The characterization by X-ray diffraction (XRD) showed
probably due to chlorine gas, eliminated by heat in sample F.
the presence of a crystalline phase of copper (II) oxide
Performing the analysis by the DSC curve, three endother-
in the samples, using copper sulfate as a precursor. How-
mic peaks were observed until 250 ◦ C, probably induced by
ever, with the same precursor, increasing the temperature to
dehydration of the nanostructured crystals. The five events
75 ◦ C caused the appearance of compounds like brochantite
exhibited by this sample are displayed in Table 5 (data esti-
(Cu4 (SO4 )(OH)6 ) and Posnjakite (Cu4 (SO4 )(OH)6 .H2 O) together
mated in OriginPro 8). Another endothermic peak appeared at
with copper (II) oxide phase, only with precursor salt concen-
about 800 ◦ C, associated with a small weight loss (0.36 %), indi-
tration of 0.1 M.
cating a probable crystalline transition, followed by a massive
All samples prepared with the copper chloride precur-
loss indicating material decomposition.
sor has been identified as a mixture of crystalline phases,
with the presence of chlorinated compounds with chemi-
4. Conclusion cal formula Cu2 (OH)3 Cl, and a copper (II) oxide phase. These
chlorinated chemical compounds exhibited a polymorphism
Nanoparticles of copper oxide nanoparticles (II) were phenomenon and its most stable form is called clinoata-
made from two precursors: copper sulfate (CuSO4 .5H2 O) camite.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(1):994–1004
The crystallite size was calculated by Scherrer formula and
lower average crystallite sizes were obtained using the cop-
per sulfate solution as a precursor. It was observed that the
increase of reaction temperature promotes the development
of the chlorinated crystalline phases during the nanostruc-
tured material formation.
Thermal analysis revealed the different behavior of the
nanostructured materials obtained. When prepared with cop-
per sulfate salt the material exhibited only 5.6 % weight
loss until decomposition temperature of CuO. As a com-
parison, the sample made from copper chloride has lost
more than 30 % of the mass, considering 800 ◦ C as the
decomposition temperature, probably due to chlorine gas
elimination.
The analysis of its elemental composition by EDX evi-
denced the presence of chlorine, copper, and oxygen in the
samples prepared with the precursor copper chloride, and,
only copper and oxygen in samples prepared from copper sul-
fate.
The morphology of the nanoparticles and their dimen-
sions were observed in TEM photomicrographs, in which the
nanoparticles were presented as aggregates of crystallites in
the form of a small rod, organized into three-dimensional
structures with average dimensions differing according to
synthesis conditions. The samples synthesized at 50 ◦ C pre-
cursor with the copper sulfate had structures with smaller
dimensions than using 75 ◦ C as reaction temperature, thereby
forming a more interesting material for future applica-
tions.
With the use of copper chloride as a precursor, leaf-like
nanoparticles were prepared, which then formed larger three-
dimensional structures with about 830 nm in length, similar
to those found with the other precursor.
The average crystallite size showed a good correlation
between the values obtained by the Scherrer method and TEM
photomicrographs. The formation of a single-phase copper
oxide (II) in the synthesized material from the precursor cop-
per sulfate, using appropriate reaction conditions allows the
preparation of copper oxide nanocrystals for numerous appli-
cations.
The coprecipitation method used revealed to be fast and
simple, using only common materials of a chemical laboratory
and with low reaction temperatures.
Conflicts of interest
The authors declare that they have no known compet-
ing financial interests or personal relationships that could
have appeared to influence the work reported in this
paper.
Acknowledgment
The authors wish to thank the National Council for Scientific
and Technological Development (CNPq) - Grant 134522/2013-
3), the Central Laboratory of Electron Microscopy (LCME), the
Federal Institute of Santa Catarina (IFSC) and the Federal Uni-
versity of Santa Catarina (UFSC).
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