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A Facile Method For Synthesis of Nanostructured Copper (II) Oxide by Coprecipitation
A Facile Method For Synthesis of Nanostructured Copper (II) Oxide by Coprecipitation
A Facile Method For Synthesis of Nanostructured Copper (II) Oxide by Coprecipitation
2 0 2 0;9(1):994–1004
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Original Article
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/).
3.1. X-ray diffraction of nanoparticles synthesized In the diffraction data obtained for the precursor copper chlo-
from copper sulfate ride, there was the formation of different crystalline phases
(Fig. 2). Copper oxide characteristic peaks were found at
The XRD patterns of prepared precipitates with copper sulfate 2 = 35,5◦ ; 2 = 38,7◦ and 2 = 48,9◦ , confirming the formation
as a precursor are presented in Fig. 1. The characteristic peaks of copper oxide in the nanostructured particles.
in the XRD patterns are shown 2 = 35,6◦ ; 2 = 38.7◦ e 2 = 48,9◦ ; However, other peaks were found, suggesting a mix-
corresponding to planes (002) and (−111); (200) and (111); and ture of crystalline phases. Peaks at: 2 = 16,3◦ ; 2 = 32,5◦ ; and
(−202) of CuO. With monoclinic crystal system, space group 2 = 39,7◦ e 2 = 53,8◦ ; indicated the formation of chlorinated
C2/c and lattice parameters: a = 4.668 Å, b = 3.423 Å, c = 5.132 Å, compounds such as clinoatacamite (Cu2 (OH)3 Cl) and its poly-
␣ = ␥ = 90◦ and  = 99.54◦ [20]. Similar results were found by morphs.
Lange et al. [33], using the coprecipitation method with a According to Frost [23], the mineral clinoatacamite (mono-
0.02 M solution of copper acetate as a precursor. Comparable clinic) has polymorphism and also is shown in the form of
XRD results were found using copper sulfate as a precursor botallackite (monoclinic) and atacamite (orthorhombic). The sta-
and the coprecipitation method for coating cotton fibers [9]; bility order for these phases is clinoatacamite > atacamite >
and using coprecipitation method with subsequent applica- botallackite and, according to the Ostwald rule in a chemical
tion of ultrasound [21]. reaction where different products are formed, the first being
In sample C, additional peaks observed are due to formed is preferably the lowest Gibbs free energy chemical
the formation of brochantite (Cu4 (SO4 )(OH)6 ) e de posnjakite compound, botallackite, in this case.
(Cu4 (SO4 )(OH)6 .H2 O), confirmed by the XRD patterns pre- It was observed in the results, that increasing tempera-
sented in Fig. 2. In the work of Darezereshki and Bakhtiari [22] ture or the precursor salt concentration favored the formation
similar results were obtained using CuSO4 as precursor salt. of chlorinated compounds. Under the synthesis conditions in
According to Frost [23], in highly alkaline medium, copper this study, the formation of a single phase of copper oxide was
(II) oxide is the most stable form and brochantite becomes the not observed.
more stable phase in case of pH in 4–6 range. As prepared, CuO nanostructured particles made with cop-
All samples exhibited similar diffraction patterns with per sulfate precursor demonstrated better purity and could be
small variations in intensity and width of the peaks. Only used in applications like antimicrobial textile materials with-
when prepared at 75 ◦ C and at 0.1 M CuSO4 the pres- out further purification. Using copper chloride as precursor
ence of compounds like brochantite and posnjakite were 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 size, and for most cases, an increase of salt concentration
causes a decrease of crystallite size.
The crystallite size, D, was estimated according to the Scher- Rodriguez and Fernandez-Garcia [24] reported crystallite
rer equation (Eq. 1), using as reference the highest intensity sizes considerably smaller in the range of 7−9 nm for copper
peak at 2 = 35.6◦ . The angle parameter () and full width at (II) oxide. The crystallite size of the CuO nanoparticles depends
half maximum (FWHM) were calculated using the OriginPro on the preparation method used. According to Aparna et al.
8 software, is the copper K␣ wavelength 1.5418 Å) and the [25], the average particle diameter is: (i) about 10 nm when pre-
results are shown in Table 2. 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-
0.9 chemical method.
D= (1)
FWHM .cos It is observed that any material which contains particles
or agglomerates of smaller sizes than 100 nm, or films, and
Smaller nanoparticles were obtained using CuSO4 as pre- filaments of this range are considered nanostructured materi-
cursor salt. The reaction temperature and concentration of als [26]. For Rodriguez and Fernandez-Garcia [24] nanoparticle
precursor salt also influenced the crystallite size, where an sizes definition includes the range from 1 to 1000 nm, which
increase of temperature generates an increase of crystallite 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 The reaction temperature also has influenced on the
and should have dimensions in the nanometric order, but for preferred orientation of crystal growth. At 50 ◦ C, the crystal-
nanoparticles, a crystalline phase is not strictly necessary. lites agglomerated and built a three-dimensional structure
with 6 edges, and at 75 ◦ C, the crystal growth followed
3.4. Transmission electron microscopy (TEM), a linear direction, forming small particles similar to a
nanoparticles prepared with copper sulfate rod.
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.
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 (%)
thermal decomposition in liquid phase: the influence of [24] Rodriguez J, Fernandez-Garcia M. Synthesis, properties, and
capping ligands on the synthesis and bactericidal activity. J applications of oxide nanomaterials. New Jersey: John Wiley
Nanoparticle Res 2014;16:2588, & Sons; 2007, http://dx.doi.org/10.1002/0470108975.
http://dx.doi.org/10.1007/s11051-014-2588-7. [25] Aparna Y, Rao KVE, Subbarao PS. Synthesis and
[17] Bhattacharjee A, Ahmaruzzaman M. Microwave assisted characterization of CuO nano particles by novel sol- gel
facile and green route for synthesis of CuO nanoleaves and method. 2012 2nd Int Conf Environ Sci Biotechnol
their efficacy as a catalyst for reduction and degradation of 2012;48:156–60, http://dx.doi.org/10.7763/IPCBEE.
hazardous organic compounds, vol. 353. Elsevier B.V.; 2018, [26] Nalwa HS. Nanostructured materials and nanotechnology.
http://dx.doi.org/10.1016/j.jphotochem.2017.11.018. Concise Ed. San Diego: Academic Press; 2002,
[18] Kida T, Oka T, Nagano M, Ishiwata Y, Zheng X-G. Synthesis http://dx.doi.org/10.1016/B978-0-12-513920-5.X5000-8.
and application of stable copper oxide nanoparticle [27] Patnaik P. Handbook of inorganic chemicals. New York:
suspensions for nanoparticulate film fabrication. J Am McGraw-Hill; 2002,
Ceram Soc 2007;90:107–10, http://dx.doi.org/10.1002/9780470238165.indcas.
http://dx.doi.org/10.1111/j.1551-2916.2006.01402.x. [28] Das D, Nath BC, Phukon P, Dolui SK. Synthesis and
[19] Karunakaran C, Manikandan G, Gomathisankar P. evaluation of antioxidant and antibacterial behavior of CuO
Microwave, sonochemical and combustion synthesized CuO nanoparticles. Colloids Surf B Biointerfaces 2013;101:430–3,
nanostructures and their electrical and bactericidal http://dx.doi.org/10.1016/j.colsurfb.2012.07.002.
properties. J Alloys Compd 2013;580:570–7, [29] Felix S, Chakkravarthy RBP, Grace AN. Microwave assisted
http://dx.doi.org/10.1016/j.jallcom.2013.07.150. synthesis of copper oxide and its application in
[20] Wang J, He S, Li Z, Jing X, Zhang M, Jiang Z. Synthesis of electrochemical sensing. IOP Conf Ser Mater Sci Eng
chrysalis-like CuO nanocrystals and their catalytic activity in 2015;73:1–6, http://dx.doi.org/10.1088/1757-899X/73/1/012115.
the thermal decomposition of ammonium perchlorate. J [30] Zhang X, Zhang D, Ni X, Zheng H. Optical and
Chem Sci 2009;121:1077–81, electrochemical properties of nanosized CuO via thermal
http://dx.doi.org/10.1007/s12039-009-0122-8. decomposition of copper oxalate. Solid State Electron
[21] Wongpisutpaisan N, Charoonsuk P, Vittayakorn N, Pecharapa 2008;52:245–8, http://dx.doi.org/10.1016/j.sse.2007.08.009.
W. Sonochemical synthesis and characterization of copper [31] Zou G, Li H, Zhang D, Xiong K, Dong C, Qian Y. Well-aligned
oxide nanoparticles. Energy Procedia 2011;9:404–9, arrays of CuO nanoplatelets. J Phys Chem B 2006;110:1632–7,
http://dx.doi.org/10.1016/j.egypro.2011.09.044. http://dx.doi.org/10.1021/jp0557363.
[22] Darezereshki E, Bakhtiari F. A novel technique to synthesis of [32] Borkow G. Using copper to improve the well-being of the
tenorite (CuO) nanoparticles from low concentration CuSO4 skin. Curr Chem Biol 2015;8:89–102,
solution. J Min Metall Sect B Metall 2011;47:73–8, http://dx.doi.org/10.2174/2212796809666150227223857.
http://dx.doi.org/10.2298/JMMB1101073D. [33] Lanje AS, et al. Synthesis and optical characterization of
[23] Frost RL. Raman spectroscopy of selected copper minerals of copper oxide nanoparticles. Advances in Applied Science
significance in corrosion. Spectrochim Acta - Part A Mol Research 2010;1:36–40.
Biomol Spectrosc 2003;59:1195–204,
http://dx.doi.org/10.1016/S1386-1425(02)00315-3.