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Journal of Nanomaterials
Volume 2014, Article ID 507978, 5 pages
http://dx.doi.org/10.1155/2014/507978

Research Article
Synthesis of Thermally Spherical CuO Nanoparticles

Nittaya Tamaekong,1 Chaikarn Liewhiran,2 and Sukon Phanichphant3

1
Program in Materials Science, Faculty of Science, Maejo University, Chiang Mai 50290, Thailand
2
Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
3
Materials Science Research Center, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

Correspondence should be addressed to Nittaya Tamaekong; [email protected]

Received 6 September 2013; Accepted 29 November 2013; Published 8 January 2014

Academic Editor: Enrico Bergamaschi

Copyright © 2014 Nittaya Tamaekong et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

Copper oxide (CuO) nanoparticles were successfully synthesized by a thermal method. The CuO nanoparticles were further
characterized by thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning
electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), and high resolution transmission electron microscopy
(HRTEM), respectively. The specific surface area (SSABET ) of CuO nanoparticles was determined by nitrogen adsorption. The
SSABET was found to be 99.67 m2 /g (𝑑BET of 9.5 nm). The average diameter of the spherical CuO nanoparticles was approximately
6–9 nm.

1. Introduction influence three important groups of basic properties in any

material. The first one comprises the structural characteris-
Metal oxides play a very important role in many areas of tics, namely, the lattice symmetry and cell parameters [12].
chemistry, physics, and materials science [1–6]. The metal Bulk oxides are usually robust and stable systems with well-
elements can form a large diversity of oxide compounds [7]. defined crystallographic structures. However, the growing
These elements can adopt much structural geometry with importance of surface-free energy and stress with decreasing
an electronic structure that can exhibit metallic, semicon- particle size must be considered: changes in thermodynamic
ductor, or insulator character. In technological applications, stability associated with size can induce modification of cell
oxides are used in the fabrication of microelectronic circuits, parameters and/or structural transformations [13], and in
sensors, piezoelectric devices, fuel cells, and coatings for the extreme cases the nanoparticle can disappear due to interac-
passivation of surfaces against corrosion and as catalysts. For tions with its surrounding environment and the high surface-
example, almost all catalysts used in industrial applications free energy [14]. Nanomaterials have become important
involve an oxide as active phase, promoter, or “support.” In owing to their small size and large surface area. They exhibit
the chemical and petrochemical industries, products worth unique properties which are not seen in bulk materials [15].
billions of dollars are generated every year through processes CuO has been studied as a 𝑝-type semiconductor material
that use oxide and metal/oxide catalysts [8]. For the control with narrow band gap of 1.2 eV, because of the natural
of environmental pollution, catalysts or sorbents that contain abundance of its starting material, low-cost production pro-
oxides are employed to remove the CO, NO𝑥 , and SO𝑥 species cessing, nontoxic nature, and reasonably good electrical and
formed during the combustion of fossil-derived fuels [9, 10]. optical properties. CuO nanoparticles were of great interest
Furthermore, the most active areas of the semiconductor due to their potential applications in a wide variety of
industry involve the use of oxides [11]. Thus, most of the chips areas including electronic and optoelectronic devices, such
used in computers contain an oxide component. as microelectromechanical systems, field effect transistors,
Oxide nanoparticles can exhibit unique physical and electrochemical cells, gas sensors, magnetic storage media,
chemical properties due to their limited size and high density solar cells, field emitters, and nanodevices for catalysis. It
of corner or edge surface sites. Particle size is expected to has also been recently emphasized that, apart from the size,
2 Journal of Nanomaterials

the shape of the nanostructure is equally important for by nitrogen adsorption at 77 K (Micromeritics Tristar) after
controlling different properties [16]. degassing the sample for 1 h at 150∘ C under nitrogen fluctua-
However copper is an essential trace element for the nor- tion. The equivalent average primary particle diameter 𝑑BET
mal function of many tissues, including the nervous system, was calculated by 𝑑BET = 6/(𝜌CuO × SSABET ) [25], where 𝜌CuO
immune system, heart, and skin, and for the formation of is the density of CuO = 6.5 g/cm3 [26]. Finally, the accurate
capillaries [17, 18], and copper is well metabolized by humans morphologies of nanoparticles were observed using HRTEM
[19]. Copper(II) oxide has extremely low bioavailability (JEOL JEM-2010).
(practically zero) and should not be taken in conditions
of copper deficiency, especially as part of a multivitamin
which also includes zinc or molybdenum [19]. Excessive zinc
3. Results and Discussion
or molybdenum intake eliminates copper from the body. The TGA/DTA profile for the CuO precursor was shown in
Copper oxide is used in vitamin supplements as a safe source Figure 1. The TGA curve showed a three-step decomposition
of copper and over-the-counter treatments. Copper oxide of the precursor to form the CuO. The weight losses were
is also used in consumer products such as pillowcases and decomposed under excited temperatures ranging 35–166∘ C,
socks, due to its cosmetic and antimicrobial properties [20– 166–287∘ C, and 287–370∘ C. The initial weight loss below
23]. The risk of dermal sensitivity to copper is considered 166∘ C (∼9%) was caused by the water evaporation (moisture)
extremely minimal [24]. and organic solvent molecules according to two minor
In this study, CuO was synthesized using ethanediolther- endotherms peaks on the DTA curves (56–160∘ C) in this
mal method. Because of its low cost CuO is applied as gas region. The second decomposition step of TGA curve at 166–
sensing material to detect combustible, toxic, and pollution 287∘ C can be attributed to the pyrolysis and combustion of
gases. Usually gas sensing properties of oxide semiconductors organic compounds form precursor and solvent which leave
strongly depend on the surface of these materials. Thus, this the system in the form of CO𝑥 (𝑥 = 1, 2) and organic
research has been concentrating on improving high specific gases. This observation was consistent with the well-resolved
surface area of CuO nanoparticles. exothermic in the DTA curves at approximately 163–300∘ C
[27]. According to the temperature that was approximately up
2. Methods and Procedures to 500∘ C, here the CuO nanopowder was calcined at 500∘ C
for 2 h.
2.1. Synthesis of Nanoparticles. CuO nanoparticles were syn- For XRD patterns of the CuO nanoparticles, all peaks can
thesized by the thermal method method. Copper (II) acetate be confirmed to be the monoclinic phase of CuO (JCPDS
(Cu(CH3 COO)2 ⋅xH2 O, Aldrich, 98%) and sodium hydrox- no. 48–1548) as shown in Figure 2. The smaller size of
ide (NaOH, Merck, 99%) were used as the precursors, and CuO nanoparticles can be predicted consistently with the
ethanediol (C2 H6 O2 , Ajex Finechem, 99.5%) was used as broadening diffraction peaks of XRD patterns. Moreover, the
the solvent. In a typical procedure to synthesize the CuO crystallite size based on the broadening diffraction peaks
nanoparticles, 25 mM of Cu (CH3 COO)2 ⋅xH2 O and 100 mM was approximately estimated from the corresponding X-ray
of NaOH were dissolved in ethanediol at 80∘ C by stirring for spectral peak employing the Debye-Scherrer’s formula (2)
2 h on the basis of the following reaction: [28]. The calculated value was estimated to be 6.1 nm:
Cu(CH3 COO)2 ⋅ 𝑥H2 O + C2 H6 O2 + 2NaOH 𝑘𝜆
(1) 𝑑 (Å) = , (3)
󳨀→ Cu(OH)2 + 2Na(C2 H5 COO) + 𝑥H2 O 𝛽 cos 𝜃

Cu(OH)2 + 2Na (C2 H5 COO) + 𝑥H2 O where 𝑘 is an empirical constant equal to 0.9 as the spherical
(2) particles, 𝜆 is the wavelength of the X-ray source (1.5405 Å), 𝛽
󳨀→ CuO + 2Na(C2 H5 COO) + 𝑥H2 O is the full width at half maximum of the diffraction peak, and
𝜃 is the angular position of the diffraction peak. According to
The pH of the solution under continuous stirring was the BET method, the specific surface area (SSABET ) of CuO
9. Then, the final products were washed with DI water and nanoparticles was measured to be 99.67 m2 /g. It was found
ethanol several times by centrifugation. The obtained brown that the calculated particle size of sample was 9.3 nm [25].
powder was subsequently dried at 80∘ C in air. The resultant The accurate particle size and morphologies of CuO nanopar-
powder was then characterized using TG/DTA for calcination ticle were confirmed by SEM and TEM bright-field images.
temperatures. Figures 3(a) and 3(b) showed the morphology of highly crys-
talline CuO nanoparticles from SEM/EDS and TEM analyses.
2.2. Powder Characterizations. The thermogravimetric anal- The SEM micrograph clearly showed rough agglomeration
ysis (TGA) and differential thermal analysis (DTA) were of nanostructural homogeneities with spherical morpholo-
carried on TGA7 and DTA7 (Perkin Elmer). The X-ray gies of CuO nanoparticles. The SEM observation showed
diffraction (XRD) patterns were correspondingly recorded the presence of agglomerated nanospheres with an average
with JEOL JDX-3530 operating with Cu K𝛼 (𝜆 = 1.5405 Å). diameter of 10–20 nm. Therefore, from this observation only
The elemental compositions of nanoparticles were analyzed the rough morphology was found. Nevertheless, the accurate
by EDS quantitative analysis (Oxford Instrument). The spe- sizes and morphology of the nanoparticles can be estimated
cific surface area (SSABET ) of the nanoparticles was measured from the TEM analysis. While the SEM images provide 3D
Journal of Nanomaterials 3

100 2.0

95
1.8

TG (%, weight)
90 TG

ΔT (∘ C/mg)
DTA
1.6
85
1.4
80

75 1.2

70 1.0
0
100
200
300
400
500
600
700
800
900
1000
1100
Temperature (∘ C)

Figure 1: TG/DTA curve of copper acetate precursor.

(002)

(111)
Intensity (a.u.)

(−202)

(−113)
(110)

(202)
(020)

∗CuO (monoclinic)
JCPDS no. 48-1548

20 25 30 35 40 45 50 55 60
2𝜃 (deg)

Figure 2: XRD patterns of CuO nanoparticles.

Cu
Element Weight% Atomic%
OK 14.72 40.67
CuK 85.28 59.33
Totals 100.00

O Cu
Cu

(a) (b)

Figure 3: (a) SEM/EDS analyses and (b) HRTEM image of CuO morphologies. Insets show the corresponding diffraction patterns of the
particles related to the CuO lattice planes.
4 Journal of Nanomaterials

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