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Materials Science and Engineering B 128 (2006) 111114

Synthesis of nickel oxide nanoparticles using nickel acetate


and poly(vinyl acetate) precursor
N. Dharmaraj a,b, , P. Prabu c , S. Nagarajan d , C.H. Kim b ,
J.H. Park b , H.Y. Kim b,
a Department of Chemistry, Government Arts College, Udumalpet 642126, India
bInorganic/Organic Nanomaterials Research Laboratory, Department of Textile Engineering,
Chonbuk National University, Chonju 561-756, Republic of Korea
c Department of Bio-nanosysytem Engineering, Chonbuk National University, Chonju 561-756, Republic of Korea
d Semiconductor Physics Research Centre, Chonbuk National University, Chonju 561-756, Republic of Korea

Received 20 August 2005; received in revised form 12 November 2005; accepted 18 November 2005

Abstract
Cubic nickel oxide (NiO) nanoparticles with uniform size around 4050 nm and well dispersion have been synthesized using a mixture of
nickel acetate and poly(vinyl acetate) (PVAc) as precursor followed by heat treatment at 723 K. The structure, morphology and crystalline phase
of the nickel oxide nanocrystals have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray
diffraction (XRD), Raman spectrum, UVvisible absorption spectrum and FT-IR. TEM images showed that the nickel oxide nanoparticles have
hexagonal structure with uniform size distribution around 4050 nm. Phase pure, cubic nickel oxide formation was identified from the XRD data.
2005 Elsevier B.V. All rights reserved.

Keywords: Nanoparticles; Nickel oxide; Poly(vinyl acetate); Raman spectroscopy

1. Introduction gle phase, cubic NiO nanoparticles with nearly uniform par-
ticle size around 4050 nm and appreciable dispersion using
Nanoscale oxide particles of transition metals are gaining nickel acetate/poly(vinyl acetate) (PVAc) composite mixture
continuous importance for various applications such as cata- as precursor followed by heat treatment at 723 K. Properties
lysts, passive electronic components and ceramic materials [1]. of NiO nanoparticles were characterized by scanning electron
Due to their small size, nanoparticles exhibit novel material microscopy (SEM), transmission electron microscopy (TEM),
properties that are significantly different from those of their X-ray diffraction (XRD), Raman, UVvisible absorption and
bulk counterparts. Nickel oxide (NiO) nanoparticles with a FT-IR spectra.
uniform size and well dispersion are desirable for many appli-
cations in designing ceramic, magnetic, electrochromic and 2. Experimental
heterogeneous catalytic materials [2]. Several researchers have
prepared NiO nanoparticles by various methods like solgel Nickel(II) acetate tetrahydrate (Aldrich), N,N-dimethy for-
[3], surfactant-mediated synthesis [4], thermal decomposition mamide (Aldrich), 2-methoxy ethanol (Aldrich) and PVAc
[5], polymer-matrix assisted synthesis [6] and spray-pyrolysis (Celanase, Mn = 50,000) were used as received without further
[7]. Some of the above methods suffer from the difficulty in purification. Nickel oxide nanoparticles were prepared as fol-
size-homogeneity and well dispersion of NiO nanoparticles. lows. Ni(OAc)2 4H2 O (0.1 mol) was dissolved in 2-methoxy
In this article, we describe a simple method to prepare sin- ethanol (1 mol) by heating at 343 K for 2 h under stirring. PVAc
(14 wt.%) solution was prepared in DMF by stirring at room
temperature. Then a mixture of nickel acetate and PVAc in the
Corresponding authors. Tel.: +82 63 270 2351; fax: +82 63 270 2348.
1:4 ratio was stirred for 3 h at room temperature. The resulting
E-mail addresses: dharmaraj67@yahoo.com (N. Dharmaraj), composite mixture was heated at 423 K to remove the solvent
khy@moak.chonbuk.ac.kr (H.Y. Kim). and water. Finally, the solid mass obtained was ground well

0921-5107/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2005.11.021
112 N. Dharmaraj et al. / Materials Science and Engineering B 128 (2006) 111114

and heated in a crucible at 723 K for 3 h in air to get the NiO


nanoparticles and characterized by various physico-chemical
methods.

2.1. Characterisation of nanoparticles

Surface morphology was studied by JEOL GSM-5900 scan-


ning electron microscope. The transmission electron micro-
graphs were taken with a JEOL JEM-2010 electron microscope.
The phase and crystallinity were characterized by using a Rigaku
X-ray diffractometer with Cu K radiation over a range of 2
angles from 30 to 70 . Raman scattering was measured at room
temperature using Renishaw Raman microscope with Ar+ laser
operating at 514.5 nm. UVvisible absorption spectrum was
obtained from Varian Cary 3E spectrophotometer in the range
200600 nm. FT-IR spectra of the nanoparticles (as pellets in Fig. 1. Scanning electron microscopic (SEM) image of NiO nanoparticles.
KBr) have been recorded in BIO-Rad Win instrument.
Fig. 2. TEM photos revealed the presence of a large number of
3. Results and discussion NiO particles with hexagonal shape and uniform size around
4050 nm and well dispersed in the bulk material. Inset in this
3.1. Scanning electron microscopic images figure shows the electron diffraction pattern of the selected area
of nanoparticles. The appearance of strong diffraction spots
Fig. 1 shows the SEM image of NiO nanoparticles synthe- rather than diffraction rings confirmed the formation of single
sized by using nickel acetate/PVAc precursor heat treated at crystalline cubic nickel oxide.
723 K. From this image it is clearly seen that the NiO parti-
cles have nearly uniform size and well dispersion in the bulk 3.3. X-ray diffraction studies
state with diameter around 4050 nm. This indicates that PVAc
played a key role in the formation of well-dispersed nanopar- The typical XRD pattern of NiO nanoparticles obtained after
ticles by avoiding their aggregation due to co-ordination with heat treatment at 723 K is presented in Fig. 3. The existence
nickel ion in the composite mixture that leads to the formation of strong and sharp diffraction peaks at 2 values 37.25, 43.30
of uniform sized NiO during heat treatment in air. and 62.90 corresponding to (1 1 1) (2 0 0) and (2 2 0) crystal
planes indicated the formation of phase pure, cubic nickel oxide
3.2. Transmission electron microscopy (bunsenite, NaCl type structure) at this temperature. The particle
size of the prepared nickel oxide calculated from XRD using the
Transmission electron micrographes have been recorded DebyeSherrer equation is about 43.92 nm, in good agreement
using a copper grid dipped in a solution containing NiO nanopar- with that observed from TEM images. The nature and positions
ticles dispersed in ethanol by ultrasonication and presented in of the above diffraction peaks are characteristic of cubic nickel

Fig. 2. Transmission electron microscopic (TEM) images of NiO nanoparticles; (a) lower magnification and (b) higher magnification (inset in (a) showed the selected
area electron diffraction pattern).
N. Dharmaraj et al. / Materials Science and Engineering B 128 (2006) 111114 113

Fig. 3. XRD pattern of NiO nanoparticles. Fig. 5. UVvisible absorption spectrum of NiO nanoparticles.

oxide phase as cited in other reports and JCPDS card ([2,8,9,11];


file number: 4-0835).

3.4. Raman spectrum

Fig. 4 shows the Raman spectrum of NiO nanoparticles syn-


thesized in this study. The Raman spectrum exhibited a strong,
broad peak at 518 cm1 due to the Ni O stretching mode [12].

3.5. UVvisible spectrum

Fig. 5 shows the UVvisible absorption spectrum of NiO


nanoparticles obtained after heat treatment at 723 K. It can be
seen that the absorption edge corresponding to NiO appeared at
320 nm.
Fig. 6. FT-IR spectra: (a) nickel acetate/PVAc precursor and (b) NiO nanopar-
ticles.
3.6. FT-IR spectra

The formation of pure nickel oxide nanoparticles after heat some strong absorption in the region 12001800 cm1 that can
treatment at 723 K was also identified by FT-IR spectral studies be assigned to PVAc molecule (curve a). The samples obtained
(Fig. 6). The spectrum of nickel acetate/PVAc precursor showed after heating at 723 K did not exhibit any such bands thereby
confirming the complete removal of PVAc at this temperature,
but new peaks were found at 445 and 490 cm1 (curve b). These
peaks were undoubtedly assigned to Ni O stretching as was
reported earlier by other researchers [9,10].

4. Conclusion

Cubic nickel oxide nanoparticles with diameter around


4050 nm were synthesized from nickel acetate/PVAc precur-
sor by heat treatment at 723 K. The particles were found to
have size-homogeneity and well dispersed in the bulk, which
was attributed to the presence of coordinated PVAc with nickel
ion in the precursor and prevents the aggregation of nickel
oxide into bulk mass during heat treatment. Though the par-
ticle size of NiO seems to be little large, the size uniformity and
fine dispersion of the particles were significant aspects of our
Fig. 4. Raman spectrum of NiO nanoparticles. study.
114 N. Dharmaraj et al. / Materials Science and Engineering B 128 (2006) 111114

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We gratefully acknowledge The Korean Research Foundation
[5] L. Xiang, X.Y. Deng, Y. Jin, Scripta Mater. 47 (2002) 219.
(KRF), Ministry of Science and Technology, Republic of Korea, [6] S. Deki, H. Yanagimito, S. Hiraoka, Chem. Mater. 15 (2003)
for awarding Brain Pool Fellowship (041S-4-12, 2004) to one of 4916.
the authors (N. Dharmaraj). We also thank Mr. Kang Jong-Gyun, [7] S.F. Liu, C.Y. Wu, X.Z. Han, Chin. J. Inorg. Chem. 19 (2003)
Electron microscope (EM) Laboratory, Center for University- 624.
[8] W. Xing, F. Li, Z.F. Yan, G.Q. Lu, J. Power Sources 134 (2004)
wide Research Facilities, Chonbuk National University, Chonju
1426.
561-756, Republic of Korea, for his help in recording the TEM [9] H. Guan, C. Shao, S. Wen, B. Chen, J. Gong, X. Yang, Inorg. Chem.
images of the nanoparticles. Commun. 6 (2003) 1302.
[10] P.S. Patil, L.D. Kadam, Appl. Surf. Sci. 199 (2002) 211.
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