Preparation and characterization of nickel oxide nanoparticles via solid state thermal decomposition...

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Research on Chemical Intermediates ISSN 0922-6168Volume 41Number 1 Res Chem Intermed (2015) 41:357-363DOI 10.1007/s11164-013-1197-x

Preparation and characterization of nickeloxide nanoparticles via solid state thermaldecomposition of dinuclear nickel(II) Schiffbase complex [Ni2(Brsal-1,3-ph)2] as a newprecursorAliakbar Dehno Khalaji, MahsaNikookar & Debasis Das

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Preparation and characterization of nickel oxidenanoparticles via solid state thermal decompositionof dinuclear nickel(II) Schiff base complex [Ni2(Brsal-1,3-ph)2] as a new precursor

Aliakbar Dehno Khalaji • Mahsa Nikookar •

Debasis Das

Received: 26 February 2013 / Accepted: 10 April 2013 / Published online: 25 April 2013

� Springer Science+Business Media Dordrecht 2013

Abstract The synthesis and characterization of nickel oxide nanoparticles via

solid state thermal decomposition of a dinuclear nickel(II) complex, [Ni2(Brsal-1,3-

ph)2] as a new precursor is reported. [Ni2(Brsal-1,3-ph)2] complex is characterized

by elemental analyses and Fourier transform infrared (FT-IR) spectroscopy. Ther-

mogravimetric analysis reveals its thermal stability and decomposition pattern.

Solid state thermal decomposition of the complex at 450 �C for 3 h produces nickel

oxide nanoparticles which are characterized by FT-IR spectroscopy, X-ray powder

diffraction, scanning electron microscopy (SEM), and transmission electron

microscopy (TEM). SEM and TEM images demonstrate the square shape of the NiO

nanoparticles of between 10 and 15 nm.

Keywords Ni(II) Schiff base complex � Nanoparticles � XRD � SEM � TEM

Introduction

In recent years, the preparation of transition metal oxide nanoparticles have been

widely studied due to their versatile applications, such as chemical sensors, catalysts,

antistatic coating, radioactive waste management, etc. [1, 2]. The synthesis and

characterization of different transition metal oxide nanoparticles with specific sizes

and morphology have been reported [3–7]. Amongst them, NiO nanoparticles have

received much attention because of their application in battery cathodes, gas sensor

materials, photovoltaic devices, etc. [8–10]. NiO nanoparticles as p-type semicon-

ductors having a stable wide band gap (3.6–4.0 eV) have been studied for their wide

A. D. Khalaji (&) � M. Nikookar

Department of Chemistry, Faculty of Science, Golestan University, Gorgan, Iran

e-mail: [email protected]

D. Das

Department of Chemistry, The University of Burdwan, Burdwan, West Bengal, India

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Res Chem Intermed (2015) 41:357–363

DOI 10.1007/s11164-013-1197-x

Author's personal copy

application in magnetic materials [11]. Thus, the size, shape, and morphology of NiO

nanoparticles are important for their technological applications. To date, NiO

nanoparticles having various morphologies have been prepared by different techniques,

such as sol–gel, thermal decomposition, evaporation, etc. [12–17]. However, thermal

decomposition techniques are considered as the most promising [18–21] because one

can control the process conditions, particle size, particle crystal morphology, and

purity. Moreover, it requires a short time, and has high yields, low costs and low power

consumption. Very recently, Salavati-Niasari and co-workers [10, 12, 18, 19, 21, 22]

have synthesized NiO nanoparticles using thermal decomposition of Ni(II) complexes.

They have a calcined tetrahedral nickel(II) complex [Ni(acta)2] in the temperature

range of 300–900 �C to get NiO nanoparticles with a size of about 24 nm [21]. Farhadi

and Roostaei-Zaniyani [20] have synthesized NiO nanoparticles by solid state thermal

decomposition of octahedral nickel(II) complexes in the temperature range of

200–400 �C to obtain NiO nanoparticles having a size about 13–15 nm.

However, various precursors have been used for the preparation of NiO

nanoparticles via the thermal decomposition method, but there are few reports on

the Ni(II) Schiff base complexes [23–25]. Recently, our group has been synthesized

NiO nanoparticles via thermal decomposition method of Ni(II) Schiff base complexes

[24, 25]. Here, we have prepared NiO nanoparticles from dinuclear nickel(II) Schiff

base complex, [Ni2(Brsal-1,3-ph)2], as a new precursor (Scheme 1). The product is

identified by FT-IR spectroscopy, XRD, SEM, and TEM studies.

Experimental

Materials and methods

All reagents and solvents for synthesis and analysis were commercially available

and used as received without further purification. Elemental analyses were carried

NH2 NH2

O

OHBrN

OH

N

OH

Br Br

NiCl2

CH3OH+

N

O

N

O

N

O

N

ONi Ni

Br

BrBr

Br

Scheme 1 Synthesis of dinuclear nickel(II)complex, [Ni2(Brsal-1,3-ph)2]

358 A. D. Khalaji et al.

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out using a Heraeus CHN–O-Rapid analyzer, and the results agreed with calculated

values. Fourier transform infrared spectra were recorded as a KBr disk on a FT-IR

Perkin–Elmer spectrophotometer. XRD pattern of the nanoparticles was recorded on

a Bruker AXS diffractometer D8 ADVANCE with Cu-Ka radiation with nickel beta

filter in the range 2h = 10�–80�. Scanning electron microscopy (SEM) images were

obtained on a Philips XL-30ESEM. Transmission electron microscopy (TEM)

images were obtained on a Zeiss-EM10C transmission electron microscope with an

accelerating voltage of 80 kV.

Synthesis of [Ni2(Brsal-1,3-ph)2] precursor

To a stirring solution of 5-bromosalicysilaldehyde (0.2 mmol, in 5 ml of methanol)

was added 1,3-phenylenediamine (0.2 mmol) in 10 ml of methanol and the mixture

was stirred for 30 min in air at room temperature. Then, the methanolic solution of

NiCl2�6H2O (0.2 mmol in 10 ml) was added dropwise and the mixture was stirred

for 1.5 h in air at room temperature. Microcrystals of [Ni2(Brsal-1,3-ph)2] were

obtained after the solvent was evaporated slowly for several days at room

temperature, then the products were collected by filtration and dried in vacuum. The

yield was 79 %. Anal. calc. for C40H28N4Ni2O4: C, 45.25; H, 2.28; N, 5.28 %.

Found: C, 44.95; H, 2.41; N, 5.36 %. FT-IR (KBr pellet cm-1): 3,058 (CH

aromatic), 1,611 (C=N), 1,534, 1,464, 1,444 (C=C aromatic).

Preparation of NiO nanoparticles

The dinuclear nickel(II) Schiff base complex, [Ni2(Brsal-1,3-ph)2], was loaded into

a platinum crucible and then placed in an oven and heated at a rate of 10 �C/min in

air. Nanoparticles of nickel oxide were synthesized at 450 �C after 3 h. The final

products were washed with ethanol at least three times to remove impurities, if any,

and dried at r.t. for 3 days. The synthesized NiO nanoparticles were characterized

by FT-IR, XRD, and SEM. FT-IR (KBr pellet cm-1): 435 (Ni–O).

Results and discussion

Figure 1 shows the FT-IR spectra of the dinuclear [Ni2(Brsal-1,3-ph)2] complex and

nickel oxide nanoparticles. In the complex, a strong band at 1,611 cm-1is due to the

C=N stretching vibration. The peak was 435 cm-1 in the FT-IR spectra of NiO

nanoparticles assigned to Ni–O stretching [10, 12, 18, 19, 21, 22]. The existence of a

free precursor is ruled out due to the absence of stretching vibrations of CH, C=N

and other groups of the ligand.

Thermal behavior (TG) of the complex has been studied under N2 atmosphere

from room temperature to 800 �C with the heating rate of 20 �C/min. The TG/DTA

plot is presented in Fig. 2. Temperature-dependent mass losses (experimental and

calculated) are summarized in Table 1.

Figure 3 shows the XRD pattern (10 \ 2h\ 80) of the NiO nanoparticles. The

diffraction peaks can be indexed to the pure NiO cubic phase [21, 22]. The

Preparation of nickel oxide via dinuclear nickel(II) Schiff base complex 359

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crystallite size (Dc) is calculated using the Debye–Scherre formula Eq. (1) from the

major diffraction peak of the NiO nanoparticles.

Dc ¼ 0:89k=bcosh ð1Þ

Where k is the X-ray wavelength used in XRD (here 1.5418 A), b is the pure

diffraction broadening of a peak at half-height, and h is the Bragg angle. Thus, the

average diameter of the NiO nanoparticles is found as 15 nm.

Fig. 1 FT-IR spectra of Ni(II) complex (a) and NiO nanoparticles (b)


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The morphology and microstructure of the NiO nanoparticles were further

investigated using SEM and TEM. Figure 4 shows the SEM and TEM images of the

NiO nanoparticles obtained from dinuclear nickel(II) Schiff base complex,

[Ni2(Brsal-1,3-ph)2], using solid state thermal decomposition at 450 �C for 3 h.

Studies show the particle size of NiO nanoparticles is about 5–15 nm. The particles

are both spherical and cubic.

Fig. 2 The TG/DTA graph of the Ni(II) complex

0

1000

2000

3000

4000

5000

6000

20 30 40 50 60 70 80

Fig. 3 XRD patterns of NiO nanoparticles obtained from [Ni2(Brsal-1,3-ph)2]

Table 1 Mass loss as a function of temperature of the Ni(II) complex

Steps T (�C) TG mass loss (%) calcd. (found) Assignments

Step 1 29–391 14.18 (12.06) C6H6

Step 2 391–665 71.65 (74.56) C14H10N2OBr2

Residual 665–744 14.02 (13.36) NiO


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The choice of complexes as precursor is a key step in the preparation of NiO

nanoparticles [9, 20, 23–25]. In Table 2, some of the precursors used in this method

are compared with the present work. According to these results, NiO nanoparticles

were synthesized successfully with suitable conditions and small size.

Fig. 4 a SEM and b TEM images of NiO nanoparticles

Table 2 Comparison of particle size of NiO nanoparticles by thermal decomposition method of Ni(II)

Schiff base complexes

Sample Precursor T (�C) Reaction time (h) Particle size (nm)

according to XRD results

Ref

1 [Ni(salen)] 500 5 15–20 [23]

2 [Ni(Brsalph)(NO3)] 550 3.5 55 [24]

3 [Ni(Salophen)] 550 3.5 35 [25]

4 [Ni(Me-salophen)] 550 3.5 70 [25]

5 [Ni(NH3)6](NO3)2 200–400 1 12 [20]

6 [Ni(en)3](NO3)2 200–400 1 15 [9]

7 [Ni2(Brsal-1,3-ph)2] 450 3 5–10 This work


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Conclusion

Pure and nanosized NiO nanoparticles with an average size of 5–10 nm have been

successfully prepared by solid state thermal decomposition (at 450 �C for 3 h) of

dinuclear [Ni2(Brsal-1,3-ph)2] complex as a new precursor. We have been able get

uniform NiO nanoparticles with narrow size. This method is facile, inexpensive,

nontoxic, and can be extended for the preparation of other transition metal oxide

nanoparticles. To the best of our knowledge, this is a rare report on the synthesis of

NiO nanoparticle from asymmetric dinuclear Ni(II) Schiff base complex.

Acknowledgments A. D. Khalaji and M. Nikookar are grateful to the Council of Iran National Science

Foundation and Golestan University for financial support.

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