Available online at www.sciencedirect.

com

ScienceDirect
Materials Today: Proceedings 4 (2017) 11690–11695 www.materialstoday.com/proceedings

ICNANO 2016

Photocatalytic Degradation of Methylene Blue by Nickel Oxide

Nanoparticles
G. Jayakumar*, A. Albert Irudayaraj†, A. Dhayal Raj‡
PG and Research Department of Physics, Sacred Heart College (Autonomous), Tirupattur - 635 601,Vellore District, Tamil Nadu, India

Abstract

NiO nanoparticles were synthesized by a chemical precipitation method using nickel nitrate as precursors and Sodium hydroxide
as precipitating agent. The NiO nanoparticles have been successfully used as a photocatalyst for degradation of Methylene Blue
dye from the aqueous medium. The synthesized nanoparticles were studied by powder XRD, FESEM, EDAX and FTIR
spectroscopy. The powder XRD result revealed that the obtained samples were nickel oxide with face centered cubic structure.
The particle size and the morphology of NiO nanoparticles were studied by the FESEM. The EDAX and FTIR analyses
confirmed the formation of NiO nanoparticles. The Photocatalytic degradation study results revealed that the NiO nanoparticles
are potential photocatalyst in degradation of Methylene blue.
© 2017 Elsevier Ltd. All rights reserved.
Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON NANOTECHNOLOGY (ICNANO-
2016).

Keywords: Methylene Blue; Photocatalytic degradation; EDAX; Face centred cubic.

1. Introduction

Wastewater treatment process is an increasing serious challenge for the whole world. Due to this reason, the
proficient treatment of wastewaters has attracted major attentions among researchers to solve the problem. Several
methods for removal of the dye contaminants from wastewater including photocatalytic degradation, adsorption,
coagulation/flocculation, advanced oxidation processes, ozonation, membrane filtration and biological treatments

*
Corresponding author.
E-mail address: gjayaphysics@gmail.com
†
airshc@gmail.com
‡
dhayalraj03@gmail.com

2214-7853 © 2017 Elsevier Ltd. All rights reserved.

Selection and Peer-review under responsibility of INTERNATIONAL CONFERENCE ON NANOTECHNOLOGY (ICNANO-2016).
 G. Jayakumar et al. / Materials Today: Proceedings 4 (2017) 11690–11695 11691

have been developed and use [1]. Amongst which, photocatalytic degradation has been recognized as the most
popular treatment process in aqueous solution with the advantages of high efficiency and simple operation. In the
past two decades, photocatalytic degradation of organic pollutant by semiconductor oxide such as TiO2, ZnO, NiO,
SnO2, Cu2O, and In2O3 has attracted due to their high photo-catalytic efficiency, low cost and low toxicity, high
physical and chemical stability, especially, strong ability of fully decomposing organic pollutant into harmless
species [2-7]. These days, much attention has been focused to synthesize high-quality and ultra-fine powders with
the required characteristics in terms of their size, morphology and microstructure. NiO can be prepared through
various methods, such as the sol-gel route, microwave and hydrothermal route, chemical co-precipitation method,
reflux method, thermo chemical process, etc [8-12]. In this work, an attempt has been made to synthesize NiO by
co-precipitation method and study the photocatalytic degradation of Methylene Blue dye from the aqueous medium
by the synthesized NiO nanoparticles in solar irradiation.

2. 2. Experimental details

2.1. Materials

All of the Chemicals used in this work were analytical grade reagents and used without further purification.
Nickel nitrate (Ni (NO3)2.6H2O) was used as precursor and sodium hydroxide (NaOH) was used as a precipitating
agent. Deionized water was used to prepare all solutions.

2.2. Preparation of Nickel Oxide nanoparticles

NiO nanoparticles were synthesized by chemical co-precipitation method. 0.5M Nickel nitrate precursor solution
1M aqueous sodium hydroxide solution was added. The mixture was stirred for 2 hrs at room temperature. The
resulting precipitate was washed to remove the Na ions and dried in air at 80ºC. This dried sample was grinded and
calcinated at 700ºC for 2 hours.

2.3. Characterization

The XRD measurements were carried out using Rigaku X-ray diffractometer with CuKα (λ = 1.54187Å) radiation
in the range of 30° – 80° at room temperature. The size and the morphology of the samples were characterized by
Field emission scanning electron microscopy. The infrared spectra (FTIR) were recorded in the range of 400- 4000
cm-1 on a Perkin-Elmer Spectrum II FT-IR spectrometer. The elements presents in the sample were identified by FEI
QUANTA FEG 250 Microscope. The Magnetic behaviour of the sample was carried out by the Vibrational Sample
Magnetometer.

3. 3. Result and discussion

3.1. The X-ray powder diffraction

Powder X-ray diffraction, which is the most useful technique for phase identification, was employed to
investigate the crystallinity and structure of the prepared samples. The XRD patterns of NiO nanoparticles are shown
in fig. 1. It is clear, without any observable peaks of impurity phases. The peaks are indexed using JCPDS (Card No.
47-1049). The NiO is found have face centered cubic structure with lattice parameter a = b = c = 4.177 Å. The
average crystallite size (D) is determined from the major peaks of the reflections employing the Debye-Scherer
equation

11692 G. Jayakumar et al./ Materials Today: Proceedings 4 (2017) 11690–11695

Where, λ is the wavelength of the X-ray radiation, K is a constant and its value is taken as 0.9, θ is the diffraction
angle and β is the full-width at half- maximum (FWHM). The average crystallite size is found 25 nm. This
observation is in agreement with the earlier report [13].

(200)
(111)
Intensity (a.u)

(220)

(311)
(222)
30 40 50 60 70 80
2θ (Degree)

Figure.1. Powder XRD patterns of NiO nanoparticles

3.2. FESEM Analysis

The morphology of the prepared NiO nanoparticles has been investigated using Field Emission Scanning Electron
Microscope. The FESEM images of NiO nanoparticles as shown in fig. 2. The NiO nanoparticles have oval shaped
particles with average particle size of 64 nm.

Figure. 2. FESEM image of NiO nanoparticles

3.3. Energy dispersive X-ray analysis

The EDX spectra of NiO nanomaterial is shown in fig. 3. The results of quantitative analysis of the NiO
nanomaterial is given in table 1. The result confirms the presence of Ni and O in the synthesised NiO nanomaterial.
 G. Jayakumar et al. / Materials Today: Proceedings 4 (2017) 11690–11695 11693

cps/eV

4 O Ni Ni

0
1 2 3 4 5 6 7 8 9 10
keV

Figure. 3. EDAX spectra of NiO nanomaterial

Table 1. Quantitative analysis of the NiO nanomaterial

Atomic unn. C norm. C Atom. C Error 1 Sigma

Elements Series
number [wt.%] [wt.%] [at.%] [wt.%]
Ni 28 L-series 72.47 72.47 41.78 12.10
O 8 K-series 27.53 27.53 58.22 5.66

3.4. FTIR Analysis

Transmittance (a.u)

1160
2351
3432

884
1590

4000 3500 3000 2500 2000

1500 1000 500
w avenum ber ( cm -1 )

Figure. 4. FTIR Spectra of NiO nanoparticles

The FTIR spectra of NiO nanoparticles are shown in fig.4. The broad absorption band around 884 cm-1 is due to
the Ni-O stretching vibration. The broadness of the absorption band indicates that the NiO powders are nanocrystals [14].
The broad absorption peak around 3432 cm-1 is due to the stretching vibrations of OH-group and the band at
11694 G. Jayakumar et al./ Materials Today: Proceedings 4 (2017) 11690–11695

1599 cm-1 is due to H-O-H bending vibrations of water present in moisture adsorbed from atmosphere when FTIR
samples were prepared in open air. The bands at 2352 cm-1 and the bands in the region 1000-1500 cm-1 are due to the
antisymmetric stretching and symmetric stretching mode of vibrations of CO2 molecule adsorbed from air [15 - 16].

3.5. VSM Analysis 0.003

0.002
Moment (emu/g)
0.001

0.000

-0.001

-0.002

-0.003
-15000 -10000 -5000 0 5000 10000 15000
H (Oe)

Figure. 5. Magnetization curve of NiO nanoparticles

The magnetization hysteresis loops recorded at room temperature for NiO nanoparticles are shown in fig.5. The
measured value of saturation magnetization (Ms) is 0.0023 emu/g remnant magnetization (Mr) is 0.088 x 10-3 emu/g,
and coercive field (HC) is 382.69 Oe for NiO nanoparticles. The magnetic measurement shows that the NiO
nanoparticles exhibit low saturation magnetization and super-paramagnetic properties at room temperature.

3.6. Photocatalytic Degradation Analysis

0.75

0 minutes

0.50
Absorbance (a.u)

150 minutes
0.25

0.00

500 550 600 650 700 750

Wavelength (nm)

Figure. 6. The absorption spectra of the MB solution in presence of NiO catalyst under solar light irradiation.
 G. Jayakumar et al. / Materials Today: Proceedings 4 (2017) 11690–11695 11695

Figure 6 shows photocatalytic activities of NiO nanoparticles were analysed through Methylene blue degradation
experiment in solar light. An aqueous solution of Methylene blue (1× 10-5 M) was mixed well with 0.031g NiO
catalyst in a glass beaker containing 500 ml double distilled water. The suspension thus obtained was kept under
solar light without stirring. During irradiation, the degraded dye was sampled in regular intervals of 30 minutes and
then centrifuged. The photo- catalytic degradation was monitored by measuring the sample absorbance with a UV
spectrophotometer. The absorption spectra clearly show that when exposed to solar radiation the degradation of
Methylene Blue (MB) from the aqueous medium increases as the reaction time increases. The results clearly indicate
that NiO nanoparticles act as photocatalyst in degradation of Methylene blue from the aqueous medium.

4. Conclusion

NiO nanoparticles are successfully prepared by chemical co-precipitation method. The powder X-ray diffraction
patterns exhibit face centered cubic phases for the synthesized NiO nanoparticles. The FESEM images of the
prepared samples indicate that the NiO nanoparticles have oval shaped morphology. The formation of NiO is
confirmed from the EDX and FTIR analyses. The amounts of different elements present in the synthesized samples
are also estimated and the samples are found to be nearly stoichiometric. VSM studies reveal that the NiO
nanoparticles exhibit super paramagnetic behaviour at room temperature. The Photocatalytic degradation study
results reveal that the NiO nanoparticles act as photocatalyst in degradation of Methylene Blue.

References

[1] F. Farzaneh, Z. Asgharpour, Journal of Sciences, Islamic Republic of Iran, 2014, 25(2), 111- 118.
[2] Wang Zhengpeng, Gong Wenqi, Hong Xiaoting, Cai Weimin, Jiang Juhui, Zhou Baoxue, Journal of Mater. Sci. Ed, 2006, 21(4), 71 – 78.
[3] Mohammad Amdad Ali, Mahmudur Rahman Idris, Md Emran Quayum, Journal of Nanostructure in Chemistry, 2013.
[4] Khizar Hayat, M.A. Gondal, Mazen M. Khaled, Shakeel Ahmed, Journal of Molecular Catalysis A: Chemical, 2011, 336, 64 -71.
[5] Elango G, Roopan S M, Journal of Photochemistry and Photobiology B, 2016, 155:34-8.
[6] Rao, Martha Purnachander, Anandan, Sambandam, Suresh, Sivan; Asiri, Abdullah M., Wu, Jerry J, Journal of Energy and Environment
Focus, 2015, 4(3), 250-255.
[7] Hossein Salavati, Hamide Saedi, Journal of Electrochem. Sci., 2015, 10, 4208 – 4222.
[8] M. Alagiri, S. ponnusamy, C. Muthamizhchelvan, Journal of Master Electron, 2012, 23, 728-732.
[9] Subhash Thota, Jitendra Kumar, Journal of physics and chemistry of solids, 2007, 68, 1951-1964.
[10] G. Anandha Babu, G. Ravi, M. Navaneethan, M. Arivanandhan, Y. Hayakawa, Journal of Mater sci: Master Electron, 2014, 25,5231-5240.
[11] A.K. Mishra, S. Bandyopadhyay, D. Das, Journal of Materials Research Bulletin, 2012, 47, 2288-2293.
[12] Miaomiao Liu, Jie Chang, Jing sun, Lian Gao, Journal of Elecrochimica Acta , 2013, 107, 9-15
[13] K. Karthik, G. Kalai selvan, M. Kanagaraj, S. Arumugam, N. Victor Jaya, Journal of Alloys and Compounds, 2011, 509, 181-184.
[14] Zhiqiang Wei, Hongxia Qiao, Hua Yang, cairong Zhang, Xiaoyan Yan, Journal of Alloys and compounds, 2009, 479, 855-858.
[15] Sukhdeep Singh, Manpreet singh, N. K. Ralhan, R. K. Kotnala, Kuldeep Chand Verma, Adv. Mat. Lett., 2012, 3(6), 504-506.
[16] Kwanruthai Wangsaprom, Santi Maensiri, Chiang Mai, Journal of Science, 2013, 40(1), 99-108.