Materials Letters 67 (2012) 128–130

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

An eco friendly and solvent free method for the synthesis of Zinc oxide nano particles
using glycerol as organic dispersant
M. Saravanan a, S. Dhivakar a, S.S. Jayanthi a, b,⁎
a
Department of Chemistry, B.S. Abdur Rahman University, Chennai-48, Tamil Nadu, India
b
Department of Chemistry, Guru Nanak College, Velachery, Chennai-42, Tamil Nadu, India

a r t i c l e i n f o a b s t r a c t

Article history: Zinc oxide nano particles can be synthesized using a simple solvent free, economic and eco friendly combus-
Received 21 June 2011 tion method. The structural characterization of synthesized nano particles are carried out using XRD and SEM.
Accepted 1 September 2011 The optical characterization was carried out using UV and Photoluminescence spectrofluorimeter. The XRD
Available online 10 September 2011
result shows that the nano particles are of hexagonal shape and the average crystal size of the Zinc oxide
nano particle is in the range of 70 nm. The SEM analysis shows that the shape of the nano particles is of
Keywords:
Nano particles
nano rods. The quality and purity of the Zinc oxide nano particles are confirmed using XRD and EDAX spectral
XRD analysis analysis.
Luminescence and optical properties © 2011 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental

The wide band gap semi conductor nano materials are area of cur-
rent interest due to their potential application in opto electronic and
micro electronic devices [1]. Zinc oxide nano particles are one of the
promising candidates for wide range of application due to its wide
band gap [2] of 3. 37 eV. These particles find application in the field
of hydrogen storage [3], field emitters [4], gas sensors [5], ultraviolet
lasers [6], solar cell [7] and photo catalysts [8]. In order to explore the
thorough application of these particles, we need a simple, economic
and eco friendly method for the synthesis of nano particles.
There are various methods used to synthesize Zinc oxide nano
particles of controlled size and shape. Some are soft chemical [9], mi-
crowave thermal evaporation [10], hydrothermal [11], vapor phase
transport [12], electrochemical deposition [13] pulsed laser deposi-
tion [14], thermal oxidation [15] and also by solid state method [16].
Combustion synthesis technique requires the use of an organic
compound like urea to initiate the reaction with oxygen [17]. The re-
action is economical and fast, but it may lead to new morphology or
even different compounds. The combustion synthesis of Zinc oxide
nano particle using urea as an organic dispersant and water as solvent
was already studied [18] and drawback in that method is to control
the highly exothermic reaction of urea and oxygen. The simple, eco-
nomic and eco-friendly synthesis of Zinc oxide nano particle using
minimum amount of glycerol as organic dispersant without the
solvent was reported here for the first time.
⁎ Corresponding author at: Department of Chemistry, B.S. Abdur Rahman University,
Chennai-48, Tamil Nadu, India. Tel.: + 91 9444641125; fax: + 91 044 22750520.
E-mail address: ajaya69@yahoo.com (S.S. Jayanthi).
The following analytical grade materials were used without fur-
ther purification: Zinc nitrate hexa hydrate Zn(NO3)2.6H2O. A.C.S. re-
agent (Sigma-Aldrich, 99% purity by wt) and the Glycerol
(anhydrous) were obtained from Merck (99%).
2.1. Synthesis of Zinc oxide
About 6.5 g of the Zinc nitrate hexa hydrate was weighed and made
in to a paste with 2 drops of glycerol in a 50 ml silica crucible. The
amount of glycerol used was optimized after several trials. The excess
glycerol leads to charring of substances. The initial temperature was
set to 50 °C and the temperature was slowly raised to 300 °C in the muf-
fle furnace. The substance is calcinated at 300 °C for 4 h. The white crys-
talline Zinc oxide powder obtained was characterized.
2.2. Characterization
The surface morphology of the synthesized nano particle was
characterized using SEM analysis. The scanning electron microscope
used for this purpose is a Jeol-JSM-3.5 CF-Japan. The elemental analy-
sis was determined using the Energy dispersive X-ray analysis
(EDAX) technique. The powder X-ray diffraction was performed
using Scifert X-ray diffractometer with a CuKα radiation. The dif-
fracted intensities were recorded from 10 to 70° angle. The average
grain size of Zinc oxide nano rods was estimated using Scherrer equa-
tion. The absorption and emission spectra were recorded using Perkin
Elmer LS 25 spectrophotometer and Perkin Elmer LS 45 spectro fluo-
rimeter respectively. For the spectroscopic analysis, Zinc oxide sam-
ple was dispersed in HPLC methanol with the help of the sonicator.

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.09.009
 M. Saravanan et al. / Materials Letters 67 (2012) 128–130 129

The Zinc oxide nano particles are sonicated in methanol for 10 min.
The spectrum was recorded under room temperature.

3. Results and discussion

3.1. Structural characterization and morphology

The structural characterization was carried out using powder XRD.

Fig. 1 shows typical XRD pattern of the as-obtained nano particles. All
the diffraction peaks can be well indexed to the hexagonal phase of
ZnO reported in JCPDS card .No. (JCPDS-89-1397).
The analysis of powder XRD pattern at room temperature shows
that the sample formed is single phase with the hexagonal symmetry.
The absence of extra peak claims the purity of the substance and also
the complete conversion of Zinc nitrate. The crystalline size of the
sample was obtained from Scherer's formula.

D ¼ 0:9λ=Bcosθ ð1Þ

´
where λ is the X-ray wavelength (1.5418 Å), B is the full width at the
half maxima of the Zinc oxide and θ is the diffraction angle. The aver-
age crystalline size calculated was around 78 nm. From the above re-
sults obtained, it is clear that the synthesis of nanoparticle becomes
simple using this method.
The surface morphology of the resulting powder was examined
using scanning electron microscope. The SEM micrographs of the
ZnO powder shown in Fig. 2 represent the formation of Zinc oxide
nano particle in single phase and the constituents are nano rods.
The nano rods grown even up to the length of 10 μm.
The EDAX analysis spectrum reported in Fig. 3 clearly reveals the
composition of Zinc and oxygen is of the order of 1:1. The atom per-
centage is 50.22 and 49.78 for Zinc and oxygen respectively. The ab-
sence of any extra peak in the EDAX spectrum shows the formation
Fig. 2. A & B. SEM micrograph of the Zinc oxide nano particle.
of pure Zinc oxide nano particles.
3.2. Optical characterization
3.1.1. Mechanism
At lower temperature, zinc nitrate is first converted to zinc perox-
The white crystalline Zinc oxide powder was not soluble in water
ide which on further heating by raising the temperature becomes
and almost in all organic solvents. Hence UV–Visible spectra was
Zinc oxide
recorded for the Zinc oxide dispersed in methanol solution and is
represented in Fig. 4. The absorption band observed at 301 nm is
ZnðNO3 Þ2 →ZnO2 þ 2NO2
the characteristic peak of Zinc oxide nano material.
The absorption peak is shifted to shorter wavelength compared to
2ZnO2 →2ZnO þ O2 :
the bulk Zinc oxide whose absorption maximum [19] occurs 373 nm.
The advantages in the above reaction are no solvent, no solid
byproducts, economic and eco friendly. The role of the glycerol is to
act as an organic dispersant to overcome the agglomeration.

Quantitative Results B
Element Net Weight % Atom %
Counts
O 12411 19.52 49.78
Zn 53964 80.48 50.22
Total 100.00 100.00

Fig. 1. XRD spectrum for the Zinc oxide nano particle. Fig. 3. The EDAX spectrum for the Zinc oxide nanoparticle.
130 M. Saravanan et al. / Materials Letters 67 (2012) 128–130

800.0
700
600
500
400
300
200
100
0.0
340.0 400 450 500 550 600.0
nm

Fig. 5. The fluorescence spectrum of Zinc oxide nanoparticle using methanol as solvent.

the direct combustion of Zinc nitrate in the presence of minimum

Fig. 4. UV–Visible spectrum of Zinc oxide nano particle by calcinations at 300 °C using
methanol as solvent.
This blue shift is due to the decrease in the size effect of nano struc-
tures. The approximate band gap value calculated from the λmax
value using the formula given below
amount of glycerol as organic dispersant.. The SEM analysis tells us
about the morphology of the particle which are of nano rods. The
XRD analysis reveals that the zinc oxide formed is of hexagonal
close packing. The absence of extra peak in the EDAX analysis and
the XRD spectrum reveals the purity of the compound. The character-
istic peaks in the absorption and emission spectrum confirms the for-
mation of Zinc oxide nano particle.
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