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Synthesis and Characterization of MnO 2 and CdO

Nanoparticles

Article in Journal of Computational and Theoretical Nanoscience · May 2012

DOI: 10.1166/asl.2012.2191

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Taimur Athar N. Topnani

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 RESEARCH ARTICLE
Copyright © 2012 American Scientific Publishers Advanced Science Letters
All rights reserved
Printed in the United States of America
Vol. 5, 1–4, 2012

Synthesis and Characterization of

MnO2 and CdO Nanoparticles
Taimur Athar1 , Neha Topnani1 , Abdul Hakeem1 , and Waqar Ahmed2 ∗
1
Indian Institute of Chemical Technology, Tarnaka, Hyderabad (A.P.), 500-007, India
2
Institute of Nanotechnology and Bioengineering, University of Central Lancashire, United Kingdom

Synthesis of cost-effective colloidal Manganese dioxide and Cadmium oxide nanoparticles has been carried out
quantitatively with monodispersity and controlled particle properties via soft chemical approach. The charac-
terization of as synthesized nanoparticles was carried out with the help of FT-IR, UV-visible, TGA/DSC, XRD,
SEM-EDX, TEM and BET. The optical band gap is used in order to determine a relationship between energy
band gaps in the nanomaterials with respects to bulk. The particle size increases with calcination which leads
to improved properties having a refined crystallinity after the removal of surface impurities. It is concluded that
the particle properties can be controlled with the help of temperature, the amount of alkali used, reaction aging
and the nature of solvents used.

Keywords: Cost-Effective, Chemical Approach, Crystallinity, Particle Properties.

1. INTRODUCTION
There is a great research interest for the synthesis of metal-oxide
nanaoparticles due to their potential applications in electronic,
optical and mechanical devices based on variable oxidation
states. Different methodologies are used to synthesize metal-
oxide nanopowder but reported procedures have limited control
on the particle functionality. So it is an urgent need to modify
the cost-effective procedure in chemical and environment friendly
approach.
These nanoparticles are of great importance because of their
unique properties like large surface to volume ratio, high crys-
tallinity, chemical purity, and phase selectivity which are differ-
ent from their bulk counter part. It has been reported that the
physical and chemical properties are relative to its stoichiometry
as well as particle size and shape. Manganese dioxide and Cad-
mium oxide nanoparticles are potentially used in various fields
such as electrodes,1 catalysis,2 sensors3 and in optoelectronics.4
Various methods have been used for the synthesis of MnO2
and CdO nanoparticles such as, Thermal process,5 Precipitation
method,6 Sonochemical method7 and microemulsion4 8 but these
methods have limited control to achieve technological grade par-
ticles for their industrial applications and these procedure are
not cost-effective and complex approach is involved which are
not environmental friendly. As we know the physical and chem-
ical properties depends on size of the particles. We report here
the synthesis of colloidal MnO2 and CdO nanoparticles in good
∗
Author to whom correspondence should be addressed.
yield via soft chemical approach with better control on particles
size, shape, crystallinity and better surface properties with homo-
geneity. MnO2 and CdO nanoparticles were characterized after
calcination at 450  C for four hours in the presence of an inert
atmosphere.
2. EXPERIMENTAL DETAILS
2.1. Nanoparticle MnO2 Synthesis
Solution was prepared by adding KOH (3.00 g, 53.47 mmol) and
MnCl2 · 4H2 O (4.23 g, 21.37 mmol) in 50 mL mixture of hexane
and benzene. The resulting solution was continuously stirred for
two hours and then refluxed for another 17 hours. The solution
was filtered, washed with a mixture of methanol and hexane till
pH becomes neutral. It was then oven dried at 150  C and sub-
sequently calcinated at 450  C for four hours in nitrogen atmo-
sphere which resulted in the formation of brown nanopowder
after removal of surface impurities.
Benzene
MnCl2 · 4H2 O + 2KOH −−−−→ MnO2 + 2KCL + 4H2 O + H2
Hexane
2.2. Nanoparticle CdO Synthesis
The calculated amount of KOH (3.28 g, 58.46 mmol) was dis-
solved in 17 mL distilled water and mixed with CdCl2 · 2H2 O
(4.70 g, 23.32 mmol). The solution was stirred for 2 hours and
then refluxed for 20 hours. Solution was filtered, washed with
distilled water till neutralization point was achieved and then
dried in oven at 150  C. A white nanopowder was obtained in
quantitative yield which was further calcinated at 450  C for four

Adv. Sci. Lett. Vol. 5, No. xx, 2012 1936-6612/2012/5/001/004 doi:10.1166/asl.2012.2191 1

RESEARCH ARTICLE
hours in nitrogen atmosphere which resulted in the formation of
brick-red nanopowder with high purity after removal of surface
impurities.
Distilled
CdCl2 · H2 O + 2KOH −−−−→ CdO + 2KCL + 2H2 O
water
2.3. Characterization
The structural and morphological characterization of MnO2 and
CdO nanoparticles were carried out with the help of following
techniques as discussed. FT-IR spectra were recorded at room
temperature in the range of 4000 to 400 cm−1 by using KBr
pellets in a Perkin-Elmer Spectrometer GX model. UV-visible
diffuse reflectance spectra UV-DRS were recorded on a GBC
UV-visible Cintra 10/20/40 spectrometer on dry-pressed disk
solid-samples using KBr as dilutor and pure KBr as the reference
in the range of 200–800 nm with a scan speed of 20 nm per
minutes. The phase purity was confirmed by thermal transforma-
tion pattern studied by TG-DSC (Mettler Toledo stare, Columbus,
OH) in air, with a heating rate of 10 /min from ambient tempera-
ture to 1000  C. X-ray powder diffraction patterns were taken in
reflection mode CuK ( = 15406 Å) radiation in the 2 range
from 0 to 80  C on a Seimens (Cheshire, UK) D 5000 X-ray
diffractometer by continuous scanning with a step size of 0.01 .
Scanning electron microscope (SEM) images were obtained on
a Hitachi S520 scanning electron microscope. EDX was taken
in an Oxford link ISIS-300 instrument. The morphologies were
investigated with a Philips Tecnai G2 FEI F12. Transmission
Electron Microscope operated at 80–100 KV. The samples were
prepared by loading a hexane-suspension onto a formvar-coated
copper grid. The BET surface area analysis was done in an
AUTOSORB 1 t under nitrogen atmosphere after degassing the
samples at 200  C for 1 h. All the other solvents and chemi-
cals were obtained from commercial sources and purified using
standard methods.9
3. RESULTS AND DISCUSSION
A novel and facile synthesis of colloidal Manganese dioxide and
Cadmium oxide nanopowder with small particle size having large
surface was synthesized in clean methodology without using any
reducing agent or capping agent. In both cases the concentra-
tion of KOH solutions and the reaction temperature played an
important role in the formation of metal oxide nanostructures
with different morphologies and controlling particle properties.
3.1. FT-IR
FT-IR spectrum corresponds to Manganese oxide and Cadmium
oxide nanoparticles respectively. The stretching and bending
frequencies have been used to confirm the formation of par-
ticles. The presence of three strong and significant peaks at
624.58 cm−1 , 521.79 cm−1 and 411.93 cm−1 which reveals the
presence of three types of M–O stretching, bending and wag-
ging frequencies respectively. The IR spectra does not have
strong M–O stretching frequencies, however a weak peak was
observed at 480 cm−1 which corresponds to the M–O stretching
frequencies, However medium range broad peak was observed
at 1139 cm−1 which attributes to the presence of asymmetric
M–O bond frequency.10 MnO2 and CdO nanoparticles after cal-
cination exhibits the aging phenomenon has limited role for
agglomeration.
2
Adv. Sci. Lett. 5, 1–4, 2012
3.2. UV-Vis Absorption
UV analysis has been carried out to investigate optical properties
of nanoparticles after calcination at 450  C. The MnO2 nanopar-
ticle does not show any significant transmittance and absorbance
due to small particle size. The peaks at 242 nm and 292 nm
support the presence of cadmium oxide nanoparticles with small
particles size. In both cases the band gaps exhibit a blue shift sup-
porting the quantum confinement effects of nanoparticles.11 The
intensity of absorption increases in the ultra violet region with
increase of temperature due to increase in particle size. The dif-
ference in band gap originates from the metal used with oxygen
vacancies which strongly depends on the synthesis procedures.
3.3. TGA and DSC
TGA-DSC reveals that Manganese dioxide and Cadmium oxide
nanoparticles respectively. A peak at 142  C indicates the
removal of water and further weight loss at 590  C, 710  C and
790  C which shows the removal of organic moieties. Subse-
quently there after no weight loss was observed and a sharp peak
was observed at 941  C supports to crystallization. In DSC an
endothermic peak at 170  C support the removal of water. DSC
graph support the formation of crystallinity at the same temper-
ature. The presence of endothermic peaks indicates the change
of phase. First weight loss was observed at 325  C which shows
the removal of water and organic moieties. At 525  C limited
weight loss was observed due to impurities present in the gel
and then leads to crystalline temperature at 910  C. DSC analy-
sis favors the presence of well-defined particles at 940  C.12 All
other peaks relates to the removal of impurities from the particle
surface.
3.4. XRD
The diffractogram peaks was compared with JCPDS data to iden-
tify the crystallographic phase of the particle. The XRD pattern
as shown in Figures 1(a and b) corresponds to Manganese diox-
ide and Cadmium oxide nanoparticles respectively. Figure 1(a)
shows sharp diffraction peaks which correspond to JCPDS card
number 44-0141. Figure 1(b) shows various diffraction peaks
which correspond to JCPDS card number 05-0640. The MnO2
and CdO particles size was calculated by using Scherer equation
which was found to be 33 nm in both particles. The presence
of sharp peaks shows existence of well-crystalline particles as
Lin (Counts)
(b)
(a)
2 10 20 30 40 50 60
2-Theta-Scale
Fig. 1. XRD Pattern for (a) MnO2 and (b) CdO nanoparticles after
calcination.
Adv. Sci. Lett. 5, 1–4, 2012 RESEARCH ARTICLE

supported by thermal analysis. It support that the presence of (a)

crystalline phase takes place without any increase in grain size.
The broad diffraction lines support nanosized structure. MnO2
nanopowder was found to be tetragonal and CdO nanoparticles
were found to be cubic. It is concluded that the growth rate plays
an important role in defining the shape of the particles with the
help of synthetic methodology. The presence of sharp peaks sup-
ports the preferential growth with high purity crystalline prod-
ucts. The diffraction peaks for both samples are almost same
supporting their paramagnetic behavior.13

3.5. SEM-EDX
SEM images of Manganese dioxide and Cadmium oxide
nanoparticles as shown below exhibit the agglomeration occurred
during the synthesis process due to the presence of Van der Waals
forces: Figure 2(a) shows that the particles are very clear with
regular shape with good crystallinity. Figure 2(b) shows the par-
ticles are fluffy with agglomeration without use of surfactant.
On calcination the degree of agglomeration is decreased with an
increase in particle size. The ratio of metal and oxygen as calcu-
lated with the help of EDX which was found to be 1:2 and 1:1 for (b)
Manganese dioxide and Cadmium oxide respectively. It is con-
cluded that the product in nanometer range exhibit air sensitivity
in the absence of surfactant.8 14

3.6. TEM
TEM images have been shown in Figures 3(a and b) corresponds
to Manganese dioxide and Cadmium oxide nanoparticles respec-
tively. XRD studies support the shape and size of as-synthesized
metal oxide nanoparticles with limited degree of agglomeration.
MnO2 nanoparticles have tetragonal and CdO nanoparticles have

(a)

Fig. 3. TEM pictures for (a) MnO2 and (b) CdO nanoparticles after
calcination.

cubic geometry respectively. A SAED pattern shows the diffrac-

tion ring spot corresponds to phase selection with crystallinity,
which are supported by XRD. The modification of the synthetic
methodology leads to the formation of a small particle size. The
(b) broad diffraction reflects to the X-ray diffraction lines which are
in agreement with the TEM observations supporting the forma-
tion of very small particles size with monodispersity. The parti-
cles in the high ionic media lead to a formation of less sensitive
crystal phase due to ageing. Both the particles have good adsorp-
tion properties. It is concluded that pH and temperature have a
large impact on the formation of the particle in the nanometer
range.15

Fig. 2. SEM images for (a) MnO2 and (b) CdO nanoparticles after
calcination.
3.7. BET
Surface area of Manganese dioxide and Cadmium oxide nanopar-
ticles was calculated after calcination at 450  C with the help of
BET N2 -adsorption technique which was found to be 28.41 m2 /g
and 8.32 m2 /g respectively.5 16 The pore volume was found to
be .286 m3 /g and .316 m3 /g respectively. It was found that the

3
 RESEARCH ARTICLE
XRD crystallite size and BET particle size are in reasonably close
agreement.
4. CONCLUSION
In summary, Manganese dioxide and Cadmium oxide nanopar-
ticles have been synthesized via soft chemical approach with
controlled morphological and surface particle properties with the
size of about 33 nm in both cases. The chemically and struc-
turally well defined particles lead to a better understanding about
knowledge and structural properties which help in designing their
potential applications. The environmental friendly method has
been successfully used for the preparation of other metal oxide
for bulk production which will with extended to the functionality
and surface morphology. It is observed that during wet synthesis
the precursor plays a model role to control the degree of agglom-
eration and the average particle size and the increase in the band
gap depends on the quantum confinement effects in the nano-
materials. Soft synthesis provides the possibility of exploring the
potential in many applications.
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Received: 3 March 2011. Accepted: 25 September 2011.