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Copyright 2013 by American Scientic Publishers
All rights reserved.
Printed in the United States of America
Journal of Nanoengineering and Nanomanufacturing
Vol. 3, pp. 15, 2013
(www.aspbs.com/jnan)
Synthesis of SnO
2
Nano Rods and
Their Photocatalytic Properties
Jagannath M. Mali, Sudhir S. Arbuj, Jalindar D. Ambekar,
Sunit B. Rane, Uttamrao P. Mulik, and Dinesh P. Amalnerkar

Centre for Materials for Electronics Technology, Off Pashan Road, Panchawati, Pune 411008, India
ABSTRACT
Ultra thin single crystalline SnO
2
nano rods were synthesized using a novel template free chemical method.
The prepared SnO
2
nano rods were characterized using uv-visible and photoluminescence spectroscopy, BET,
XRD, FE-SEM and TEM analysis techniques. The broad XRD peak conrms the formation of nano crystalline
SnO
2
having tetragonal crystal structure. PL spectra exhibit the broad emission peak at 365 nm corresponding
to the band edge excitation. FE-SEM indicates the formation of SnO
2
nanostructures having size less than
10 nm. TEM conrms the formation of rod like morphology having diameter 41 nm and length around 6 to
10 nm. The observed BET surface area for the SnO
2
nanorods is 134 m
2
/gm and this higher surface area
exhibits excellent ability to remove organic pollutant from wastewater by enormous surface adsorption. The
photocatalytic activity of prepared SnO
2
was studied by observing the degradation of aqueous methylene blue
(MB) dye. The rate constant observed for photocatalytic MB degradation using SnO
2
was 5.410
2
min
1
. The
photocatalytic activity was compared with P-25 degussa TiO
2
under same reaction conditions.
KEYWORDS: Tin Oxide, Photocatalysis, Dye Degradation, Methylene Blue.
1. INTRODUCTION
As an important member in the family of wide-band
gap semiconductors, tin dioxide (SnO
2
) has been exten-
sively investigated due to their unique properties and novel
applications.
1
SnO
2
is having band gap of 3.6 eV, it is used
for gas sensors, optical sensors and photoconductors.
2, 3
At the same time, it has been widely used in photo-
catalysis, optoelectronic devices, lithium batteries, solar
cells and eld effect transistors.
47
Many studies have
proven that change in size, shape and morphologies greatly
enhances the optoelectronic properties of SnO
2
.
810
Partic-
ularly, one-dimensional (1D) nanostructures exhibit inter-
esting optoelectronic properties, associated with directional
mobility of charge carrier, a large aspect ratio, and the
quantum connement effect. Also two and three dimen-
sional (2D, 3D) such as sheets and hierarchical nano archi-
tectures exhibit unique properties different from those 1D
structures due to their complicated structures.
1113
In order
to synthesize desired morphology, variety of physical and
chemical methods such as chemical vapor deposition,
physical vapor deposition, solgel, combustion, hydrother-
mal and solvothermal techniques have been used.
1418
Utilizing these methods considerable effort has been

Author to whom correspondence should be addressed.

Email: amalnerkar@cmet.gov.in
Received: xx Xxxx Xxxx
Accepted: xx Xxxx Xxxx
devoted to fabricate various SnO
2
nanostructures includ-
ing nanorods, nanowires, nanobelts, nanosheets, hierarchi-
cal nanostructures and so on.
1923
However most of the
physical techniques require complicated controlling pro-
cesses which are unfavorable for inexpensive and large
scale synthesis. Therefore, it is of great importance and
necessity to develop a technique to synthesize SnO
2
under
ambient reaction conditions. However, the development of
template and surfactant-free low temperature routes for
the synthesis of ultrathin SnO
2
single crystalline nanorods
remains a challenge. For this purpose, hydrothermal is well
suited for synthesis of nanostructure materials, because
of its relatively low processing cost, much milder reac-
tion conditions and the ability to control the grain size.
In this study, we have synthesized SnO
2
nanorods using
hydrothermal method. The synthesized SnO
2
nanostructure
was characterized using different spectroscopic techniques.
The photocatalytic activity was evaluated by following the
degradation methylene blue (MB).
2. EXPERIMENTAL DETAILS
2.1. Synthesis of SnO
2
Nanostructures
In a typical synthesis, 10 mmol of stannic(IV) chloride
hydrated (SnCl
4
5H
2
O, Sigma-Aldrich), was dissolved in
a mixture of 30 mL of ethanol and 10 mL of deionized
(DI) water, these mixture was stirred for 5 min at room
temperature. To the above solution 0.7 g of NaOH was
J. Nanoeng. Nanomanuf. 2013, Vol. 3, No. 2 2157-9326/2013/3/001/005 doi:10.1166/jnan.2013.1116 1
Synthesis of SnO
2
Nano Rods and Their Photocatalytic Properties Mali et al.
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slowly added with constant stirring. After 10 min vigorous
stirring the mixture was transferred to teon lined auto-
clave, sealed and then heated in an oven at 160

C for 24 h.
The obtained product was washed several times with DI
water and dried at 50

C in oven. The dried powder was
grinded in an agate mortar and pestle and used for further
studies.
2.2. Characterization
The X-ray powder diffraction (XRD) pattern of the syn-
thesized material was recorded on Bruker AXS model
D-8, (10 to 70

range, scan rate = 1

min
1
) equipped
with a monochromator and Ni-ltered Cu Ko radiation.
Crystallite size was calculated using the Scherrers for-
mula, J =0.9\,Bcos 0 where \ is the incident wavelength
(Cu Ko = 1.5406 ), p is the full width at half max-
imum (FWHM) of the corresponding diffraction peaks,
and 0 is the angle of reection. Diffuse reectance UV-
Visible absorbance spectra was recorded using Shimazu
UV-Vis-NIR spectrophotometer (Model UV-3600) over a
wavelength range of 200 to 800 nm. The photolumines-
cence analysis was performed on shimadzu (RF-5301 PC)
spectrophotometer. The BET surface area was calculated
from the N
2
adsorption isotherms of the samples at liquid
N
2
temperature using Quantachrome NOVA-1200 instru-
ment. The morphological characterization of the samples
was performed on HITACHI S-4800. Transmission Elec-
tron micrographs were performed using Technai 20 G2
(FEI, Netherlands) microscope operating at 200 kV.
2.3. Photocatalytic Activity Study
For the evaluation of photocatalytic activity, 50 mg of pow-
dered SnO
2
was suspended in a 100 ml of aqueous MB
solution (10 ppm MB, pH = 7) in a 250 ml conical ask
and stirred for 15 min in dark at room temperature. Then
the mixture was continuously stirred under 400 W mer-
cury lamp irradiation in closed box. The mercury vapour
lamp was kept vertically in the quartz tube, provided with
the water circulation arrangement in order to minimize the
heating effect due to IR radiation. At regular intervals of
time, aliquots of aqueous solution were taken from the
ask, centrifuged and the UV-visible absorption spectrum
of clear solution was recorded using a double beam spec-
trophotometer. The decrease in the absorbance value at
664 nm wavelength, corresponding to the typical peak for
the absorption spectra of MB, was utilized to determine
the extent of degradation of MB and the photocatalytic
acitivity of the sample with respect to irradiation time.
3. RESULTS AND DISCUSSION
3.1. X-Ray Diffraction Analysis
The powder XRD pattern of the synthesized SnO
2
nano-
structures is shown in Figure 1. The diffraton peaks at
Fig. 1. X-ray diffraction of SnO
2
nanostructure.
20 =26.6, 33.9, 37.9, 51.8, 54.7, 57.8, 61.8 and 65.9

cor-
responds to the hkl planes of (110), (101), (200), (211),
(220), (002), (310) and (301), can be readily indexed
to a tetragonal structure of SnO
2
(JCPDS Card File
No. 41-1445) respectively. The broad and intense diffrac-
tion peaks suggest the formation of highly crystalline nano
sized SnO
2
material. The crystallite size calculated using
Scherrers formula was found to be around 4 nm.
3.2. UV-Visible and Photoluminescence Analysis
The UV-visible and diffuse reectance absorbance spec-
trum of SnO
2
nanorods was measured and the result is
depicted in Figure 2. The absorbance at 280 nm indicates
the formation of nano sized SnO
2
(bulk SnO
2
350 nm). The
blue shift conrms the quantum connement effect. DRS
shows the absorbtion edge around 360 nm corresponds
to the band gap 3.4 eV. The maximum absorbance is
observed at 280 nm in liquid as well as solid UV-Visible
absorbance spectra. The photoluminescence spectrum is
shown in Figure 3. For this purpose the SnO
2
powder was
dispersed in DI water and the spectra were recorded at
the excitation wavelength of 250 nm. The emission peak
observed at 365 nm can be attributed to the near band edge
emission. The other emission peaks were not observed
Fig. 2. UV-Visible and diffuse reectance absorbance spectra of SnO
2
nanostructure.
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Mali et al. Synthesis of SnO
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Fig. 3. Photoluminescence spectra of SnO
2
nanostructure.
at 250 nm excitation wavelength conrming formation of
defect free SnO
2
nanorods.
3.3. FE-SEM and TEM Analysis
The morphology and structure of SnO
2
nano structure
were further investigated by FESEM and TEM analysis.
FE-SEM images are depicted in Figure 4 which indicates
Fig. 4. FE-SEM micrographs of SnO
2
.
Fig. 5. TEM micrographs of SnO
2
nanostructures, inset of (a) is
HRTEM of SnO
2
and inset of (b) is SAED pattern of SnO
2
.
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Synthesis of SnO
2
Nano Rods and Their Photocatalytic Properties Mali et al.
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the uniformly distributed SnO
2
nanoparticles having size
below 10 nm. TEM conrms the formation of rod like
morphology having size in the range of 36 nm (Fig. 5).
The high resolution images clearly shows inter planar
spacing of 0.25 nm matching with (101) h, k, I plane of
tetragonal SnO
2
structure (inset of Fig. 5(a)). The SAED
pattern shown in the inset of Figure 5(b) conrms the
crystalline nature of SnO
2
nanoparticles and calculated J
values supports the XRD results.
3.4. Photocatalytic Activity
The photocatalytic activity of SnO
2
nanorods was mea-
sured by following the degradation of 10 ppm MB solu-
tion under 400 W mercury vapor lamp. The decrease in
the absorbance of MB with irradiation time is plotted in
Figure 6(a). The 93% of MB degradation was observed
using SnO
2
nanorods in 1 hrs of irradiation time. The
photocatalytic acitivity of SnO
2
was compared with P-25
degussa TiO
2
. P-25 TiO
2
showed higher activity than that
of the synthesized SnO
2
nanostructure. The reason for
lower photocatalytic acitivity of SnO
2
is due its higher
band gap as compare to TiO
2
. As the photocatalytic dye
degradation follows pseudo rst order kinetics and in good
(b)
(a)
Fig. 6. (a) Photocatalytic degradation of MB using SnO
2
catalyst.
(b) Graph of ln C
o
,C
t
versus Irradiation time.
agreement with Langmuir-Hinshelwood equation.
24, 25
For
activity comparison, the plot of ln C
0
,C
t
versus irradia-
tion time are plotted. The slope of the graph indicates the
apparent rate constant. The plot of ln C
0
,C versus irradi-
ation time (shown in Fig. 6(b)) indicates the pseudo rst
order kinetic and observed apparent rate constant for MB
degradation using SnO
2
and P-25 TiO
2
are 5.410
2
and
11.2 10
2
respectively. Means the acitivity of SnO
2
is
almost half than that of P-25 TiO
2
, though the activity of
SnO
2
is lower it provides an alternative catalyst for envi-
ronmental remidiation.
4. CONCLUSIONS
We have successfully synthesized SnO
2
nanorods and
nanoparticles using hydrothermal synthesis technique.
Formation of tetragonal phase was conrmed by XRD
analysis. The UV-visible absorbance and PL analysis indi-
cate absorbance and emission peaks at 280 and 365 nm
respectively. TEM indicates the formation of rod like mor-
phology having size 36 nm. The rate constant observed
for photocatalytic MB degradation using SnO
2
was 5.4
10
2
min
1
. To summarise SnO
2
can be utilized as an
alternative catalyst for MB degradation.
Acknowledgments: One of the author Jagannath M.
Mali would like to thank University Grant Commission,
New Delhi, India, for nancial support and Dr. B. B. Kale,
C-MET, Pune for useful discussion.
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