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Photocatalytic degradation of methyl orange using TiO2/SnO2 binary nano

composite

Conference Paper  in  AIP Conference Proceedings · August 2018

DOI: 10.1063/1.5051285

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Photocatalytic degradation of methyl orange using TiO2/SnO2 binary nano composite
Manmeet Singh, Pritpal Singh, and Jeewan Sharma

Citation: AIP Conference Proceedings 2006, 030029 (2018); doi: 10.1063/1.5051285

View online: https://doi.org/10.1063/1.5051285
View Table of Contents: http://aip.scitation.org/toc/apc/2006/1
Published by the American Institute of Physics
 Photocatalytic Degradation of Methyl Orange using
TiO2/SnO2 Binary Nano Composite
Manmeet Singh1, Pritpal Singh1 and Jeewan Sharma2*

1
Department of Chemistry, Sri Guru Granth Sahib World University, Fatehgarh Sahib-140 407, Punjab, India.
2
Department of Nanotechnology, Sri Guru Granth Sahib World University, Fatehgarh Sahib-140 407, Punjab,
India.

*
Corresponding author: jeewansharma29@gmail.com

Abstract. Removal of organic dyes effluents in water, which is a major source of environmental pollution, has become a
important area of research these days. In the present study, photocatalytic degradation of hazardous dye methyl orange (MO)
using binary TiO2/SnO2 nanocomposite has been studied. Nanocomposite in a TiO 2:SnO2 ratio of 95:5 has been synthesized from
TiO2 (anatase) and SnO2 (rutile) nanoparticles using hydrothermal method. The synthesis of composite has been confirmed using
various characterizations. The phase structure, particle size, surface morphology and optical properties have been estimated using
X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy
(FT-IR) analysis and UV-Visible spectroscopy. The binary nanocomposites degraded the hazardous dye methyl orange with high
speed as compare to pure TiO2 nanoparticles, under UV-light illumination. Addition of SnO2 to TiO2 leads to enhanced
degradation capacity owing to formation of intermediate band gap. The photocatalytic activity of compound has also been
compared with previously reported anatase TiO2 nanoparticles.

INTRODUCTION
Dyes find a great use in the cloths, food, beauty products, photographic and paper industries. They can stick to well
matched surfaces of solution, by forming covalent bond or complexes with salts or metals, by surface adsorption or
by mechanical holding [1]. Dyes may include azo dyes, reactive dyes, metal-complex dyes and functional dyes. Azo
dyes are organic compounds with functional group R−N=N−R′, in which R and R′ are generally aryl [2]. Methyl
orange (MO) is one of the azo dyes, among its various types. Chemicals associated with azo dyes are azo stains,
which does not dissolve in water and other liquids [3, 4]. The effluents from dye factories are strongly colored and
poisonous. 90% of reactive fabric dyes enters the activated slurry treatment plants discharge into rivers and cause
problems such as (a) decrease in penetration of sunlight in the streams, (b) poisonous for fishes and mammals life,
(c) stops the growth of microorganisms specially at high amounts and (d) some positively charged compounds (like
triphenylmethanes) affect the plants and animals. The methods or processes involved in dye degradation are:
adsorption, precipitation, advanced oxidation process and biological routes, which involve oxidase and hydroxylase
enzymes [5]. Advanced oxidation process is a new technique, with has some advantages over conventional methods.
This technique is based on the reproduction of very reactive species or super oxides like hydroxyl radicals that
oxidizes ample range of organic pollutants instantly and non-selectively [6, 7]. Photocatalytic activity of TiO2
nanoparticles predicts that this material has good efficiency in decline of organic pollutants owing to its good
features like non-toxicity, physical-chemical stability, high reactivity and low cost [8, 9]. In contrast with TiO2,
SnO2 is semiconducting material with wide and direct band gap. SnO2, when coupled with TiO2 leads to
intensification of photocatalytic activity; due to formation of intermediate band gap [10-12]. In the present study, TS
(TiO2/SnO2) binary nanocomposite is synthesized to enhance the photocatalytic activity of TiO2 towards MO dye
under UV-light irradiation. TS binary nanocomposite shows excellent photocatalytic efficiency towards MO dye.

National Conference on Recent Advances in Experimental and Theoretical Physics (RAETP-2018)

AIP Conf. Proc. 2006, 030029-1–030029-5; https://doi.org/10.1063/1.5051285
Published by AIP Publishing. 978-0-7354-1722-9/$30.00

030029-1
 EXPERIMENTAL SECTION
To synthesis of TiO2, Titanium tetrachloride, (TiCl4, purity > 99.9%), was used as a precursor. A 250 ml beaker was
kept in an ice bath and 5 ml of TiCl4 was added drop wise in a solution of 100 ml distilled water and 5 ml HCl (30
%) with continuous stirring. The solution was kept at room temperature for 24 hours. To synthesize SnO2, 1.30 g of
(SnCl2.2H2O) in 0.7 ml of 38 wt. % HCl diluted with 20 ml distilled water. 1.30 g Urea was added into the SnCl2-
HCl solution with vigorous stirring. Precipitates were obtained after the resulting solution was kept at 90 °C for 12
hours in oven. For drying, precipitates were kept at 110 °C for about 24 hours [13]. Hydrothermal method was used
for the synthesis of binary TiO2/SnO2 nanocomposite. The solution was poured into a stainless steel autoclave
(Teflon-lined) and heated for 18 hour at 180 °C. As the reaction completes, the solution was centrifuged and final
product was washed with double distilled water and ethanol to remove impurities. A vacuum oven was used for
over-night drying at 75 °C [14]. XRD results were obtained using X’pert PRO X-ray diffractrometer in 2θ range
from 20° to 70° with CuKα radiations (λ = 1.54 Å). HR-TEM images were recorded using Tecnai G2 20, 200KeV
FEI. The UV-Vis spectrometer was operated in wavelength range 200-800 nm (Model. UV-2600, SHIMADZU copp
01197). The photocatalytic degradation of MO dye was investigated using UV-Vis spectrophotometer. In this
process, 25 mg sample of TiO2/ binary nanocomposite was added separately in 10 ppm solution of MO dye. This
mixture of dye solution and catalyst suspension was stirred with magnetic stirrer for 30 minutes and placed in dark
to attain the adsorption–desorption equilibrium. Degradation efficiency of dye was calculated by using the following
formula:
C0 - Ct
Percentage of dye removal
C0
×100 (1)

where Co is initial and Ct is final concentrations of the dye. The experiments were performed in a reactor of 1000
mL capacity with a 175 W metal halide lamp (Philips) positioned inside a cylindrical vessel. The test solutions were
then exposed to ultraviolet radiation. The samples from exposed test solution were taken out at regular intervals,
centrifuged for 10 min at 3500–4000 rpm and their absorbance was recorded for MO dye using spectrophotometer.

RESULTS AND DISCUSSION

The binary TiO2/SnO2 nanocomposite with ratio 95:5 has been prepared by hydrothermal method named as TS.
Figure 1 shows the XRD pattern of TS binary nanocomposite. The 2θ values for SnO2 rutile phase are recognized at
26.79°, 34.04°, 38.17°, 52.13° and 65.96°; corresponding to (110), (101), (200), (211) and (310) hkl planes
respectively (ICDD file no. 41-1445). The peaks observed at 48.06° and 62.21° corresponding to (200) and (213)
planes respectively, are related to anatase phase of TiO2 (ICDD file no 21-1272).

*TiO 2
# # SnO2
(110)
Intensity (a.u.)

#
(101)

# #
* *
(211)
(200)

#
(200)

(213)
(310)

20 30 40 50 60 70
2T(degree)
FIGURE 1. X-ray diffraction pattern for TiO2/SnO2 binary nanocomposite

030029-2
 The presence of both types of peaks in pattern confirms the formation of binary nanocomposite. The crystallite size
of TS binary nanocomposite is calculated using the Debye-Scherer formula as:

D= (2)

where k is the constant (0.9), O is the wavelength of X-rays (O = 1.54 Å), β is the full width half maximum
(FWHM and θ is the reflection angle. The average crystallite size of the TS binary nanocomposite calculated using
above formula for different peaks lies between 8-12 nm.

(a) (b)

FIGURE 2. HR-TEM images of TiO2/ SnO2 binary nanocomposite at (a) 100 nm and (b) 50 nm magnification.

Figure 2 (a-b) shows HR-TEM micrographs of the TS binary nanocomposite (dried at 75 °C) at two different
magnifications. It can be seen that the mixed anatase- and rutile- type TiO2-SnO2 nanocomposite has particle few
nm. These results are in good agreement with that of XRD results. The absorption peak observed at 3522 cm–1 is
attributed to O-H stretching vibrations. This might be due to the surface adsorbed water. Two peaks observed
between 400 cm–1 to 600 cm–1 are related to the Ti-O-Ti bonds and Sn-O-Sn bond vibrations.

(a) (b)
Transmittance (a.u.)

Transmittance (a.u.)

Ti-O-Ti
Sn-O-Sn
O-H bending

3500 3000 2500 2000 1500 1000 600 575 550 525 500 475 450 425 400
Wavenumber (cm-1) Wavenumber (cm-1)
FIGURE 3. (a-b) FT-IR spectra for TiO2/ SnO2 binary nanocomposite.

The degradation of MO was investigated under UV irradiation for TS binary nanocomposite. Figure 4 (a) represents
the absorption spectra for nanocomposite, at different time intervals. Maximum absorbance is observed for pure MO
dye (without catalyst). As the sample (with catalyst) is placed in dark, very small decrease in absorbance is seen due
to adsorption reaction of catalyst. The UV light irradiation for different time intervals shows that absorbance goes on
decreasing with increased time period. Minimum absorbance is observed for 40 minutes UV irradiation which
means dye is completely degraded after 40 minutes of UV light irradiation. This degradation of MO dye with UV
light irradiation can be attributed to advance oxidation process.

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 (a) 1.0 (b)
(MO dye)
0.8 MO dye
Absorbance (a.u)

(In dark for 60 min.)

(10 min.) (without catalyst)
(20 min.) 0.6 TS

Ct/C0
(30 min.) (binary composite)
(40 min.) 0.4

0.2

0.0
200 300 400 500 600 700 800 0 10 20 30 40 50
Wavelength (nm) Time (minutes)

FIGURE 4. (a) Variation in absorbance versus wavelength and (b) Ct/Co versus time
A blank experiment was performed without catalyst and very small amount of degradation is observed, reflects that
degradation activity largely depends upon presence of catalyst (Fig. 4 (b)). The variation of C t/Co with time is given
in fig. 4 (b). Here, complete degradation of MO dye is observed for 40 minutes of UV irradiation. Whereas in our
previous study, degradation of MO dye using TiO2 and commercial photocatalyst Degussa TiO2 (P-25) catalyst is
achieved in 50 and 70 minutes, respectively [15]. Karthikeyan et. al also reported 90% degradation of MB dye in
120 minutes, for TiO2/ SnO2 nanocomposite with 30 ppm concentration [16]. Figure 4 (c) presents the change in
color of MO dye with UV light irradiation for different time intervals, in the presence of TS binary nanocomposite.

(c)
(c)

FIGURE 4. (c) Representation of change in color of MO dye with time.

CONCLUSIONS
The TiO2 / SnO2 binary nanocomposite has been successfully synthesized via sol-hydrothermal method. The particle
size of the TiO2 / SnO2 binary nanocomposite was in range of 8-10 nm. MO dye being the target pollutant, the
photocatalytic performance has been systemically investigated. It is found that MO dye completely degraded in 40
minutes of UV light irradiation, in the presence of TS binary nanocomposite. This shows that cost effective TS
binary nanocomposite has potential to be used in photocatalytic applications.

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