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Page 1 of 27 RSC Advances
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DOI: 10.1039/C6RA10532G
Ethylene glycol mediated synthesis of SnS quantum dots and their application
towards degradation of eosin yellow and brilliant green dyes under solar irradiation
Arpita Paul Chowdhury1, Baban H. Shambharkar1*, Sachin Ghugal2, Suresh S. Umare2, and
Published on 07 November 2016. Downloaded by Freie Universitaet Berlin on 09/11/2016 07:42:46.
Ashok Shende2
RSC Advances Accepted Manuscript

1
Chemistry Department, National Institute of Technology Silchar-788 010, Assam, India
2
Chemistry Department, Visvesvaraya National Institute of Technology Nagpur-440 010,
Maharashtra, India
Abstract
SnS (Tin sulfide) quantum dots (QDs) were synthesized by chemical coprecipitation
method using ethylene glycol as a solvent and capping agent and thiourea as a sulfur
source at a temperature of 160 oC, 4h. The as synthesized SnS QDs were characterized by
X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-Vis-NIR
spectroscopy and FT-Raman spectroscopy. XRD pattern shows the formation of single
phase SnS QDs with rhombohedral structure. Ethylene glycol mediated synthesis resulted
2.5-3 nm SnS QDs. UV-Vis-NIR optical absorption spectra of SnS QDs displayed that
SnS QDs possess the absorption profile across the whole visible-light and near-infrared
region. The direct band gap and indirect band gap energy for SnS QDs are found to be 1.17
eV and 1.11 eV, respectively. FT-Raman spectra of SnS QDs demonstrate vibrational
modes at 73, 97, 162, 188, 222 cm–1. The Brunauer-Emmett-Teller (BET) surface area of
SnS QDs was found to be 5.63 m2/g. SnS QDs showed powerful photodegradation
*
Corresponding author: B. H. Shambharkar, Email: baban.shambharkar@gmail.com
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activity towards degradation of dyes: eosin yellow and brilliant green under sunlight. The
enhanced photocatalytic activity of SnS QDs is attributed to improved visible light
absorption and efficient separation of photogenerated charge carriers. In addition the

quenching effects of different quenchers suggest that superoxide radicals play a major role

in the photodegradation process.
Keywords: SnS quantum dots; TEM; UV–Vis-NIR; FT-Raman; Photodegradation; eosin
yellow; brilliant green, Quenchers
1. Introduction
Nowadays the pollution of the environment by textiles, cosmetics and food industries is
increasing. Industrial waste water mostly contains dyes like eosin yellow, brilliant green
etc, which are used in textile industries. These are very hazardous for environment due to
their toxicity to living organisms and carcinogenetic effects. Therefore, these dyes have to
be removed in order to reuse the water. Different materials like mesoporous TiO21, carbon
functionalized TiO2 nanofibers2, Ag nanoparticles-coated TiO2 nanofiber composites3,
TiO2–NiO mixed oxide nanocrystals4, nanofibrous TiO2-core/conjugated polymer
composite5 etc. have been employed for removal of dyes from waste water. The
degradation of organic dyes is achieved under UV-light. Photocatalytic degradation of
organic pollutants from wastewater using solar radiation is a potential approach to control
the environmental pollution as solar energy is renewable. Hence, it is essential to develop
effective, visible light responsive catalytic materials to solve the issues related to energy
and environment. For harnessing the solar radiation effectively as solar radiation contains
around 40% visible light, researchers are developing the suitable semiconductor
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6-9
photocatalysts based on metal oxides, sulfides, oxynitrides and graphitic carbon nitride
to make the process efficient. An improved visible light absorption and enhanced
photodegradation has been informed in number of cases.

The IV-VI series of semiconducting materials like CdS, CdSe, PbS, SnS, PbSe and SnTe

etc. are of interest primarily because of their narrow band gap and potential applications in
solar cells, detectors as a optically active components in the near-infrared and infrared
spectral region10. These materials show efficient multiple exciton generation which is the
ability to generate more than one electron-hole pair per high energy photon absorbed and
provide a way to overcome the Shockley–Queisser efficiency 11.
SnS (Tin Sulfide) is an important binary chalcogenide. It is a layered semiconductor and
possess an orthorhombic crystal structure. It is an inexpensive, environmentally benign and
has good chemical stability. Tin sulfide exist in different phases12, 13 such as SnS, SnS2,
Sn2S3, Sn3S4 and Sn4S5. Among these, SnS is p-type and SnS2 is n-type semiconductor14.
SnS has both a direct optical gap located at 1.3 eV and indirect optical band gap located at
1.09 eV. The absorption coefficient of SnS is 104 cm−1 and possess high conductivity15.
SnS have been used as a light absorber in photovoltaics, anode material in lithium ion
batteries, sensors, capacitors, near-infrared detector and holographic recording and a
visible light driven photocatalyst 16-17.
Quantum dots (QDs) have unique advantages18, 19 of having simple synthesis, tunable band
gap energy by controlling the particle size, multiple exciton generation from single photon
absorption and large intrinsic dipole moment. To our knowledge, there are a very few
reports that present synthetic methodologies to forming SnS QDs and their application in
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the photocatalysis. Muthuvinayagam et al.17 prepared SnS QDs (2-5 nm) by one-pot
hydrothermal approach using SnCl2⋅2H2O and thiourea at 200 °C, 8 h. Prastani et al.11
prepared SnS QDs with a size of ∼4 nm using colloidal route. The synthesis was carried
out using precursors such as SnCl2⋅2H2O, triethanolamine, sodium sulphide, ethylene

glycol and trioctylphosphine oxide at room temperature under nitrogen atmosphere. Xu et
al.20 prepared SnS QDs using triethanolamine ligand, SnBr2 and Sodium sulfide. Deepa
and J. Nagaraju21 prepared SnS QDs by SILAR method. Tang et al.22 synthesized SnS
nanoparticles (5 nm) using starting materials like SnCl2·2H2O, octadecene,
trioctylphosphine, oleic acid, oleyamine and thioacetamide at 135 °C and reported their
photocatalytic activity towards Rhodamine B under halogen lamp. Das and Dutta23
prepared SnS nanorods by using mercaptoacetic acid as capping agent and proved to be an
efficient photocatalyst for dye degradation of trypan blue dye under sunlight.
In the present study, we report facile synthesis of SnS QDs by chemical coprecipitation
method using ethylene glycol as a solvent and complexing agent and thiourea as a sulfur
source at 160 oC, 4 h. This method is a simple, economical route and requires low reaction
temperature and short reaction time to synthesize SnS QDs. By using this route spherical
SnS QDs were obtained. For the first time, we evaluated the photodegradation activity of
as- synthesized SnS QDs in the degradation of eosin yellow and brilliant green under solar
irradiation. Our results indicate that the formed SnS QDs showed the enhanced
photodegradation for eosin yellow and brilliant green because of improved visible light
absorption and efficient separation of photogenerated charge carriers.
2. Experimental Section
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2.1. Materials
Stannous chloride, SnCl2·2H2O (Merck, 99%), ethylene glycol (Himedia, 99%), thiourea
(SCN2H4) (Merck, 99%), P25 TiO2 (Sigma Aldrich, 99.5%), eosin yellow and brilliant
green (Himedia) were of analytical-reagent grade and was used as received.

2.2. Synthesis of SnS QDs
24-25
SnS QDs were prepared by chemical coprecipitation method by treating SnCl2 with
thiourea in ethylene glycol medium. Briefly, SnCl2 (2.25 g, 0.1M) was dissolved in 100 ml
water and mixed this solution with 100 ml ethylene glycol (EG). The mixture was then
transferred to three necked flask fitted with air condenser and 10 g thiourea was added
into it and refluxed to 160 oC for 4h. The black precipitate was obtained. It was then
centrifuged and washed with methanol and dried at 80 oC, 1h.
Sn2+ ions form a complex with EG. Upon addition of thiourea into preformed Sn–EG
complex, a competition between the thiourea and EG is introduced. The strong
complexation between Sn2+ ions and thiourea leads to the formation of Sn–thiourea
complex in the precipitation method which prevent the production of a large number of
free S2- in the solution. SnCl2 and thiourea both easily dissolves in ethylene glycol solvent
which indicates the formation of [Sn(SCN2H4)n]2+ complex. The produced complex serve
as both the tin source and the sulfur source. On heating at 160 oC, Sn–thiourea complex
undergo thermal decomposition to produce EG capped tin sulfide QDs due to the rupture
of coordinate bonds between Sn2+ and thiourea. EG acts as the stabilizing ligand. Hydroxyl
groups on EG control the size of SnS QDs. EG has two hydroxyl groups to bind more
strongly to the QDs as they grow.
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2.3. Characterization
Crystal structure of SnS QDs were determined by using X-Ray diffraction (XRD) analysis

conducted on ‘X’Pert PRO, PANalytical X-ray diffractometer using CuKα radiation (λ =
1.5406 A). Measurements were performed in the 2θ range from 10o to 90o. High resolution
transmission electron microscope (TEM) imaging was done by using JEOL Model JEM-
2100. UV–Visible Diffuse reflectance spectra (DRS) of SnS QDs was recorded on Varian,
Cary 5000 UV-Vis-NIR spectrophotometer. Fourier Transform (FT)-Raman spectra of SnS
QDs was recorded on Bruker RFS 27 Stand-alone FT-Raman spectrometer with scan range
50-4000 cm-1 and resolution 2 cm-1. The laser source was Nd: YAG 1064 nm. The
Brunauer-Emmett-Teller (BET) surface area of SnS QDs was determined by nitrogen
adsorption-desorption isotherms using Micromeritics ASAP 2010 surface area analyzer by
nitrogen adsorption at 77 K. Photocatalytic activity of SnS QDs was evaluated by using
dye solutions such as eosin yellow (20 mgL-1) and brilliant green (10 mgL-1) under solar
radiation. The absorbance spectra of the dye solutions before and after photo degradation
were recorded on UV-Vis spectrophotometer (Cary 100 Bio).
25 mg and 100 mg of SnS particles was dispersed in a beaker containing 100 ml of eosin
yellow and brilliant green solution, respectively (pH = 7.5). The mixture was continuously
stirred using a magnetic stirrer at ambient temperature in the dark for 15 min in order to
attain adsorption-desorption equilibrium prior to light irradiation. 5 ml of the aliquot was
withdrawn at regular time intervals. The aliquot was centrifuged and quantitative
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determination of eosin yellow was performed by measuring its absorbance at λ = 509 nm
and for brilliant green at λ = 624 nm. The photodegradation efficiency of SnS QDs was
determined by equation, % degradation = [(C0-Ct) /C0] x 100. Where C0 is the initial

concentration of dye and Ct is the concentration of dye after ‘‘t’’ minutes visible light

irradiation. The degradation profiles19 were fitted in first order equation ln (C0/C) = kt,
where C is the concentration after degradation and C0 is the concentration of the dye after
dark adsorption, respectively, k is rate constant and t is time for light irradiation. The rate
constant (k) was calculated from slope of straight line obtained by plotting ln (C0/C) versus
time (t).
3. Results and discussion
3.1. Structural, morphological and optical studies
Figure 1 shows the XRD pattern of SnS QDs. The XRD pattern of SnS QDs matches with
JCPDS file 01-073-1859 (SnS) and has rhombohedral structure. The set of lattice planes
and their corresponding d-spacing are shown in table 1. The lattice parameters of the
synthesized SnS QDs were calculated by using cell refine software, and were found to be a
= 11.98Å, b = 3.98Å, c = 4.32Å. These values are consistent with JCPDS 01-073-1859.
The crystallite size of SnS QDs was calculated by using Debye Scherer equation,
D=0.99λ/βCosθ where, β full width at half maximum of the strongest peak, λ is the X-ray
wavelength and θ is the angle of diffraction and was found to be 15 nm.
Figure 2(a, b) shows TEM image of SnS QDs. TEM images showed the formation of
spherical SnS QDs with size of 2.5-3 nm. The selected area electron diffraction (SAED)
pattern of SnS QDs (figure (2c)) obtained from spherical particles revealed the formation
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of circular diffraction rings, which reflects the polycrystalline nature of SnS QDs. The size
distribution of SnS QDs is uniform and average particle size is 5.1 nm (the histogram in
figure (2d)). Energy dispersive X-ray spectroscopy (EDX) measurement was done to
know the chemical composition of SnS QDs. The EDX spectrum revealed the

characteristic L X-ray peak of Sn and the K X-ray peak of S (Figure. 3). The atomic
concentrations of Sn and S were measured as 54.69% and 45.31% respectively.
Figures 4 (a) and 4(b) shows the UV-Vis-NIR optical reflectance and absorption spectra of
SnS QDs, respectively. The spectra displayed a continuous absorption from the UV-Vis
region to near infra-red region. The broad spectrum allows SnS QDs to act as a good
visible light-sensitive photocatalyst to drive photocatalytic degradation of organic
pollutants. The optical band gap of the prepared SnS QDs was obtained from the UV-Vis-
NIR optical absorption curve (Figure 4(b) using the tangent line extrapolation technique on
the curve. The band gap energy (Ebg) was calculated by using simple equation: Ebg =
1240/λ (absorption edge), assuming that the prepared SnS QDs are direct crystalline
semiconductor. The as-synthesized SnS QDs exhibits an absorption onset at 1070 nm,
which corresponds to band gap energy of 1.15 eV. In order to get more precise values of
the optical band gaps, the values of Eg were calculated with the help of the Tauc
equation26, (αhѵ) = A (hѵ - Eg)n, where α is the absorption coefficient. hѵ and A are the
photon energy and a constant relative to the material, respectively and n is either 2 for a
direct allowed electronic transition (direct band gap) or 1/2 for an indirect allowed
electronic transition (indirect band gap). For this purpose, (αhѵ)1/2 was plotted as a
function of photon energy hѵ (eV) for the indirect gap and (αhѵ)2 against photon energy
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hѵ (eV) for the direct gap. Figure 4(c)-(d) are presentation of these plots. The linear
intercept at hv on x-axis gives the value of optical band gap. The direct band gap and
indirect band gap energy for SnS QDs are found to be 1.17 eV and 1.11 eV, respectively.
The direct band gap is very close to that of silicon (1.11 eV) 27. The band gap energy varies

with synthetic temperature of reaction according to previous reported results28. The optical
direct band gap and indirect band gap16 in SnS nanoparticles are 3.6 eV and 1.6 eV,
respectively and in bulk SnS, the direct band gap and the indirect band gap are 1.3 eV and
1.09 eV respectively. Band gap energy values of as prepared SnS QDs are compared with
nanoparticles, it is seen that direct and indirect transition of SnS QDs are shifted towards
lower energy values. Compared to bulk SnS, blue shift of 0.13 eV is observed for direct
transition. This is because of enhancement of quantum confinement effect resulting from
the decrease in the size of nanoparticles.
Raman spectroscopy (RS) is used to probe the detailed structure of materials. It is a
scattering technique based on Raman Effect, i.e., frequency of a small fraction of scattered
radiation is different from frequency of monochromatic incident radiation. It is based on
the inelastic scattering of incident radiation through its interaction with vibrating
molecules. The 24 vibrational modes29 for orthorhombic structure of SnS are represented
as Γ = 4Ag + 2B1g + 4B2g + 2B3g + 2Au + 4B1u + 2B2u + 4B3u.
Among them, SnS has 21 optical phonons, of which 12 are Raman active modes (4Ag +
2B1g + 4B2g and 2B3g), seven infrared active modes (3B1‫ ݑ‬+ 1B2‫ ݑ‬and 3B3u) and two are
inactive (2Au). Figure 5 shows the FT-Raman spectra of the as-synthesized SnS QDs. SnS
QDs shows vibrational modes at 73, 97, 162, 188, 222 cm–1. The peak at 73 cm–1, 97 cm–1
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and 162 cm–1 are corresponding to B1g or B2g mode, Ag mode and B3g mode, respectively.
The peaks at 188 cm–1 and 222 cm–1 can be assigned to the Ag mode. It has been reported
that vibrational modes14, 30

for SnS nanoparticles was detected at 77, 95, 163, 191, and
220 cm–1. Vibrational modes of as prepared SnS QDs shows a slight shift towards lower

wave number in comparison to SnS nanoparticles. This is attributed to phonon
confinement. FT-Raman results indicate that the formation of SnS QDs from the present
process.
3.2. BET surface area
Figure 6 shows the nitrogen adsorption–desorption isotherms of as-prepared of SnS QDs.
The SnS QDs shows type III isotherm. This indicates that there is a weak interaction
between adsorbate and adsorbent i.e. between N2 molecules and SnS QDs. BET surface
area of SnS QDs is found to be 5.63 m2/g and pore volume of 0.035 cm3/g. Type III
isotherm is mainly due to ink–bottle pores and the mesoporosity of pore size distribution is
under pore diameter 25 nm. Results from desorption BJH pore volume distribution and
pore area distribution confirmed mesoporous structure of prepared SnS QDs.
3.3. Evaluation of photodegradation activity
Figure 7 (a) shows the absorbance spectra of eosin yellow dye solution in presence of SnS
QDs under solar irradiation. The maximum absorbance for eosin yellow is observed at 509
nm that disappears completely after solar irradiation indicating the complete destruction of
the chromophoric structure of the dye. The photodegradation efficiency of eosin yellow by
SnS QDs is represented by figure 7 (b). It is observed that 91.67% of eosin yellow
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degraded photochemically within 60 min by SnS QDs. The photodegradation rate constant
of eosin yellow was calculated from figure 7(c) and was found to be 0.0235 min-1.
Figure 8(a) shows the absorbance spectra of brilliant green dye solution in presence of SnS
QDs under sunlight irradiation. The maximum absorbance of brilliant green dye exhibits at

624 nm which disappears completely in presence of solar irradiation. The
photodegradation efficiency of brilliant green using SnS QDs is represented by figure 8(b).
From the graph, it is evident that 88.82% of brilliant green dye degraded using SnS QDs as
a photocatalyst within 90 min of sunlight irradiation. The photodegradation rate constant of
brilliant green was calculated from figure 8 (c) and was found to be 0.0158 min-1.
The photodegradation activity of SnS QDs was compared with commercial P25 TiO2. The
rate of degradation of eosin yellow using P25 TiO2 is found be same as that of SnS QDs,
while P25 TiO2 decomposes only 68.36 % of brilliant green within 90 min under sunlight
irradiation. The enhanced photocatalytic activity of SnS QDs is attributed to improved
visible light absorption and efficient separation of photogenerated charge carriers.
The used catalysts was regenerated by centrifugation and washing with methanol and
finally dried in air oven.
To elucidate the active species responsible for the visible light photocatalytic degradation,
various quenchers were added to aqueous solution containing dyes: eosin yellow (20 mgL-
1
) and 25 mg SnS, brilliant green (10 mgL-1) and 100 mg SnS and the photodegradation
activity were studied. Quenchers are certain chemicals which hinder the action of certain
specific species for the degradation reaction by trapping them during the course of
photocatalytic experiment. The quenchers31 employed were 5 ml isopropanol (Pr) for
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hydroxyl radicals, 0.1 g ammonium oxalate (AO) for holes, 10-3 M 1, 4-benzoquinone
(BQ) for superoxide radical. Figure 7(d) and figure 8(d) shows the effect of different
quenchers on the photocatalytic activity of SnS. On adding isopropanol no distinct changes

in the performance of SnS were observed. This indicates that bulk hydroxyl radicals do not

take part in the degradation process. When AO is added to the solution the decolorization
rate of eosin yellow is also increased. That means that holes (h+) do not take part in the
degradation process. When BQ was added into the reaction solution, photocatalytic
efficiency SnS QDs was decreased indicating superoxide radicals (O2•-) are responsible for
degrading eosin yellow under solar light irradiation. Similar kind of reaction was also
observed with brilliant green dye degradation when BQ was added in the solution in
presence of solar light irradiation (figure 8(d)). It is obvious that addition of BQ shows a
major effect on the photodegradation process, manifesting that (O2•-) played a significant
role in photodegradation of dyes: eosin yellow and brilliant green. On addition of BQ,
there has been 29.17 % and 43.73 % decrease in degradation efficiency of eosin yellow
and brilliant green occurred, respectively. On the basis of above results, a possible reaction
mechanism occurring during the photocatalytic degradation process of eosin yellow and
brilliant green over SnS QDs are given below.
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In the presence of visible light, electrons in the valence band (VB) of SnS QDs are
promoted to the conduction band (CB). As a result of this, a high amount of negative-
electron (e–) and positive-hole (h+) pairs are generated. Both e– and h+ pairs can migrate to
the catalyst surface, where they can enter in a redox reaction with dyes present on the
surface. e-CB can react with O2 to produce superoxide radical anion of oxygen which have a
powerful oxidation ability to degrade eosin yellow and brilliant green dyes. The stability of
SnS QDs photocatalyst was checked by running the degradation experiment for three
repeated cycles using the same catalyst. From figure 7(e) and figure 8(e), it is clear that
photocatalytic activity is same for three repeated cycles indicating that the catalyst is stable
and can be reused.
4. Conclusions
In this paper, we reported a cost-effective process for synthesizing SnS QDs by
coprecipitation method using ethylene glycol solvent and thiourea as a sulfur source where
ethylene glycol acts as a good complexing and capping agent. The formation of SnS QDs
took place within 4h at 160 oC. X-ray powder diffraction pattern and transmission electron
microscope images showed that the product is stannous sulphide, SnS which is well
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crystallized. TEM images showed the formation of spherical SnS QDs with an average
diameter of 3 nm. XRD and SAED pattern confirms the rhombohedral crystalline structure
of SnS QDs. EDX measurement revealed the presence of tin and sulfur. FT-Raman study
also endorses the formation of SnS QDs by EG route. The direct optical band gap of

synthesized SnS QDs (1.17 eV) calculated through Tauc plot shows a blue shift of optical
band gap energy from the bulk SnS (1.3 eV) because of quantum confinement effect. The
photodegradation studies reveal that as-synthesized SnS QDs act as an efficient catalyst in
the removal of eosin yellow and brilliant green dyes from waste water. The complete
decolorization of eosin yellow and brilliant green took within 60 minutes and 90 minutes
of solar irradiation, respectively. Superoxide ions are the main active species involved in
photodegradation of eosin yellow and brilliant green dyes. SnS QDs are found to be photo-
stable and can be recycled. SnS QDs play very important role in the photocatalytic
property which may help in solving issues related to environmental pollution by utilizing
solar energy effectively.
Acknowledgement
The author thanks to following institutions for providing technical support: STIC Cochin,
SAIF Chandigarh, VNIT Nagpur and SAIF Madras for XRD, TEM, EDX, UV-Vis-NIR
and FT-Raman studies. One of the author Arpita Chowdhury is thankful to Director NIT
Silchar for PhD fellowship.
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30. C. An, K. Tang, G. Shen, C. Wang, Q. Yang, B. Hai, and Y. Qian, J. Crystal Growth,
244, 2002, 333.
31. S. G. Ghugal, S. S. Umare and R. Sasikala, Mater. Res. Bull., 2015, 61, 298.
16
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Figure Captions
Figure 1: XRD pattern of SnS QDs.
Figure 2: TEM image of SnS QDs (a-b) and (c) SAED pattern of SnS QDs and (d)
Histogram of SnS QDs size distribution.

Figure 3: EDX pattern of SnS QDs.
Figure 4: UV–Visible-NIR (a) reflectance and (b) absorbance spectrum of as-prepared
SnS QDs. Tauc plots for direct band gap (c) and indirect band gap (d).
Figure 5: Raman spectra of as-prepared SnS QDs.
Figure 6: N2 adsorption-desorption isotherms of as-prepared SnS QDs.

Figure 7: (a) UV-Visible absorbance spectra of eosin yellow (20 mgL-1) before and after
solar light irradiation. (b) Percentage efficiency of photodegradation of eosin yellow with
time. (c) Plot of ln(C0/C) versus irradiation time for photodegradation of eosin yellow dye
using as synthesized SnS QDs. (d) Effect of different quenchers on photodegradation of
eosin yellow using SnS QDs in 60 minutes. (e) Recyclability.
Figure 8: (a) UV-Visible absorbance spectra of brilliant green (10 mgL-1) under solar light
irradiation. (b) Percentage efficiency of photodegradation of brilliant green with time. (c)
Plot of ln(C0/C) versus irradiation time for photodegradation of brilliant green dye using as
synthesized SnS QDs. (d) Effect of different quenchers on photodegradation of brilliant
green using SnS QDs in 90 minutes. (e) Recyclability.
17
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Figure 1: XRD pattern of SnS QDs.
DOI: 10.1039/C6RA10532G
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Figure 2: TEM image of SnS QDs (a-b) and (c) SAED pattern of SnS QDs and (d) Histogram of SnS QDs size
distribution.
254x190mm (96 x 96 DPI)

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Figure 3: EDX pattern of SnS QDs.
DOI: 10.1039/C6RA10532G
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DOI: 10.1039/C6RA10532G

Figure 4: UV–Visible-NIR (a) reflectance and (b) absorbance spectrum of as-prepared SnS QDs. Tauc plots
for direct band gap (c) and indirect band gap (d).
254x190mm (96 x 96 DPI)

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DOI: 10.1039/C6RA10532G

Figure 5: Raman spectra of as-prepared SnS QDs.
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DOI: 10.1039/C6RA10532G

Figure 6: N2 adsorption-desorption isotherms of as-prepared SnS QDs.
279x215mm (150 x 150 DPI)

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DOI: 10.1039/C6RA10532G

Figure 7: (a) UV-Visible absorbance spectra of eosin yellow (20 mgL-1) before and after solar light
irradiation. (b) Percentage efficiency of photodegradation of eosin yellow with time. (c) Plot of ln(C0/C)
versus irradiation time for photodegradation of eosin yellow dye using as synthesized SnS QDs. (d) Effect of
different quenchers on photodegradation of eosin yellow using SnS QDs in 60 minutes. (e) Recyclability.
307x203mm (96 x 96 DPI)

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DOI: 10.1039/C6RA10532G

Figure 8: (a) UV-Visible absorbance spectra of brilliant green (10 mgL-1) under solar light irradiation. (b)
Percentage efficiency of photodegradation of brilliant green with time. (c) Plot of ln(C0/C) versus irradiation
time for photodegradation of brilliant green dye using as synthesized SnS QDs. (d) Effect of different
quenchers on photodegradation of brilliant green using SnS QDs in 90 minutes. (e) Recyclability.
307x203mm (96 x 96 DPI)

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DOI: 10.1039/C6RA10532G
Table 1. Lattice planes and their corresponding d-spacing of SnS QDs
2[theta]o d- spacing (Å) h k l values

16.57 5.34 (2 0 0)
22.15 4.01 (1 0 1)
26.15 3.40 (2 0 1)
27.57 3.23 (2 1 0)
30.57 2.92 (0 1 1 )

31.62 2.82 (1 1 1 )
32.00 2.79 (3 0 1)
39.09 2.30 (3 1 1)
44.77 2.02 (4 1 1)
45.53 1.99 (0 2 0)
48.68 1.87 (3 0 2)
50.35 1.81 (2 1 2)
51.30 1.78 (5 1 1)
54.29 1.68 (6 1 0)
56.6 1.62 (4 2 0)
64.24 1.44 (5 1 2)
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This is an Accepted Manuscript, which has been through the

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RSC Advances Accepted Manuscript

X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-Vis-NIR

enhanced photocatalytic activity of SnS QDs is attributed to improved visible light

absorption and efficient separation of photogenerated charge carriers. In addition the

RSC Advances Accepted Manuscript

Keywords: SnS quantum dots; TEM; UV–Vis-NIR; FT-Raman; Photodegradation; eosin

yellow; brilliant green, Quenchers

functionalized TiO2 nanofibers2, Ag nanoparticles-coated TiO2 nanofiber composites3,

TiO2–NiO mixed oxide nanocrystals4, nanofibrous TiO2-core/conjugated polymer

degradation of organic dyes is achieved under UV-light. Photocatalytic degradation of

the environmental pollution as solar energy is renewable. Hence, it is essential to develop

photodegradation has been informed in number of cases.

RSC Advances Accepted Manuscript

provide a way to overcome the Shockley–Queisser efficiency 11.

SnS (Tin Sulfide) is an important binary chalcogenide. It is a layered semiconductor and

possess an orthorhombic crystal structure. It is an inexpensive, environmentally benign and

batteries, sensors, capacitors, near-infrared detector and holographic recording and a

visible light driven photocatalyst 16-17.

out using precursors such as SnCl2⋅2H2O, triethanolamine, sodium sulphide, ethylene

RSC Advances Accepted Manuscript

nanoparticles (5 nm) using starting materials like SnCl2·2H2O, octadecene,

absorption and efficient separation of photogenerated charge carriers.

green (Himedia) were of analytical-reagent grade and was used as received.

RSC Advances Accepted Manuscript

centrifuged and washed with methanol and dried at 80 oC, 1h.

complex, a competition between the thiourea and EG is introduced. The strong

strongly to the QDs as they grow.

RSC Advances Accepted Manuscript

Cary 5000 UV-Vis-NIR spectrophotometer. Fourier Transform (FT)-Raman spectra of SnS

Brunauer-Emmett-Teller (BET) surface area of SnS QDs was determined by nitrogen

adsorption-desorption isotherms using Micromeritics ASAP 2010 surface area analyzer by

nitrogen adsorption at 77 K. Photocatalytic activity of SnS QDs was evaluated by using

were recorded on UV-Vis spectrophotometer (Cary 100 Bio).

attain adsorption-desorption equilibrium prior to light irradiation. 5 ml of the aliquot was

determination of eosin yellow was performed by measuring its absorbance at λ = 509 nm

determined by equation, % degradation = [(C0-Ct) /C0] x 100. Where C0 is the initial

RSC Advances Accepted Manuscript

3. Results and discussion

3.1. Structural, morphological and optical studies

wavelength and θ is the angle of diffraction and was found to be 15 nm.

RSC Advances Accepted Manuscript

concentrations of Sn and S were measured as 54.69% and 45.31% respectively.

visible light-sensitive photocatalyst to drive photocatalytic degradation of organic

RSC Advances Accepted Manuscript

transition. This is because of enhancement of quantum confinement effect resulting from

the decrease in the size of nanoparticles.

Raman spectroscopy (RS) is used to probe the detailed structure of materials. It is a

radiation is different from frequency of monochromatic incident radiation. It is based on

as Γ = 4Ag + 2B1g + 4B2g + 2B3g + 2Au + 4B1u + 2B2u + 4B3u.

that vibrational modes14, 30

RSC Advances Accepted Manuscript

3.2. BET surface area

Figure 6 shows the nitrogen adsorption–desorption isotherms of as-prepared of SnS QDs.

pore area distribution confirmed mesoporous structure of prepared SnS QDs.

3.3. Evaluation of photodegradation activity

RSC Advances Accepted Manuscript

a photocatalyst within 90 min of sunlight irradiation. The photodegradation rate constant of

irradiation. The enhanced photocatalytic activity of SnS QDs is attributed to improved