Materials Chemistry and Physics xxx (2016) 1e9

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Synthesis and characterization of CdS nanocrystallites and

OMWCNT-supported cadmium sulfide composite and their
photocatalytic activity under visible light irradiation
Amol S. Pawar a, Shivram S. Garje a, *, Neerish Revaprasadu b
a
Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai 400 098, India
b
Department of Chemistry, University of Zululand, Private Bag X1001, Kwadlangezwa, 3886, South Africa

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The carbon based nanocomposite of

CdS (CdS-OMWCNT) have been
prepared.

Simple solvothermal decomposition
method has been used.

Single-source molecular precursor in
presence of carbon nanotubes has
been employed.

The photocatalytic activity of CdS NPs
and CdS-OMWCNT composite have
been studied.

The photocatalytic activity of CdS-
OMWCNT composite is more than
that of CdS NPs.

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

Article history: CdS nanocrystallites and CdS- oxidized multiwalled carbon nanotubes (OMWCNT) composite were
Received 7 December 2015 prepared by the solvothermal decomposition of a single-source molecular precursor, [Cd(pip.dtc)2]
Received in revised form (pip.dtc ¼ piperidine dithiocarbamate) in the presence of ethylene glycol. The as prepared CdS nano-
14 August 2016
crystallites and CdS-OMWCNT composite were characterized by powder X-ray diffraction (XRD), scan-
Accepted 20 August 2016
Available online xxx
ning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), transmission electron
microscopy (TEM), UV-vis and Raman spectroscopy. Peak broadening in the XRD shows the formation of
nanocrystalline CdS. TEM images of CdS nanocrystallites revealed the nearly spherical shape morphology
Keywords:
Chalcogenides
of the particles, whereas, TEM images of composite showed the deposition of CdS nanocrystallites on the
Electron microscopy (TEM and SEM) OMWCNT. EDX measurements matches with a 1:1 stoichiometry of Cd and S in CdS nanocrystallites,
Adsorption whereas, that of the composite showed the presence of Cd and S along with C. The vibrational properties
Optical properties of CdS nanocrystallites and their composite with OMWCNT were studied by Raman spectroscopy.
Furthermore, the photocatalytic activity studies for the degradation of methylene blue under visible light
irradiation using these materials were carried out. The surface area calculated using BET surface analyzer
for CdS-OMWCNT composite (148.31 m2/g) was found to be more compared to bare CdS nanocrystallites
(56.78 m2/g). The CdS-OMWCNT composite exhibited very good photocatalytic activity for the degra-
dation of methylene blue under visible light irradiation which has been attributed to the increased
surface area and synergistic effect in the composite compared to bare CdS nanocrystallites.
© 2016 Elsevier B.V. All rights reserved.

* Corresponding author.
E-mail addresses: ssgarje@chem.mu.ac.in, ssgarje@yahoo.com (S.S. Garje).

http://dx.doi.org/10.1016/j.matchemphys.2016.08.040
0254-0584/© 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
2 A.S. Pawar et al. / Materials Chemistry and Physics xxx (2016) 1e9
1. Introduction
Cadmium sulfide is an important n-type semiconductor with a
direct band gap of 2.41 eV at 300 K. Recently many efforts have
been undertaken to synthesize and study the optical properties of
CdS nanoparticles and quantum dots due to their wide range of
applications such as laser light emitting diodes, solar cells and
optoelectronic devices based on nonlinear properties [1e5]. Their
optoelectronic applications include photoelectrochemical cells and
heterogeneous photocatalysis [6e8]. They also have outstanding
potential applications owing to their luminescent properties
[9e12] and quantum size effect [13]. They are used in laser
communication [14], hydrogenation processes, CO-shift reactions
[15,16] and photocatalysis [17].
Carbon nanotubes (CNTs) and carbon nanocomposites have
attracted attention because of their extraordinary properties such
as excellent Young's modulus, good flexibility, high electrical and
thermal conductivity, low density, high specific surface area and
thermal and mechanical stability. They are recognized as re-
inforcements for high-performance, multifunctional composites
[18]. CNTs can be either metallic or semiconducting, depending on
their geometry. One of their most remarkable properties is
electron-transfer processes that can efficiently give rise to a rapid
photo-induced charge separation and a relatively slow charge
recombination [19]. The combination of photocatalysts such as
metal sulfide and CNTs may provide an ideal system to achieve an
enhanced charge separation by photo-induced electron transfer
[20]. These materials have emerging applications in different fields
such as catalysts and sensors because of their rapid electron ki-
netics, semi- and superconducting electron transport and high
tensile strength. They also have applications in biomedical field as
drug delivery systems, as well as in the magnetic separation of
biomolecules [21e24].
The synthesis and characterization of composite systems has
gained prominence in the past few years. Examples of these sys-
tems include carbon nanotubes in contact with TiO2 [25], CdSe
[26,27] and CdS [28]. Of these, CdSeCNT composite is of particular
interest as it is capable of generating photocurrent from visible light
with unusually high efficiency [29].
Various methods have been reported for the synthesis of CdS
nanocrystallites such as microemulsion [30], hydrothermal [31],
microwave [32], thermal evaporation [33] and ultraviolet irradia-
tion [34] routes. In recent years, the doping of CdS nanostructures
has attracted considerable attention due to their applications for
the removal of pollutants from aqueous solutions. It was reported
that some novel physical and chemical properties of CdS could be
obtained either by controlling the particle size and the micro-
structure of CdS or by combining with some other layered com-
pound or solid porous material, such as titanate nanotubes [35],
mesoporous silica [36] and titanosilicate zeolite [37]. One of the
convenient methods for the preparation of metal chalcogenide
nanoparticles and thin films is the use of single-source molecular
precursors (SSPs) in techniques such as solvothermal decomposi-
tion, hot injection method or the aerosol-assisted chemical vapor
deposition technique. The SSPs have many advantages over mul-
tiple source precursors. These include their air stability, low
toxicity, limited pre-reactions and control over stoichiometry.
Herein, we report the use of bis(dipiperidinyldithio-carbamato)
cadmium(II), [Cd(pip.dtc)2] as a single source precursor to pre-
pare cadmium sulfide nanocrystallites and CdS-OMWCNT com-
posite. The composite was fabricated through a one-pot
solvothermal decomposition method using the dithiocarbamate
complex. The as prepared CdS nanocrystallites and CdS-OMWCNT
composite were used for the photodegradation of methylene blue
(MB) under visible light irradiation.
Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
2. Experimental details
2.1. Materials
Cadmium chloride (CdCl2) and ethylene glycol were procured
from S.D. fine-chemicals. Multi-walled carbon nanotubes
(MWCNTs) were purchased from Sigma-Aldrich. The chemicals
were used as purchased without any purification.
2.2. Instrumentation
Elemental analyses (C, H, N and S) of the ligand and the pre-
cursor were carried out by Thermo Finnigan, Italy Model FLASH EA
1112 Series elemental analyzer. Infrared spectra of ligand, precur-
sor, CNTs, CdS nanocrystallites and CdS-OMWCNT composite were
recorded on a Perkin Elmer Spectrum One FTIR Spectrometer in
the 4000 - 400 cm1 range. The thermogravimetric analysis (TGA)
was carried out using a Perkin Elmer instrument, Pyris Diamond
TG/DTA model with heating rate of 10  C min1 in air. 1H and 13C
{1H} NMR spectra were recorded in 5 mm NMR tube in dmso-d6 on
a Brucker-300 spectrometer. The chemical shifts are relative to
internal standard tetramethylsilane. XRD studies were carried on
XRD-7000, Shimadzu X-ray diffractometer using CuKa radiation at
a scan rate of 0.5 min1. The morphologies and elemental analysis
of the materials were carried out using FEI Quanta e 200 Scanning
Electron Microscope (SEM) with an operating voltage of 20 kV and
energy dispersive X-ray analysis (EDX), respectively. Transmission
electron microscopy (TEM) and selected area electron diffraction
(SAED) studies were performed on a PHILIPS, CM 200 microscope
with operating voltages between 20 and 200 kV. The absorption
spectra were recorded on a UV-2450 PC Shimadzu spectrometer in
800e200 nm range. Raman spectra were recorded using the
514 nm line from a diode pumped Nd3þ: YAG laser (RENISHAW in
Via Raman Microscope, Laser 514 nm, Lens 100 xs). The BET ni-
trogen adsorption-desorption isotherms of the samples at liquid
nitrogen temperature (77 K) and gas saturation vapor tension
range were measured by using the surface area analyzer (SMART
SORB 92/93 BET). Approximately 0.1e0.2 g of powder samples
placed in a glass test tube were allowed to degas for 2 h in flowing
nitrogen. This removes contaminants such as water vapors and
adsorbed gases from the samples. The static physisorption iso-
therms were obtained within liquid nitrogen, the amount of liquid
nitrogen adsorption, or desorption from the material as a function
of pressure (P/P0 ¼ 0.025e0.999). Data were obtained by admit-
ting or removing a known quantity of adsorbing gas in or out of a
sample cell containing the solid adsorbent maintained at a con-
stant temperature (77 K). As adsorption or desorption occurs, the
pressure in the sample cell changes until equilibrium is estab-
lished. From the static physisorption isotherm of the samples to
obtain the single layer adsorption capacity, the specific surface
area of the sample was calculated from the BET adsorption
equation.
2.3. Preparation of precursor
The precursor was prepared according to the method described
in Ref. [38].
2.3.1. Preparation of bis(dipiperidinyldithio-carbamato)
cadmium(II) complex
A solution of sodium piperidine dithiocarbamate ligand
(2.1742 g, 9.92 mmol) was added dropwise to a solution of CdCl2
(0.9088 g, 4.96 mmol) dissolved in 30 cm3 water. The reaction
mixture was cooled in an ice bath to 0  C and it was stirred for 1 h.
The white colored precipitate formed was filtered, washed with
 A.S. Pawar et al. / Materials Chemistry and Physics xxx (2016) 1e9
excess distilled water and dried overnight in an oven at 70  C.
(Yield, 1.7980 g, 83.87%, M.P. 258  C).
(Elemental analyses (%) for CdC12H20N2S4 found (calcd): Cd:
26.44 (25.99) C: 32.79 (33.03) H: 4.84 (4.66) N: 6.26 (6.47) S: 28.95
(29.46).
IR: 1484 cm1 (yC-N), 961 cm1 (yC-S), 408 cm1 (yCd-S).
NMR (d in ppm) 1H: 1.65 (m, 8H, -NCH2CH2-), 1.72 (m, 4H,
-NCH2CH2CH2-), 4.15 (t, 8H, -NCH2-).
13 1
C{ H}: 201.831 (C]S), 54.456, 25.891, 23.403 (aliphatic
carbons).
2.4. Surface treatment of MWCNTs [39]
Before carrying out solvothermal decomposition, pristine mul-
tiwalled carbon nanotubes (MWCNTs) were modified by acid
treatment to functionalize the CNTs surface with carboxylic groups
to improve the hydrophilic property. Crude CNTs were immersed in
conc. HNO3 and refluxed for 2 h at 120  C. The resultant mixture
was separated by centrifugation and the material obtained was
washed with deionized water until pH of the solution reached to 7.
Finally, the treated powders were washed with water three times
and dried in an oven at 110  C.
2.5. Synthesis of cadmium sulfide nanoparticles
Cadmium sulfide nanoparticles were prepared by refluxing
0.300 g of precursor in 20 cm3 of ethylene glycol in a 100 cm3 round
bottom flask. The reaction mixture was refluxed under nitrogen
atmosphere for 2 h, the color of the mixture changed to yellow. The
reaction mixture was then cooled to room temperature to give a
viscous yellow solution with suspended particles. Most of the solid
product was recovered by precipitating the solution by addition of
methanol. The particles thus obtained were washed repeatedly
with methanol and dried under vacuum.
2.6. Synthesis of CdS-OMWCNT composite using Cd(pip.dtc)2
precursor by solvothermal decomposition method
In a typical experiment, 60 mg of OMWCNTs were taken in a
250 cm3 two necked round bottom flask. To this 20 cm3 of ethylene
glycol was added and sonicated for half an hour. A black colored
suspension obtained was allowed to stir and reflux in presence of
nitrogen. In another, separate 100 cm3 round bottom flask, 100 mg
of Cd(pip.dtc)2 was taken and dissolved in 20 cm3 of ethylene
glycol. This was then injected into the refluxing solution of
OMWCNT in ethylene glycol. The reaction was allowed to continue
for 2 h followed by cooling under N2 atmosphere. The suspension
obtained was centrifuged at 9000 rpm, washed with methanol and
finally dried under vacuum. The black colored solid powder ob-
tained was characterized by XRD, TEM, EDX, UV, IR and Raman
techniques.
2.7. Photodegradation of methylene blue
The photodegradation study of methylene blue under visible
light irradiation was carried out in absence and presence of CdS
nanocrystallites and the CdS-OMWCNT composite using Hally Uv-
S
00C
Na+
CdCl2 + 2 N -
S S
Scheme 1. Synthesis of bis(dipiperidinyldithio-carbamato)cadmium(II).
Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
3
visible chamber. Analytical reagent grade methylene blue was
used without further purification. A stock solution (100 ppm) of dye
was prepared by dissolving its required quantity in double distilled
water. Further concentrations were prepared by diluting the known
volume of stock solution to the desired volume.
In a typical experiment, 10 ppm solution of MB was prepared
from the stock. 10 mg each of CdS nanocrystallites and CdS-
OMWCNT composite were taken into two separate beakers. To
this, 50 cm3 of 10 ppm solution of MB was added and sonicated for
10 min. The suspensions were magnetically stirred in the dark for
30 min to attain adsorption-desorption equilibrium between dye
and the photocatalyst at room temperature. In a separate glass
beakers, 50 cm3 of 10 ppm MB solution was taken without adding
any catalyst for the point of reference. All beakers were irradiated
under visible lamp for 30 min. The solutions were then centrifuged
to remove the photocatalyst followed by filtration through What-
man filter paper 41. The UV-visible spectra were recorded to eval-
uate the change in absorbance for these samples.
3. Results and discussion
Dithiocarbamates are the compounds obtained by the reaction
of primary or secondary amines with carbon disulfide. Dithiocar-
bamate anions readily react with many metal salts and are versatile
ligands for the formation of the complexes. The precursor was
prepared by reacting CdCl2 with sodium salt of piperidine dithio-
carbamate, pip.dtc (pip.dtc ¼ piperidine dithiocarbamate). The
chemical reaction for the preparation of precursor is given in
Scheme 1.
The ligand, sodium piperidine dithiocarbamate and its cadmium
complex are white in color. The precursor is microcrystalline, stable
in air and soluble in some organic solvents. The ligand and complex
were characterized by elemental analysis, IR and NMR (1H and 13C
{1H}) spectroscopy. The infrared spectrum of the complex has been
compared with the spectrum of ligand and from the shifts in peak
positions and from the intensity lowering, coordination sites have
been ascertained. The band due to yC¼N is observed at ~1484 cm1
in complex which is shifted to lower wavenumber compared to
band positions in the spectrum of the ligand. The band observed at
~961 cm1 in the complex is assigned to y(C-S). In the 1H NMR
spectrum of Na(pip.dtc), the methylene proton signals are observed
as three different chemical shifts at 1.49, 1.51 and 4.23 ppm. There is
no significant change in the peak positions in the spectrum of
cadmium complex.
Before using OMWCNTs for the preparation of CdS-OMWCNT
composite, it was necessary to characterize both pristine
MWCNTs as well as oxidized MWCNTs in order to check whether
functionalization has taken place or not. The pristine MWCNTs and
oxidized MWCNTs were characterized using FTIR, XRD, Raman and
thermogravimetric analysis (TGA) techniques. The details of FTIR
studies are given in section 1.1 in supporting information and the
FTIR spectra of pristine MWCNTs and OMWCNTs are shown in
supplementary Figure S1 (a, b). An increased functionalization of
MWCNTs after treatment with HNO3 is observed [40,41]. Section
1.2 and Figure S2(a, b) in supporting information gives details of
XRD studies and X-ray diffraction patterns of pristine and oxidized
MWCNTs. They have similar diffraction patterns [41]. The Raman
S S
Cd N
N
S
4 A.S. Pawar et al. / Materials Chemistry and Physics xxx (2016) 1e9
Fig. 1. XRD patterns of (a) CdS nanocrystallites and (b) CdS-OMWCNT composite.
spectroscopic studies were carried out to find out magnitude of
disorder incorporated in pristine MWCNTs after the oxidation.
Section 1.3 in supporting information describes the details of this
study. Figure S3 (a) and (b) indicates the Raman spectra of pristine
MWCNTs and OMWCNTs, respectively. The higher ID/IG ratio for
OMWCNTs is due to increased functionalization of CNTs [42,43].
The peaks observed in the Raman spectra of these materials are
consistent with those reported in the literature [44]. Figure S4 (a, b)
show TG curves for pristine MWCNTs and OMWCNTs. The details of
TGA analysis of pristine MWCNTs and OMWCNTs are discussed in
Section 1.4 in the supporting information.
The cadmium complex was used for the synthesis of CdS
nanocrystallites and composite using the solvothermal method.
The solvothermal decomposition of the precursor was carried out
in ethylene glycol. The use of polyols such as ethylene glycol is
Fig. 2. SEM images of (a) CdS nanocrystallites, (b) CdS-OMWCNT composite, EDX of (c) CdS nanocrystallites and (d) CdS-OMWCNT composite.
Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
advantageous as it can control the growth rate of crystal faces of
metal sulfide (CdS) nanostructures and influence the oriented
growth by interacting with these faces via adsorption and
desorption [45]. A similar growth mechanism has been reported for
the preparation of CdS nanostructures in ethylenediamine [45,46].
During solvothermal decomposition the color of the reaction
mixture turned to yellow after refluxing under nitrogen atmo-
sphere finally yielding a yellow powder which was separated by
centrifugation.
Fig. 1(a) shows the XRD pattern of hexagonal CdS. The diffrac-
tion peaks at 2q values of 25.9 , 26.5 , 28.3 and 43.7 can be
indexed to the characteristic (100), (002), (101) and (110) reflection
planes of hexagonal CdS (JCPDS:00-041-1049) with lattice param-
eters a ¼ 4.225 Å and c ¼ 6.280 Å, which are consistent with the
standard values of a ¼ 4.140 Å and c ¼ 6.719 Å (JCPDS:00-041-
1049). The average grain size of 5.2 nm of the CdS nanocrystallites
was calculated using the Scherrer formula from the full width at
half maxima (FWHM) of the peak corresponding to 2q ¼ 26.5 in
Fig. 1(a).
The XRD pattern of the CdS-OMWCNT composite is depicted in
Fig. 1(b). For the CdS-OMWCNT composite, the peaks due to the
(002) and (110) reflections around 2q of 25.9 and 43.7 of the
graphitic carbon were observed. These peaks overlap with the
hexagonal (002) and (110) reflections around 2q of 25.9 and 43.7
of hexagonal CdS. The intensity of these peaks in CdS-OMWCNT
composite is stronger than that of CdS nanocrystallites.
The morphology of the as-prepared CdS nanocrystallite and
CdS-OMWCNT composite were further examined by SEM and TEM.
Fig. 2 (a, b) shows SEM images of CdS and its composite obtained
from the solvothermal decomposition of precursor, respectively.
Cadmium sulfide nanoparticles have the spherical shape
morphology and the nanoparticles are uniform in size. It is found
that the CdS nanoparticles are uniformly deposited on the
OMWCNT (Fig. 2(b)). The as-prepared CdS-OMWCNT composites
display a tendency to agglomerate. The agglomeration may occur
because when the particle size is very small, the particles can easily
 A.S. Pawar et al. / Materials Chemistry and Physics xxx (2016) 1e9
Fig. 3. TEM images of (a) CdS nanocrystallites, (b) CdS-OMWCNT composite, SAED
pattern of (c) CdS nanocrystallites and (d) CdS-OMWCNT composite.
agglomerate due to weak surface forces [47]. Elemental composi-
tion of synthesized products analyzed by EDX reveals the presence
of Cd and S in the atomic ratio close to 1:1 (Fig. 2(c)). The EDX
spectrum of composite also shows the presence of carbon along
with Cd and S (Fig. 2(d)).
The morphology of CdS nanocrystallite and decorated CdS
nanoparticles on oxidized MWCNTs (CdS-OMWCNTs) were exam-
ined by TEM at different magnifications as shown in Fig. 3 (a, b),
respectively. Fig. 3(a) shows the TEM image of CdS nanocrystallites
obtained from solvothermal decomposition showing particles with
a spherical morphology. The SAED pattern contains well defined
rings suggesting presence of highly crystalline materials. The
spacing of the crystallographic planes from the SAED pattern are
0.359 nm, 0.207 nm and 0.189 nm corresponding to the charac-
teristics planes at (002), (110) and (103), respectively (Fig. 3(c)).
Fig. 3 (b) shows the TEM image of CdS-OMWCNT composite
showing dark spots corresponding to CdS nanoparticles and light
tubes corresponding to MWCNTs. The CdS nanocrystallites are
uniformly deposited on sidewalls of oxidized multiwalled carbon
Fig. 4. Absorbance spectra of (a) CdS nanocrystallites and (b) CdS-OMWCNT
composite.
Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
5
nanotubes. Fig. 3(d) shows the SAED pattern of CdS-OMWCNT
composite.
Bulk CdS has an optical band gap of 2.41 eV (515 nm) at room
temperature [32]. The band-edge for CdS samples prepared in this
study is blue-shifted compared to that of the bulk material. This
effect is associated with the CdS nanoparticles being smaller than
the exciton radius of bulk CdS. During preparation there is generally
an increase of particle size of the nanoparticles with time, which is
consistent with an Ostwald ripening process. After injection of the
precursor there is a critical size dependence on the concentration of
the precursor. The depletion of the precursor causes the size dis-
tribution to broaden because smaller, less stable particles aggregate
to form larger particles [48]. Fig. 4(a) shows absorption spectrum of
the CdS nanocrystallites. The optical band-edge shows a blue-shift
in relation to the bulk, an indication of the decrease in particle size.
The absorption spectrum of the CdS-OMWCNT composite is shown
in Fig. 4(b). The absorption peak at 245 nm observed for oxidized
MWCNT remains constant in the CdS-OMWCNT composite spec-
trum [49]. The optical band gap of CdS nanocrystallites calculated
using Tauc plots [50] was found to be 3.03 eV (Fig. 5(a)). The band
gap of CdS-OMWCNT composite was calculated and it was found to
be 2.12 eV shown in Fig. 5(b). The CdS-OMWCNT composites have a
narrower band gap and an increased level of absorption in the
visible-light region. The significant narrowing in band gap was
observed due to the incorporation of CNT into CdS, indicating the
strong interactions between CdS and CNT [51].
Fig. 6 (a, b) shows the FTIR spectra of ethylene glycol capped CdS
nanocrystallites and CdS-OMWCNT composite, respectively. The
infrared spectrum of the CdS nanocrystallites showed the presence
of bands due to ethylene glycol, confirming its role as a capping
agent. The broad band in the 3390e3626 cm1 range can be
assigned to OeH stretching vibrations of pure ethylene glycol [52].
This band is observed at 3395 cm1 in the IR spectrum of CdS
nanocrystallites. The asymmetrical (asym CH2) and symmetrical
(sym CH2) stretching bands were observed at 2949 and 2865 cm1,
respectively. The bending vibrations of CeH bonds of methylene
group occur at 1449 cm1 in pure ethylene glycol [52,53]. These
bands occur at nearly the same position in ethylene glycol capped
CdS nanocrystallites. The FTIR spectrum of the CdS-OMWCNT
composite is shown in Fig. 6 (b). The peak observed at 1713 cm1
is assigned to the characteristic C]O stretching vibration. The shift
of this peak toward lower wave number as compared to oxidized
MWCNT is an indication of the carboxylic ion binding between
nanoparticles and the nanotube. The peak at 3424 cm1 is due to
the OH group of the capped ethylene glycol.
The Raman spectra of the CdS nanocrystallites and CdS-
OMWCNT composite are shown in Fig. 7(a, b). For bulk CdS, the
frequencies for the first order 1LO (longitudinal optical phonon)
and second order 2LO are 305 cm1 and 609 cm1, respectively
[54,55]. In the present study these peaks are observed at
299.19 cm1 and 596.88 cm1 as shown in Fig. 7(a). This kind of
shift in frequency was studied by Tong et al. [56]. It has been
attributed to the grain size and stress effects. Fig. 7(b) shows Raman
spectrum of CdS-OMWCNT composite. It shows the presence of two
strong peaks. The peak at 1589.61 cm1 (G lines) is the Raman-
allowed phonon high-frequency E2g first-order mode. The disor-
der induced peak at 1356.40 cm1 (D lines) may originate from
defects in the curved graph sheets, tube ends, and turbostratic
structure [57,58]. However, two new peaks appeared at
300.69 cm1 and 601.03 cm1 can be attributed to the CdS nano-
crystallite present in the composite. The intensity of these peaks is
low as compared to those of the bare CdS nanocrystallites. The
intensity (ID/IG) ratio shows no increase after deposition of CdS
nanoparticles on oxidized MWCNTs indicating that no significant
sidewall damage has taken place. It also suggests a charge-transfer
6 A.S. Pawar et al. / Materials Chemistry and Physics xxx (2016) 1e9

Fig. 5. Tauc's plot for (a) CdS nanocrystallites and (b) CdS-OMWCNT composite.

Fig. 7. Raman spectra of (a) CdS nanocrystallites and (b) CdS-OMWCNT composite.
Fig. 6. FTIR spectra of (a) CdS nanocrystallites and (b) CdS-OMWCNT composite.

process and chemical interaction between the CdS nanoparticles

[43].
Surface area of the CdS nanocrystallites and CdS-OMWCNT
composite were measured using BET surface area analyzer. The
Nitrogen gas was used as an adsorbent for the analysis. The results
are interpreted based on the adsorptionedesorption of N2 at 77 K.
The BET surface area values obtained for the CdS nanocrystallites
and CdS-OMWCNT composite were 56.78 and 148.31 m2/g,
respectively. The high surface area of CdS-OMWCNT composite
suggests that additional adsorption sites are available due to
attachment of CdS nanoparticles to oxidized multiwalled carbon
nanotubes. This indicated that the cadmium sulfide nano-
crystallites doped on the surface of CNTs, as shown by TEM images,
enhanced their surface area and hence increased the number of
sites for adsorption.
Photocatalysis is a process by which a semiconductor material
absorbs light of energy greater than or equal to its band gap,
causing excitations of valence band electrons in the conduction
Fig. 8. Photocatalytic degradation of Methylene blue dye under visible light irradiation
band. Such charge separation leads to the formation of electron- by using CdS nanocrystallites and CdS-OMWCNT composite.
hole pairs which can further generate free radicals in the system.
The resulting free-radicals such as hydroxyl (
OH) are very efficient
oxidizers of organic materials and can degrade pollutants [59,60]. extensively studied visible-light-driven photocatalyst [61,62].
CdS with a band gap of 2.4 eV, is a simple and probably the most However, the efficiency of CdS is very low because of the rapid

Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
 A.S. Pawar et al. / Materials Chemistry and Physics xxx (2016) 1e9
recombination of the photogenerated electrons and holes. Most of
the studies concerning CdS are focused on the enhancement of
photocatalytic efficiencies by preparing nanocomposites contain-
ing CdS and other semiconductors, such as TiO2, ZnO, MoS2, PdS or
layered titanate nanosheets, to suppress the fast recombination of
electrons and holes [63e68]. On the other hand, recent studies have
revealed that carbon nanomaterials, particularly carbon nanotubes
(CNTs), are promising co-catalysts in photocatalysis. The enhance-
ment effects of CNTs on the photocatalytic performance of TiO2, a
UV-light-driven photocatalyst, have been investigated by several
research groups [69e72].
It is proposed that CNTs are capable of accepting, transporting
and storing electrons, and thus retarding or hindering the recom-
bination of the electrons with the holes remaining on the semi-
conductor particles. However, the studies on the enhancement
effects of carbon nanomaterials on photocatalytic behaviors of CdS
are not numerous. Kamat and co-workers [73] reported that the
deposition of CdS onto CNTs could lead to a fast electron transfer
from photo-excited CdS into CNTs. Recently, several studies dis-
closed that the incorporation of CNTs into CdS could promote its
photocatalytic performance [74,75].
Two steps are involved in the photocatalytic decomposition of
dyes. These are, adsorption of dye molecules and photo-
degradation. In order to exclude the influence of adsorption pro-
cess, catalyst-dye mixture was allowed to equilibrate for 30 min to
achieve adsorption equilibrium before the photocatalytic reaction.
The photocatalytic activity of the prepared samples was evaluated
by the photodegradation of methylene blue aqueous solution under
visible light irradiation. Fig. 8 represents the degradation of
methylene blue over the CdS nanocrystallites and CdS-OMWCNT
composite under the visible light irradiation. It can be clearly
seen that the absorbance of methylene blue gradually decreases
from blank MB (without catalyst) to that containing CdS nano-
crystallites. In presence of CdS-OMWCNT composite the absorption
decreases drastically suggesting almost complete degradation of
the MB. The degradation efficiency of CdS nanocrystallites and CdS-
OMWCNT composite were calculated according to the equation
reported in literature [76]. It is observed that the best photo-
catalytic degradation of methylene blue occurs with CdS-OMWCNT
composite where 92.23% degradation is complete in 30 min and
80.09% degradation is completed for CdS nanocrystallites.
It is evident from the above discussion that CdS-OMWCNT
composite shows best photo-catalytic efficiency for degradation
Fig. 9. Samples of (a) 10 ppm MB (without light) (b) 10 ppm MB (with light) (c) MB
(CdS nanocrystallites) and (d) MB (with CdS-OMWCNT composite) after photo-
degradation for 30 min.
Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040
7
of methylene blue dye. The photographs of degraded methylene
blue dye samples after exposure to visible light in presence of CdS
nanocrystallites and CdS-OMWCNT composite are shown in Fig. 9.
The color intensity decreases from blank MB to composite con-
taining MB.
The degradation efficiency of CdS-OMWCNT composite is found
to be better than that of CdS nanocrystallites which can be attrib-
uted to relatively higher surface area in case of former (148.31 m2/
g). In addition, the high activity can also be attributed to the syn-
ergistic effects due to high electron absorptivity and high charge
mobility of carbon nanomaterials [77].
4. Conclusion
The one pot synthesis of CdS nanocrystallites and CdS-OMWCNT
composite was achieved by a simple solvothermal decomposition
method. The materials obtained were further characterized by XRD,
SEM, EDX, TEM, UV-visible and Raman techniques. The oxidized
multiwalled carbon nanotubes obtained by chemical treatment
were found to be good support for decorating CdS nanoparticles on
them which leads to formation of CdS-OMWCNTs composite. The
oxidation of MWCNTs breaks some bonds and inserts functional
groups that can be considered as defects. The CdS-OMWCNT
composite has excellent photocatalytic activity over CdS nano-
crystallites for the degradation of MB solution under visible light
irradiation, which has been assigned to higher surface area of
composite and also to synergistic effect of carbon materials due to
high electron absorptivity and high charge mobility.
Acknowledgements
The financial support provided under DST-PURSE scheme is
highly acknowledged. Thanks are also due to SAIF, IIT Bombay for
providing TEM images and SAED patterns, Icon Analytical labora-
tory for providing SEM facility and Department of Physics, Uni-
versity of Mumbai for Surface area measurements. The authors also
acknowledge the India/Brazil/South Africa (IBSA) program of
collaboration for funding.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.matchemphys.2016.08.040.
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Please cite this article in press as: A.S. Pawar, et al., Synthesis and characterization of CdS nanocrystallites and OMWCNT-supported cadmium
sulfide composite and their photocatalytic activity under visible light irradiation, Materials Chemistry and Physics (2016), http://dx.doi.org/
10.1016/j.matchemphys.2016.08.040