Nano-Structures & Nano-Objects 16 (2018) 24–30

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Nano-Structures & Nano-Objects

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

CdS sensitized TiO2 nano heterostructures as sunlight driven

photocatalyst
Jithesh Kavil a , Ahmed Alshahrie b , Pradeepan Periyat a, *
a
Department of Chemistry, University of Calicut, Kerala, 673635, India
b
Centre of Nanotechnology, King Abdul Aziz University, Jeddah, 21589, Saudi Arabia

graphical abstract

article info a b s t r a c t
Article history: Sunlight harvesting nano heterostructure materials with excellent photocatalytic activity has received
Received 10 January 2018 considerable attention in recent years. Here we meticulously investigated the effect of CdS nano crystal
Received in revised form 12 March 2018 loading on the light absorption capacity and the photocatalytic activity of TiO2 nanomaterials by assem-
Accepted 27 March 2018
bling TiO2 -CdS heterostructures. A distinct heterostructure was established in the presently reported
hybrid system with 10 wt% CdS incorporation into TiO2 and the photocatalytic study showed that TiO2 -
Keywords:
CdS10 has 3.5 times higher catalytic activity than bare TiO2 . This superior photocatalytic performance
Photocatalyst
Nano heterostructure is attributed to the excellent light absorption, high surface area and the slow rate of recombination of
Nanomaterials photogenerated charge carriers of TiO2 -CdS10 hetero structures. A mechanism was also proposed for the
CdS CdS sensitized sunlight driven photocatalytic degradation of methyl orange dye in presence of CdS–TiO2
TiO2 nano heterostructure.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction harvesting photocatalyst [5,6]. Visible light response of TiO2 has

TiO2 based heterogeneous catalysis becomes an efficient tech-
nique for the photocatalytic oxidative removal of dissolved organic
and inorganic contaminants in water due to its cost effective-
ness, and the distinctive photocatalytic activity [1–4]. It is the
bandgap energy of TiO2 (3.2 eV) that limits its application as solar
* Corresponding author.
E-mail address: pperiyat@uoc.ac.in (P. Periyat).
been modified by various approaches such as metal and nonmetal
doping in an attempt to tailor the band gap [7,8], photosensi-
tization by anchoring organic chromospheres [9] etc. In recent
years heterojunction photocatalyst fabrication via hybridizing TiO2
with suitable narrow band gap semiconductors such as CdS, Cu2 O,
ZnO, etc. had received considerable attention among the scientific
community due to its excellent light absorption ability, improved
photocatalysis and also photo stability [10–12].

https://doi.org/10.1016/j.nanoso.2018.03.011
2352-507X/© 2018 Elsevier B.V. All rights reserved.
 J. Kavil et al. / Nano-Structures & Nano-Objects 16 (2018) 24–30
CdS act as an excellent sunlight harvesting material owing to
its narrow band gap (2.4 eV) and can be used as a sensitizer for
wide band gap semiconductors [13]. Valance band and conduction
band levels of CdS semiconductor lies above that of TiO2 which
facilitate effective charge separation by reducing the possibility for
photo generated electron–hole pair recombination [14]. CdS sen-
sitized TiO2 catalysts have also been exploited as photocatalyst for
hydrogen production from water [15,16] as photoelectrode in dye
sensitized solar cells to improve the efficiency of the cells [17,18]
and as highly efficient charge carriers in heterogeneous photo-
catalysis [19,20].
Photocatalytic activity of CdS sensitized catalysis by TiO2
nanoparticles have been reported recently by Shuli Bai et al., and
Li et al., for the degradation of Rhodamine B and NO gas oxidation
respectively [21,22]. They found that the surface incorporation
of CdS crystals had a marked effect on the photoactivity of TiO2 .
The selective oxidation of alcohol to aldehyde in presence of CdS
nanorods on the surface of TiO2 was reported by Liu et al. [23]. Very
recently tremendous work on visible light driven CdS decorated
TiO2 photocatalysts have been developed for the oxidative removal
of organic dyes from aqueous textile effluents, which is one of the
major components in water pollution [24,25]. Xu et al., [26] have
developed a simple design for encapsulating CdS nano spheres
into a thin TiO2 shell in order to improve the charge transport
properties and the selective redox reactions under visible light.
In this work remarkable increase in photoactivity was obtained
due to effective interfacial hybridization between CdS and TiO2 .
As compared previous reports the present work embodies our
attempt to fabricate CdS hybridized TiO2 photocatalysts in which
special attention was made to optimize the minimum concen-
tration of CdS required to sensitize TiO2 matrix. Hydrothermal
method was adopted to fabricate the different compositions of
TiO2 -CdS nano hybrid systems (0%, 1%, 5% and 10%), out of which
10% CdS incorporation was found to be the optimum concentration
for the oxidative removal of organic pollutant. Toxic and mutagenic
methyl orange dye [27] was selected as the reference system to
study the photocatalytic properties of the CdS sensitized TiO2 nano
hybrid system. Hopefully the work would provide an insight for the
further development of TiO2 based nano hetero systems for energy
and environmental applications.
2. Experimental
2.1. Synthesis of CdS nanoparticles
All the chemicals used in these experiments were used as
purchased without further purification. CdS nanoparticles were
synthesized by hydrothermal method. In a typical procedure 0.1
M cadmium nitrate (Merck) was dissolved in 50 mL deionized
water, then 0.3 M aqueous thiourea (Merck) solution was added to
the above solution and the stirring continued for another 30 min.
The homogeneous solution obtained was transferred to 100 mL
Teflon lined stainless steel autoclave and kept at a temperature of
150 ◦ C/12 h. The obtained precipitate was washed with water and
dried at a temperature of 80 ◦ C/12 h.
2.2. Synthesis of TiO2 -CdS heterostructure
TiO2 -CdS nano hetero systems with different weight percentage
of CdS (0, 1, 5, and 10%) was prepared by hydrothermal method
and the samples were labeled as TiO2 , TiO2 -CdS1, TiO2 -CdS5 and
TiO2 -CdS10. Briefly, for the synthesis of the composite samples,
calculated amount of synthesized CdS nano crystals were ultra-
sonically dispersed in 50 ml, 1:1 mixture of water and ethanol.
The above dispersion was added carefully in to a 250 ml beaker
containing 0.4 M titanium tertiary butoxide (Sigma Aldrich) in
25
50 mL isopropyl alcohol (Merck). The titania precursor undergo
hydrolysis and condensation reaction in water–ethanol medium
to form a sol. The obtained sol was vigorously stirred for 4 h
and transferred to 100 mL stainless steel autoclave and kept at a
temperature of 180 ◦ C/12 h. The product was washed several times
with ethanol acetone mixture, dried and calcined at 300 ◦ C/2 h in
a muffle furnace. Bare TiO2 nanoparticles (TiO2 -CdS0) were also
synthesized by a similar method without the addition of CdS.
X-ray diffraction studies of all the samples were carried out
using Bruker X-ray diffractometer using CuKα radiation. FTIR spec-
tra was analyzed using Jasco-FT/IR-4100 spectrometer. UV–visible
absorption and diffuse reflectance spectral studies were carried
out on a Jasco-V-550-UV–vis spectrophotometer. HRTEM images
were obtained from JEOL, JEM-ARM200F transmission electron
microscope. Raman spectra of the samples were recorded on a
Thermo scientific DXR 532 nm laser Raman microscope. X-ray
photoelectron spectroscopy (XPS) analysis was carried out from
Ultra axis Kratos Analytical, U. K, XPS instrument with an Al Kα X-
ray source. BET surface area measurements (N2 adsorption) of the
samples were done by Micromeritics Tristar 2 USA surface area and
porosity analyzer after degassing at 200 ◦ C for 2 h. Photolumines-
cence of the different catalysts were measured using Perkin Elmer
LS55 fluorescence spectrometer.
2.3. Photocatalytic study
Methyl orange (herein referred onwards as MO) degradation
in presence of TiO2 -CdS heterostructure photocatalyst was inves-
tigated under natural sunlight with light intensity ∼75,000 lux.
Accurately 0.05 g in 500 mL (0.1 gL−1 ) of the different catalysts
was separately dispersed in 10−4 M MO solution for 20 min for
better adsorption of the sensitizer on catalyst surface. After stirring
in the dark, 5 mL of the analyte solution was taken out from
the system, centrifuged to remove any catalyst present and initial
concentration (Co ) was determined using UV–visible absorption
spectrometer. The concentrations (C ) of the analyte after the com-
mencement of the photodegradation at different time intervals
were measured by monitoring the decrease in intensity of the
absorption maxima of the dye.
3. Results and discussion
3.1. Crystal structure and morphology
X-ray diffraction patterns of pure TiO2 and CdS along with
different composition of TiO2 -CdS is shown in Fig. 1. XRD peaks
in Fig. 1(a) at 2θ values 25.4◦ , 38.1◦ , 48.1◦ , 54.6◦ , 62.9◦ is obtained
from the diffracted beams from (101), (103), (200), (105) and (211)
crystal planes of anatase TiO2 (JCPDS No. 21-1272). Diffraction
peaks in Fig. 1(e) at 26.5◦ , 43.9◦ and 52.0◦ could be indexed to
(111), (220) and (311) phases of cubic crystalline CdS (JCPDS No.
10-0454). It was observed that the characteristic peaks of anatase
TiO2 and CdS (marked as *) are preserved at TiO2 -CdS10 (Fig. 1(d))
composite which indicates an effective hybridization between the
two phases for this particular composition.
3.2. Transmission electron microscopy (TEM)
TEM was used to analyze the microstructure and the particle
size of different catalysts. TEM images in Fig. 2(a) displays the
homogeneous dispersion of CdS nano crystals in TiO2 matrix with
an average particle size of 10–15 nm. The crystallite size calculated
from the XRD data by using Debye Scherrer method was found to
be 8–10 nm. HRTEM image (Fig. 2(b)) of the TiO2 -CdS10 displays
two types of lattice planes with interplanar distance 0.34 nm (101
plane of TiO2 ) and 0.32 nm (111 plane of CdS) composite unequiv-
ocally confirm wonderful hybridization established between TiO2
and CdS nanoparticles in TiO2 -CdS10 heterostructure photocata-
lyst.
26 J. Kavil et al. / Nano-Structures & Nano-Objects 16 (2018) 24–30

Table 1
BET surface area and pore size measurements.
Catalyst BET surface area/m2 g−1 Pore volume/cm3 g−1 BJH desorption pore size/nm
TiO2 134 0.48 12.6
TiO2 -CdS1 140 0.47 11.2
TiO2 -CdS5 126 0.29 8.2
TiO2 -CdS10 153 0.31 6.8
CdS 39 0.14 11.4

Fig. 1. XRD patterns of (a) TiO2 (b) TiO2 -CdS1 (c) TiO2 -CdS5 (d) TiO2 -CdS10 and (d)
CdS.

3.3. Raman spectroscopy

Fig. 3 shows the room temperature Raman spectra of TiO2

and TiO2 -CdS nano crystals along with the spectra of CdS. Ac-
cording to factor group analysis tetragonal anatase TiO2 exhibits
four Raman active vibration modes A1g+B1g+B2g+Eg. The peak at
144 cm−1 corresponds to Eg mode and the peak at 396 cm−1 is due
to B1g vibration modes of anatase TiO2 [28]. The peak at 516 cm−1 Fig. 3. Raman spectra of TiO2 , TiO2 -CdS10 and CdS.
is resulted from the B1g and A1g modes of anatase TiO2 and the
Raman band at 639 cm-1 can be attributed to Eg vibration of anatase
phase [29]. Raman spectra of CdS is dominated by well-defined
broad peak at 296, 593 and 890 cm−1 which is ascribed to the first 3.4. X-ray photoelectron spectroscopy (XPS)
order longitudinal optic (LO) vibration mode (E1) and second order
LO (E2) and third order LO of CdS unit cell [30,31]. Relatively broad Surface probe technique was used to determine the surface
band for CdS is due to reduced crystallinity of CdS phase and which chemical state and composition of the materials. As depicted in
is evident from the XRD studies. Raman spectra of composite TiO2 - the survey XPS spectrum in Fig. 4(a), the elemental composition
CdS10 is dominant with its component phases, shows excellent on the surface of the composite, TiO2 -CdS10 was found to be Ti,
dispersion of CdS over TiO2 matrix. Cd, S and O elements. Peaks at 464.05 and 458.35 eV in Fig. 4(b) are

Fig. 2. TEM image of (a) TiO2 -CdS10 and (b) HRTEM image of TiO2 -CdS10.
 J. Kavil et al. / Nano-Structures & Nano-Objects 16 (2018) 24–30 27

Fig. 4. XPS spectra of TiO2 -CdS10 nanocomposites: (a) The whole survey spectrum; (b) Ti2p XPS spectrum; (c) O 1 s XPS spectrum; (d) Cd 3d XPS spectrum and (e) S 2p XPS
spectrum.

the characteristic peaks correspond to Ti2p3/2 and Ti2p1/2 binding
energies. The difference between the two peaks was found to be
5.7 eV which is the characteristics of the abundance of Ti4+ on the
surface of the catalyst [32]. XPS spectrum in Fig. 4(c) at 529.6 eV
is obtained from O1s binding energy and the shoulder peak of O1S
spectra is due to the contribution from CO3 2− species (530–531 eV)
present in the low temperature processed samples [33]. Two sharp
peak observed in Fig. 4(d) at binding energies of 405 and 412 eV
can be assigned to Cd3d3/2 and Cd3d5/2 respectively. Moreover a
spin orbit separation of 6.7 between these two peaks confirms the
presence of Cd2+ on the surface of the material [24]. The doublet
peak in Fig. 4(e) at 160.5 and 161.9 eV indicates the presence of
S2− ions on the surface of the heterostructure which corresponded
to S2p1/2 and S2p3/2 states [24]. The shoulder peak in S2p at 162–
163 eV can be attributed to the contribution from R–S–H groups
at the surface of the TiO2 -CdS nanocomposite sample which is also
originated from the partial decomposition of organic groups in the
catalyst [34,35]. XPS spectral data further confirms the formation
of heterostructure between TiO2 and CdS.
3.5. BET surface area
Photocatalytic activity of a material is greatly influenced by the
change in surface property of the material. BET-N2 gas adsorption
studies were normally used for determining the surface area, and
pore size distribution of the solid materials. The N2 adsorption–
desorption isotherms in Fig. 5 and BJH pore-size distribution curves
of the different catalyst materials were given as inset figure. BET
surface area, pore sizes and pore volumes were summarized in
Table 1. Adsorption isotherm indicates a type IV physisorption
curve with H3 hysteresis loop which is the characteristic feature
of a mesoporous material with pore size between 2–50 nm [36]. It
28 J. Kavil et al. / Nano-Structures & Nano-Objects 16 (2018) 24–30
Fig. 5. BET N2 adsorption isotherm of various catalysts and the inset shows their
pore size distribution curves.
Fig. 6. (a) UV–visible absorption spectra and (b) Tauc plot of the catalyst samples.
was observed from Fig. 5 that compared to other samples capillary
condensation or hysteresis closure was observed at low pressure
region for CdS10 and CdS. This difference in adsorption isotherm
may be due to wide range of pore size distribution in these samples
as evidenced from inset Fig. 5. In addition to crystallinity and rate of
electron–hole pair recombination, surface area of the catalyst play
a key role in photocatalysis. It is clearly observable from Table 1
that the surface area of TiO2 -CdS10 composite is greater than that
of other catalysts. The significant increase in photoactivity for TiO2 -
CdS10 was attributed to the high surface area which can provide
more reactive sites during photodegradation.
Fig. 7. Photoluminescence (PL) Spectra of the various catalysts.
Fig. 8. (a) Photodegradation curve and (b) First order rate constant (k, min−1 ) value
of methyl orange degradation in presence of TiO2 , TiO2 -CdS1, TiO2 -CdS5, TiO2 -
CdS10 and CdS.
3.6. UV–visible absorption spectra and Tauc plot
UV–visible absorption spectra and the Tauc plot of all samples
were given in Fig. 6. Two distinct absorption edges possessed by
the composite samples strongly supported the sensitization of
TiO2 by the chromaphoric CdS semiconductor. It can be seen from
Fig. 6(a) that the light absorption capability of bare TiO2 is limited
to ultraviolet region due to its wide band gap (3.24 eV) and the
band edge occurs at around 400 nm. While introducing the CdS
phase in TiO2 the light absorption shifted to visible light due to
the influence of narrow band gap CdS which act as a sensitizer to
harvest visible region of the spectra. The light absorption of the
composites; CdS1, CdS5, CdS10 were shifted to 405, 565 and 574
nm which corresponds to respective band gap of 3.20, 2.15 and 2.12
eV respectively (Fig. 6b).
 J. Kavil et al. / Nano-Structures & Nano-Objects 16 (2018) 24–30
3.7. Photoluminescence spectra
Photoluminescence (PL) spectroscopy is a powerful technique
to determine the fate of photo excited charge carriers in semicon-
ductors [37]. To correlate the photocatalytic efficiency with the
charge separation efficiency of the catalysts, fluorescence quench-
ing of the materials where analyzed at an excitation wavelength of
280 nm (Fig. 7). The obtained peak at 573 nm for all the samples
arises due to the recombination of excited charge carriers at the
band edge [38]. Compared to other samples PL intensity is weaker
for TiO2 -CdS10, this lower intensity is ascribed to the lower rate
of electron–hole recombination and effective separation of charge
carriers in this particular system [39]. Photocatalytic study showed
that amongst the studied samples, TiO2 -CdS10 exhibit greater
photocatalytic efficiency and the results are in agreement with the
fluorescence quenching data. Even though the PL intensity of bare
TiO2 is very low, the photocatalytic efficiency was found to lesser
than TiO2 -CdS10 because of the reduced surface area possessed by
bare TiO2 catalyst as described in Table 1.
3.8. Photocatalysis
Photocatalytic activity of the prepared catalysts TiO2 , TiO2 -
CdS1, TiO2 -CdS5, TiO2 -CdS10 and CdS have been studied under
sunlight in presence of MO as the target system. The degradation
curve, C/CO Vs time of MO degradation in presence of various
catalysts is shown in Fig. 8(a). CdS10 nano hybrid systems have ex-
hibited an excellent catalytic activity among the various catalysts
and almost complete degradation of the dye solution was occurred
in 40 min of sunlight illumination. The photocatalytic results are
in agreement with fluorescence spectral studies. PL results show
a decrease in intensity with blue shift for the particular hybrid
material TiO2 -CdS10 which indicates an effective charge transfer
between the two phases.
Dye degradation kinetics in presence of various catalysts obeys
Langmuir–Hinshelwood first order equation ln(Co/C) = kt, where
Co and C are the concentrations of the dye solutions before and
after exposure to sunlight respectively. Slope of the straight line
obtained by plotting ln(Co/C) Vs time t gives the value of k (min−1 ).
Calculated rate constant of the disintegration reaction for different
catalytic reactions are arranged as bar diagram in Fig. 8(b). The
rate of the reaction is dramatically enhanced by incorporating 10
wt% CdS nano crystals in anatase TiO2 (TiO2 -CdS10). Highest rate
constant of 2.8 × 10−2 min−1 , which is about 3.5 times that of bare
TiO2 unequivocally supports the superior catalytic performance of
10 wt % CdS sensitized TiO2 nano heterostructure photocatalyst.
3.9. Mechanism for MO degradation in presence of CdS sensitized TiO2
Based on the above results and discussions a plausible mecha-
nism was proposed for the sunlight driven photocatalytic degra-
dation of MO dye over TiO2 -CdS nano heterostructure photocata-
lyst. As depicted in graphical abstract, on illumination with solar
radiation electrons were ejected from the VB to CB of CdS due to
its narrow energy gap of around 2.2 eV. Since the CB of anatase
TiO2 is about 0.5 eV more positive than CB of TiO2 , photogen-
erated electrons are transferred from the CB of CdS to that of
TiO2 whereas the VB of CdS acts as hole centers due to the local-
ized electrons [34]. This charge delocalization remarkably reduces
the rate of electron–hole recombination and thereby facilitates
oxidation–reduction process. The CB electrons are trapped by O2
to form reactive oxygen species (O2−. ) and H2 O2 . These interme-
diates react together to form hydroxyl radical (OH. ) which is a
powerful oxidizing agent capable of degrading dissolved organic
29
pollutants [40–44]. The possible reactions for the photocatalytic
MO degradation are given as follows
TiO2 /CdS + hγ (visible) → e− CB + h+ VB
e− CB + O2 → O2 .−
.
h+ −
VB + OH → OH
O2 .− + 2H+ + 2e− → O2 + H2 O2
O2 .− + H2 O → H2 O. + OH−
H2 O. + H2 O → H2 O2 + OH.
H2 O2 → 2OH.
OH. + MO dye → CO2 + H2 O
4. Conclusions
In summary, nano crystalline TiO2 -CdS nano hybrid systems
were synthesized by hydrothermal method and the visible light
absorption capability of the bare TiO2 nanoparticles were found
to be dramatically improved by CdS incorporation. XRD, Raman
studies and TEM analysis strongly supported the coupling between
two heterogeneous phases. Amongst the synthesized catalysts,
TiO2 assembled with 10 wt% CdS (TiO2 -CdS10) shows excellent
sunlight driven photocatalytic activity towards the degradation
of methyl orange, with a degradation rate of 2.8 × 10−2 min−1 ,
which is about 3.5 times faster than that of bare TiO2 . From the
fluorescence quenching studies and BET results it can be concluded
that the effective charge separation efficiency, high surface area
and the synergetic action of all these factors are responsible for
the remarkable enhancement in the photocatalytic activity of TiO2 -
CdS10 photocatalyst. Present work may be good reference for the
development of sunlight harvesting nano heterostructure photo-
catalytic materials for energy and environmental applications.
Acknowledgment
One of the authors Jithesh Kavil is grateful to University Grants
Commission, Govt. of India for FDP fellowship.
Conflict of interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
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