Materials Research Bulletin 74 (2016) 387–396

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Materials Research Bulletin

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

Microwave-assisted polyol synthesis and characterization of

pvp-capped cds nanoparticles for the photocatalytic degradation of
tartrazine
Maher Darwisha , Ali Mohammadia,b,* , Navid Assia
a
Department of Drug and Food Control, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran
b
Nanotechnology Research Centre, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Article history: Polyvinylpyrrolidone capped cadmium sulfide nanoparticles have been successfully synthesized by a
Received 16 June 2015 facile polyol method with ethylene glycol. Microwave irradiation and calcination were used to control the
Received in revised form 1 November 2015 size and shape of nanoparticles. Characterization with scanning electron microscopy revealed a restricted
Accepted 3 November 2015
nanoparticles growth comparing with the uncapped product, hexagonal phase and 48 nm average
Available online 10 November 2015
particle size were confirmed by X-ray diffraction, and finally mechanism of passivation was suggested
depending on Fourier transform infrared spectra.
Keywords:
The efficiency of nanoparticles was evaluated by the photocatalytic degradation of tartrazine in
A. Chalcogenides
A. Nanostructures
aqueous solution under UVC and visible light irradiation. Complete degradation of the dye was observed
B. Chemical synthesis after 90 min of UVC irradiation under optimized conditions. Kinetic of reaction fitted well to the pseudo-
C. X-ray diffraction first-order kinetic and Langmuir–Hinshelwood models. Furthermore, 85% degradation of the dye in 9 h
D. Catalytic properties under visible light suggests that cadmium sulfide is a promising tool to work under visible light for
environmental remediation.
ã 2015 Published by Elsevier Ltd.

1. Introduction higher surface area-to-volume ratio, and increased band-gab

During the last two decades, photocatalytic materials received a
large quantity of research interest as they have a great potential to
be applied in detoxification of environmental organic pollutants
and as a clean energy source [1]. Semiconductor heterogeneous
photocatalysts such as TiO2, ZnO, SnO2, WO3, Fe2O3, and CdS have
been intensively investigated in the area of water and air
purification and in remediation reactions [2].
Like other advanced oxidation procedures (AOPs), the common
characteristic of photocatalytic materials is the generation of very
reactive species such as, principally but not exclusively, hydroxyl
radicals (HO
), which initiate a series of reactions leading
eventually to the destruction of the target pollutant [3]. Recently,
nanostructures of these photocatalysts have attracted more
consideration as they are expected to have higher photocatalytic
activity than their bulk counterparts due to their smaller size,
* Corresponding author art: Department of Drug & Food Control and
Nanotechnology Research Centre, Faculty of Pharmacy, Tehran University of
Medical Sciences, P.O. Box 14155-6451, Tehran, Iran. Fax: +98 21 88358801.
E-mail addresses: m-darwish@razi.tums.ac.ir (M. Darwish),
alimohammadi@tums.ac.ir (A. Mohammadi), navid_a30@yahoo.com (N. Assi).
energy which in turn lead to higher redox potentials [4].
Cadmium sulfide (CdS), a typical metal chalcogenide semicon-
ductor with a direct band gap Eg  2.43 eV at room temperature [5],
has become one of the most considerable materials in research
communities due to its diverse promising applications in the field
of solar cells, photoelectronic devices and photocatalysis [6]. This
material has shown better catalytic functions compared to those of
TiO2 due to the rapid generation of electron–hole pairs by
photoexcitation [7]. Nevertheless, CdS has the fatal photocorrosion
problem due to the self-oxidation by the generated hole [8]. To
overcome such a problem, an effective approach is to cover the
nanoparticle core surface with a polymeric capping agent which
might also help to stabilize the surface, control the growth, and
prevent agglomeration of the nanoparticles [9–11].
Many methods have been utilized for the synthesis of CdS
nanostructures such as co-precipitation [7,12], polyol [13],
solvothermal [14,15], hydrothermal [16], non-aqueous chemical
method [17], and chemical bath deposition [18]. Among these
different processes, the polyol method appears as an easy to carry
out with many other advantages: a uniform shape, a narrow size
distribution, and a low degree of agglomeration [19]. This method
generally uses poly-alcohol like ethylene glycol (EG), diethylene

http://dx.doi.org/10.1016/j.materresbull.2015.11.002
0025-5408/ ã 2015 Published by Elsevier Ltd.
388 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396
glycol (DEG) or 1,2-propanediol as both solvent and reducing agent
[20]. Furthermore, due to the relatively high dipole moment and
loss factor of polyol solvents, they are also suitable for microwave
assisted route. In this regard, using microwave in the synthesis of
nanoparticles is considered a modern and rapidly developing
method. It has been evidenced that microwave irradiation gives a
narrow particle size distribution of nanocrystals with a high purity
in a short reaction time in addition of being cheap and
environmentally friendly [21–23].
Tartrazine (Acid Yellow 23; FD&C Yellow No. 5), as an azo dye,
has been chosen for this study due to its extensively use as a
colorant in food, cosmetics, pharmaceuticals and textile industry
[24], as well as its high stability against biodegradation and
conventional wastewater treatment procedures after disposal
from industrial effluent [25]. The toxic concentration of tartrazine
on human has been reported to be 7.5 mg k1 [26]. This compound
is known to cause allergic reactions such as asthma and urticaria
and appears to cause more allergic and intolerance reactions than
other azo dyes [27].
Previously reported works on the removal of tartrazine from
aqueous solutions include mainly conventional methods like
adsorption [28,29], ecocoagulation [30], and filtration [31] which
are known not to effectively degrade pollutant but merely transfer
it to another phase where it is more concentrated [32]. Whereas
other reports have shown that tartrazine could be degraded
employing AOPs like: ozonation [33], electrochemical oxidation
[34], photo Fenton oxidation [35], UV/H2O2 [36,37], photolytic
[38], and photocatalytic oxidation [27,39–46].
Most of photocatalytic methods have utilized TiO2, which was
extensively studied and known to have some drawbacks such as
expensive precursors and inability to absorb visible light [47,48].
Hence, the aim of the present work was first, to fabricate CdS
nanoparticles by a chemical synthesis utilizing the polyol method
with ethylene glycol as a solvent and polyvinylpyrrolidone (PVP) as
a capping agent. Microwave irradiation followed by calcination
was used for size and shape controlling. Further, to investigate the
structure, size, and morphology of the synthesized products using
various characterization techniques. In second, the work aimed to
Fig. 1. A schematic of the preparation of PVP-CdS nanoparticles.
study the catalytic properties of these nanoparticles for oxidation
of tartrazine, as an organic pollutant, in aqueous solution under
UVC and visible light irradiations, taking in consider the effect of
different parameters such as initial pH of solution, amount of
nanoparticles, and concentration of pollutant in the degradation
process.
2. Expermental
2.1. Materials and reagents
All reagents used in our experiments were of analytical grade
and used as received without any further purification. Tartrazine
powder ( 85%) was obtained from Sigma–Aldrich (Germany).
Cadmium chloride 2.5-hydrate (CdCl2 2.5H2O) and thiourea (SC
(NH2) 2) were obtained from Scharlau (Spain). Polyvinylpyrroli-
done (MW  25,000 g mol1), ethylene glycol, glacial acetic acid,
and ammonia solution (25%) were obtained from Merck
(Germany). Double distilled water was used for the preparation
of all samples.
2.2. Synthesis of nanoparticles
In a typical process, 9 g of cadmium chloride 2.5-hydrate and 3 g
of PVP were separately dissolved in 30 mL and 20 mL of EG,
respectively, and then heated with stirring for 60 min at 75  C. The
two solutions were then mixed slowly and heated with stirring for
40 min at 100  C. Concurrently, 3 g of thiourea was dissolved in
20 mL of EG and heated with stirring for 100 min at 75  C and then
added slowly to the hot solution of (PVP-Cd2+). The temperature of
the new mixture was gradually raised to 170–180  C within 45 min
and kept at this temperature until most of the solvent was
evaporated. In this stage, the color of the solution changed from
light yellow into a dark orange suspension indicating the formation
of CdS. Next, the suspension was microwaved (LG MC-2820S
microwave) for 5 min with a power of 720 W and 50% duty cycle
(30 s of irradiation and 30 s stop). The obtained powder was then
calcined in a furnace (Sybron Thermolyne Type 1500) for 120 min
 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396 389

at 450  C and finally, black crystallites of PVP-capped CdS
nanoparticles were obtained. The scheme of preparation is
illustrated in Fig. 1. A control synthesis in the absence of PVP
and the exact other steps was carried out to evaluate the impact of
PVP on the yielded product.
2.3. Characterization of the CdS nanoparticles
out using (OSRAM HWL 160 W) lamp in the same experimental
setup used under UVC irradiation. In addition, a light protected
experiment under the same conditions of visible light experiment
was carried out and considered as a blank to assess the
mineralization of tartrazine after same time of irradiation. Samples
were analyzed by a total organic carbon analyzer type (TOC-V,
Shimadzu).

The synthesized CdS nanoparticles were characterized using
various analytical techniques. Scanning electron microscopy
(KYKY-EM3200 SEM) was used to investigate the morphologies
of nanoparticles. X-ray diffraction patterns of the nanoparticles
were recorded by a Bruker AXS D8-ADVANCE diffractometer fitted
with a (Cu Ka l = 1.5418 Å) radiation tube. The average crystallite
size of the synthesized CdS was calculated with well-known
Scherrer’s equation (Eq. (1)) with full width at half maxima
(FWHM) of X-ray diffraction pattern:
0:89l
D¼
bcosu
where l is the wavelength of X-ray radiation source, b is FWHM of
the peak and u is Bragg’s diffraction angle.
Furthermore, in order to determine the chemical composition
of nanoparticles and study the behavior of PVP, Fourier transform
infrared spectra in the range of 400–4000 cm1 of many samples
during the synthesis process was recorded in transmission mode
(Thermo Nicolet 8700 FTIR), the powder samples were grounded
with KBr and compressed into a pellet for analysis.
3. Results and discussion
3.1. Morphology and structure
The SEM images presented in Fig. 2 show that PVP-capped CdS
(PVP-CdS) particles are in the range of nanometer with narrower
particle size distribution (40–59 nm) and less agglomeration
comparing to those of the uncapped CdS which has an average
particle size of 115 nm (75–180) indicating clearly the advantages of
PVP in restricting the growth and preventing agglomeration. This is
ð1Þ simply due to the stereo-hindrance effect resulted from repulsive
force among the polyvinyl groups of PVP and due to the restrained
Ostwald ripening kinetics in such a way that the growth rate was
decreased with the size of CdS nanoparticles. Consequently, smaller
particles with enhanced monodispersity were obtained.
X-ray powder diffraction patterns of the capped nanoparticles
presented in Fig. 3 show a perfect match with the hexagonal phase
of CdS (JCPDS No. 01-089-2944). Diffraction peaks of monoclinic
sulfur are also found (JCPDS No. 01-074-2108). The average

2.4. Photocatalytic activity under UVC light

Photocatalytic activity of the nanoparticles was evaluated by

measuring the degradation of tartrazine which was used as a test
pollutant. An amount of (5–50) mg of the catalyst was dispersed in
200 mL of tartrazine aqueous solution (10–100) mg L1. The pH of
the suspension was adjusted to the desired value by ammonia or
glacial acetic acid solutions and determined by a digital pH meter
(Metrohm pH lab 827). The suspension in the photoreaction
container was exposed to UV light source (CH Lighting T8 30 W
UVC) positioned 10 cm above for 90–180 min. At given intervals of
illumination, 5 mL samples were taken out and centrifuged
(Hettich EPA 12) at 2500 rpm for 10 min in order to completely
remove all nanoparticles. The degradation ratio was monitored
using UV–vis spectrophotometer (T80 + UV–vis Spectrometer PG
Instruments Ltd.). According to the Beer–Lambert law, the
concentration of tartrazine is proportional to its absorbance.
Hence, the degradation efficiency was calculated by the following
formula:
   
ðC 0  CÞ ðA0  AÞ
D% ¼  100 ¼  100 ð2Þ
C0 A0
C0 and A0 are the initial concentration and absorbance, respective-
ly, while C and A are the concentration and absorbance after
intervals of illumination (t). The reaction rate constant (k) was
calculated using plots of ln (C/C0) versus illumination time
according to the following formula:
 
C
ln ¼ kt ð3Þ
C0

2.5. Photocatalytic degradation and mineralization under visible light

After obtaining the optimal conditions for tartrazine degrada-

tion with the synthesized nanoparticles under UVC, an assessment
of the activity of these nanoparticles under visible light was carried
Fig. 2. SEM images of (a) uncapped and (b) PVP-capped CdS nanoparticles.
390 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396
Fig. 3. XRD patterns of the PVP-CdS nanoparticles.
crystallite size of the capped nanoparticles calculated from XRD
patterns using the Scherrer’s equation was about 48 nm which is in
agreement with the result obtained from SEM image.
FTIR spectra of pure PVP and PVP-CdS prior to and after
calcination are shown in Fig. 4. In pure PVP spectrum, the O H
stretching vibration observed as a broad and strong peak at
3517 cm1 is due to H2O absorption on the surface of the sample.
The two bands at 2952 and 1423 cm1 correspond to C H
asymmetric stretching vibration and bending vibration, respec-
tively. The broad peak with high intensity at 1665 cm1 is ascribed
to the C¼O bond stretching and the band at 1286 cm1 corresponds
to C N bond stretching of the pyrrolidone structure.
Two observations can be found when comparing pure PVP
spectrum with the other two spectra. First, a decrease in all peaks
intensities after exposing the sample to microwave irradiation and
more decrease after calcination. This can be explained in the light
of thermal degradation of PVP. Loría-Bastarrachea et al. [49], in
agreement with earlier reports, stated that at 450  C the main
product obtained from thermal degradation of PVP is its
corresponding monomer, i.e., vinyl pyrrolidone or less unsaturated
compounds such as PVP oligomers. The second observation is the
shift to lower wavenumber of some peaks, specifically C¼O and
CN stretching vibrations. These shifting indicate the interaction
between PVP and Cd2+. The mechanism of this interaction as
suggested by Abdelghany et al. [50] implies the formation of
coordinate bonds between nitrogen and/or oxygen atoms of the
PVP with cadmium ions in four different probabilities as shown in
Fig. 5. Hence, the preceding findings indicate the formation of short
polymeric chain-capped CdS nanoparticles.
3.2. Effect of tartrazine solution initial pH
The pH of the reaction medium is one of the most crucial
parameters in photocatalytic degradation of organic pollutants. It
affects the surface charges of both the catalyst and pollutant and
consequently the adsorption of the pollutant on catalyst surface
[51].
In order to study the role of pH on the adsorption of tartrazine
on the catalyst surface, 20 mg L1 solutions of the dye and a fixed
amount of PVP-CdS (25 mg) were set at pH 3.5, 5.5, 7 or 11 and kept
in dark place with constant stirring for 90 min in order to reach the
equilibrium adsorption. In addition, photolysis experiments, in the
absence of catalyst and presence of UVC light with the same other
experimental setup used in the adsorption study, were carried out
also over 90 min. The role of pH on photocatalytic degradation of
tartrazine was investigated in the same conditions of photolysis in
the presence of 25 mg of PVP-CdS or uncapped CdS over 90 min.
The results are shown in Fig. 6.
As can be seen, a decrease in the dye concentration between 3
and 8% was obtained among the different pH values in the presence
of PVP-CdS only without UVC irradiation. Whereas about 4.5–12%
of the initial tartrazine concentration was removed at different pH
values in the presence of UVC irradiation alone without nano-
particles. On the other hand, maximum photocatalytic degradation
percentage of PVP-CdS was observed in alkaline region. The
degradation increased with increasing pH and reached its
maximum value at pH 11. For uncapped CdS, neutral medium
was favorable.
Our suggested interpretation is the following: tartrazine has a
pKa = 9.4 and so is negatively charged in alkaline medium due to its
ionization to the related phenyl salt. Likewise, CdS has a zero point
charge at about pH 7 and is also negatively charged in pH (8–12). As
a result, the adsorption of tartrazine on CdS surface is minimum at
pH 11. Here, the enhancement of capped catalyst activity in
alkaline medium could be imputed to the attachment of CdS with
pyrrolidone ring that might have acted as a mediator to trap the
carriers generated in the catalyst and adsorb the water or dye
molecules or even the abundant hydroxyl ions, which would
subsequently facilitate the generation of hydroxyl radicals that
initiate the oxidization of the pollutant.
Unsurprisingly, PVP-CdS has shown a superior activity over
uncapped CdS in extreme acidic and basic conditions whereas in
neutral conditions, the activities were nearly equivalent. This is
ascribed to two factors: first, the smaller particles size that offered
more surface area for photocatalytic reaction in the case of PVP-
CdS and second, the photocorrosin or dissolution that uncapped
CdS might underwent in extreme conditions which has reduced
drastically its activity. Meanwhile, PVP-CdS maintained an
 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396 391

Fig. 4. FTIR spectra of (A) pure PVP, (B) PVP-CdS after microwave irradiation and, (C) PVP-CdS after calcination.

approximate percentages of degradation in acidic and neutral
conditions as a consequence of PVP passivation.
3.3. Effect of the catalyst loading
Catalyst loading is a critical parameter in photodegradation of
organic pollutants. It affects the reaction rate and consequently the
cost of treatment [52].
The effect of PVP-CdS dosage on the degradation of tartrazine
was investigated in the presence of different amount of catalyst (5–
50 mg) with 50 mg L1 initial concentration of tartrazine at pH 11
for 90 min of irradiation. The results are shown in Fig. 7.
As is noted, the photodegradation of the tartrazine was found to
increase with the increased catalyst loading within the range of
study. Increasing the catalyst loading gave a rise to a higher
number and density of nanoparticles, which in turn caused more
photons to be absorbed and dye molecules to be adsorbed leading
to better degradation [53]. The opacity of the suspension was not
greatly affected by the increased amount of PVP-CdS and no
hindering to light penetration was observed. On the other hand,
after 25 mg of catalyst amount there was no considerable
392 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396

Fig. 4. (Continued)

Fig. 5. Suggested mechanism of interaction between PVP and Cd2+.

Ref. [50].

enhancement in the degradation profile. Hence, 25 mg of PVP-CdS

nanoparticles was chosen to be the optimal amount for further 3.4. Effect of the initial concentration of tartrazine
studies.
The influence of pollutant concentration on photocatalytic
degradation has also been studied. Experiments have been carried
out at different initial concentrations in the range (10–100) mg L1
with constant amount of nanoparticles (25 mg) and initial
solution’s pH 11. The results shown in Fig. 8 indicate that
increasing the concentration of tartrazine had decreased the
degradation from 100% (10 mg L1) to 92.9% (50 mg L1) and 36.2%
(100 mg L1) in 60 min.
This can be explained in the light of photocatalytic degradation
mechanism; a single layer of adsorbed water molecules exists on
the surface of PVP-CdS. After photon is adsorbed, the holes
generated in valence band transfer to the surface and oxidize water
molecules and hydroxyl ions to produce HO
radicals. These
radicals rapidly attack tartrazine molecules and oxidize them to
intermediates which in turn would be mineralized with subse-
quent attacks of HO
radicals.
PVP  CdS þ hn ! eCB þ hVBþ ð4Þ

Fig. 6. Effect of different pH values (3.5–11) on adsorption, photolysis and,

photocatalytic degradation of tartrazine over 90 min.
 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396
Fig. 7. Photocatalytic degradation of tartrazine by varying the amount of PVP-CdS
nanoparticles (5–50 mg) with Tartrazine concentration (50 mg L1) and pH 11.
þ 3.5. Kinetic study
h þ H2 O ! HO
þ Hþ ð5Þ

of tartrazine, Langmuir–Hinshelwood (L–H) model was used. This
HO þ TA ! Intermediates ð6Þ
HO
þ Intermediates ! CO2 þ H2 O ð7Þ
Increasing the initial dye concentration means more tartrazine
molecules to surround the nanoparticles and decrease the path
length of the photons entering the solution resulting in lower
photon absorption by the catalyst and reaction sequence is slowed
down. Consequently, rate of degradation is decreased. At this
juncture, we believe that PVP passivation has an important role in
the separation of the photogenerated carriers. This is attributed to
the prohibition of nonradiative decay of carriers by covering
dangling bonds that may work as exciton traps. Also, the
coordination of nanoparticles surface atoms which minimizes
the trap states lie within the band gap and increases quantum yield
by providing alternative pathways of electron–hole separation.
More importantly, complexation between Cd and the lone pair of
nitrogen/oxygen makes pyrrolidone moiety of PVP act as a hole
acceptor that traps the photogenerated holes and transfers them to
the target objects. It is worth mentioning here that partial
decomposition of PVP, during the synthesis process, was beneficial
for exposing trapping sites of pyrrolidone to those targeted objects
to promote the catalytic reaction sequence.
Fig. 8. Photocatalytic degradation of varying initial concentrations of tartrazine
(10–100 mg L1) with pH 11 and 25 mg amount of PVP-CdS nanoparticles.
393
Fig. 9. Plots of ln (C/C0) versus illumination time for different concentrations of
tartrazine.
In order to study the pattern of the photodegradation reaction
model has been successfully used for heterogeneous photo-
catalysis to describe the exact relationship between the rate of
degradation and the concentration of pollutant in photocatalytic
reaction [31]. The rate constant (k) of degradation reaction was
calculated according to the Formula (3). As shown in Fig. 9, a linear
relation between tartrazine concentrations and illumination time
has been observed implying a pseudo-first order kinetics of the
photodegradation reaction. The pseudo-first order rate constant
decreased dramatically with increased initial concentration of
tartrazine. This is because, as aforementioned, with high concen-
trations of the pollutant, less hydroxyl radicals in active sites of the
catalyst are generated and the majority of photons are absorbed by
pollutant molecules rather than catalyst [54].
In order to cover the adsorption properties of the substrate on
the catalyst surface, the experimental data have been rationalized
in terms of the modified form of L–H kinetic model. The modified
Langmuir–Hinshelwood expression that explains the kinetics of
heterogeneous catalytic systems is given by:
dc kr KC
r¼ ¼ ð8Þ
dt ð1 þ KCÞ
where r represents the rate of reaction that changes with time
(mg L1 min1), kr is the reaction rate constant (mg L1 min1), and
K is the adsorption coefficient of the reactant onto the catalyst
particles (L mg 1).
Fig. 10. Plot of 1/r0 versus 1/C0 of the photocatalytic degradation of tartrazine.
394 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396

when compared with pollutant adsorption onto the surface of the

catalyst.

3.6. Reusability

Reusability of capped catalyst was investigated in order to

verify its stability and the protective role of PVP in preventing
catalyst degradation. After a first round of catalytic reaction, the
mixture (catalyst+slurry) was filtered and washed with a mixture
of water and ethanol (1:1) then dried in an oven at 65  C for 6 h. The
recovered catalyst was used again to degrade tartrazine under
same conditions used before. A third round was carried out in the
same procedure. Results depicted in Fig. 11 show a very slight
deference in catalytic activity among the first used and reused
catalysts. A small change in the kinetic could be seen but, the
Fig. 11. Reusability of PVP-CdS nanoparticles.
overall degradation in 90 min of study was not importantly
affected. It is our believe that photocorrosion suppression is due to
The applicability of L–H equation for the degradation has been prolonged life time of electron–hole pairs as a consequence of hole
confirmed by the linear plot obtained by plotting the reciprocal of trapping and transferring mediated by PVP.
initial rates (1/r0) against reciprocal of initial concentrations of
tartrazine (1/C0) as shown in Fig. 10. 3.7. Photodegradation and mineralization under visible light
   
1 1 1 irradiation
¼ þ ð9Þ
r0 kr kr KC 0
A 50 mg L1 solution of tartrazine with pH 11 was mixed with
In this study, a reasonable agreement (R2 = 0.969) was obtained 25 mg of PVP-CdS nanoparticles and exposed to visible light
between the experimental results and the linear form of the L–H irradiation in the same experimental setup used under UVC
expression. irradiation. As can be seen in Fig. 12, approximately 85% of the dye
The values of kr and K have been determined from the slope and was degraded and about 69% of the total organic content compared
intercept of this plot and found to be 1.908 and 0.036, respectively, with the blank solution was removed after 9 h.
indicating that photocatalytic degradation is a dominant factor

Fig. 12. Photocatalytic degradation and mineralization of 50 mg L1 tartrazine with pH 11 and 25 mg of PVP-CdS nanoparticles under visible light irradiation.
 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396
4. Conclusion
Polyol synthesis with microwave irradiation and calcination
have been used as an efficient method to fabricate cadmium sulfide
nanoparticles in an average crystallite size of about 48 nm when
PVP was used as a capping agent and about 115 nm without
capping. The prepared nanoparticles have been effectively used as
a photocatalyst for the degradation of tartrazine in aqueous
solution. Total degradation of tartrazine was obtained after 90 min
using 25 mg of the PVP-CdS with initial dye concentration of
50 mg L1 and pH 11 under UVC irradiation. The role of PVP in
controlling the growth and stabilizing the nanoparticles was
demonstrated by the compassion with the uncapped product
which has shown more growing and less catalytic activity.
The Langmuir–Hinshelwood models indicated that tartrazine
underwent a pseudo first order kinetics of the reaction and that
photocatalytic degradation was prevailing compared with pollut-
ant adsorption on PVP-CdS surface. In addition, results has shown
that our nanoparticles can work sufficiently under visible light
with about 85% abatement of initial tartrazine concentration and
69% mineralization after 9 h of irradiation.
In conclusion, PVP-CdS nanoparticles synthesized in this work
might be used effectively in environmental treatment processes to
remove organic pollutants from water. These nanoparticles are
promising to work under visible light sources to reduce greatly the
expense of treatment.
Acknowledgment
The authors wish to thank Tehran University of Medical
Sciences for the financial and instrumental support of this
research.
References
[1] H. Zhang, G. Chen, D.W. Bahnemann, Photoelectrocatalytic materials for
environmental applications, J. Mater. Chem. 19 (29) (2009) 5089–5121, doi:
http://dx.doi.org/10.1039/b821991e.
[2] C.C. Kaan, A.A. Aziz, S. Ibrahim, M. Matheswaran, P. Saravanan, Heterogeneous
photocatalytic oxidation an effective tool for wastewater treatment–a review,
Studies on Water Management Issues, InTech, 2012, pp. 219–236, doi:http://
dx.doi.org/10.5772/30134.
[3] M.I. Litter, Heterogeneous photocatalysis: transition metal ions in
photocatalytic systems, Appl. Catal. B: Environ. 23 (2–3) (1999) 89–114, doi:
http://dx.doi.org/10.1016/s0926-3373(99) 00069-7.
[4] H.R. Pouretedal, M.H. Keshavarz, M.H. Yosefi, A. Shokrollahi, A. Zali,
Photodegradation of HMX and RDX in the presence of nanocatalyst of zinc
sulfide doped with copper, Iran J. Chem. Chem Eng. 28 (2009) 13–19.
[5] A. Mercy, R.S. Selvaraj, B.M. Boaz, A. Anandhi, R. Kanagadurai, Synthesis,
structural and optical characterisation of cadmium sulphide nanoparticles,
Indian J. Pure Appl. Phys. 51 (6) (2013) 448–452.
[6] H.R. Pouretedal, H. Eskandari, M.H. Keshavarz, A. Semnani, Photodegradation
of organic dyes using nanoparticles of cadmium sulfide doped with
manganese, nickel and copper as nanophotocatalyst, Acta Chim. Slov. 56
(2009) 353–361.
[7] R. Chauhan, A. Kumar, R.P. Chaudhary, Visible-light photocatalytic degradation
of methylene blue with Fe doped CdS nanoparticles, Appl. Surf. Sci. 270 (0)
(2013) 655–660, doi:http://dx.doi.org/10.1016/j.apsusc.2013.01.110.
[8] Y. Yu, Y. Ding, S. Zuo, J. Liu, Photocatalytic activity of nanosized cadmium
sulfides synthesized by complex compound thermolysis, Int. J. Photoenergy
2011 (5) (2011) , doi:http://dx.doi.org/10.1155/2011/762929.
[9] S. Peretz, D.F. Anghel, E. Teodor, G. Stanciu, C. Stoian, G. Zgherea, M. Florea-
Spiroiu, Improving the properties of CdS nanoparticles by adding polymers,
Part. Sci. Technol. 29 (3) (2011) 229–241, doi:http://dx.doi.org/10.1080/
02726351.2010.494707.
[10] G. Ghosh, M. Kanti Naskar, A. Patra, M. Chatterjee, Synthesis and
characterization of PVP-encapsulated ZnS nanoparticles, Opt. Mater. 28 (8–9)
(2006) 1047–1053, doi:http://dx.doi.org/10.1016/j.optmat.2005.06.003.
[11] A.F. Hezinger, J. Tessmar, A. Gopferich, Polymer coating of quantum dots-a
powerful tool toward diagnostics and sensorics, Eur. J. Pharm. Biopharm. 68 (1)
(2008) 138–152, doi:http://dx.doi.org/10.1016/j.ejpb.2007.05.013.
[12] L. Saravanan, S. Diwakar, A. Pandurangan, R. Jayavel, Synthesis, structural and
optical properties of PVP encapsulated CdS nanoparticles, Nanomater.
Nanotechnol. 1 (2) (2011) 42–48, doi:http://dx.doi.org/10.5772/50959.
395
[13] N. Soltani, E. Saion, M.Z. Hussein, R.B. Yunus, M. Navaseri, Characterization of
CdS nanoparticles synthesized using microwave-assisted polyol method, Adv.
Mater. Res. 667 (2013) 122–127, doi:http://dx.doi.org/10.4028/www.scientific.
net/amr.667.122.
[14] Q. Xia, X. Chen, K. Zhao, J. Liu, Synthesis and characterizations of
polycrystalline walnut-like CdS nanoparticle by solvothermal method with
PVP as stabilizer, Mater. Chem. Phys. 111 (1) (2008) 98–105, doi:http://dx.doi.
org/10.1016/j.matchemphys.2008.03.020.
[15] Z. Jing, L. Tan, F. Li, J. Wang, Y. Fu, Q. Li, Photocatalytic and antibacterial
activities of CdS nanoparticles prepared by solvothermal method, Indian J.
Chem. A 52 (1) (2013) 57–62.
[16] S.H. Liu, X.F. Qian, J. Yin, X.D. Ma, J.Y. Yuan, Z.K. Zhu, Preparation and
characterization of polymer-capped CdS nanocrystals, J. Phys. Chem. Solids 64
(3) (2003) 455–458, doi:http://dx.doi.org/10.1016/s0022-3697(02) 00333-5.
[17] M. Pattabi, B. Saraswathi Amma, K. Manzoor, Photoluminescence study of PVP
capped CdS nanoparticles embedded in PVA matrix, Mater. Res. Bull. 42 (5)
(2007) 828–835, doi:http://dx.doi.org/10.1016/j.materresbull.2006.08.029.
[18] R. Pawar, J.-Y. Lee, E.-J. Kim, H. Kim, C.S. Lee, Synthesis of CdS with graphene by
CBD (chemical bath deposition) method and its photocatalytic activity, Korean
J. Mater. Res. 22 (10) (2012) 504–507, doi:http://dx.doi.org/10.3740/
MRSK.2012.22.10.504.
[19] F. Fiévet, R. Brayner, The polyol process, in: R. Brayner, F. Fiévet, T. Coradin
(Eds.), Nanomaterials: A Danger or a Promise?, Springer, London, 2013, pp. 1–
25, doi:http://dx.doi.org/10.1007/978-1-4471-4213-3_1.
[20] G.G. Couto, J.J. Klein, W.H. Schreiner, D.H. Mosca, A.J.A. de Oliveira, A.J.G.
Zarbin, Nickel nanoparticles obtained by a modified polyol process: synthesis,
characterization, and magnetic properties, J. Colloid Interface Sci. 311 (2)
(2007) 461–468, doi:http://dx.doi.org/10.1016/j.jcis.2007.03.045.
[21] Z. Poormohammadi-Ahandani, A. Habibi-Yangjeh, Fast, green and template-
free method for preparation of Zn1xCdxS nanoparticles using microwave
irradiation and their photocatalytic activities, Phys. E 43 (1) (2010) 216–223,
doi:http://dx.doi.org/10.1016/j.physe.2010.07.009.
[22] R. Shahid, M.S. Toprak, M. Muhammed, Microwave-assisted low temperature
synthesis of wurtzite ZnS quantum dots, J. Solid State Chem. 187 (0) (2012)
130–133, doi:http://dx.doi.org/10.1016/j.jssc.2012.01.007.
[23] S.K. Choubey, K. Tiwary, Microwave assisted synthesis of CdS nanoparticles for
structural and optical characterization, IJIRSET 3 (3) (2014) 10670–10674.
[24] T. Tanaka, Reproductive and neurobehavioural toxicity study of tartrazine
administered to mice in the diet, Food Chem. Toxicol. 44 (2) (2006) 179–187,
doi:http://dx.doi.org/10.1016/j.fct.2005.06.011.
[25] E.S. Beach, R.T. Malecky, R.R. Gil, C.P. Horwitz, T.J. Collins, Fe-TAML/hydrogen
peroxide degradation of concentrated solutions of the commercial azo dye
tartrazine, Catal. Sci. Technol. 1 (3) (2011) 437–443, doi:http://dx.doi.org/
10.1039/c0cy00070a.
[26] H.M. El-Wahab, G.S. Moram, Toxic effects of some synthetic food colorants
and/or flavor additives on male rats, Toxicol. Ind. Health 29 (2) (2013) 224–232,
doi:http://dx.doi.org/10.1177/0748233711433935.
[27] S.K. Al-Dawery, Photo-catalyst degradation of tartrazine compound in
wastewater using TiO2 and UV light, J. Eng. Sci. Technol. 8 (6) (2013) 683–691.
[28] A. Mittal, L. Kurup, J. Mittal, Freundlich and Langmuir adsorption isotherms
and kinetics for the removal of tartrazine from aqueous solutions using hen
feathers, J. Hazard. Mater. 146 (1–2) (2007) 243–248, doi:http://dx.doi.org/
10.1016/j.jhazmat.2006.12.012.
[29] A. Mittal, J. Mittal, L. Kurup, Adsorption isotherms, kinetics and column
operations for the removal of hazardous dye, tartrazine from aqueous
solutions using waste materials-bottom ash and de-oiled soya, as adsorbents,
J. Hazard. Mater. 136 (3) (2006) 567–578, doi:http://dx.doi.org/10.1016/j.
jhazmat.2005.12.037.
[30] N. Modirshahla, M.A. Behnajady, S. Kooshaiian, Investigation of the effect of
different electrode connections on the removal efficiency of tartrazine from
aqueous solutions by electrocoagulation, Dyes Pigment 74 (2) (2007) 249–257,
doi:http://dx.doi.org/10.1016/j.dyepig.2006.02.006.
[31] C. Aydiner, Y. Kaya, G. Beril, Z. onder, I. Vergili, Evaluation of membrane fouling
and flux decline related with mass transport in nanofiltration of tartrazine
solution, J. Chem. Technol. Biotechnol. 85 (9) (2010) 1229–1240, doi:http://dx.
doi.org/10.1002/jctb.2422.
[32] K. Rajeshwar, M.E. Osugi, W. Chanmanee, C.R. Chenthamarakshan, M.V.B.
Zanoni, P. Kajitvichyanukul, R. Krishnan-Ayer, Heterogeneous photocatalytic
treatment of organic dyes in air and aqueous media, J. Photochem. Photobiol. 9
(4) (2008) 171–192, doi:http://dx.doi.org/10.1016/j.
jphotochemrev.2008.09.001.
[33] H.-Y. Shu, C.-R. Huang, Degradation of commercial azo dyes in water using
ozonation and UV enhanced ozonation process, Chemosphere 31 (8) (1995)
3813–3825, doi:http://dx.doi.org/10.1016/0045-6535(95) 00255-7.
[34] R. Jain, M. Bhargava, N. Sharma, Electrochemical studies on a pharmaceutical
azo dye: tartrazine, Ind. Eng. Chem. Res. 42 (2) (2003) 243–247, doi:http://dx.
doi.org/10.1021/ie020228q.
[35] P. Oancea, V. Meltzer, Photo-Fenton process for the degradation of tartrazine
(E102) in aqueous medium, J. Taiwan Inst. Chem. Eng. 44 (6) (2013) 990–994,
doi:http://dx.doi.org/10.1016/j.jtice.2013.03.014.
[36] F. Parolin, U.M. Nascimento, E.B. Azevedo, Microwave-enhanced UV/H2O2
degradation of an azo dye (tartrazine): optimization, colour removal,
mineralization and ecotoxicity, Environ. Technol. 34 (2013) 1247–1253, doi:
http://dx.doi.org/10.1080/09593330.2012.7444319-12).
396 M. Darwish et al. / Materials Research Bulletin 74 (2016) 387–396
[37] P. Oancea, V. Meltzer, Kinetics of tartrazine photodegradation by UV/H2O2 in
aqueous solution, Chem. Papers 68 (1) (2014) 105–111, doi:http://dx.doi.org/
10.2478/s11696-013-0426-5.
[38] T.C. dos Santos, G.J. Zocolo, D.A. Morales, A. Umbuzeiro Gde, M.V. Zanoni,
Assessment of the breakdown products of solar/UV induced photolytic
degradation of food dye, Food Chem. Toxicol. 68 (2014) 307–315, doi:http://dx.
doi.org/10.1016/j.fct.2014.03.025.
[39] V.K. Gupta, R. Jain, A. Nayak, S. Agarwal, M. Shrivastava, Removal of the
hazardous dye—tartrazine by photodegradation on titanium dioxide surface,
Mater. Sci. Eng. C 31 (5) (2011) 1062–1067, doi:http://dx.doi.org/10.1016/j.
msec.2011.03.006.
[40] N. Modirshahla, A. Hassani, M.A. Behnajady, R. Rahbarfam, Effect of
operational parameters on decolorization of acid yellow 23 from wastewater
by UV irradiation using ZnO and ZnO/SnO2 photocatalysts, Desalination 271
(1–3) (2011) 187–192, doi:http://dx.doi.org/10.1016/j.desal.2010.12.027.
[41] M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic
degradation of C.I. acid yellow 23 by ZnO photocatalyst, J. Hazard. Mater. 133
(1–3) (2006) 226–232, doi:http://dx.doi.org/10.1016/j.jhazmat.2005.10.022.
[42] K. Tanaka, K. Padermpole, T. Hisanaga, Photocatalytic degradation of
commercial azo dyes, Water Res. 34 (1) (2000) 327–333, doi:http://dx.doi.org/
10.1016/s0043-1354(99)00093-7.
[43] C. Andriantsiferana, E.F. Mohamed, H. Delmas, Photocatalytic degradation of
an azo-dye on TiO2/activated carbon composite material, Environ. Technol. 35
(3) (2014) 355–363, doi:http://dx.doi.org/10.1080/09593330.2013.828094.
[44] A. Jodat, A. Jodat, Photocatalytic degradation of chloramphenicol and
tartrazine using Ag/TiO2 nanoparticles, Desalin. Water Treat. 52 (13–15) (2014)
2668–2677, doi:http://dx.doi.org/10.1080/19443994.2013.794115.
[45] M. Teimouri, P. Aberoomand, S. Moradi, M. Zhalechin, S. Piramoon, Synthesis of
nickel-doped TiO2 nano crystalline by the sol–gel method and influence of
ultrasonic irradiation for the photo catalytic degradation of Tartrazine dye, The
4th International Conference on Nanostructures (ICNS4): 12–14 March (2012) .
[46] N. Arabzadeh, A. Khosravi, A. Mohammadi, N.M. Mahmoodi, Enhanced
photodegradation of hazardous tartrazine by composite of nanomolecularly
imprinted polymer-nanophotocatalyst with high efficiency, Desalin. Water
Treat. (2014) 1–10, doi:http://dx.doi.org/10.1080/19443994.2014.989414.
[47] M. Umar, H.A. Aziz, Photocatalytic degradation of organic pollutants in water,
Organic Pollutants—Monitoring, Risk and Treatment, InTech, 2013, doi:http://
dx.doi.org/10.5772/53699.
[48] S.M. Gupta, M. Tripathi, A review of TiO2 nanoparticles, Chin. Sci. Bull. 56 (16)
(2011) 1639–1657, doi:http://dx.doi.org/10.1007/s11434-011-4476-1.
[49] M.I. Loría-Bastarrachea, W. Herrera-Kao, J.V. Cauich-Rodríguez, J.M. Cervantes-
Uc, H. Vázquez-Torres, A. Ávila-Ortega, A TG/FTIR study on the thermal
degradation of poly(vinyl pyrrolidone), J. Therm. Anal. Calorim. 104 (2) (2011)
737–742, doi:http://dx.doi.org/10.1007/s10973-010-1061-9.
[50] A.M. Abdelghany, E.M. Abdelrazek, D.S. Rashad, Impact of in situ preparation of
CdS filled PVP nano-composite, Spectrochim. Acta A Mol. Biomol. Spectrosc.
130 (2014) 302–308, doi:http://dx.doi.org/10.1016/j.saa.2014.04.049.
[51] M. Mrowetz, E. Selli, Photocatalytic degradation of formic and benzoic acids
and hydrogen peroxide evolution in TiO2 and ZnO water suspensions, J.
Photochem. Photobiol. 180 (1–2) (2006) 15–22, doi:http://dx.doi.org/10.1016/j.
jphotochem.2005.09.009.
[52] T.A. Gad-Allah, M.E.M. Ali, M.I. Badawy, Photocatalytic oxidation of
ciprofloxacin under simulated sunlight, J. Hazard. Mater. 186 (1) (2011)
751–755, doi:http://dx.doi.org/10.1016/j.jhazmat.2010.11.066.
[53] N. Assi, A. Mohammadi, Q. Sadr Manuchehri, R.B. Walker, Synthesis and
characterization of ZnO nanoparticle synthesized by a microwave-assisted
combustion method and catalytic activity for the removal of ortho-
nitrophenol, Desalin. Water Treat. 54 (7) (2014) 1939–1948, doi:http://dx.doi.
org/10.1080/19443994.2014.891083.
[54] H.R. Pouretedal, A. Kadkhodaie, Synthetic CeO2 nanoparticle catalysis of
methylene blue photodegradation: kinetics and mechanism, Chin. J. Catal. 31
(11–12) (2010) 1328–1334, doi:http://dx.doi.org/10.1016/s1872-2067(10)
60121-0.