Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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One-pot green synthesis of CdS quantum dots using Opuntia ficus-indica

fruit sap
K. Kandasamy a, M. Venkatesh b, Y.A. Syed Khadar c, Paramasivan Rajasingh d,⇑
a
Department of Chemistry, K.S.R. College of Arts and Science for Women, Tiruchengode 637 215, Tamil Nadu, India
b
Department of Physics, K.S. Rangasamy College of Arts and Science (Autonomous), Tiruchengode 637 215, Tamil Nadu, India
c
Department of Physics, K.S.R. College of Arts and Science for Women, Tiruchengode 637 215, Tamil Nadu, India
d
Department of Chemistry, Chikkanna Government Arts College, Tiruppur 641 602, Tamil Nadu, India

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

Article history: A simple and novel one-pot synthesis of CdS, quantum dots from naturally available fruit sap Opuntia
Received 24 April 2019 ficus-indica was performed. We have investigated a green route for the synthesis of CdS QDs using
Received in revised form 28 May 2019 eco-friendly and naturally renewable Opuntia ficus-indica fruit sap as green template. Synthesized CdS
Accepted 2 June 2019
QDs were determined by Fourier transform infrared spectroscopy, UV–visible (323 nm), X-ray diffraction
Available online xxxx
(cubic structure), X-ray fluorescence, Dynamic light scattering (d50 = 9.56 nm), High resolution transmis-
sion electron microscopy (Spherical shaped). Overall the present work describes the green synthesis of
Keywords:
CdS nanoparticles from Opuntia ficus-indica fruit sap with extrinsic crystallite size control in the quantum
Opuntia ficus-indica
CdS
confinement range.
Quantum dots Ó 2019 Elsevier Ltd. All rights reserved.
Green synthesis Selection and peer-review under responsibility of the scientific committee of the International Confer-
High-resolution transmission electron ence on Emerging Materials and Modeling.
microscopy

1. Introduction
Biosynthesis of low-dimensional semiconductor quantum dots
(QDs) (<10 nm) have unique properties such as optical sensing,
photo-degradation and bio-sensing compared to their high dimen-
sional (>10 nm) nanoparticles (NPs). Synthesis of cadmium sulphide
(CdS) QDs is one of the major challenges through green synthesis
method [1]. The preparations of CdS QDs have been carried out using
several methods such as microwave heating [2], hot injection [3],
colloidal synthesis [4], plasma synthesis [5] and ultrasonic irradia-
tion [6]. Generally, the chemical synthesis methods are complicated
due to their cost, slow rate of reaction, low yield, risky and human
health hazard concerns [7]. In the recent years, natural plant and
agriculture waste extract are used as reducing, stabilizing and cap-
ping agents for the synthesis of QDs because of better biocompatible,
environmental friendly and cost effective nature [8,9]. Especially,
fruits sap contains remarkable organic capping agents like cellulose,
carbohydrates, proteins, pectin, vitamins and minerals [10]. Opuntia
ficus-indica (O. ficus-indica) fruits are rich source of flavonoids, ter-
penoids, steroids and carotenes [11]. These molecules have major
functional groups such as amine (proteins), carboxylic acid (pectin)
and hydroxyl group (cellulose) [12]. These functional groups are
believed to play a major role in bio-reduction reaction and they read-
ily bond with inorganic materials. For example, recently 3–5 nm
scaled CdS QDs synthesis was reported using tea-leaf extract which
plays a key role in size reducing and as capping agent [13]. O. ficus-
indica sap contains 80–90% of water, 10–20% of macronutrients
and organic capping molecules like vitamins (12–81 mg) and
antioxidants (10–60 mg) [14]. These chemical compositions of O.
ficus-indica fruits sap play a main role in the synthesis of CdS QDs.
This work highlights the synthesis of lower dimensional semicon-
ductor CdS QDs via biocompatible materials.
The present novel research work reports an one-pot simple
approach for the synthesis of CdS QDs using a O. ficus-indica fruit
sap. We have made an attempt to synthesis CdS QDs using
eco-friendly and naturally renewable source such as O. ficus-indica
fruit sap as green template. The effect of sap concentration on the
particle size, morphology, crystalline behavior, elements distribution
of the as-synthesized CdS QDs has been reported.
2. Experimental section

⇑ Corresponding author. Cadmium sulfate (CdSO4, HiMedia and 99% purity) and sodium
E-mail address: sprajasingh@gmail.com (P. Rajasingh). sulfide (Na2S, Molychem and 98% purity) were purchased.

https://doi.org/10.1016/j.matpr.2019.06.003
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Emerging Materials and Modeling.

Please cite this article as: K. Kandasamy, M. Venkatesh, Y. A. Syed Khadar et al., One-pot green synthesis of CdS quantum dots using Opuntia ficus-indica
fruit sap, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.06.003
2 K. Kandasamy et al. / Materials Today: Proceedings xxx (xxxx) xxx

Deionized (DI) water used throughout the experiment was

obtained from ultra-pure water purification system followed by
KMnO4 distillation method.

2.1. Preparation of O. ficus-indica fruit sap

The O. ficus-indica fruits were obtained from local village area

(Tiruchengode, Namakkal) in India. First, fruits were washed with
DI water, peel was removed and then the sap was collected from
O. ficus-indica fruits. Later the sap was filtered through Whatman
qualitative filter paper (Grade number 1) and this freshly prepared
extract was used for synthesis.

2.2. One-pot green synthesis of QDs

To synthesize the CdS QDs in a single step, 100 mL of O. ficus-

indica fruit extract was stirred for 30 min. Then freshly prepared
0.5 M of CdCl2
H2O solution was added into it and further 0.5 M Fig. 1. FT-IR Spectrum of O. ficus-indica CdS QDs.

of Na2S
H2O was added drop by drop until it attains orange-

yellow color which indicates the formation of CdS. The above
aromatic CAH bending vibration. The medium band at
mixture was stimulated using magnetic stirrer for 24 h at room
1069 cm 1 shows the CAO stretching vibration of primary alcohol
temperature. The obtained orange-yellow coloured CdS nanoparti-
and also CAN stretching vibration of amine groups. A weak peak
cle was centrifuged, washed with DI water for five times and then
observed at 624 cm 1 indicates the formation of CdS QDs [15,16].
dried at 110 °C for 4 h.

4.2. Ultra violet visible absorption spectroscopy (UV–Visible)

3. Analytical techniques
Fig. 2 shows the absorption spectrum taken for O. ficus-indica
The crystalline properties of CdS sample powder were charac-
CdS QDs to identify the characteristic energy absorption edge.
terised by XRD using CuKa as a radiation source (k = 1
5406 Å)
We could observe that the absorption band of CdS QDs was shifted
which is generated at 40 keV and 40 mA. The samples were
to short wavelength. The ‘‘blue shift” shows that there is decrease
scanned in the 2h range from 10 to 80°. X-ray fluorescence (XRF)
in size and formation of QDs. The CdS QDs formed indicate the
is used to identify the nano powder employing qualitative and
presence of low-dimensional semiconductor property [17,18].
quantitative elemental analysis and composition of the products.
The absorption spectrum maximum for CdS QDs is at 323 nm
To confirm the presence of organic compounds from the O. ficus-
which corresponds to band gap energy of 3.8 eV and the observed
indica fruit sap on CdS, the FT-IR spectra was recorded at room
biomineralized Cds QDs are within the well-known quantum con-
temperature from the range of 4000 to 400 cm 1 where, 100 mg
fined size range for CdS [19,20].
of potassium bromide (KBr) was used as a reference to discover
the presence of functional groups. The ultraviolet (UV)-visible
absorption spectra of CdS QDs was measured using Cary 5000 4.3. Structural studies (XRD)
UV–VIS Spectrophotometer. The absorption spectra of the samples
were recorded in standard 10 nm quartz cuvettes. The particle size Fig. 3 shows the XRD pattern of the as-synthesized CdS QDs and
analyses were carried out using Sympa NANOPHOX Dynamic Light confirms the crystalline nature. The XRD peaks found at 2h values
Scattering (DLS) and measured with the sub micrometer particle of 26.8°, 44.1° and 52.2° attributes to (1 1 1), (2 2 0) and (3 1 1)
size analyzer. The particle size of the samples measured in the diffraction planes of cubic structure CdS QDs which is correspond-
range of 1–100 nm at the scattering angle of 90°. The HR-TEM ing to the JCPDS file number 10-0454 [16,21]. The broad peaks
was operated at 200 kV to obtain TEM images. To prepare TEM
sample, the CdS QDs were ultrasonically dispersed in acetone
and then a drop of the CdS QD solution was introduced onto a
copper-carbon TEM grid. Then, the resulting TEM grid was dried
in the air.

4. Result and discussion

4.1. Vibrational spectroscopy (FT-IR)

The FT-IR spectrum of the CdS QDs is shown in the Fig. 1 which
gives the information about the functional groups involved in the
reduction of cadmium ions and detects some possible biomole-
cules that are capped on CdS QD. The FT-IR spectrum shows
wavenumber peaks at (cm 1) 3417, 2917, 1597, 1402, 1069, 624.
The broad band at 3417 cm 1 corresponds to the polymeric OH
stretching vibration and a weak peak at 2917 cm 1 shows CAH
asymmetric stretching vibration. The FT-IR spectrum of CdS QDs
shows absorption band due to asymmetric C@O stretching vibra-
tion at 1597 cm 1. The peak is observed at 1402 cm 1 indicating Fig. 2. Absorption Spectrum of O. ficus-indica CdS QDs.

Please cite this article as: K. Kandasamy, M. Venkatesh, Y. A. Syed Khadar et al., One-pot green synthesis of CdS quantum dots using Opuntia ficus-indica
fruit sap, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.06.003
 K. Kandasamy et al. / Materials Today: Proceedings xxx (xxxx) xxx 3

Table 2
XRF analysis confirming the co-existence of Cd and S in the QDs.

Analyst Result Line

Cd 80.210% Cd Ka
S 18.882% S Ka
K 0.908% K Ka

Fig. 3. Powder XRD pattern of O. ficus-indica CdS QDs.

indicate that the particles were obtained in the nature of small

crystalline sizes and also no impurity peak was observed. The
mean crystallite sizes (D) of the CdS QDs (3–5 nm) was calculated
using Debye Scherrer’s formula. The inter-planar spacing value dhkl
was 3.32 Å and dislocation density value is 1.20 which is shown in
Table 1 [8]. The result indicates that O. ficus-indica fruits sap acts as Fig. 4. Representative DLS spectrum of O. ficus-indica CdS QDs.
a stabilizing and capping agent.

4.4. X-ray fluorescence (XRF)

XRF elemental analysis was done for the synthesized CdS QDs to
confirm the independent quantitative measurements of nanoparti-
cles distributed. Concentration distribution of the CdS QDs sample
is shown in Table 2. The results of XRF analysis showed 80.210% of
Cd and 18.882% of S. The above result shows that the prepared NPs
consist of CdS QDs [22].
4.5. Dynamic light scattering (DLS)
The DLS analysis was done in order to determine the particle
size distribution of the synthesized CdS QDs (Fig. 4). The result
obtained from the DLS analysis showed the average particle size
of CdS QDs was 9.56 nm [23]. (It is supported by HRTEM analysis).
4.6. High-resolution transmission electron microscopy (HRTEM)
HRTEM image of O. ficus-indica CdS QDs is shown in Fig. 5 which
confirms the shape and size of the CdS QDs and matches with that
of the XRD results [24]. HRTEM clearly shows the spherical shaped
CdS QDs and their average diameter range from 3 to 5 nm [25] and
the result confirms the formation of quantum dots (<10 nm) [26].
This represents that the resultant CdS QDs are suitable to (1 1 1)
cubic crystalline structure of CdS [13]. The comparison of XRD
results with HRTEM confirms similarities in the particle size and
hence the formation of CdS QDs. In addition, the DLS results are
also in agreement with these observations.
5. Conclusion
One-pot green synthesis of CdS QDs was successfully achieved
using O. ficus-indica fruit sap. The organic moieties such as carbo-
hydrate, flavonoids, terpenoids, steroids, carotenes and proteins
present in the O. ficus-indica fruit sap play a key role as stabilizing
and capping agent and form highly homogeneous CdS spherical
nanoparticle with an average size range of 3–5 nm. The XRD and
XRF spectra support the formation of crystalline QDs. The capping
of biomolecules onto CdS QDs from O. ficus-indica fruit sap was
confirmed by FTIR. The spherical shaped particles were confirmed
by HRTEM analysis. From the studies it is clear that O. ficus-indica
fruit sap can be efficiently used as a stabilizing and capping agent
for synthesis of CdS QDs using our green protocol. The obtained
result suggests that O. ficus-indica fruit sap could be considered
for synthesizing CdS semiconductor quantum dots. The synthe-
sized O. ficus-indica fruit sap mediated CdS QDs are promising
low dimensional biomedical tools used for a wide range of biomed-
ical applications such as antibacterial, bioimaging, catalysis and
therapeutic.

Table 1
XRD peak list of CdS QDs.

2h of intense peak (deg) Height FWHM[b] d-spacing [Å] hkl Average crystallite size (nm) Average Dislocation Density
[cts]
26.6802 265.58 0.4920 3.34129 111 3–5 1.20
43.9936 162.71 1.1808 2.05827 220
52.5651 123.32 0.7872 1.74106 311

Please cite this article as: K. Kandasamy, M. Venkatesh, Y. A. Syed Khadar et al., One-pot green synthesis of CdS quantum dots using Opuntia ficus-indica
fruit sap, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2019.06.003
4 K. Kandasamy et al. / Materials Today: Proceedings xxx (xxxx) xxx
Fig. 5. HRTEM image of O. ficus-indica CdS QDs.
Acknowledgements
This work was supported by Science and Engineering Research
Board (SERB-DST). Project Order No. SB/EMEQ-265/2013. Author P.
R sincerely thanks SERB-DST for the financial support provided.
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