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A R T I C L E I N F O
Article history:
Received 29 March 2016
Received in revised form 14 August 2016
Accepted 30 August 2016
Available online 31 August 2016
Keywords:
A. Semiconductors
C. Electron microscopy
C. X-ray diffraction
D. Optical properties
D. Catalytic properties
A B S T R A C T
This paper describes a facile, green method for the synthesis of cadmium sulphide (CdS) nanoparticles
from Chlamydomonas reinhardtii. Morphological analysis by electron microscopy revealed the presence of
spherical particles measuring approximately 5 nm. Structural analysis by powder X-ray diffraction and
Fourier transform infrared spectroscopy conrmed the presence of cubic CdS nanoparticles that were
capped with algal proteins. Optical analysis showed a signicant blue shift in the optical band gap that
could be ascribed to quantum connement. The photocatalytic ability of these nanoparticles against
methylene blue under UV light was studied & was found to degrade 90% of the dye within 90 min.
Trapping experiments indicate that photogenerated holes, OH were the main reactive species
responsible for dye degradation. This one-step strategy using algal cell free extract to produce CdS
nanoparticles is an economical, environmentally friendly approach for the large-scale synthesis of CdS
nanoparticles that can be used in photocatalysis.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Cadmium sulphide (CdS) belongs to the IIVI group of
semiconductor nanoparticles. Due to quantum connement, these
nanoparticles have unique optoelectronic properties that signicantly differ from the bulk material. They have been extensively
studied in photocatalysis [36], used as biological sensors [17] and
light emitting diodes [38]. The expansion of industries and
growing concern over environmental impact of organic dyes in
water bodies has led us to evaluate alternate strategies for water
purication. Semiconductor nanoparticles like CdS with their
unique photophysical and photochemical properties are ideal for
use in the degradation of organic dyes via photocatalysis, using UV
or visible light as a source of illumination [14]. Conventional
methods of fabrication include chemical methods, microwave
heating, hydrothermal approaches and precipitation from liquid
reactions [34]. These methods usually employ high temperatures
and extremely toxic reagents for prolonged periods of time; they
are also expensive and in many cases require specialized
equipment.
* Corresponding authors.
E-mail addresses: divyarau@gmail.com (M. D. Rao), pgautam@annauniv.edu
(G. Pennathur).
http://dx.doi.org/10.1016/j.materresbull.2016.08.049
0025-5408/ 2016 Elsevier Ltd. All rights reserved.
65
25 ml of the cell-free extract was made up to 100 ml with deionized water; this was placed in a water bath set at 65 C.
Cadmium chloride and sodium sulphide were added to the extract
to obtain a nal concentration of 1 mM. The reaction was
completed in twenty minutes, following which the cadmium
sulphide nanoparticles were separated by centrifuging at 8720 g.
The pellet was washed repeatedly (three times) with de-ionized
water to remove other organic matter that may be bound to the
nanoparticles.
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peaks indicated the ne size of the grains; the particle size was
determined by measuring the fwhm (full width half maximum)
and calculated using the Debye-Scherrer formula.
D
0:9l
bCosu
average grain size from XRD analysis was 6 nm, which was roughly
similar to the sizes measured using HR- TEM. However, the XRD
results overestimated the size of the nanoparticles, this disagreement in the results from two different techniques is justiable
because the XRD line broadening does not take into account other
factors such as lattice defects and strain [10].
The size and morphology of the nanoparticles were analyzed
using HR- TEM, large numbers of spherical nanoparticles were
observed in the HR- TEM micrographs (Fig. 2). Over 50 particles
were measured using ImageJ software and the particles ranged
from 2 to 7 nm. Average particle size was determined to be 4.8 nm.
Possible reasons for the appearance of aggregates could be due to
the large concentration of sample loaded on the grid as well as the
duration of probe sonication applied to disperse the powdered
sample into solution [6]. However, the lattice fringes can be clearly
distinguished (Fig. 2D) indicating the crystalline nature of the
nanoparticles. The lattice fringe spacing for the sample is 3.36 ,
which corresponds to the (1 1 1) phase of cubic zinc blende
structure. The selective area diffraction pattern (SAED) pattern
showed bright concentric rings and is indicative of the crystalline
nature of the nanoparticles (Fig. 2E). Intracellular synthesis of
cadmium sulphide nanoparticles using Escherichia coli demonstrated similar results with narrower size distribution (25 nm)
[30]. Whereas, extracellular synthesis using fungi produced larger
sized particles ranging from 520 nm [23,1]. Interestingly, the algal
cell free extract was able to produce comparatively smaller sized
particles in spite of using extracellular material.
HR-SEM is capable of functioning at high magnications
making it an important tool in determining the topography of
the as-synthesized K1 and is therefore suited to image nanometer
sized objects. The HR-SEM image as seen in Fig. 3 indicated the
formation of large number of spherical nanostructures that were
Fig. 2. HR-TEM images of cadmium sulphide nanoparticles synthesized using Chlamydomonas cell free extract. (AC) HR-TEM micrographs from lower to higher
magnications; (D) Images of CdS nanoparticles showing lattice fringes, (E) SAED image of CdS nanoparticles.
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Fig. 4. (A) Hydrodynamic size distributions of cadmium sulphide nanoparticles with an average hydrodynamic radius of 38 nm as measured by DLS; (B) Zeta potential of
cadmium sulphide nanoparticles synthesized using the cell free extract of the microalga Chlamydomonas reinhardtii.
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Fig. 5. (A) UVvis spectrum of cadmium sulphide nanoparticles synthesized using Chlamydomonas reinhardtii cell free extract; (B) Tauc Plot of cadmium sulphide
nanoparticles for band gap determination.
Fig. 6. Fluorescence emission spectra of cadmium sulphide nanoparticles synthesized using Chlamydomonas reinhardtii cell free extract.
Based on the UVvis spectra, the average particle size of the CdS
nanoparticles was estimated to be 3.06 0.1 nm indicating that
particle size had reduced by about 45% in comparison to bulk (5.6
3.06 nm) based on quantum connement. This phenomenon could
be due to the stabilizing inuence of algal proteins that act as
capping agents. The optical band gap energies for the assynthesized CdS nanoparticles were evaluated using the Tauc
relation [10]. The average band gap values were determined from
the linear intercept of the Tauc plot on the hn axis as shown in
Fig. 5b and was found to be 2.93 0.02 eV. This value is higher than
the reference bulk value for CdS, which is 2.42 eV, the difference in
band gap energies was measured to be 0.51 eV. This increase in
energy is referred to as a Blue shift and is due to the bound state
of electron-hole pairs in the quantum conned semiconductor
nanoparticle [13]. To the best of our knowledge there are no reports
on the aqueous synthesis of CdS nanoparticles using algal
biomolecules as capping agents.
Fluorescence emission in semiconductor nanoparticles is
generally due to contributions from excitonic recombination,
which usually occurs at the absorption edge and due to emissions
2R
0:1
0:1338 0:0002345 lexc
Fig. 7. FTIR spectrum of (A) algal cell free extract and the (B) as-synthesized
cadmium sulphide nanoparticles with the characteristic peaks.
69
70
determined by plotting In CC0 as shown in Fig. 9 and corresponds
to the slope of the tted curve. The rate constant was measured to
be 0.018 min1 and was found to surpass results obtained with a
composite catalyst composed of CdS cross-linked with chitosan
[39]. Our results were comparable with an earlier study that
employed a biotemplated approach for the synthesis of CdSbacterial cellulose derived hybrid nanobres in photocatalysis
under visible light [37]. An earlier report on the degradation of
methylene blue by CdS and ZnS nanoparticles reported a rate
constant of 0.00361 min1 [29]. These results indicate that the
biologically synthesized cadmium sulphide nanoparticles are
better photocatalysts under ultra violet irradiation.
The effect of initial dye concentration on photodegradation was
studied by taking different concentrations of methylene blue
(515 ppm) in the presence of CdS nanoparticles (0.75 g/L) under
UV light. As the concentration of the dye was increased the
photocatalytic efciency correspondingly decreased from approximately 86% to 71% as seen in Fig. 10. The ratio of photocatalytic
degradation can be correlated with the probability of hydroxyl
radicals being generated on the photocatalysts surface to their
reaction with dye molecules [39]. When 5 ppm of dye was used
there was greater degradation of the dye, this could be attributed to
greater interaction between dye molecules and the oxidising
species. As the concentration of the dye was increased, there were
signicantly greater numbers of dye molecules while there is only
a limited amount of hydroxyl radicals, as the catalyst concentration
remains constant. Further, all the active sites on the catalysts
surface would be obscured by the dye, resulting in a loss of
efciency.
Catalyst loading is an important parameter that should be
considered during photodegradation; it inuences the reaction
rate and by extension, the cost of the treatment [4]. The effect of
nano-CdS dosage on the degradation of methylene blue was
investigated in the presence of different amounts of catalyst (37.5
150 mg) with 10 ppm of dye for 90 min of irradiation. The results
are shown in Fig. 11 and as expected an increase in catalyst dosage
was found to augment photodegradation (from 74% to 90%).
Greater catalyst loading meant that there was a higher density of
nanoparticles, which led to improved adsorption of photons and
dye molecules and thereby enhanced degradation [4]. Usually,
when catalyst dosage is increased it may result in a turbid solution,
limiting the penetration of UV light and thus reducing
Fig. 10. Plot of (C/C0) versus time corresponding to the effect of initial dye
concentration in the photodegradation of methylene blue.
Fig. 11. Plot of (C/C0) versus time corresponding to effect of catalytic dosage in the
degradation of methylene blue.
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holes. Charge separation of electron and holes improves photoreactivity and inhibits photocorrosion [28]. To assess the photostability and anti-photocorrosion potential of the biogenically
synthesized CdS nanoparticles the concentration of elemental
sulphur as well as Cd2+ released into the solution after the
degradation of methylene blue was measured. After ve rounds of
recycling the photocatalyst, elemental sulphur concentration had
marginally increased from 1.5 ppm to little more than 3.5 ppm
(Fig. 14A). While Cd2+ concentration slowly increased from
approximately 2 ppm to 9.5 ppm (Fig. 14B) by the end of the fth
run. An earlier report that compared the photostability of bare CdS
as well as a composite composed of CdS nanoparticles intercalated
between titanate sheets found that bare CdS released 62.5 ppm
while the composite released around 15 ppm [28]. These results
demonstrate the inherent photostability of the algal-synthesized
nanoparticles. This could be attributed to the proteins capping the
nanoparticles, which enhance charge transfer from the nanoparticle to the attached protein thereby reducing recombination of
electrons and holes and thus improving photocatalytic ability of
these nanoparticles.
Active species trapping experiments were conducted to gain
insights into the photocatalytic mechanism of biosynthesized CdS
nanoparticles under UV light. 2-propanol (0.2 mol/L) was added
the dye solution to act as a hydroxyl radical (OH) scavenger, while
benzoquinone (BQ, 0.02 mol/L) was added to capture superoxide
radicals (O2) respectively. Disodium ethylenediaminetetraacetate (EDTA-2Na; 0.05 mol/L) was added to scavenge photogenerated holes [40]. Photocatalytic activity of the nanoparticles was
signicantly inhibited following the addition of EDTA-2Na,
indicating that photogenerated holes play a key role in the process
as seen in Fig. 15. Addition of EDTA degraded approximately 38% of
the dye while in its absence the photodegradation efciency
increased to 86% as seen in Fig. 15. 2-Propanol was also found to
inhibit the nanocatalysts ability to breakdown methylene blue by
reducing efciency to approximately 55% while benzoquinone was
found to play a less signicant role in dye degradation. These
results indicate that OH radicals as well as photogenerated holes
play an important role in the UV-light driven photocatalytic
degradation of methylene blue.
Irradiation of CdS nanoparticles produces a number of electronhole pairs that are powerful oxidising and reducing agents. These
holes are able to oxidize adsorbed water and produce hydroxyl
radicals.
CdS + hn ! h++ e
(3)
h+ + H2O ! OH + H+
(4)
Fig. 13. Plot depicting the reusability of CdS photocatalysts in the photodegradation
of methylene blue.
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Fig. 14. Estimation of (A) Elemental sulphur and (B) Photocorrosion of CdS after ve consecutive cycles of photodegradation of methylene blue.
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