Journal of Saudi Chemical Society (2015) 19, 589594

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Synthesis and characterization of TiO2 quantum

dots for photocatalytic application
Lalitha Gnanasekaran
a
b

a,*

, R. Hemamalini

a,*

, K. Ravichandran

Department of Physics, Queen Marys College, Chennai 600 004, India

Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai 600 025, India

Received 27 February 2015; revised 29 April 2015; accepted 5 May 2015

Available online 14 May 2015

KEYWORDS
Quantum dots;
TiO2;
Solgel method;
Photocatalytic activity;
UV light;
Recycle

Abstract In the present study, TiO2 quantum dots (QDs) were effectively synthesized by the sol
gel method and it was characterized by several techniques. The structure of the TiO2 QDs, before
and after calcination, was analyzed by the powder X-ray diffraction technique. The XRD results
indicate that after calcination, TiO2 QDs have pure anatase phase with tetragonal structure without
any other phases and impurities. The morphology and size of the TiO2 QDs were determined from
FE-SEM and TEM analysis. The optical band gap of TiO2 QDs was estimated using Kubelka
Munk function from diffuse reectance spectroscopy. The photocatalytic activity and recycling
ability of the TiO2 QDs have been investigated. The TiO2 QDs were used to degrade the model dyes
such as methyl orange and methylene blue under UV light irradiation and their results have been
discussed. A mechanism is proposed and discussed accordingly in detail.
2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
In recent years, quantum dots (QDs) have attracted much
attention due to their large surface area and high activity.
The physical and chemical properties of QDs have been found
to be different from those of bulk materials [13]. The

* Corresponding authors.
E-mail addresses: lalitha1887@gmail.com (L. Gnanasekaran), hemaphy.qmc@gmail.com (R. Hemamalini).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

efciency of several applications such as solar cell, fuel cells,

photocatalyst and antibacterial activity can be enhanced due
to the surface property of QDs [13]. Titanium dioxide
(TiO2) and zinc oxide (ZnO) are considered to be signicant
materials in the area of pollutant degradation due to their high
photo catalytic efciency [46]. TiO2 is a predominant semiconductor photocatalyst because of its stability, non-toxicity,
low cost production and eco-friendly nature [4,5]. The efciency of photo catalytic activity of TiO2 can be further
enhanced by various physical and chemical methods. Since
the synthesis of TiO2 QDs uses sophisticated methods like
chemical vapor deposition (CVD), Ultra high vacuum
(UHV) etc., their synthesis by a cost effective method is essential and at the same time it remains a challenge.
Water is the most important natural resource for living
organisms. According to the World Health Organization,
nowadays, it is uncertain about the quality of water and due

http://dx.doi.org/10.1016/j.jscs.2015.05.002
1319-6103 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

590

L. Gnanasekaran et al.

to poor hygienic condition nearly 1.5 million children die every

year worldwide [7]. Increasing environmental pollution, especially water pollution, plays a key factor in destroying green
environment. Various technologies have been developed to
sustain green environment [8]. The heterogeneous catalytic
activity has paid much attention in the treatment of waste
water. Even under mild conditions of temperature and pressure the complete degradation of pollutants can be attained.
The most signicant feature of this process is its costeffectiveness [916].
In this work, TiO2 QDs have been synthesized by a simple
and low cost method. The synthesized TiO2 QDs were characterized by several techniques and the results have been discussed. The degradation of various model dyes was achieved
by the photo catalytic method in the presence of the prepared
quantum dots under UV light irradiation. The recycling ability
of the catalyst has also been veried.

100 mL of dye (MO/MB) solution (initial concentration of

5 105 moles/L) in a 500 mL cylindrical beaker containing
water jacket so as to maintain a constant temperature
(25 C). Later, the suspension was magnetically stirred under
the dark condition for 20 min to establish adsorption/desorption equilibrium condition. The irradiated sample was collected every 20 min and the sample was centrifuged and
ltered. The concentrations of the irradiated MO and MB
solution were determined by UVVis spectrophotometer to
the corresponding kmax 464 nm and 664 nm, respectively. The
degradation efciencies of MO and MB were calculated using
the following formula:


C
 100
1
g 1
C0

2. Experimental details

2.4. Characterization details

2.1. Materials

The powder X-ray diffraction technique was used to nd the

phase, structure and crystallite size of the synthesized TiO2
QDs at room temperature (2h = 2070) using a D5000
(Siemens, USA) diffractometer with CuKa1 (k = 1.5406 A)
radiation. The surface morphology of the synthesized TiO2
QDs was analyzed with (FEI quanta FEG 200, USA) Field
Emission Scanning Electron Microscope. The size and chemical composition of the material were conrmed by TEM
(Tecnai G2 20 TEM, FEI, Netherlands) with EDX detector.
The optical band gap of the quantum dots was determined
from the UVVis diffuse reectance spectra which were
recorded at room temperature using (VARIAN CARY 5E,
USA) UVVisNIR spectrophotometer. The photocatalytic
activity was measured by a UVVis spectrophotometer
(Perkin Elmer Lambda 35, USA).

The required chemicals such as titanium (IV) isopropoxide

(TTIP), isopropanol, cetyl trimethyl ammonium bromide
(CTAB), methyl orange (MO) and methylene blue (MB) were
procured from SigmaAldrich. P-25 TiO2 (2030 nm) was
obtained from Degussa and these chemicals were used without
further purication. All the aqueous solutions were prepared
using double distilled water.
2.2. Preparation of quantum dots

where, C0 and C are the concentrations of the solution before

illumination (t = 0) and after illumination of light for t minutes respectively.

The procedure followed in the synthesis of TiO2 QDs is as follows: Initially 5.0 mL of TTIP was taken in a syringe and it
was dissolved in 150 mL of isopropanol in a 500 mL beaker.
Then, the mixed solution was stirred for more than 1 h.
0.01 mole of aqueous CTAB was added drop-wise into the
mixed solution. The resulting solution was stirred mechanically
for about 24 h. Finally, a white dry powder was obtained. This
was removed from the beaker and transferred to the mortar for
grinding. The nely ground sample was transferred into an alumina boat and calcinated at 350 C for 30 min in a mufe
furnace.

In the present study, synthesis of TiO2 QDs was achieved using

the solgel method. The proposed method is simple and cost
effective compared to other methods because it does not
require any special equipment. The prepared TiO2 QDs effectively degraded the MO and MB under UV light irradiation.

2.3. Photocatalytic activity

3.1. Structural analysis

The photocatalytic studies were carried out as reported by

Saravanan et al. [6]. The synthesized TiO2 QDs were used as
a catalyst for the degradation of MO and MB solution under
UV light irradiation. At rst, the photo stability of the dyes
was tested without a catalyst. The MO and MB aqueous solutions were magnetically stirred under the dark condition for
2 h under UV light irradiation. The irradiated samples were
later analyzed using UVVis spectrophotometer and it was
found that there was no change in the concentration of the
solution. This implies that the dyes are stable enough under
UV light. The source of UV light (8 W mercury vapor lamp
of 365 nm wavelength) is sealed by cylindrical quartz glass tube
to prevent direct contact with the dye solution. The photocatalytic suspension was prepared by taking 100 mg of TiO2 in

The X-ray diffraction pattern of the as synthesized TiO2 QDs

is shown in Fig. 1. Fig. 1(a) clearly shows that there are no
peaks in the diffraction pattern which reveals that as synthesized TiO2 QDs are amorphous in nature. In contrast, after
the calcination, several diffraction peaks were apparent which
is evident from Fig. 1(b). The result conrms that after calcination the synthesized TiO2 QDs become crystalline in nature.
The scientic software XRDA 3.1 and Origin 8 were used
to index the diffraction peaks. The peaks at the 2h values
25.3, 38.1, 47.4, 54.3, and 62.1 were tted and their h k l
planes were identied as (1 0 1), (1 1 2), (2 0 0), (1 0 5), and
(2 1 3) respectively, which coincides with the JCPDS card no
84-1285. The 2h values and the planes reveal that the as synthesized TiO2 QDs are in pure anatase phase having tetragonal

3. Results and discussion

Synthesis and characterization of TiO2 quantum dots for photocatalytic application

591

plot of the TiO2 QDs was also measured which was found in
the range of 37 nm and is shown by the Fig. 3(c). Further
the chemical composition of the synthesized TiO2 QDs was
analyzed using EDS spectrum. Fig. 3(d) shows EDS spectrum
which conrms that the TiO2 QDs contain titanium and oxygen without any other impurities.
3.3. Band gap determination

Figure 1 The X-ray diffraction pattern of the as synthesized

TiO2 QDs (a) before calcination, and, (b) after calcination.

structure. The calculated lattice parameter values are,

a = 3.826 A and c = 9.403 A. The XRD data clearly indicate
that there are no other phases (Rutile and brookite) or impurities of any other kind. Using Scherrer formula, the average
crystallite size of the as synthesized TiO2 QDSs was calculated
as 4.8 nm. The X-ray diffraction results hereby conrm that
the synthesized TiO2 QDSs are pure anatase phase having
tetragonal structure.
3.2. Morphology, size and elemental analysis
The surface morphology and size of the as synthesized TiO2
QDs were investigated using FE-SEM and TEM analysis.
Fig. 2(a), (b) and (c) represents the FE-SEM images of as
synthesized TiO2 QDs at different scales. It was observed from
all the FE-SEM images that the spherical shaped particles are
tightly bound. The agglomeration of the TiO2 limited the accurate measurement of the size of the TiO2 QDs. Therefore, the
size of the as synthesized TiO2 QDs was measured using TEM.
Fig. 3(a) shows the TEM image of as synthesized TiO2
QDs which clearly shows the random distributions of homogenous ne spherical shaped particles. Its equivalent selected
area electron diffraction (SAED) pattern is shown by
Fig. 3(b). The SAED pattern illustrates that there are several
electron diffraction rings. The d-spacing of the rings corresponding to the h k l planes (1 0 1), (1 0 5), (1 1 2) and (2 1 3)
was identied. These h k l planes of pure anatase phase having
tetragonal structure of TiO2 QDs were in agreement with the
XRD data. From the TEM image, the particle size distribution

Figure 2

The UVVis diffuse reectance spectra (DRS) were used to

nd the optical band gap of the TiO2 QDs as shown by
Fig. 4(a). The spectrum exhibits a strong reection edge which
is at around 340 nm. The band gap energy of the TiO2 QDs
was evaluated using KubelkaMunk (KM) function [13].
Based on this function, F(R)hm versus hm plot (Fig. 4(b)) give
the band gap energy of TiO2 QDs was 3.79 eV and its equivalent wavelength exists in the UV region of the electromagnetic
spectrum. Hence, the results of the UVVis DRS indicate that
the excitation occurs in the synthesized TiO2 QDs on the irradiation of UV light.
3.4. Photocatalytic degradation of MO and MB
This work mainly focused on the degradation of model dyes
such as methyl orange (MO) and methylene blue (MB) using
the synthesized TiO2 QDs. The UVVis DRS results conrmed
that the photocatalytic activity can be performed using UV
light since the band gap of TiO2 QDs is 3.79 eV. The time
dependent (MO or MB) degradation percentage is shown in
Fig. 5. Fig. 5 shows that with increasing irradiation time, the
MO/MB degradation percentage is increasing which suggests
the complete degradation of the dyes. After 80 min of irradiation, the model dyes were almost completely degraded with the
use of synthesized TiO2 QDs and its degradation efciency is
97.1% and 97.9% which was calculated using Eq. (1). It
was found that the synthesized TiO2 QDs exhibited superior
photocatalytic degradation than that of commercial Degussa
P-25 TiO2 catalyst.
Few researchers synthesized TiO2 for photo catalytic applications [1724]. However, the result of the present work
depicts higher degradation when compared to these reports
[1724]. The difference in degradation time depends on the
preparation methods, size and morphology of the samples [6].
The proposed mechanism of photocatalytic activity is presented in the schematic diagram as shown in Fig. 6.
The photocatalytic activity can be initiated by the irradiation of the UV light on the mixed solution (aqueous

The FE-SEM images of the as synthesized QDs at different scales (a) 1 lm, (b) 500 nm, and (c) 300 nm.

592

L. Gnanasekaran et al.

(b)

(a)

(105)
(101)
(112)
(213)

(c)

(d)
Ti
O

Figure 3

Figure 4

(a) The TEM image, (b) SAED pattern, (c) Size distribution plot, and (d) EDS spectrum of TiO2 QDs.

(a) Diffuse reectance spectrum of TiO2 QDs, and, (b) Determination of band gap of TiO2 QDs based on KM function.

dye + TiO2 QDs). The valence band electrons move to the

conduction band due to the irradiation of the UV light. This
creates holes in the valence band and electrons in the conduction band. The holes react with water molecules present in the
dye (oxidation) and simultaneously the electrons in the conduction band react with oxygen molecules (reduction). In both
processes, the OH radical is produced. The OH radicals effectively degrade the organic pollutants (dye) under UV light irradiation. Based on the earlier reports, the photocatalytic
reaction mechanism is proposed as follows [6]:

dark condition


TiO2 UV light irradiation ! TiO2 h
mb ecb

irradiation

irradiation

TiO2 h
! Oxidation
mb MO or MB
TiO2 e
! Reduction
cb MO or MB
Oxidation and reduction process
irradiation

aqueous dye ! Degradation of dyes

Synthesis and characterization of TiO2 quantum dots for photocatalytic application

Figure 5
25.

593

The time dependent percentage degradation of (a) MO, and (b) MB using as synthesized TiO2 QDs and commercial Degussa P

MO. After recycling, there were no remarkable changes in

the degradation. This clearly indicates that the synthesized
TiO2 QDs are reusable and stable enough.
4. Conclusions

Figure 6

The mechanism of photocatalytic activity of TiO2 QDs.

In summary, the TiO2 QDs having anatase phase and tetragonal structure were successfully synthesized by the solgel
method. The average size of the TiO2 QDs was about 5 nm
which was conrmed by TEM. The KM function exhibits
the optical band gap value of synthesized TiO2 QDs at
3.79 eV which lies in the UV region. The photocatalytic
results indicate that the synthesized TiO2 QDs effectively
degraded the model dyes MO and MB under UV light. The
degradation efciency was calculated and found to be
97.1% and 97.9% for MO and MB respectively in 80 min
of irradiation. Further, the recycling results imply that the catalyst is stable enough and could be easily reused which is
favorable for potential environmental and industrial
applications.
Acknowledgements
We acknowledge SAIF-IIT Chennai, India and IIC-IIT
Roorkee, India for FE-SEM and TEM characterizations.
References

Figure 7

The recycling ability of TiO2 QDs for MO degradation.

For industrial and environmental applications, the recycling ability of catalysts is essential to nd the stability and
the reusability of the catalyst. To achieve real time applications, the photocatalytic activity is repeated ve times. Fig. 7
shows the recycling process and the ability to degrade the

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