Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Effect of annealing temperature on photocalaytic dye degradation study

of TiO2 nanoparticles prepared by non-conventional sol-gel technique
Debabandana Apta a, Susanta Kumar Das b, Maya Devi a,⇑
a
Dept. of Physics, School of Applied Sciences, Kalinga Institute Of Industrial Technology Deemed to be University, Bhubaneswar, Odisha 751024, India
b
School of Physics, Gangadhar Meher University, AmrutaVihar, Sambalpur, Odisha 768004, India

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

Article history: Titanium dioxide (TiO2) nanoparticles (NP) find several applications starting from window layer of solar-
Available online xxxx cell to dye degradation due to its varied optical and electrical properties. In this paper a low cost synthesis
method of TiO2 nano powder is reported using non-conventional sol-gel method and used for dye degra-
Keywords: dation study. Here the starting material used was TiO2 micropowder instead of alkoxide. The prepared
XRD nano-powders were annealed at various temperatures for the variation in physical properties. The struc-
SEM tural, morphological and photocatalytic properties of the prepared samples were studied. The XRD con-
Photocatalysis
firm the crystalline phase of all prepared samples and also shows the variation of crystallite size with
Methylene blue(MB) dye
annealing temperature. The morphological characterization by SEM confirms the uniform spherical shape
of the grains. The grain size significantly decreases due to annealing. The prepared samples were used for
methylene blue (MB) dye degradation study using an indegeneously built UV-reactor and compared with
the degradation rate of the same dye by using raw powder. It is observed that there is four times
enhancement in the degradation rate with the prepared samples at 500 degree annealing temperature
in comparison to the procured raw powder.
Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Sympo-
sium on Semiconductor Materials and Devices – 2022.

1. Introduction photocatalytic dye decomposition application [4–8]. Metal alkox-

In today’s world fresh water resources are is being polluted by
different dyes released from industries like textile, pharmaceuti-
cals, leather and paper etc. Non bio-degradable dyes are very diffi-
cult to be removed by conventional water treatment methods [1].
Photocatalytic dye degradation is one of the promising green tech-
nologies where semiconductor NPs are used to decompose dyes in
presence of light. The heterogeneous photocatalysis process is
quite competent, effective and beneficial as compared to homoge-
neous photocatalysis process due to easy and low cost effective
separation process [2]. Semiconductors nanoparticles like TiO2
seeks attentions in photocatalytic application for its wide band
gap, low cost, non-toxicity, chemical stability and recyclability
[3]. Out of the various synthesis methods sol-gel method is very
often preferred for growth of TiO2 NPs because of cost effective-
ness, simplicity and ease of preparation. Generally alkoxides are
used for growth of TiO2 NPs in conventional sol-gel method for
⇑ Corresponding authors.
E-mail address: mdevifpy@kiit.ac.in (M. Devi).
ides show higher reactivity to nuclophillic compounds and show
rapid hydrolysis resulting in precipitation. The rapid hydrolysis
affects the homogeneity and microstructure of the nanopowders.
It makes the heating time prolonged which in turn reduces the
specific surface area. So to achieve homogeneity and the required
microstructure control over the hydrolysis rate of alkoxide is
required. So modification of alkoxide with chelating agent is
required, which affect the rate of hydrolysis, oligomerization and
hence the formation of by product [9]. This process is very much
dependant on entropy change and along with this a number of
complexes are formed. So to avoid the effect of rapid hydrolysis,
in this work we have adopted a modified sol-gel method where
instead of alkoxide TiO2 powder is taken as precursor. The reaction
mechanism in the preparation of the TiO2 nanopowder is pre-
sented in the following equations.
TiO2 þ 4ðCH3 COOHÞ ! ðCH3 COOÞ4 Ti þ 2H2 O
ðCH3 COOÞ4 Ti þ H2 O ! TiðOHÞ4 þ CH3 COOH

https://doi.org/10.1016/j.matpr.2023.05.498
2214-7853/Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Symposium on Semiconductor Materials and Devices – 2022.

Please cite this article as: D. Apta, S.K. Das and M. Devi, Effect of annealing temperature on photocalaytic dye degradation study of TiO2 nanoparticles pre-
pared by non-conventional sol-gel technique, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2023.05.498
D. Apta, S.K. Das and M. Devi
TiðOHÞ4 ! TiO2 þ 2H2 O "
Various studies show annealing significantly affect the physico-
chemical properties of nanopowders. It plays an important role in
phase transition from amorphous to tetragonal or tetragonal to
rutile. The crystallinity of the sample significantly affects the other
properties [10]. It is found that the optical properties like transmit-
tance and band-gap and the topography of the samples are varied
by the effect of annealing temperature which can be utilised to
prepare the samples for specific applications [11]. The photocat-
alytic study of TiO2 shows that the anatase phase shows better
results than the rutile because of higher density of localised states,
which in turn slower the charge recombination rate. The conver-
sion of anatase to rutile phase occurs at very high temperature.
So in this paper we have considered low annealing temperature
for our sample preparation and using the prepared TiO2 nanopow-
der the photocatalysis of MB dye is performed and effect of differ-
ent processing parameters on the performance of photocatalytic
dye decomposition has been studied in details.
2. Experimental details
2.1. Material preparation and its characterization
All the preliminary materials such as TiO2 powder with 99.99%
purity, nitric acid and acetic acid were procured from Merck, India.
The samples were prepared from the procured powder by sol-gel
method as shown in the flow chart [12] Fig. 1. The processed NPs
are designated as T1, T2 and T3 for as-prepared, 250 °C annealed
and 500 °C annealed respectively. The prepared samples were
characterised to study their structural and morphological parame-
ters and by using X-ray diffraction and scanning electron micro-
scopy and BET characterizations.
2.2. Characterization of samples
The crystal structure of all the powder samples are analyzed by
x-ray diffraction using Bruker D8 advance diffractometer at 40Kv
anode voltage and 40 mA current. The x-ray diffractogram is
recorded using Cu-Ka radiation attached with a graphite crystal
monochromator in the range of 10° to 80° angle with 1° step count.
Fig. 1. Flow chart of Synthesis process of samples.
2
Materials Today: Proceedings xxx (xxxx) xxx
The grain size and morphological study have been done by SEM
analysis of the samples by using ZEISS EVO 18. The surface area
was calculated by BET using Quantachrome Autosorb iQ Station
and UV–Vis analysis has been carried out by Agilent cary 60 UV–
Vis–NIR spectro-photometer.
2.3. Photocatalysis study
Studies on dye degradation were conducted using the prepared
samples. For the study, MB dye of 2.5  105 M concentration was
employed [13]. An indigenously built UV reactor with two UV-A
light sources (emitting at 365 nm) and 6 Watt each was used to
conduct the photocatalysis experiment. To achieve equilibrium,
adsorption and desorption under complete darkness, continuous
stirring of 100 ml of the dye solution and 0.1 gm of TiO2 powder
was carried out for thirty minutes. The mixture was illuminated
by UV light source kept at 10 cm distance [14]. The absorbance
measurement was done in every 5 min interval of time by collect-
ing 4 ml of the dye solution till the dye solution become colourless.
This process was repeated for all prepared samples along with the
procured raw powder for comparative studies.
3. Results and discussions
3.1. Structural analysis
The XRD patterns of samples T1, T2 and T3 have been shown in
Fig. 2. It is observed that the NPs have tetragonal structure with
crystallographic parameters as indicated in Table 1.The diffraction
angles of the processed samples T1, T2 and T3, have shown good
agreement with the reported work of J.K Burdett et al. [15].The
highest peak corresponding to (1 0 1) plane shows a slight left shift
which may be due to the increase in lattice strain [16]. A compar-
ative analysis of crystallite size and strain has been shown in
Table 1. It is observed that the crystallite size decreases with
increase in annealing temperature upto 250 °C which may be
due to restructuring process [17]. With increase in annealing tem-
perature upto 500 °C the crystalline size increases which is indicat-
ing phase stability of the prepared nanoparticles.
Fig. 2. Peaks of XRD pattern of TiO2 NPs annealed at different temperatures and
shift in the peak positions of (1 0 1) phase of TiO2 NPs annealed at different
temperature.
D. Apta, S.K. Das and M. Devi Materials Today: Proceedings xxx (xxxx) xxx

Table 1
The structural parameters of sample T1, T2, T3 and Procured Raw powder.

Sl.No Sample Name 2h in degree Lattice _

Crystallographic parameters [A] Crystallite size (nm) Strain
indices
h k l a b c
1 T1 25.4585 1 0 1 3.7760 3.7760 9.4860 20 0.0797
2 T2 25.3663 1 0 1 3.7822 3.7822 9.5023 15 0.1066
3 T3 25.3735 1 0 1 3.7822 3.7822 9.5023 20 0.0799
4 Procured Raw 25.3211 1 0 1 – – – – –

Fig. 3. SEM micrograph of TiO2 NPs along with their particle size analysis histogram (a) as-prepared (b) annealed at 250 °C (c) annealed at 500 °C (d) Procured raw TiO2
powder.

3.2. Morphological study
SEM image of the samples T1, T2, T3 and procured raw TiO2 par-
ticles are shown in Fig. 3. From the SEM micrograph it is observed
that the particles have nearly spherical shape, which may be
responsible for the enhanced photocatalytic activity [16–21]. The
calculated grain size using Image J are found to be nearly
123 nm, 124 nm, 95 nm and 177 nm for T1, T2, T3 and procured
raw TiO2 powders respectively. The grains are existing in clusters.
Initially with increase in annealing temperature the grain size is
almost remaining same which may be due to the restructuring
but with increase in annealing temperature grain size is reducing
which may be due to the increase in nucleation density [22]. This
supports that this temperature is close to the transition of anatase
to rutile phase [23].
3.3. Study on the degradation of dye by UV photocatalysis
The absorbance spectra and dye degradation studies of samples
T1, T2, T3 and procured raw TiO2 powder are shown in Fig. 4 and
Fig. 5 respectively. From the studies it is observed that raw powder
takes 40 min for complete dye degradation where as with the
annealed sample at 500 °C complete degradation occurs in 15 mins
time with UV light exposure. According to photocatalytic investi-
gation, the sample T3 shows superior photocatalytic activity in
3
comparison to T1 (25 min.) and T2 (20 min.) samples, respectively.
As degradation rate is dependent on particle size and surface area
[24]. The highest degradation rate of sample T3 may be attributed
to the smallest particle size (95 nm) and highest surface area
(10.477 m2/g) among all samples. This enhanced photocatalytic
activity of sample T3 may be due to the defects produced by the
strain in the crystal lattice, which is confirmed by the XRD plot
annotations. These defects in the crystal lattice may give rise to
trapping of charge carriers in the lattice structure. As a result photo
generated electron hole pair recombination time may be pro-
longed. This trapping of charge carriers are responsible for the
enhancement in the photocatalytic activity [24–26].
The C/Co graph of all the prepared samples are shown in Fig. 5,
where C0 represents the initial MB dye concentration before illumi-
nation and C represents the MB dye concentration following a
specific amount of UV exposure. It is evident that T3 takes the
shortest amount of time to degrade the colour. From the ln(C/C0)
versus time graphs, as illustrated in Fig. 6, pseudo first order reac-
tion kinetics can be used to obtain the rate constant. The solid line
shows the linear fit of the experimental data, which demonstrates
the pseudo-first order reaction kinetics given by
C
ln ¼ Kt
C0
D. Apta, S.K. Das and M. Devi Materials Today: Proceedings xxx (xxxx) xxx

Fig. 4. Absorption spectra of MB dye solution by using TiO2 NPs (a) as-prepared (b) annealed at 250° (c) annealed at 500 °C (d) Procured raw TiO2 powder. Inset shows image
of MB dye solutions with a certain time gap.

Fig. 5. Normalized MB dye concentrations with a time gap of TiO2 NPs (a) as-prepared (b) annealed at 250° (c) annealed at 500 °C (d) Procured raw powder.

4
D. Apta, S.K. Das and M. Devi
Fig. 6. Time versus ln (C0/C) graphs of TiO2 NPs for (a) as-prepared (b) annealed at 250 °C (c)annealed at 500 °C (d) Procured raw powder.
Table 2
Dye decomposition comparison table of samples T1, T2, T3 and Procured raw powder.
Sl. No Sample Description
1 T1
2 T2
3 T3
4 Procured raw powder
Fig. 7. Histogram for reaction rate constant of different samples as-prepared,
annealed at 250 °C, annealed at 500 °C and procured raw powder.
Here, K is the rate constant and t is the time period. The calcu-
lated rate constants for all samples are presented in the Table 2. It
is observed that the rate constant is highest for sample T3 which
may be due the structural modification during synthesis process.
The variation of dye degradation rate of different prepared sam-
ples having varied particle size is shown in Table 2. The histogram
Materials Today: Proceedings xxx (xxxx) xxx
Particle size Decomposition Rate constant
(nm) Time of MB dye (min1)
(min)
123 25 0.1441
124 20 0.1715
95 15 0.1982
177 40 0.0543
indicating the reaction rate constant of various samples is shown in
Fig. 7. It is observed that T3 has almost four times higher degrada-
tion rate in comparison to raw powder.
4. Conclusions
The synthesised TiO2 NPs using non-conventional sol-gel pro-
cess were annealed at various temperatures and the suitability of
their use as photocatalyst for degradation of MB dye is studied. It
is observed that the nanoparticles annealed at low temperature
are showing crystalline anatase structure but the variation in
structural parameters occur with annealing. The microstructure
analysis shows anomalous variation in particle size with annealing
like significant decrease in particle size with increased annealing
temperature which may be due to increase in nucleation density.
From the photocatalytic study of the prepared samples using MB
dye it is observed that in all samples the reaction rate follows
pseudo first order kinetics with different reaction rate constants.
The changes in structural parameters significantly affect the reac-
tion rate constant. The sample annealed at 500 °C shows higher
rate constant in comparison to others which may be due to the sig-
nificant decrease in particle size. This may be responsible for the
occurance of defects which are cause of the delay in recombination
of electron – hole pairs. The dye degradation rate of the sample
annealed at 500 °C is four times faster than the procured raw pow-
der. So from this study we find that processing parameters of the
nanoparticles during synthesis significantly affect the use of them
as photocatalyst.
5
D. Apta, S.K. Das and M. Devi Materials Today: Proceedings xxx (xxxx) xxx

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