International Conference on Mechanical, Industrial and Materials Engineering 2022 (ICMIME2022)

20-22 December, 2022, RUET, Rajshahi-6204, Bangladesh.

Paper ID: ICMIME2022_070

Sol-Gel Synthesis and Characterization of Titanium Dioxide Nanoparticles

Most. Mahfuza Khatun1, M. Bodiul Islam1*, and Hasnat Jahan Sumona1

1
Dept. of Glass & Ceramic Engineering, Rajshahi University of Engineering & Technology (RUET),
Rajshahi-6204, Bangladesh
E-mail: mbi@[Link]

Abstract

Fabrication of Titanium dioxide (TiO2) nanoparticles was performed by sol-gel route from titanium tetra
isopropoxide (TTIP) precursor. The synthesized particles were dried at 100ºC for 24 hours and calcined at
400ºC for 2 hours. The particles were characterized by X-ray diffractometer (XRD), Scanning Electron
Microscopy (SEM), and UV-vis Spectrophotometry characterization. The dominance of the tetragonal anatase
phase of the synthesized nanoparticles was confirmed by the XRD patterns. The lattice parameters & crystalline
behavior of the prepared samples were investigated. The present work focuses on the fabrication of TiO2
nanoparticles with a simple sol-gel synthesis method and its structural, morphological, and optical
characterization.

Keywords: Titanium dioxide, Nanoparticles, Sol-Gel, Anatase.

1. Introduction
Nanomaterials are technologically important over from their bulk counterpart as they possess unique and
physico-chemical and opto-electronic properties [1]. Among various nanoparticles, TiO2 is one of the most
researched materials because of its better characteristics like cost effectiveness, highly photocatalytic activity,
non-toxicity, high chemical stability, and environmentally friendly properties [2]. The utilization of the
nanoparticles of titanium dioxide in the field of photocatalysis is in demand because of its increased surface
area, ease of preparation and biocompatibility [3]. TiO2 has been investigated intensively and is one of the most
prominent scientific interest because of its numerous applications in diverse areas which can ranges from daily
use commercial products to high-end applications such as pigment in paints [4], nanomedicine [5]–[7],
electrolysis of water to generate hydrogen [8], water treatment [3], [9], solar cells [10], [11], capacitors [12],
environmental purification [13] etc.
TiO2 naturally has three well-known polymorphs rutile, brookite, and anatase [14]–[16]. Anatase and rutile
adopts a tetragonal structure, while brookite show orthorhombic structure [17]. Among these three polymorphs
the most considered forms of nanostructured TiO2 are rutile and anatase [18]. Rutile is the most stable form of
TiO2 while anatase TiO2 is more active form as compared to rutile TiO2 in the matter of photocatalytic activity
owing to longer lifetime, which hinders the electron-hole pairs of recombination [19]. Anatase TiO2 plays a key
role in industrial purposes such as photovoltaic cells, photocatalytic process and electrochromic applications
[20]. For the preparation of TiO2 nanomaterial with some unique properties various processes have been
developed such as vapour deposition [21], microwave method [22], hydrothermal method [23],
electrodeposition [24], sol-gel method [25]–[28], solvothermal method [29], [30], laser ablation method [31],
etc. Among these sol-gel method is one of the most efficient methods to produce TiO2 nanoparticles as sol-gel
procedure of metal oxides provides advantages such as good homogeneity,high purity, stoichiometry control,
etc. [32], [33]. The present work focuses on the fabrication of the pure TiO2 nanoparticles by sol-gel process at
400°C calcination temperature and characterization of the prepared samples for determining the crystallite size
using Debye Scherer equation, degree of crystallinity, energy band gap level and microstructural properties.

2. Materials and methods

Raw materials
The titanium isopropoxide (TTIP) (SRL, India), hydrochloric acid (HCL) (Sigma-Aldrich, USA), distilled water
and absolute ethanol (Analytical Reagent, 99.9% purity) were used as prime materials. All the chemicals were
used without any further purification.
 Synthesis of TiO2 nanoparticles
The fabrication of TiO2 nanoparticles were performed by sol-gel process. The sol-gel reaction begins with
hydrolysis that is the formation of Ti–OH moieties and this formation takes place by the substitution reaction of
water with Ti–OR groups. The precursors go through condensation reactions to make Ti–O–Ti bonds by
oxolation or Ti–OH–Ti bonds by olation. The mechanisms for the formation of TiO2 nanoparticles could be
found elsewhere [34]. For the preparation of 1M 50 ml solution by maintaining the molar ratio summarized in
Table 1, 14.21 ml of TTIP, 142.1 ml of ethanol, 71.05 ml of distilled water and 1.825 ml of HCL acid were
used. For the synthesis of pure TiO2 nanoparticles, Titanium (IV) isopropoxide (TTIP) was dissolved in absolute
ethanol under constant magnetic stirring for 15 minutes for obtaining a homogeneous state. Then distilled water
was added for the initiation of the ionization process and the as prepared solution was stirred continuously for
45 minutes. After that the mixture was adjusted to pH of 3 with 1 M HCl. Afterwards, the acquired sol was
stirred continually for two hours and was subjected for ageing for a day at the room temperature. In the
meantime, the gel was formed, filtered and then washed frequently with distilled water and ethanol and dried in
an oven for 24 hour at 100°C to remove volatile solvents. The fabricated materials were ground. After that it
was calcined at 400°C for 4 hour (at the heating rate of 5 °C/min).

Table 1. Molar ratio maintained in fabricating TiO2

Raw Materials Molar ratio
Titanium tetraisopropoxide, TTIP 1
Absolute ethanol 10
Distilled water 5
Hydrochloric acid, HCl 1

3. Materials characterization
The structural analysis was performed through X-ray diffraction analysis by engaging 40 kV-30 mA over the
scanning range of 2θ from 10 to 80° and at a scan speed of 2°/min utilizing CuKα (λ= 0.154 nm) radiation. For
analyzing the morphological characteristics, the scanning electron microscopy (ZEISS EVO 18, UK) was used.
The particles were optically analyzed by UV-Vis spectroscopic technique considering the range of 250–650nm.

4. Results and discussion

XRD analysis

Pure TiO2
(101)
Intensity(a.u)

(200)
(004)

(105)

(204)

(215)
(116)

10 20 30 40 50 60 70 80
2Theta (degree)

Fig. 1. XRD spectrum of pure titania sample calcined at 400ºC

XRD patterns were utilized to recognize the crystal structure and related properties of the fabricated TiO2
nanoparticles. Obtained XRD patterns are revealed in Fig. 1. From the XRD patterns it confirms the presence of
tetragonal anatase phase. The peaks at 25.33º, 37.91º, 48.06º, 54.63º, 62.86º, 69.74º and 75.41º correspond to the

2
(101), (004), (200), (105), (204), (116) and (215) planes was detected. XRD peaks show the existence of anatase
phase having the tetragonal crystal system of TiO2 JCPDS card no.01-084-1285 [20]. An additional phase was
not observed.

Inter-planar spacing between atoms (d spacing) of each catalyst was calculated using the Bragg’s equation [20],

(1)
nλ = 2d sinθ
(2)
or, d = (nλ)/(2sinθ)

Here λ is used to denote the wavelength of the X-ray (for Cu source it is 0.154 nm), n is used to denote the order
of diffraction (n = 1), and θ is the Bragg angle.

The crystallite size (D) was measured through the Debye Scherer formula which is generally considered as the
accepted method to evaluate the average crystallite size [20].

D = (0.9)/(cosθ) (3)

Here β is used to denote the full width at half maximum (FWHM), λ is used to denote the wavelength of the X-
ray in nm (0.154 nm for Cu source) and θ is used to denote the Bragg angle. The average crystallite size of the
prepared TiO2 nanoparticles was ~ 5.66 nm and the crystallite sizes are given in Table 2.

Table 2. Structural characteristics of pure TiO2

Peak Position Miller FWHM Crystallite Band gap
d spacing(Å)
(°) indices(hkl) (°) size(nm) (eV)
101 7.225363525 3.511402842
25.33415 1.12649
004 4.561209393 2.370180547
37.91537 1.84088
200 6.71191285 1.890822339
48.06192 1.29543
105 4.420193999 1.677723891 3.03
54.63941 2.02212
204 5.400018428 1.476577634
62.86264 1.72348
116 4.899180315 1.346762997
69.74348 1.97569
75.41788 215 1.56041 6.432804079 1.258888881

The crystallinity percent (XC %) was determined by the following relations [35] :

Total areas under crystal peaks

XC % = Total ×100 (4)
areas under crystal and amorphous peaks

This value was calculated to be 81.67%, corresponding to the high crystallinity of the as-prepared TiO2. The
higher crystallinity leads to the lesser lattice strain value [36].

SEM analysis
Fig. 2 exhibits the scanning electron micrographs of TiO2 nanoparticles taken at an operating voltage of 20 kV.
From the figure, it is noticed that the specimen displayed the morphology of particle with irregular spherical
shape with diameter majority of 80-100 nm, which is relatively close to the other particle size of TiO2 obtained
by other researchers [37]. Besides this, small agglomeration is observed in the nanoparticles. The size
distributions of the particles are shown in Fig. 2. They mainly show some single particles with some clusters of
particles.

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 Fig.2. SEM image and diameter frequency distribution of TiO2 nanoparticle

UV–Visible spectroscopic analysis

Fig. 3. Optical absorption spectrum of TiO2 nanoparticle and Tauc Plot ((αhv)1/2 vs. energy plot) in inset for
band gap calculation

Fig. 3. reveals the spectrum of optical absorption of TiO2 nanoparticle. It is clearly shown that the TiO2
responded better in the UV region. The band gap energy (E g) of the nanoparticles was calculated by the
following relation [38].

αhν = A ( hν-Eg)n (5)

Here A is a constant, hν is the light energy (eV) and α is used to denote the absorption coefficient of the sample.
The parameter n = ½ for indirect transition and the determined indirect band gap energy of the nanoparticles of
TiO2 is 3.03 eV (Table 2), whose value is very close to the pure anatase TiO2 (3.2 eV) [20].

7. Conclusion
A high crystalline anatase TiO2 powder with the tetragonal crystal system, was fabricateded easily via a simple
sol-gel technique. Using the well-known Scherrer equation, the average crystallite size of the as-manufactured
sample was determined to be 5.66 nm. The crystallinity was estimated to be 81.67%, and the morphology of
TiO2 exhibits the irregular spherical shaped grains with majority diameter of 80-100 nm. The indirect band gap
was calculated to be 3.03 eV for the nanoparticles of TiO2.

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8. Acknowledgement
The authors would like to thank the Glass & Ceramic Engineering Department at Rajshahi University of
Engineering & Technology (RUET); Dr. Md. Badrul Islam, Principal Scientific Officer & Division In-Charge,
BCSIR Laboratories, Rajshahi and Dr. Md. Salim Khan, Director (In-Charge), BCSIR Laboratories, Rajshahi in
Bangladesh for their assistance in carrying out this research.

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