Titanium Dioxide Nanoparticles Synthesis Methods: A Review

*1
Asep Bayu Dani Nandiyanto, 1Egan Reyhansyah Nugraha

1
Departemen Pendidikan Kimia, Fakultas Pendidikan Matematika dan Ilmu Pengetahuan Alam, Universitas
Pendidikan Indonesia,
Jl. Dr. Setiabudi no. 229, Bandung 40154, Jawa Barat, Indonesia

Email: [email protected]

Abstract
Titanium dioxide (TiO2) nanoparticles is a metal oxide nanoparticle that gained
popularity due to their applications on environmental uses as photocatalyst. This paper
will discuss various methods to synthesis TiO2 nanoparticles based on study literature
from journal sources. Methods that will be discussed in this paper are sol-gel method,
hydrothermal method, co-precipitation method, and hydrolysis method. From the result
of this study, it was found that sol-gel method is the most effective way to synthesis TiO 2
because the product properties could be tuned by changing some of the parameters used
such as temperature, pH, and solvent compared to other methods. The result of this
review are expected to provide necessary informations on methods to synthese TiO 2
nanoparticles.

Keywords: TiO2, nanoparticles, synthesis methods

1. Introduction

Nanoparticles in general are defined as matters with at least one dimension that is
less than 100nm [1]. Currently, nanomaterials and nanoparticles gained a lot of
attention due to their tunable physical, chemical, and bioactivity properties compared
to their bulk counterparts [2]. TiO2 nanoparticles is a metal oxide nanoparticles that is
used as photocatalyst, coating to keep rust away and defending from UV, removing
pollutants, antibacterial, and medicine [3-5].
Currently, several methods have been tested to synthesize TiO2 which includes
sol-gel method, spray pyrolysys method, electrochemical anodized method that is
reviewed [5]. However the review did not include characterization of nanoparticle
created by each method.
In this paper we will compare the methods side by side and aim to include the
characterization of nanoparticle from each method. This comparison between each
method and its characterization result is expected to help aspiring researcher to
choose with precision the method that suits their purpose the best.
 2. Method

The method that is used in this paper is literature review from various journal on
TiO2 synthesis with differing method and its characterization.

Table 1. Comparison of Method used in TiO2 Synthesis

Method Procedure Advantage Disadvantage Ref
Sol-Gel Mix 7.21mL Capable of Wide distribution [7] [8]
dibutyl pthalate large scale of particle size and
with 20mL of production, aggregation of
absolute high surface particles
ethanol then stir area, high
for 30min with degree
magnetic stirrer flexibility with
and label it as its parameters
Liquid A. Make
Liquid B by
mixing 1.5mL
aquadest with
20mL of
absolute
ethanol then
add 3 drops of
conc. HCl. Add
liquid B into A
then stir
intensely for 30
minutes then
left it for 12
hours. After 12
hours put the
gel in constant-
temperature
box of 80˚C for
7 hours.
Porphyrize the
product and
bake it for
2hours at 550
˚C muffle and
obtain the
nanoparticles
after cooling it
down.
Co- add 10 mL HCl Low energy Starting sediment [8] [9]
precipitation in the beaker requirement have to be high
with 40 purity
aquadest then
put the beaker
in the ice-water
bath. Add 6 mL
pure solution of
titanium
tetrachloride
drop by drop
while stirring
and prepare the
expected
solution. Keep
the temperature
under 10 °C,
add excessive
H2O2 into it.
While stirring
with magnetic
stirrer, add
ammonia
gradually in the
above-
mentioned
solution and
adjust the pH to
10. Heat it to
50 °C and make
it constant for
30 minutes and
left for 18
hours. Wash
the sediment
properly. After
the seasoning,
several layers
are formed in
the solution.
The lower layer
is light yellow
cottonshaped
sediment. Take
the clear
solution from
the upper part
 of the beaker
by straw. Pour
the rest of the
solution into
the
microburette to
centrifugate it
for 5 min. Pour
out the solution
from the
microburette,
add aquadest
and use
ultrasonic
dispersion,
centrifugate it
again, repeat
the action for
three times. Put
the sediment
into the 60 °C
drying box for
30 minutes and
the white
powder is
formed. Heat it
at 500 °C
muffle for 2
hours and white
anatase
titanium
dioxide will be
produced.
Hydrothermal Add 1 g pollen Good for Not suitable for [8] [9]
with 25 mL nanotubes and large-scale
pure ethanol, nanofibers production.
use ultrasonic synthesis. Good
dispersion. Add photocatalytic
4 mol dibutyl activity
phthalate into
the solution and
use ultrasonic
dispersion for
20 minutes.
Add 3 drops of
aquadest into it
 then continue
ultrasonic
dispersion for 3
minutes.
Transfer the
solution to the
high-pressure
autoclave,
conduct the
hydro-thermal
treatment for 90
minutes under
105 °C in the
drying box and
then
centrifugate it
quickly. Pour
out the
solution, dry
the solid for 17
hours under 40
°C and get soil-
like products
which is a little
bit red. Place
the sample in
the crucible for
1 h, keep the
temperature for
2 hours after
the temperature
rises from room
temperature to
400 °C.
Continue rising
the temperature
to 550 °C in 1
hour, for 2
hours. Then
cool it and get
the white
titanium
dioxide
powder.
Hydrolysys Hydrolysys of [10]
TTIP with 250
ml solution of
distilled water
with various pH
at 60–70 ◦C for
almost 18–20 h.
After
peptization
process, the
volume of the
solution
decreases and
produced a
suspension.
Wash the
precipitates
with ethanol
then dry it at
100˚C in a
vaccuum
system for 3
hours. Anneal
the powder at
200-800˚C for
2 hours to get
the finalized
product
3. Result and Discussion

3.1. TiO2 Synthesis Methods

3.1.1. Sol-Gel Method

Sol-gel method is a wet-chemical method that is widely used as

metal-oxide nanomaterials development method. This method is called
sol-gel because the liquid precursor transformed into sol during metal-
oxide nanoparticle syntheis and then became a network called gel [11].
One of the procedure to synthesize TiO2 using this method is: Mix 7.21mL
dibutyl pthalate with 20mL of absolute ethanol then stir for 30min with
magnetic stirrer and label it as Liquid A. Make Liquid B by mixing 1.5mL
aquadest with 20mL of absolute ethanol then add 3 drops of conc. HCl.
Add liquid B into A then stir intensely for 30 minutes then left it for 12
hours. After 12 hours put the gel in constant-temperature box of 80˚C for 7
hours. Porphyrize the product and bake it for 2 hours at 550 ˚C muffle and
obtain the nanoparticles after cooling it down[7]. Characterization of the
product is done with SEM for morphology and phase analysis
characterization with XRD [7][12].
TiO2 nanoparticles synthesized by this method will have different
properties decided by the preparations and paramaters used such as solvent
and pH differences during synthesis process [13-16]. TiO2 nanoparticles
with lower pH will be more rutile phased than TiO 2 nanoparticles with
higher pH[14-15] which can be seen from XRD results in Fig.1.
 Figure 1. XRD patterns of nanocrystalline TiO2 samples by sol-gel method with
several pH condition as (light blue) pH 9, (green) pH 7, (red) pH 5,
(indigo) pH 3 and (dark blue) pH 1.[14]

Morphology of TiO2 also changed based on pH condition where

nanoparticles with lower pH shows rod-like shaped crystalline and the
crystalline turns more spherical when pH is higher[14] as shown in Fig.2
 Figure 2. Effect of pH on the TiO 2 nanoparticles: (a) sample prepared at pH 1(b)
sample prepared at pH 3(c) sample prepared at pH 5. [14]

Morphology is also affected by solvent used during synthesis as

shown in Fig.3.
 Figure 3. SEM micrographs of TiO2 nanoparticles prepared in (a) Isopropanol
(b) Methanol (c) Ethanol [16]

Nanoparticles with isopropanol showed a dense structure with

agglomerations consisting of many nanoparticles. Nanoparticles prepared
with methanol showed high homogeneity of the particles with fewer
aggregated particles consisting of compact secondary particles, while
nanoparticles prepared in ethanol showed increased aggregation of
primary particles and large pores[16].

3.1.2. Co-Precipitation Method

3.1.3. Hydrothermal Method

3.1.4. Hydrolysys Method

4. Conclusion
5. References