1

Nowadays, the rapid development of the industries and increase of human population
has greatly causes the high demand of the clean water . As the result, this matter have
caused the problem of water shortage in all places around the world.
The disposal of the organic pollutant to the environment is raised up as a
challenge for a lots industries. One of the common type of the synthetic organic
compounds is dye. In general, dye is commonly used for production of plastic, food,
paper, cosmetic and others.As you can see from images on the slides. The picture the
waste of the dye solution is discharged to the river and all kind of water resources.
Dyes will be absorbed through water and therefore lead to water pollution. This
is because the content of the dyes content will contaminated the water resource and
this circumstances will prevebt sunlight from passing through the water, which will
cause the interruption of the photosynthesis process that is needed for the living of
aquatic organism. In fact, organic pollution will causes the human disorder such as
skin irritation, blood, liver and kidney failure
The water treatment technologies that are existing such as absorption,
ionization and coagulation functioning by transferring the pollutants into other phases,
instead of remove them complete. On the other hand, there are also ordinary water
treatment techniques such as sedimentation and filtration which is equipped with
chemical and membrane technologies that require expensive operation cost. Therefore,
some studies pointed out the usage of the catalyst is useful for the water treatment by
absorbing sunlight. It is claimed that the nano-sized of titanium dioxide, TiO2 has the
high efficiency in the photocatalytic activity.
`For the important study, Semiconducting oxide materials is used as an alternative
water treatment by eliminating the harmful substance using ultraviolet radiation. TiO2-
based photo catalyst is used in water treatment in a large scale due to high
photocatalytic activity. This study brought exposure to the fabrication of
TiO2nanotubes using anodization method and presented the comparative analysis on
the photocatalytic performance and microstructure of TiO2. The key parameters of
applied anodization potential on the formation of TiO2 nanotubes was studied.
In this problem statement, preparation of electrolyte for the anodization could
be challenging task to do. Because some of electrolyte used in some of the resarchers
studies and they used different type and different concentration of acid solution. And
they will tune of a suitable electrolyte for anodization. Therefore, oxalic acid is
selected as electrolyte in this study because can saving time and complexity of the
preparation of electrolye. There is no work on the formation of TiO2 nanotubes by
using oxalic acid has been reported. Besides that, the range of voltage is also a concern
in this study to determine growth of the titanium nanotubes.

The aim in this study is to investigate the influenced of voltages on the formation of
nanoporous TiO2 using anodizing method. The objectives of this work are:
i. To determine the effect of the oxalic acid as the electrolyte for anodization
process.
 2

ii. To investigate morphological, structural and photoelectrochemical properties

of TiO2 nanotubes.
iii. To correlate the photocatalytic properties of TiO2 nanotubes in methylene blue
dye solution.

The scopes of this study are the influential of anodizing voltages and oxalic acid
as the electrolyte for the formation of the TiO2 nanotubes. One of the limitations of
this study is the targeted applied voltages used for the anodization such as 50, 60, 70
and 80 V. Besides, anodization time is set for 30 min while the annealing time for the
sample is 2 h. The concentration of the electrolyte is 0.3 M of oxalic acid.
In the past decade, nanostructured materials have been receiving great interest as
catalysts because of their unique and outstanding characteristics. There are lots of
effort has concentrated on the metal oxides such as TiO2.. TiO2, is an n-type
semiconductor material with electronic band gap larger than 3.0 eV which absorbs
light mainly in the UV region. Anatase type TiO2 has a dipyramidal crystalline
structure and is used mainly as a photocatalyst under UV irradiation. Rutile type TiO2
also has a prismatic type tetragonal crystal structure of Rutle is mainly used as white
pigment in paint. Brookite type TiO2 has an orthorhombic kindly crystalline structure.
TiO2 therefore is a versatile material that has applications in various products such as
paint pigments, sunscreen lotions, food coloring and so on.
The word photocatalysis is a composite word which is composed of two parts, photo
and catalysis. Catalysis is the process where a catalyst is used to modify the rate of
a chemical transformation of the reactants without being achange or consumed in the
end. That mean, photocatalysis is a reaction which uses light to activate a catalyst and
modifies the rate of a chemical reaction without being involved itself. Photocatalyst
breakdown the organic matter to carbon dioxide and water in the presence of light.
There are lots of fabrication method of the TiO2, commonly called as Sol-gel
technique, Hydrothermal method, Solvothermal, Chemical Vapor Deposition,
Anodization.
The purpose of the anodization is to apply electrochemical oxidation to produce a
uniform oxide layer on surface of metal substrate. Anodization of metals is
implemented with two-electrode of electrochemical cell in a way that the metal
material is using as anode and platinum material is used as cathode under a consistent
potential. By applying this method, it has several outcomes such as great specific
surface area and good dimensions and morphologies of nanostrcuture. Additionally,
nanostructures that are fabricated by anodization are vertically oriented.
So I would explain the general formation mechanism of TiO2 nanotube, .Before
anodization, a nano-scale TiO2 layer is on the Ti surface. When constant voltage is
applied, a pit is formed on the TiO2 layer. As anodization time increases, the pit grows
longer and larger, and then it becomes a nanopore. Nanopores will to continuous to be
deepen After specific anodization time, completely developed nanotubes are formed
on the Ti surface. The changes in colour of the TiO2 layer begin from dark purple to
 3

blue, followed by yellowish colour and finally green throughout the process of
anodization. The occurrence of the variation in the colour due to the increment of the
TiO2 nanotubes thickness.

The flow chart described my all of practical work task of my study. which is begin the
anodization of titanium foil sample. After the anodization, the morphological,
structural, photocatalytic , photoelectrochemical properties of the TiO2 would be
studied.
Before the anodization, the Ti foil was cleaned carefully using ultrasonic cleaner with
ethanol for the duration of 15 minute. The anodization of Ti process took place in a
two-electrode electrochemical cell using a Ti foil as anode and a platinum rod as
cathode as shown in Figure 3.1. The anodization process was constructed and
performed at 50, 60, 70 and 80V for 30 minute in the electrolyte that contained 0.3 M
oxalic acid. These anodization parameters are having the capability to produce TiO2
nanotubes structure. Upon the completion of the anodization, the Ti foil was rinsed
with deionized water and the annealing process was conducted at 400 C in air for
duration of 2 h to induce crystallinity of the nanotubes layer.

The surface morphology of the prepared sample was examined using the field-
emission scanning electron microscopy (FESEM) system (Hitachi FE-SEM S4800.)
The FESEM system was used to examine the surface and cross-sectional morphologies
of the sample. The sample was prepared by placing the sample on a sample holder
using a carbon tape.
Structural analysis of TiO2 nanotubes is studied to obtain the phase composition and
crystal structure of the sample. X-ray diffraction (XRD) method was implemented at
the room temperature using X-ray diffractometer device (Bruker D8 Discover XRD)
equipped diffracted beam graphite monochromator at 50kV and 40mA ( Cu K with
= 1.54187 ). The XRD analysis was performed in the range of 2 = 1090 , where
is the angle between the incident x-ray and the scattering plane.

Ismail et al. (2017) conducted anodization with voltages of 10V (a), 40V (b) and 60V
(c) in electrolytes composed of ethylene glycol (EG), ammonium fluoride (NH4F), and
hydrogen peroxide (H2O2). The d-f images is their cross-sectional view. At 10V, the
anodic layer has porous-like top structures. At this voltage nanotubular is hardly seen
however smaller pores (~ 20 nm) can be seen on the surface of the anodic film. It is
because the formation of oxide layer is too thin when the anodization at 10 V. As the
voltage increased to 40V pores enlargement occurred. The cross section of the Figure
2(e) indicate that the nanotubes is formed and large pores formation with diameter
about 100 nm can be seen in the inset of Figure 2(b). At 60V nanotubes with larger
diameter (~ 180 nm) are formed (Figure 2(c)). Nanotubular arrays are seen to have
well organized and single layer oxide. Unlike samples made at 40 V, sample made at
60 V is consisted of prominent nanotubular arrays with ruptured tubes mouth. Due to
the higher electric field (higher voltage), the pores formation is dominated by the
 4

electric field dissolution. Pore growth is effected by electric field. Thus, more pore
formation happens, as higher field is established across the sample. It was found that
higher voltage normally yielded larger tube diameter and length. Hence the stability of
the structure is easily disturbed which eventually caused the rupture of the tubes mouth.

In the case study presented in Srimala et al. (2011), electrochemical anodization was
successfully conducted in electrolyte that contained glycerol with 6 wt% ethylene
glycol (EG) and 5 wt% ammonium fluoride (NH4F). This combination of the
electrolytes are considered depend on preparatory researches that acknowledge the
construction of satisfactory alignment TiO2 nanotubes arrays. The anodization is
conducted using the voltage range from 20, 30, 40, 50 and 60 V. Figures 2.6 evidently
showed that effects of applied voltage on the changes to surface morphology and
nanotubes adjustment of titanium foil. It is found that organized nanotubes with regular
patterns are formed when less than 30 V is supplied, whereas the self-organized
nanotubes structure became uniformly at 50 V and appear to be damaged at 60 V. Thus,
50 V is seen to be the highest voltage to provide stable anodization behaviour. As the
anodizing voltage increased, the outer length and diameter of the nanotubes array will
increase as well
In other case, Pasikhani et al. (2016) pointed that in Figure 2.7, show the images of the
TiO2 nanotubes fabricated at voltages of 40, 50 and 60 V. According to Figure 2.7(a)
(c), it can be seen that the TiO2 nanotubes have regular and honeycomb surface
structures. The results presented in Table 2.3 show that due to an increase in the voltage
from 40 to 60 V, the legnth, diameters,wall thickness of the nanotubes have increased,

Annealed TiO2 nanotubes was immersed in a beaker that containing 10 ppm methylene
bue dye solution. The photocatalytic properties of TiO2 nanotubes were determined
under the illumination of UV light (1 W cm-2 of light intensity). Afterwards, 2cm2 of
TiO2 was immersed in 50 mL of methylene blue dye solution. At every hour, 3 mL
amount of methylene blue dye solution was taken out in order to measure the dye
concentration using ultraviolet-visible spectrophotometer

Three-electrode photoelectrochemical cell were used to determine the

photoelectrochemical properties of the TiO2 nanotubes sample. The TiO2 nanotubes,
platinum rod and saturated Ag/AgCl served as the working electrode, counter and
reference electrode respectively. The electrolyte used in this photoelectrochemical
measurement is 1 M KOH solution. The three electrodes were connected to the
potentiostat (Metrohm Autolab Type III, the Netherlands). The light source
equipment for sample measurement of current and voltage used was UV light. The
photoelectrochemical set-up is showed at the Figure 3.3
5