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CHAPTER 4
TITANIUM DIOXIDE FILM BASED PHOTOCATALYTIC
APPLICATION FOR DEGRADATION OF DYES

Noor Kamalia Abd Hamed1, Mohd. Khairul Ahmad1, Muhammad Hazli Mazlan2,
Nur Hanis Hayati Hairom3

1Microelectronics and nanotechnology-Shamsudin Research center

(MiNT-SRC), Universiti Tun Hussein Onn Malaysia, Parit Raja, Batu

Pahat, 86400 Johor, Malaysia

2Facultyof Electrical and Electronic Engineering, Universiti Tun Hussein

Onn Malaysia, Parit Raja, Batu Pahat, 86400 Johor, Malaysia

3Department of Chemical Engineering Technology, Faculty of

Engineering Technology, Universiti Tun Hussein Onn Malaysia, Parit

Raja, Batu Pahat, 86400 Johor, Malaysia

ABSTRACT

Titanium dioxide (TiO2) is a potential material as a photocatalyst for

environment remediation including photocatalytic degradation of organics
pollutants in waste water treatment, dye sensitized solar cell (DSSC), self-
cleaning panels and sensors. Although, a numerous number of methods
have been employed to fabricate TiO2 film, the cost of the film is highly
depending on sophisticated machine and hence, made the fabrication costly.
Simple and cost-effective films have been introduced in dye degradation via
the photocatalytic process. Dyes are organic pollutants or the by-product of
food and printing industries. Due to high demands from society for food
and printing, the wastes produced are relatively high and harmful to the
environment. Hence, TiO2 film fabricated using hydrothermal method was
proposed for the degradation of dyes. In this chapter, the photocatalytic
property of TiO2 thin film for degradation of dyes and the advantage of
TiO2 film will be discussed.

Keywords: TiO2, photocatalytic, dyes, methyl orange.

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4.1 INTRODUCTION

Recently, waste water treatment received a lot of attention from research

community in nanotechnology. The goal of nanotechnology technology is
to solve the problem of increasing pollution, control contamination and
waste remediation. A perfect waste water treatment process should employ
practical and inexpensive items and any perilous residues must be avoided
by the end of the process. Titanium dioxide (TiO2) with nanostructures has
the potential to reduce the harm of the contaminants through its
photocatalytic property. TiO2 is generally recognized with large redox
potential with respect to water, minimal cost production and chemically
stable [1].

In the past two decades, photocatalysis process has been initiated as a

standout amongst the best ecological innovations for waste water treatment,
due to its ability to expelled the natural impurity [2]. Photocatalytic
degradation can be defined as a degradation process of natural contaminant
in water by ultra violet (UV) light with help of TiO2 that act as a catalyst.
Organic or natural pollutants may be destroyed and oxidized due to
photocatalytic activity since superoxide radicals and highly oxidizing
hydroxyl may be formed. Usually, photocatalytic process based on powder
is applied in the slurry system. However, a few issues had ascended in the
slurry system in which, TiO2 applied at high concentration tends to form
powder aggregates and creates blockage. Thus, in the continuous flow
system, the catalyst in powder form is not applicable [3]. In order to
overcome the difficulties which could bring a huge benefit to the
photocatalytic activity of post separation, the catalytic film should be
immobilized. The degradation of methyl orange (MO) was studied by
focusing onto the photocatalytic activity of flowerlike rutile-phased titanium
dioxide film since it may dominate a huge demand in industrial of waste
water treatment.

4.2 TITANIUM DIOXIDE NANOSTRUCTURED

TiO2 is a semiconductor material generally utilized for various applications

such as gas sensor, photocatalyst, optical filter, dye-sensitized solar cell
(DSSC) and anti-reflection [4]. TiO2 can be referred to as a significant
material in optical films, it is widely utilized as color in coating and paint
elements. This is because of its chemical durability in the visible and near
infrared (IR) region and its high refractive index and transparency [5]. The
numerous advantages of TiO2 are such as non-toxicity, low cost and high
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stability. This enables TiO2 to be applied widely in different fields [6]. A

TiO2 film has a great transmittance of visible light and useful optical and
electrical properties.

TiO2 was extracted from the nature in different crystalline phases such as
minerals brookite (orthorhombic), anatase (tetragonal) and rutile
(tetragonal) [7]. Figure 1 shows the crystal structure of brookite, anatase and
rutile. Typically, brookite phase is just stable at low temperature and not so
useful for many applications. While rutile and anatase phases are in
tetragonal crystal lattice.

Figure 1: Crystal structure of (A) Anatase (B) Rutile (c) Brookite

In addition, rutile phase is more stable in the region of high temperature

while brookite and anatase phases are metastable plus both are able to
change in the phase of rutile if both are set up at high temperature [8]. Each
crystalline has different physical properties of band gap and surface state.
For further information, band gap can be defined as the energy gap between
the valence and conduction band [9]. Rutile phase has a lower band gap
energy than anatase phases that are 3.0 eV and 3.2 eV, respectively [10]. For
photocatalytic process to take place, the electrons must acquire equal or
more energy than energy band gap to excite from the valence band (VB) to
the conduction band (CB).

As report by previous study, the research group declared that rutile phase
exhibited a lower band gap than anatase phase and has a thermodynamically
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stable phase [11]. Despite that, anatase phase possesses a higher energy band
gap than rutile. Moreover, numerous researchers mentioned that anatase
phased showed better reaction with ultraviolet photons that utilized for
photocatalysis [7].

Numerous studies [12] have demonstrated the application of the

nanostructures of TiO2 in various field. The different derivatives of TiO 2
nanostructured are such as nanobelts, nanoparticles, nanowires, nanoflower
and nanorods. Different structures of TiO2 influences the TiO2 optical
properties [13]. As an example, porous film is good for gas sensor while
opaque structure film is suitable for solar cell application. Moreover, for
biomedical field, amorphous film is very useful because of its
biocompatibility in blood, while TiO2 film demonstrated more advantages
than the TiO2 powder in photocatalysis application. This is due to the
reason that TiO2 film is very easy to be removed from the solution [7]. In
addition, the combination of flower and rod structures in rutile phase
exhibits better electron mobility with higher surface area.

Titanium isopropoxide (TTIP), titanium tetrachloride and titanium

butoxide (TBOT) are the examples of specific precursors that are used to
fabricate TiO2 nanostructured [14]. Previous researcher claimed that the
morphological structure of the thin film between TBOT and TTIP are
identical [15]. The higher chemical reactivity for titanium tetrachloride is
difficult to be handled compared with other precursors. Thus, TBOT was
suggested to be the precursor for this research to fabricate rutile phase TiO 2
rods/flower film structure.

In order to degrade the waste water, rutile phase TiO2 rods/flower film
structure was used. The structure of rutile phase TiO 2 rods/flower was
applied as a photocatalyst agent for methyl orange (MO) dye treatment that
was taken as a model of waste compound. The degradation process of
organic on MO will be increased due to the combination of rod/flower
TiO2 which led to a better electron mobility compared to P25 (commercial
TiO2) and increased the surface area of the structure.

4.3 DISTINCT APPROACH FOR THE PREPARATION OF

NANOSTRUCTURE OF TiO2 FILM

In this section, construction of nanostructured TiO 2 will be examined and

reviewed. Sol-gel, hydrothermal and spray pyrolysis deposition (SPD) are

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the examples of method used to fabricate TiO2 film.

4.3.1 Spray Pyrolysis Deposition Method

In spray pyrolysis deposition film process, the solution will be atomized to

be deposited on the substrate in tiny droplets at suitable pressure. The
fabricated film relies on the droplet size, distance of nozzle spray to
substrate and spray rate. [10]. The choice of the mixture solution is crucial
to ensure just no undesirable material will be dissipated during the
deposition. Figure 2 shows a schematic diagram of a typical setup of spray
deposition.

Precursor

Nozzle

Air
Compressor

Sample

Hot Plate

Figure 2: A setup of typical spray deposition

The spray pyrolysis deposition method could produce anatase phase of high
porosity TiO2 film [16]. This method is applicable for gas sensor fabrication.

4.3.2 Sol-gel Method

The way of changing solution into gel phase can be categorized as sol-gel
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technique [17]. Sol forms from a series of hydrolysis and condensation

processes. At a certain temperature point, the condensed sol particle forms
into gel. Normally, condensation, hydrolysis and solvent reaction will be
used in the sol-gel process [18]. It has been reported that, anatase phase
with a coarse film indicated formation of nanostructured TiO 2 from sol-
gel preparation [19]. Subsequently, the nanostructured TiO2 need to
undergo calcination process at 300oC to obtain rutile phase and 800oC to
achieve the anatase phase [20]. This process causes a problem in fabricating
rutile phase and the surface morphology will be destructed when the
process involves calcination process at higher temperature.

4.3.3 Hydrothermal Method

The procedure of a solution react under controlled pressure and

temperature in a closed system with addition of water that act as a solvent
can be defined as hydrothermal method [21]. Usually, teflon lined stainless
steel autoclave or can be called as steel vessel pressure is used as a medium
for hydrothermal method. During the process, a chemical reaction
happened in the aqueous solution with a controlled pressure or
temperature. For the application temperature, it can enlarge beyond the
boiling point of water until it reached a pressure of saturation vapor. Then,
the internal pressure is influenced by the amount of mixed solution
combined to the Teflon lined autoclave and its temperature. Figure 3 shows
the image of an autoclave used for the hydrothermal system in an oven.

Autoclave

Figure 3: An autoclave with teflon for hydrothermal system in the oven

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In addition, stable pressure and temperature of the homogeneous film can

be obtained by applying hydrothermal method. Moreover, hydrothermal
method gives a huge benefit since the synthesis process is simple yet cost
effective compared to other techniques to fabricate TiO 2. The
morphologies and crystalline film of TiO2 can be tuned or changed by
varying the hydrothermal condition for examples, molar ratio, temperature,
pH and concentration of the reactants [22]. Thus, compared with other
fabrication method, hydrothermal can be applied to fabricate a material
since it is able to synthesize at a higher pressure in a tightly closed system
with a low temperature of the oven.

Ideal temperature for hydrothermal method which was obtained from

previous studies [23] 150˚C exhibits an optimal temperature to TiO2
nanorod/nanoflower to growth which has been proved by Meidan Ye [21].
The morphological flower structure cannot be grown if the temperature is
below 100 ˚C but TiO2 film started to detach from the substrate when the
temperature was to high [24]. While the reaction time can be fixed to 10
hours since it is the optimum one for the reaction to occur. Previous finding
mentioned that if the reaction time less than 10 hours, then the flower
cannot be grown [25]. However, TiO2 film begins to detach from FTO
substrate if 20 hours or more reaction time among the crystal growth
because of the hydrolysis rate of titanium [24]. Previous researcher
mentioned that, anatase phased TiO2 came from a base environment [26].
Thus, in order to fabricate rutile phase TiO2, this research focused on
hydrothermal as a method in acidic solution.

The conceivable development procedure of rutile phased TiO 2 can be

planned as follows. [Ti(OH)4] was yielded from solution that contain
TBOT that was produced from hydrothermal process. This composition is
the crucial part for growing nanostructured TiO2 on the FTO (SnO2)
substrate. Then, epitaxial growth of the rutile phased TiO 2 as a result since
the SnO2 layer also has the rutile phased crystallinity [22]. Rutile phased of
TiO2 and SnO2 possess an identical lattice parameter and tetragonal crystal
for rutile TiO2 and SnO2 is rutile TiO2 a= 4.594Å, c=2.959Å and SnO2 a=
4.687Å, c=3.160Å, respectively. In addition, [Ti(OH)4] controls the
development of TiO2 in the solution. The growth of the rutile phased TiO2
begun from a high concentration of HCl. TiO2 would become soluble in
high acidic solution, pH < 7 due to the dissolution-precipitation process
that occurs rapidly. The flourish rutile flowers were grown and deposited
on top of rutile rod TiO2 due to the gravity when undergo a hydrothermal
process in a free space. Figure 4 the growth of rutile phased TiO2 on a FTO
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substrate using hydrothermal technique.

Figure 4: The growth mechanism of rutile phased TiO2 by applying a

method of hydrothermal

4.6 PHOTOCATALYSIS

A process where reaction of catalytic engaging the construction of a catalyst

by absorption of light can be called as photocatalysis process [27].
Photocatalysis is categorized into homogenous and heterogenous
photocatalysis. H2O2 (hydrogen peroxide), O3 (ozonation) and Fe3+ (ferric)
are the catalysts that were used for homogeneous photocatalysis under
powerful irradiation of UV lamp [9]. Whereas, the generation of electron
and hole pairs process under light irradiation of semiconductor materials
can be referred to heterogenous photocatalysis. The examples of
homogeneous photocatalysis are such as hydrogen peroxide and UV
irradiation (H2O2/UV), photo-fenton system (fe3+/H2O2/UV) and
ozonation and UV irradiation (O3/UV). Table 1 indicates the advantages
and disadvantages among homogenous and heterogenous photocatalysis.

4.6.1 Photocatalytic Activity of TiO2

In the last decade, the heterogeneous photocatalytic processes received a

lot of attention among the decontamination technique due to the organic
compounds present in waste water can be completely oxidized. Numerous
viewpoints considered in creating a high photocatalysis process, for
example, biological and chemical inertness, photostability, capacity can be
used in visible light or UV light, low cost and environmental friendliness
[9].

There are the examples of semiconductors remain such as iron oxide

(Fe2O3), tungsten trioxide (WO3), cadmium sulfide (CdS), zinc oxide
(ZnO), tin oxide (SnO2), chromium oxide (Cr2O3), indium oxide (InO2),
vanadium oxide (V2O5), cerium oxide (CeO2), Copper Oxide (CuO) and

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titanium dioxide (TiO2). Late finding mentioned that the irrelevant

dissolution to yield Zn(OH)2 on ZnO particles in activate the catalyst over
time making ZnO to be unstable [30-34]. Among other materials, TiO2
received a lot of attention due to its unique characteristic in its biological
and chemical inertness, photostability, and low manufacturing cost.
Photocatalytic air and water purification using TiO 2 lead to a dominating
progressive oxidation process (AOP) because of its eco-friendliness and
efficiency [33].

Table 1: The compiled among homogenous and heterogeneous

photocatalysis

Photocatalysis References Advantages Disadvantages

Homogenous [27] • Maximum absorption • The ozone must
efficiency. destroy before
[28] • Lower sludge generation. releasing to
environment since it
might be poisonous
• Longer duration of
Degradation process
• To abolish hydrogen
peroxide and irons
salt residue
afterwards the
process
• High cost of
generation for
ozone.
Heterogenous [29] • Low energy UV light/ • For industrial
solar light. purposes, huge
[30] • The catalyst can be amount of catalyst is
reusable and the process needed.
less expensive.
• The production CO2
and H2O after
degradation process
make the process more
environmental friendly
• Only used atmospheric
O2 other than expensive
chemical.

In dye-sensitized solar cells, TiO2 can be a transport medium of electron,

energy catalyst in water splitting to produce hydrogen fuel, or an
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environmental catalyst in air and water purification showed that it is a

multifunctional semiconductor photocatalyst.

The improvement of photocatalyst performance and the preparation of

catalysts with high photocatalytic activity are priorities fundamental
research that must be studied. Figure 5 shows the mechanism of
photocatalysis of TiO2 in waste water treatment. TiO2 will be exposed
under the UV light. The electrons absorb this energy and be promoted
from the valence band to the conduction band, if the TiO 2 is illuminated
with photo energy equal or greater than the band gap energy [9]. At the
valence band, the positive charged of holes will produce hydroxyl radicals
(-OH) when it reacts with water molecule. At the conduction band, the
electron will react with dissolved oxygen and will produce superoxide
anions (·O2−).

The active oxygen series which are (·O2−) and (-OH) will be reduced into
H2O and CO2 via the photocatalysis process and hence, becoming eco-
friendly to the environment. This cycle continues as long as the light is
present. The photocatalysis of TiO2 mechanism is summarized by equation
(1) to (5).

Figure 5: The mechanism of TiO2 photocatalytic process

TiO2 photocatalytic degradation begun if the photon possesses identical or
higher energy than band gap of TiO2 which lead to the production of
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electron-hole pair:
hv
TiO2 (h+ + e-) (1)

At conduction band, the production of O2 superoxide anion is present due

to the reaction of electron with molecular:

e - + O2 · O2− (2)

At valence band, the production of super hydroxyl radical are present due
to the reaction of the holes with H2O or hydroxide ions:
h+ + OH- · OH (3)
h+ + H2O · OH (4)

These hydroxyl radical and superoxide anions will strike the green element
and yield water and CO2 which endangered to society and environment;

Organic substance + ·O2− + ·OH CO2 + H2O

(5)
In this study, the photocatalytic activity will produce a free radical which
will attack the organic molecule in water that contaminated. MO will act as
an example compound of waste water in obtaining the ability of TiO2 film
in rutile phased [34]. The reaction produces carbon dioxide (CO2) and
water (H2O) which are harmless to the environment.

4.7 IMMOBILIZATION OF PHOTOCATALYST

It has been reported that heterogeneous photocatalysis has been carried

out by using TiO2, in powder form. However, the separation post between
the treated water and TiO2 powder presented problems. It is hard to curb
with high concentration of waste water over a longer period of time. To
circumvent this problem, various substrates of immobilized TiO 2 were
used.

There are multiple substrates which have been utilized in the degradation
of photocatalysis in various applications such as glass [35], stainless steel
woven meshes [36], sponge [37], carbon [38], polymeric material [39] and
silica [40]. Various immobilization techniques for example sol gel [41],
solvothermal [42], chemical vapor deposition [43], sputtering [44] and
electrospinning [45] which used to fabricate immobilized TiO2. Previous
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researchers stated that the surface area of photocatalysis form powder are
larger compared to immobilized TiO2 [46]. However, previous researchers
also highlight that the efficiency of photocatalysis degradation were
unaffected by immobilized TiO2 [47]. The flower-like rutile phased TiO2
contributed contribute to larger surface area because of the flower-like
structured. Thus, the flower-like structure will enhance the photocatalytic
activity which provides more active surface area. High efficiency of
photocatalysis degradation is still puzzling many researchers. The high
efficiency can be contributed by the condition of the photocatalysis
environment and the preparation of fabricated catalyst.

4.8 DYES

Dyes are broadly used in different industries for instant food, plastics,
leather, cosmetic and textile industries. Table 2 demonstrates a few types
of common dyes used in the industry. The effluent that contains dyes will
acquaint potential threat to the marine biological community. There are
different techniques used to dispense the dyes from the waste water system
such as flocculation, reverse osmosis, biological and chemical method,
ultrafiltration, and adsorption. Nonetheless, dyes with the complex
structure cannot be disrupted with the traditional technique such as
biological method for decolorization [48]. Also, a portion of the dyes are
not adsorbed and degraded on the sludge. Harmful natural compounds will
be discharged to the aquatic system without proper treatment. Thus,
resulting in various health hazards due to the improper waste management.

For organic compound, methyl orange could be decomposed via the

catalytic ability of rutile-phased TiO2. Methyl orange is a common azo dye
used in the leather, paper and printing textile industries. Unfortunately, the
inappropriate administration of waste in the enterprises could contribute a
genuine contamination to the earth which affect the living aquatic
organism. Azo dye is known as a dangerous waste and potential as
carcinogenic substance. Table 2 shows the different types of dyes exist in
the enterprises. Along this line, the problem may be solved by the new
enhanced treatment which is rutile phase TiO2 microsized rods/flowers
film.

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4.6 SUMMARY OF TiO2 APPLICATIONS

Nanotechnology of TiO2 has attracted an extraordinary consideration from

the nation in worldwide. This is on account of the quality of the
innovations circulates various advantages to the general public. TiO 2 has
been utilized for Dye Sensitized Solar cell (DSSC) [48-49]. Malaysia has
plentiful of solar energy through the year. In this manner, the new source
of electrical energy can be replaced with DSSC because the fact that the
natural source has been exhausted. At this point, TiO 2 was found to have
a capacity in eliminating microorganism (bacteria) [50–53]. This was an
intriguing region which could help in medication field.
For gas sensor application, TiO2 has a capacity to detect different types of
gas, for example, ammonia and oxygen [54-55]. Next, it was discovered
that the TiO2 has a capacity in self-cleaning for the building which enables
a financially savvy technology for the industries [56-57].

Table 2: List of dyes

No Dyes Chromophoric Example of dye

groups
1 Acridine dyes Acridine ring Acridine orange

2 Anthraquinone Anthraquinone ring Alzarin

dyes

3 Arylmethane Methine group, Auramine

dyes C=N

4 Azo dyes Azo group Methyl orange

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Table 2: List of dyes (Con’t)

5 Nitro dyes Nitro groups, NO2 Picric acid

6 Nitroso dyes Nitro groups, NO2 Nephthol yellow S

7 Quinone-imine Methine group, Indophenol

dyes C=N

8 Azin dyes Methine group, Safranin O

C=N

9 Xanthene dyes Xanthene ring Erythrosin B

10 Oxazin dyes Oxazine group Nile blue

ue

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Besides that, TiO2 has a greater of photocatalytic activity compares to the

other semiconductor material which lead to a huge benefit. It is believed
that TiO2 could enhance the waste water treatment. Various types of
polluted water such as palm oil mill effluent (POME), dyes and paper mill
effluent may easily be decomposed by photocatalysis of TiO 2 [28], [58–63].

ACKNOWLEDGEMENT

The authors acknowledged the financial support given by the Research

University Grant from Universiti Tun Hussein Onn (Tier 1 Vot No. U932
and GPPS Vot No. U958).

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