1.

INTRODUCTION
The word photocatalysis is derived from Greek language in which the first word photo means
any light and catalysis means to tear apart. Photocatalysis in general sense means to enhance the
rate of photochemical process by using certain materials which are activated in the presence of
light called photocatalyst. Without light, it is not possible to carry out photocatalysis. The whole
photocatalytic process is depended on the creation of electrons and holes pairs which further
generate radicals like hydroxyl radicals. These radicals undergo further reaction to produce final
product. First major application of Photocatalysis came into existence when it was found that
water can be electrolysed by using photocatalyst like titanium dioxide and zinc oxide. During
research it was found that semiconductors are best suited to be used as photocatalyst because
they can be easily excited and they have good light absorbing capacity. Pure semiconductors
have less conductivity. So doping is done to increase their conductivity. Small band gap exists in
case of doped semiconductors. The electron-hole recombination process is found to be extremely
low in case of semiconductors. So they exchange charge with the substance present on its surface
and hence chemical reaction occur and we get final product[1].

1. PHOTOCHEMISTRY
According to Grotthuss, photochemistry is most important branch of chemistry which deals with
interactions between atoms, molecules and light (infrared, visible, ultraviolet, vacuum ultraviolet
light). Common examples which we daily see related to photochemical reaction are
photosynthesis and plastic degradation. E xcited species are created when light is absorbed by
photocatalytic material. They undergo different reactions like:[2].
1) Unimolecular reactions: Dissociation, Ionization and Isomerization
2) Bimolecular reactions: a) Reactions between two molecules

2.1 ADVANTAGES OF PHOTOCHEMISTRY

The main difference between photochemical and thermal reaction is that rate of
photochemical reaction increases very fast once it is initiated.
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 Some products are impossible to produce without photocatalysis .

They are eco friendly as they do not create pollution.
They are energy saving
It requires least chemicals

2.2 LAWS OF PHOTOCHEMISTRY

1st law of photochemistry:
This law was proposed by two scientists. They are Grotthuss and Draper. The law statement in
general language is given as Absorption of light is basic requirement for initiation of
photochemical process.

2nd law of photochemistry:

This law was also proposed by two scientists. They are Starck and Einstein. The general
statement of this law isWhen one photon is absorbed then only one molecule is excited
[3].

2.3 QUANTUM YIELD

It is the ratio of number of moles of reactant disappearing or product formed to the Einsteins of
light absorbed. Mechanism of reactions can be easily studied with the help of quantum yield. It
gives an idea of effectiveness of a photochemical process occurs in a given conditions. Due to
the complex nature of some photochemical reaction, their quantum yield is always known before
so that there is no problem during studying those reactions.

2.3.1 TYPES OF QUANTUM YIELD

Primary quantum yield
Product quantum yield
Quantum yield of fluorescence
Quantum yield of Phosphorescence
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 Quantum yield of Decomposition

Quantum yield of Rearrangement

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In general sense, quantum yield of primary reaction is always less than 1.In some reactions such
as chain reactions, rate of formation of product is higher because of production of free radicals
and hence they have quantum yield greater than one .Small quantum yields indicate deactivation,
fluorescence or other processes that lead to a small chemical change. Large quantum yields is
the indication of the photochemical change forming the products.

2. BASIC CONCEPT OF PHOTOCATALYSIS

An electronic property of different materials is given by band theory. We know that in solids
atoms are closely spaced. As a result their energy levels are very near to each other which results
in the formation of band. Each band is characterized by different energy and filling of electrons
takes place from lowest energy level to highest energy level. Valence band has highest energy of
all bands in which electrons are filled. Above the valence band, there lies conduction band. Band
gap separated valence band from conduction band. When electric field is applied to solids,
electrons will be excited from valence band to conduction band. Large band gap exists in case of
insulators so electrons cannot jump from valence to conduction band. In case of metals, due to
small band gap or absence of band gap, electrons can be easily excited from valence to
conduction band. Now in semiconductors, band gap is moderate which means it is in between
conductors and insulators. By irradiating it with light, electrons can easily be excited to
conduction band [4].

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Fig 3.1 Energy band gap in 1) insulator 2) semiconductor 3) conductor [5]

2.1 MECHANISM OF PHOTOCATALYSIS

Pairs of electrons and holes are formed when titanium dioxide absorbs ultraviolet light . When
light is passed through titanium dioxide material, electrons present in valence band excites to
conduction band. Due to this, holes are created and negative charge is developed in conduction
band. Titanium dioxide is then said to be photoexcited. Light source having wavelength around
390 nm is required for this purpose. Hydrogen gas is released when holes created by photo
excitation reacts with molecules of water. Electrons having negative charge react with
atmospheric oxygen to produce oxide anion. The whole process is continuously repeated until
light source is available.

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Fig 3.2 Mechanism of photocatalysis [6]

SC + hv SC*
SC* e + h+
+
h + H2O H+ + OH
S + OH Products

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Fig 3.3 Photocatalysis mechanism in TiO2 [7]

2.2 TYPES OF PHOTOCATALYSIS

Photocatalysis is generally divided into two main types. They are as follows:(1) Homogeneous photocatalysis
(2) Heterogeneous photocatalysis

3.2.1 HOMOGENEOUS PHOTOCATALYSIS

In this first type, reactants and products are in the same phase. Two most commonly used
homogeneous photocatalysts in todays modern world are photo-Fenton system and ozone.
Hydroxyl radical is the main reactant which carry out many functions. There are two paths which
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ozone follows for production of radicals of hydroxyl. They are:

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O3 + hv O2 + O
O + H2O OH + OH
O + H2O H2O2
H2O2 + hv OH + OH

Similar to above process, this process forms hydroxyl radical by another way which is given
below:

2+

3+

Fe + H2O2 HO + Fe + OH
3+

2+

Fe + H2O2 Fe + HO2 + H
2+

3+

Fe + HO Fe + OH

In this process, two additional means of producing hydroxyl ions are developed in presence of
Ultraviolet light. They are like: breakdown of Hydrogen Peroxide and reduction of Fe

3+

ions [8].

H2O2 + h HO + HO
3+

2+

Fe + H2O + h Fe + HO + H

Concentration of hydrogen peroxide, intensity of UV and pH are the parameters which

influences the overall efficiency of Fenton system.

3.2.2 HETEROGENEOUS PHOTOCATALYSIS

In this type of photocatalysis, the catalyst and reactants are in different phase. The two majorly
used heterogeneous photocatalyst are transition metal oxides and semiconductors. In the
semiconductors, there is a band gap which is present between valence and conduction band.
When they absorb photon with energy greater than its band gap, excitation of electrons takes
place. As a result, holes are generated in valence band. Both holes and electrons are important.
So they must not recombine with each other. If they recombine then efficiency will be low.
Electrons which are excited reacts with an oxidizing agent to give reduced product and holes
produced react with reducing agent to give oxidized product. Due to the generation of electrons
and holes, oxidation and reduction reactions between substrate and excited species takes place at
the surface of semiconductors. In the oxidation reaction, holes interact with water to form
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hydroxyl radical.
Reactions due to oxidation as a result of photocatalysis are:
UV + MO MO (h + e)
MO means oxides of metal

h + H2O H + OH
+

2 h + 2 H2O 2 H + H2O2
H2O2 HO + OH
Reduction reactions due to photocatalysis are:

e + O2 O2
+

O2 + HO2 + H H2O2 + O2
HOOH HO + OH

3.3 FACTORS

AFFECTING

KINETICS

OF

PHOTOCATALYTIC

PROCESS

There are mainly 5 factors which affects kinetics of photocatalytic process. They are:
Catalyst weight
Light wavelength
Reaction temperature
Initial concentration of reactants
Photonic flux

3.3.1 INFLUENCE OF PHOTOCATALYST WEIGHT

The rate of reaction of a photocatalytic process is directly proportional with catalyst weight.
Higher than certain value of mass of photocatalyst the reaction rate becomes independent of the
mass.
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3.3.2 INFLUENCE OF LIGHT WAVELENGTH

The rate of reaction is a function of wavelength which follows the absorption spectrum of the
catalyst, with a threshold value that corresponds to the energy of Band-Gap.

3.3.3INFLUENCE OF INTIAL REACTANT CONCENTRATION

In general sense, the kinetics of the process follows Langmuir- Hinshelwood mechanism.
The rate of reaction changes proportionally with the degree according to
r = k= k(KC/1+KC)
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3.3.4 INFLUENCE OF REACTION TEMPERATURE

The rate of reaction maximizes initially with increase in temperature upto a certain value. After
that reaction rate remains constant for a certain range of temperature and then finally rate
decreases with further increase in temperature.

3.3.5 INFLUENCE OF PHOTONIC FLUX

The reaction rate is directly proportional to photonic flux upto its threshold value. After the
threshold value the reaction rate becomes proportional to

0.5

4. PHOTOCATALYST
It is a substance which is used to alter the rate of photochemical reaction and without being
consumed at the completion of reaction. Chlorophyll is a good example of natural photocatalyst
whereas nanotechnology prepared TiO2 is a man made photocatalyst. Chlorophyll make use of
sunlight to convert water and carbon dioxide into glucose and oxygen whereas TiO2 creates
powerful oxidizing agents and electronically positively charged holes which decomposes organic
substances to release carbon dioxide and water in the presence of light source . There are mainly
4 types of photocatalyst used. They are:1) Semiconductors
2) Spinel
3) Perovskite
4) Mixed oxides

4.1 SEMICONDUCTORS
Semiconductors are widely used and most important photocatalyst. They behave as
heterogeneous photocatalyst. TiO2 is the most efficient and effective photocatalyst till date. The
efficiency of photocatalytic process using semiconductors as photocatalyst is low. But it can be
increased or improved by the use of co-catalyst. These co-catalyst present on the surface of
semiconductor will enhance the catalytic process and will increase the overall efficiency. Cocatalyst promote charge separation and transfer.. Dual co-catalysts serve as more better means of
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enhancing efficiency of photocatalytic process because they reduce the activation energy b
arriers for both oxidation and reduction reactions.

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Table 4.1 Optical properties of some photocatalytic conducting materials [7]

Semiconductor

Band gap (eV)

Band gap equivalent

wavelength(nm)

BaTiO3

3.3

375

CdO

2.1

590

CdS

2.5

497

CdSe

1.7

730

Fe2O3

2.2

565

GaS

1.4

887

GaP

2.3

540

SnO2

3.9

318

SrTiO3

3.4

365

TiO2

3.0

390

WO3

2.8

443

ZnO

3.2

390

ZnS

3.7

336

4.2 SPINEL
Spinel belongs to an important class of mixed metal oxides. They are a group of mineral oxides
which have similar crystalline structures. They have a general formula of (X)(Y) 2O4 in which X
and Y represents metal cations. The whole group of spinels is named after their representative
mineral spinel which is magnesium aluminium oxide and whose formula is MgAl 2O4. The whole
spinel group consists of more than 20 minerals. It includes ores such as chromite, magnetite,
franklinite. The representative mineral spinel is very important as it produces gem quality stones.
Actually spinel is a very shiny material so it is mistaken as ruby and sapphire. Pure spinels are
colorless but due to the presence of impurities it occurs in variety of colours ranging from pink to
red, blue to orange, yellow, brown and black. Black Prince Ruby is the historical spinel
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gemstone which was mistaken as ruby due to its red colour. Spinels differ considerably from
ruby and sapphire as it has octahedral structure and single refraction. Also spinel has low Mohs

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hardness as compared to ruby and sapphire. Their luster is vitreous. The crystals are transparent
to translucent and sometimes nearly opaque. They possess isometric crystal system. Their
specific gravity ranges from 3.5-4.1.

Fig 4.1 Vibrant red Tanzanian Spinel [9]

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Fig 4.2 Crystal structure of MgAl2O4 spinel[10]

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4.2.1 LIST OF SPINELS USED AS PHOTOCATALYST

1) ZnFe2-xCrxO4 nanoparticles are used for the removal of azo dye from aqueous solution.
2) ZnAl2O4 is used for the photodegradation of methyl orange dye, Procion red dye, Chromium
Acidic black dye and Rhodamine B dye from its aqueous solution.
3) ZnCr2O4 nanoparticles are used for decomposition of anionic dyes like Eosin-Y and phenol red
which are polluting water.
4) MgCr2O4 is used as a catalyst for the oxidative degradation of dyes like Xylenol Orange and
photo degradation of dyes like Rhodamine-6G(Rh-6G) which are environment pollutants.
5)

ZnMn2O4 is used as a catalyst to reduce NO to N2.

6) MgAl2O4 is used a photocatalyst for the degradation of Methylene blue dye from its aqueous
solution with an efficiency of 88%.
7) CuFe2O4 is used as a catalyst for photo degradation of Methylene blue dye with an efficiency of
95.9%. Also it is used for the degradation of AF dye in aqueous solution.

4.3 PEROVSKITES
Perovskites are an important photocatalytic material which possesses general formula of ABO3.
Here A is the cation of larger molecular mass and B is the cat of smaller molecular mass. They
have wide range of applications. Compounds like PbZrO3 are used as piezoelectric compounds
while compounds like SrTiO3 show photocatalytic properties. B cations have strong interactions
with O while A cations have weak interactions with O. Photocatalytic properties of perovskites is
due to its crystal structure.
Fig 4.3 Crystal structure of perovskite BaTiO3 [11]

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Perovskites can offer favourable band edge potential which might be very useful for carrying out
photoinduced reactions. When we compare perovskites with mixed oxides then we find that
perovskites has sufficient cathodic conduction band energy for the evolution of hydrogen. One of
the main advantage of using perovskites as a photocatalyst is that they are both visible light and
UV light active.

4.3.1 TITANATE PEROVSKITES

Most of the titanate perovskites produce mindblowing catalytic properties under UV radiation.
They have band gap value greater than three. But by doping them with suitable materials we can
change their response from UV to visible light. Some titanates have conduction band (CB)
energy more negative than TiO2 . As a result they are used instead of them for hydrogen fuel
generation. Two important characteristics of titanates are that they offer good photostability and
they are also resistant to corrosion in aqueous solution. Some examples are:

1)

SrTiO3

It has a simple cubic structure with a band gap of 3.25 eV. When we dope it with co-catalyst like
Rh, it shows water splitting under UV light. When we dope Ti with some materials like Mn, Ru
and Ir, it induces mid gap states in the band gap which then allows it to absorb visible light. It
has been found that when we dope it with Mn and Ru, then it is useful for O2 evolution and when
we dope it with Ru and Rh it is found to be useful for H2 evolution.

2)

BaTiO3

It has a band gap of 3.6 eV. When we dope it with Cu, it changes its response from UV to visible
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light absorption and shows photocatalytic water decomposition. Other advantage of doping it
with Cu is that it also enhances H2 evolution under UV light when we use NiO x is used as a cocatalyst. Alkali metal titanates like Ca, Ba, etc have enough conduction band potential for
hydrogen evolution. But there are transition metals titanate which have enough CB potential but
then also they do not show hydrogen evolution. Such materials can be used for degradation of
organic compounds or other photocatalytic processes.

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3)

NiTiO3

It has a band gap of 2.16 eV. It is widely used for the degradation of nitrobenzene in the presence
of visible light

4)

CdTiO3

It has a band gap of around 2.8 eV. It is widely used for the degradation of rhodamine 6G dye in
the presence of visible light.

4.4 MIXED OXIDES

These are mixture of sulfides or nitrides and oxides which are prepared to understand structure of
band of oxide photocatalyst which are suitable for absorbing visible light. In oxynitrides, if
oxygen is replaced by nitrogen at lattice sites then the band gap will become narrow. Also the
electron hole recombination will be prevented. Similar action takes place with oxysulphides.
Oxynitrides compounds for example CaNbO2N, SrNbO2N, BaNbO2N, and LaNbON2 have
crystal structure similar to perovskites. There are some compounds like CaTaO 2N and BaTaO2N
in which platinum is used as a co-catalyst in the presence of Pt/WO 3 which is widely used for Z
scheme splitting of water. Other compounds like BaTaO2N and BaZrO3 were investigated and
later found that they can be used for hydrogen and oxygen evolution.

5. TiO2 PHOTOCATALYST
Titanium dioxide is an oxide of titanium which occurs naturally. The main source of titanium
dioxide are Ilnemite, anatase and rutile. It occurs naturally in minerals like rutile, anatase and
brookite. Ilnemite is the mostly used source of titanium dioxide. The next major source of
titanium dioxide is rutile which contains 98% TiO 2 in its ore. TiO2 possesses high refractive index
and brightness due to which it finds extensive uses as a pigment. It is used in paints and coatings,
food, fibres, plastics, pharmaceutical and cosmetics products. The main advantage of titanium
dioxide is that it is resistant to discoloration when it is exposed to UV light. Due to this, plastics
remain as it is when it is exposed to light. Its colour does not change. In sunscreens also titanium
dioxide is used as a blocker so that skin is protected from UV light.

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Fig 5.1 TiO2 powder[11]

But nowadays it is seen that TiO 2 is widely used as a photocatalyst because it has high reactivity,
chemically inert and stable, low cost and less toxic. When we use it in nanoparticle form, we can
improve water splitting efficiently into hydrogen and oxygen and we can also generate electricity
from it. As a result, it finds application in LCD and LED. It can also be used as an oxygen sensor
because in the presence of reducing atmosphere, it will lose oxygen and will become
semiconductor. So if oxygen content is low in atmosphere it will show high electrical resistance.
In this way it can be used as an oxygen sensor.

5.1 TiO2 crystallographic forms

1) Rutile: It is most stable and it is chemically inert. It can be used to absorb both UV as well as
visible light.
2) Anatase: Active under visible light and can be transformed to rutile form at high temperature.
3) Brookite: Insensitive to UV light and the orthorhombic crystals system of it can be converted to
rutile form by giving heat.

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Fig 5.2 Crystal structure of Rutile, Anatase and Brookite [11]

Fig 5.3 Crystal images of Rutile, Anatase and Brookite [11]

5.2 SUPER HYDROPHILIC PROPERTY

When we expose the surface of thin film of photocatalyst to light source, there is a reduction in
the contact angle between surface of photocatalyst and water. After the light is exposed for
enough

time, it becomes super hydrophilic. It means that the photocatalyst is no longer

hydrophobic. As a result, water does not exist in form of drops but it starts spreading on the
surface of molecule of substrate.

Fig 5.4 Super hydrophilic property of TiO2[12]

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5.3 EFFECTS OF TiO2

There are mainly 4 effects of TiO2 .They are:

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1) Anti- bacterial effect

Titanium dioxide is widely used as an anti bacterial agent. This is because it not only kills the
bacteria but it also decomposes the end toxin which is produced at the death of the cell. The
photocatalytic action of titanium dioxide works even when bacteria are present on the surface.
Titanium dioxide shows a long term anti bacterial effect as it not deteriorated easily. It has been
found that titanium dioxide is three times more effective as compared to chlorine and 1.5 times
more effective than ozone as an anti-bacterial agent.

2) Air purifying effect

This is one of the major application of titanium dioxide. The photocatalytic activity of titanium
dioxide can be applied to remove or eliminate air pollutants like NO x, cigarette smoke and other
volatile compounds which arise from the construction sites. As a result tents can be prevented
from becoming sooty and dark. Harmful compounds like chlorofluorocarbons and its substitutes,
greenhouse gases, nitrogen and sulphur containing compounds undergo degradation either
directly or indirectly in the presence of sunlight. In this way titanium dioxide can be used to
purify air. Air can be purified with 99.9% purity.

3) Deodorizing effect
Due to the photocatalytic activity of titanium dioxide, hydroxyl radicals are generated which
helps in the breakdown of volatile organic compound by breaking its molecular bonds. As a
result, organic gases are generated which will combine to form a single molecule which will not
harm human beings and thus air will indirectly get purified. Examples of odor molecules include
gasoline, smoke, formaldehyde and other hydrocarbon molecules present in the air.

4) Self cleaning effect

We know that the exterior walls of the house gets covered with automobile exhaust fumes which
mainly contains oily compounds. So if we will coat the exterior walls with titanium dioxide , it
will decompose the oily components due to its photocatalytic activity and walls will get clean.
Dirt present on the walls will be removed along with rainfall.

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Fig 5.5 Self cleaning effect of TiO2 [12]

6. REVIEW PAPER ANALYSIS

The review paper is basically related to the applications of TiO2 photocatalyst. It also involves
case study of how wastewater from rice hull disinfection is treated in Japan.

6.1 Treatment of wastewater used for disinfecting rice hull

Rice hull are generally infected with chemicals like pesticides. So water is used to remove these
toxic chemicals from it. Wastewater is amounted to around 600000 metric tons per year in
countries like Japan and America. To handle this wastewater the technically minded Japanese
researchers developed the glass wool mat with a large surface area which was deposited with
nanoparticles of TiO2. The waste water is taken into the mat which spread over the ground.
Chemicals were degraded within few weeks. The initial total organic carbon values of thousand
ppm level decreased to zero in around one week.
6.2 Treatment of chemically destroyed soil
Compounds like trichloroethylene are more commonly used as solvents for dry cleaning agent
for clothes. They are polluting ground-water as well as soil . The main problem is that they are
highly toxic in nature. The solution to above problem is that we can actually supply heat so that
volatile matter can vaporize and we get soil free from impurities. In doing this practically,
efficiency was found to be very less.
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Figure 6.1 Purification system for pollutant soil utilizing photocatalytic sheet[13]
Above figure shows that soil is first dug and then it is covered with sheet of TiO 2 containing
charcoal. Soil is heated and as a result gases are released which are taken up by adsorption on
charcoal on the sheet.
6.3 Treatment of wastewater containing hair colorants
Wastewater from bathroom was collected and treated with reactor system containing
photocatalytic material.. The result showed that there was a significant decrease in COD and
toxicity of wastewater in the period of 5 hours. After treatment was over, flocs were observed.

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6.4 Treatment of Dyes

Photocatalytic bed is prepared to treat textile waste water. The azo dye causes environmental
damage. Shortage of water is major problem in many countries. Recycling of water is highly
appreciated to meet water needs. To solve this problem, the reactor was added with short quartz
tube loaded with TiO2 which shows better catalytic activity. The rate of decolourization of
methyl orange is around 98.7% under UV radiation for 8 hours.
6.5 Photocatalytic Decomposition of Benzene Derivatives
Derivatives of benzene are widely used as pesticides and herbicides. The organic compounds
are broken down into water and carbon dioxide. This advanced oxidation technique should be
used on few aromatics which are resistant to normal oxidation reactions. TiO 2 absorbs light and
transfer energy into derivative through redox reactions. When compared with other
photocatalyst, TiO2 is excellent because of its excellent photocatalytic activity, stability and low
cost. It is followed by oxidation of organics by reactions with the holes.

7. SUMMARY
The scope of photocatalysis is increasing in the modern world as it has wide range of
applications ranging from air purification to fuel generation . New photocatalysts like
perovskites are under research which can work under both visible and UV light. TiO2
applications in found in different industry like paints, fibres, food, plastics, pharmaceutical,
etc. Spinels are also used in fields where other photocatalyst gives low efficiency.
Photocatalysis is also widely applied for degradation of microbes like bacteria. It has been
found out that TiO2 is three times more better antibacterial agent as compared to chlorine and
1.5 times than ozone. Photocatalysis is widely used for wastewater treatment which is
generated from different industries.

REFERENCES
1) Dimitris I. Kondarides photocatalysis Department of Chemical Engineering, University
of

Patras, Greece (EOLSS), (2008), 1-10

2) Zalouk S, Barbati S, Sergent M, and Ambrosio M , Chemosphere, 74(2), (2009), 193

3) Calvert, J. G.; Pitts, J. N. Photochemistry. Wiley & Sons: New York, US, 1966. Congress
Catalog number: 65-24288
4) Ohama, Y; van Gemert, D. Application of Titanium Dioxide Photocatalysis to Construction
Materials; Springer: London, UK, (2011); pp. 1533.
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5) Serpone, M. and Pelizzetti, E. (Editors). Photocatalysis: Fundamentals and applications.

John Wiley & Sons, Inc.(1989),15-17.
6) Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T. "Photocatalysis on TiO2 Surfaces:
Principles, Mechanisms, and Selected Results". Chemical reviews (1995).
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red 14 in water on ZnO as an alternative catalyst to TiO2". Journal of Photochemistry and
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8) Wu, CH; Chang, CL (2006). "Decolorization of Reactive Red 2 by advanced
oxidation processes: Comparative studies of homogeneous and heterogeneous
systems". Journal of hazardous materials 128 (23): 26572.
9) Dave Barthelmy. "Spinel Mineral Data 2014
10) Ismail, B., Hussain, S.T., Akram, S.: Adsorption of methylene blue onto spinel
magnesium aluminate nanoparticles: adsorption isotherms, kinetic and thermodynamic
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11) http://www.wikipedia/photocatalysis, 10/03/2016, 18:30
12) http://www.u-tokyo.ac.jp/en/utokyo-research/feature-stories/the-world-of-titaniumdioxide/ 12/03/2016, 17:45
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Fijushima. 2005

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