Topic: Photocatalysis

FinalSubmitted
Report by: Muzammil Anjum
ENS-762
Submitted to: Dr. Mohamed A.
Barakat

ADVANCE METHODS FOR WASTEWATER

TREATMENT

(150342
1)

Department of Environmental Sciences

Faculty of Metrology, Environment and Arid Land Agriculture

King Abdulaziz University, Jeddah, Saudi Arabia

Photocatalysis

ENS-795

ID: 1503421)
CONTENTS

1.
2.

INTRODUCTION TO PHOTOCATALYSIS...................................................................3
PRINCIPLE AND MECHANISM......................................................................................3
2.1. Pollutant Degradation..................................................................................................4
2.2. Role of Oxidation Potential.........................................................................................4
3. TYPES OF PHOTOCATALYSIS.......................................................................................5
3.1. Homogeneous Photocatalysis......................................................................................5
3.2. Heterogeneous Photocatalysis.....................................................................................5
4. APPLICATION OF PHOTOCATALYSIS..........................................................................6
4.1. Environmental Applications........................................................................................6
4.2. Chemical synthesis......................................................................................................8
4.3. Energy Production.......................................................................................................8
5. MODIFICATION OF PHOTOCATALYST........................................................................9
5.1. Doping of Photocatalyst..............................................................................................9
5.1.1.Cation Doping...................................................................................................10
5.1.2.Anion Doping....................................................................................................11
5.2. Sensitization..............................................................................................................11
5.2.1.Dye sensitization...............................................................................................11
5.2.2.Composite Semiconductor................................................................................12
5.3. Noble metal loading..................................................................................................13
5.4. Metal ion-implantation..............................................................................................13
6. SELECTION OF THE DOPENT.....................................................................................14
7. METHODS OF DOPING.................................................................................................15
7.1. Methods for Metal Ion DopingMicro-emulsion method...........................................15
7.2. Non metal doping Methods.......................................................................................16
7.3. Sol-Gel Methods........................................................................................................17
7.3.1. Advantages of Sol-Gel Method.......................................................................19
8. ADVANTAGES AND DISADVANTAGES OF PHOTOCATALYSIS..........................19
8.1. Advantages.................................................................................................................19
8.2. Disadvantages............................................................................................................19
9. CONCLUSION.................................................................................................................20
10. REFERENCES..................................................................................................................20

1. INTRODUCTION
The word photocatalysis is a composite word which is composed of two parts, photo
and catalysis. Catalysis is the process where a substance participates in modifying the rate
of a chemical transformation of the reactants without being altered or consumed in the end.
This substance is known as the catalyst which increases the rate of a reaction by reducing the
activation energy. In catalysed photolysis, light is absorbed by an adsorbed substrate. In
photogenerated catalysis, the photocatalytic activity (PCA) depends on the ability of the
catalyst to create electronhole pairs, which generate free radicals (e.g. hydroxyl radicals:
OH) able to undergo secondary reactions.
The field of photocatalysis has expanded rapidly within the last four decades, having
undergone various developments especially in relation to energy and the environment. It can
be defined as the acceleration of photoreaction in the presence of a catalyst. The two most
significant applications of photocatalysis have been in solar water splitting and the
purification of air and water containing low concentrations of pollutants. The
multidisciplinary nature of the field has also increased significantly and includes
semiconductor physics, surface sciences, photo and physical chemistry, materials science and
chemical engineering. Heterogeneous photocatalysis can be described as the acceleration of
photoreaction in the presence of a catalyst. In the contexts of history and research, interest in
heterogeneous photocatalysis can be traced back to many decades when Fujishima and Honda
discovered in 1972 the photochemical splitting of water in to hydrogen and oxygen in the
presence of TiO2. From this time, extensive research, much of it published, has been carried
out to produce hydrogen from water in oxidation reduction reactions using a variety of
semiconductor catalyst materials.

2. PRINCIPLE AND MECHANISM

The acceleration of a chemical transformation by the presence of a catalyst with light is
called photocatalysis. The catalyst may accelerate the photoreaction by interaction with the
substrate in its ground or excited state and/or with a primary photoproduct, depending upon
the mechanism of the photoreaction and itself remaining unaltered at the end of each catalytic
cycle. Heterogeneous photocatalysis is a process in which two active phases solid and liquid
are present. The solid phase is a catalyst, usually a semiconductor. The molecular orbital of
3

semiconductors has a band structure.The bands of interest in photocatalysis are the populated
valence band (VB) and its largely vacant conduction band (CB), which is commonly
characterized by band gap energy (Ebg). The semiconductors may be photoexcited to form
electron-donor sites (reducing sites) and electron-acceptor sites (oxidising sites), providing
great scope for redox reaction. When the semiconductor is illuminated with light (h) of
greater energy than that of the band gap, an electron is promoted from the VB to the CB
leaving a positive hole in the valence band and an electron in the conduction band.
If charge separation is maintained, the electron and hole may migrate to the catalyst
surface where they participate in redox reactions with sorbed species. Specially, h +vb may
react with surface-bound H2O or OH -to produce the hydroxyl radical and e cb is picked up
by oxygen to generate superoxide radical anion (O2 ), as indicated in the following equations

2.1. Pollutant Degradation

It has been suggested that the hydroxyl radical (OH o) and superoxide radical anions (O2
o-

) are the primary oxidizing species in the photocatalytic oxidation processes. These

oxidative reactions would results in the degradation of the pollutants.

2.2. Role of Oxidation Potential

For oxidation reactions to occur, the VB must have a higher oxidation potential than the
material under consideration. The redox potential of the VB and the CB for different
semiconductors varies between +4.0 and -1.5 volts versus Normal Hydrogen Electrode
4

(NHE) respectively. The VB and CB energies of the TiO 2 are estimated to be +3.1 and -0.1
volts, respectively, which means that its band gap energy is 3.2 eV and therefore absorbs in
the near UV light (<387 nm). Many organic compounds have a potential above that of the
TiO2 valence band and therefore can be oxidized. In contrast, fewer organic compounds can
be reduced since a smaller number of them have a potential below that of the TiO 2 conduction
band.

3. TYPES OF PHOTOCATALYSIS
Photcatalysis process can be carried out by two ways, therefore categorized in to two
types:
o Homogeneous photoctalysis
o Heterogeneous photocatalysis
3.1. Homogeneous Photocatalysis
In homogeneous photocatalysis, the reactants and the photocatalysts exist in the same
phase. The most commonly used homogeneous photocatalysts include ozone and photoFenton systems (Fe+ and Fe+/H2O2). The reactive species is the OH which is used for
different purposes. The mechanism of hydroxyl radical production by ozone can follow two
paths.

3.2. Heterogeneous Photocatalysis

Heterogeneous catalysis has the catalyst in a different phase from the reactants. In
heterogeneous photocatalysis two or more phases are used in the photocatalytic reaction. The
photo-generated holes at the surface of the irradiated semiconductor can oxidize a variety of
hazardous species in water. Most common heterogeneous photocatalyts are transition metal
oxides and semiconductors, which have unique characteristics. Unlike the metals which have
a continuum of electronic states, semiconductors possess a void energy region where no
5

energy levels are available to promote recombination of an electron and hole produced by
photoactivation in the solid. The void region, which extends from the top of the filled valence
band to the bottom of the vacant conduction band, is called the band gap. When a photon
with energy equal to or greater than the materials band gap is absorbed by the semiconductor,
an electron is excited from the valence band to the conduction band, generating a positive
hole in the valence band. The excited electron and hole can recombine and release the energy
gained from the excitation of the electron as heat. Recombination is undesirable and leads to
an inefficient photocatalyst. The ultimate goal of the process is to have a reaction between the
excited electrons with an oxidant to produce a reduced product, and also a reaction between
the generated holes with a reductant to produce an oxidized product. Due to the generation of
positive holes and electrons, oxidation-reduction reactions take place at the surface of
semiconductors. In the oxidative reaction, the positive holes react with the moisture present
on the surface and produce a hydroxyl radical.
Oxidative reactions due to photocatalytic effect is given as follows:

4. APPLICATION OF PHOTOCATALYSIS
4.1. Environmental Applications
Environment pollution, including water air and soil is becoming an increasingly serious
problem today. The environmental applications of photocatalysis is enlisted below.

Wastewater treatment for degradation of pesticides, dyes, organic pollutants in

pharmaceuticals, drugs, cosmetics, petrochemical and various industrial pollutant.

Production of value added products such as bio solvents, solid fuel, liquid fuels,

syngas, pharmaceutical intermediates and etc.

Disinfection of surfaces is in order to reduce the concentration of bacteria and to

prevent bacterial transmission and disinfection of drinking water.

Self cleaning materials: Antibacterial materials (glass and ceramics containing TiO 2,
for hospitals and buildings.

Figure: Photocatalytic glass and mirrors.

4.1.1. Case Study I: Detoxification of wastewater used for rice hull disinfection
Disinfection solutions for rice hulls (to stop the spread of plant diseases) contain highly
concentrated agricultural chemicals. The corresponding wastewater is mostly disposed of by
pouring onto the ground, which causes soil pollution. The system composed of a glass wool
mat with a large surface area deposited with very photoactive TiO 2 nanoparticles;

the

wastewater solution is easily purified using the photocatalytic mat under only solar light. The
treatment method is very simple, i.e., the wastewater is poured onto mats that are spread over
a wide area on the ground. The agricultural chemicals were completely decomposed under
sunlight in a few days.
4.1.2. Case Study II: Water treatment of hydroponic
A recycling system in a hydroponic culture system using the TiO 2 photocatalyst and
solar light has been developed. The wastewater from the hydroponic culture with a planting
area of about 80 m2 was introduced into a shallow vessel with a bottom area of 4m 2 and a
depth of 10 cm in which porous ceramic plates coated with TiO 2 photocatalyst nanoparticles
were placed.
The organic contaminants in the wastewater were easily decomposed under solar light,
but the nutrient compounds contain-ing nitrogen, phosphorous and potassium were not,
because these components ex-isted in their most oxidized forms, NO 3, PO43 and K+, in the
nutrient solution. Therefore, this system is also expected to serve as a nutrient-saving
technology.

4.1.3. Case Study III: Treatment of VOC-polluted soil

Volatile chlorinated organic compounds (VOCs), such as trichloroethylene and
tetrachloroethylene, have been widely used as solvents for the dry cleaning of clothes and
washing of semiconductors. The photocatalytic sheets to purify the polluted soil on the
ground using sunlight were developed. The polluted soil is dug up and covered with the
sheet, which is made of corrugated paper containing both TiO2 powder adsorbed on activated
carbon powders. Then the covered soil is heated (for example, by mixing with calcium
oxide), volatilizing the pollutant gases captured by adsorption on activated carbon
incorporated in the sheet material. The sheet is allowed to remain undisturbed under sunlight,
while TiO2 in the sheet decomposes the pollutants completely by photocatalytic reaction.

Figure: Application of TiO2 photocatalysis in various fields.

4.2. Chemical synthesis

The photcatalysis process has wide application in synthesis variety of chemicals. Some
examples of synthetic products using different types of catalysis are summarized in the table.
4.3. Energy Production
Hydrogen fuel production has gained increased attention as oil and other non-renewable
fuels become increasingly depleted and expensive. Methods such as photocatalytic water
splitting are being investigated to produce hydrogen fuel, which burns cleanly and can be
used in a hydrogen fuel cell. Water splitting holds particular interest since it utilizes water, an

Table: Chemical of synthesis of various compounds through photocatalysis.

8

Reactants
Olephins (Prophilene)

Cataysts
TiO2, MoO3

Products
Alcohols, aldehydes, and ketones

Toluene
Cumene
Butadienes
Propene

TiO2
TiO2
TiO2
TiO2 SnO2, Sb2O4

Benzaldehyde
Acetophenone
Acetaldehyde
Acetaldehyde, acetone, acroelin

Cyclohexane
Cyclohexane
Ethylbenzene

V2O5/ZrO2
MoO3/TiO2
MoO3/g-Al2O3

cyclohexanol, cyclohexanone
Benzene, cyclohexene
Styrene

inexpensive renewable resource. Photocatalytic water splitting has the simplicity of using a
powder in solution and sunlight to produce H 2 and O2 from water and can provide a clean,
renewable energy, without producing greenhouse gases or having many adverse effects on the
atmosphere. A general reaction of water splitting is given as follows.

5. MODIFICATION OF PHOTOCATALYST
5.1. Doping of Photocatalyst
Research into photocatalyst doping has spanned several decades. Usually doping
involves the use of metals or non-metals and is designed to extend the photocatalytic activity
of a semiconductor lower energy excitation. Technically, doping is the introduction of foreign
elements into the parent photocatalyst without giving rise to a new crystallographic forms,
phases or structures and the aims are to enhance the net separation of photo generated
charges and thereby efficiently harness the wide visible-light component of about 43% in the
solar spectrum as opposed to the narrow ultraviolet component of 5%. It is thus an area of
increasing research activity in photocatalysis. For modification of photocatalyst two types of
doping are applied. The doping is of two types:

1. Cation Doping
2. Anion Doping

5.1.1. Cation Doping

Transitional metal ion doping and rare earth metal ion doping have been extensively
investigated for enhancing the TiO2 photocatalytic activities. A study carried out a systematic
investigation to study the photoreactivity of 21 metal ions doped into TiO2. It was found that
doping of metal ions could expand the photo-response of TiO 2 into visible spectrum. As metal
ions are incorporated into the TiO2 lattice, impurity energy levels in the band gap of TiO2 are
formed, as indicated below:

where M and Mn+ represent metal and the metal ion dopant, respectively. Furthermore,
electron (hole) transfer between metal ions and TiO2 can alter electron-hole recombination
as:

The energy level of Mn+/M(n-1)+should be less negative than that of the CB edge of TiO 2,
while the energy level of Mn+/M(n-1)+ should be less positive than that of the VB edge of TiO 2.
For photocatalytic reactions, carrier transferring is as important as carrier trapping. Only if
the trapped electron and hole are transferred to the surface, photocatalytic reactions can
occur. Therefore, metal ions should be doped near the surface of TiO 2 particles for a better
charge transferring. In case of deep doping, metal ions likely behave as recombination
centres, since electron/hole transferring to the interface is more difficult. Furthermore, there
exists an optimum concentration of doped metal ion, above which the photocatalytic activity
decreases due to the increase in recombination. Among the 21 metal ions studied, Fe, Mo, Ru,
Os, Re, V, and Rh ions can increase photocatalytic activity, while dopants Co and Al ions
cause detrimental effects. The different effects of metal ions result from their abilities to trap
and transfer electrons/holes. For example, Cu and Fe ions can trap not only electrons but also
holes, and the impurity energy levels introduced are near to CB as well as VB edges of TiO 2.
Therefore, doping of either Cu or Fe ions could be recommended for enhancement of
photocatalytic activity.

10

5.1.2. Anion Doping

The use of anion doping to improve hydrogen production under visible light is rather a
new method with few investigations reported in open literature. Doping of anions (N, F, C, S
etc.) in TiO2 crystalline could shift its photo-response into visible spectrum. Unlike metal
ions (cations), anions less likely form recombination centers and, therefore, are more
effective to enhance the photocatalytic activity. The substitutional doping contents of C, N, F,
P and S for O in anatase TiO2 is also determined.
Dopants such as C and P are less effective as the introduced states were so deep that
photo-generated charge carriers were difficult to be transferred to the surface of the catalyst.
The nitrogen doped TiO2 thin film was prepared by sputtering TiO2 in an N2 (40%)/Ar gas
mixture, followed by annealing at 550 oC in N2 for about 4h. Nitrogen doped TiO2powder
was also prepared by treating TiO2 in NH3 (67%) = Ar at 600 oC for 3h. The N-doped TiO2
was reported to be effective for methylene blue decomposition under visible light (4400nm).
5.2. Sensitization
Sensitization often is characterized by an enhancement of response to a whole class of
stimuli in addition to the one that is repeated. Sansitization process of modification of the
catalyst may be done by two way:
1. Dye sensitization
2. Composite Semiconductor
5.2.1. Dye sensitization
Dye sensitization is widely used to utilize visible light for energy conversion. Some dyes
having redox property and visible light sensitivity can be used in solar cells as well as
photocatalytic systems. Under illumination by visible light, the excited dyes can inject
electrons to CB of semiconductors to initiate the catalytic reactions. Even without
semiconductors, some dyes, for example safranine O/EDTA and T/EDTA, are able to absorb
visible light and produce electrons as reducing agents strong enough to produce hydrogen.
The excitation, electron injection and dye regeneration can be expressed as follows:

11

Figure: Mechanism of dye-sensitized photocatalytic hydrogen production under visible light

irradiation
5.2.2. Composite Semiconductor
Semiconductor composition (coupling) is another method to utilize visible light for
photocatalysis reaction. When a large band gap semiconductor is coupled with a small band
gap semiconductor with a more negative CB level, CB electrons can be injected from the
small band gap semiconductor to the large band gap semiconductor. Thus, a wide electronhole separation is achieved.
The process is similar to dye sensitization. The difference is that electrons are injected from
one semiconductor to another semiconductor, rather than from excited dye to semiconductor.
Successful coupling of the two semiconductors for photocatalytic water-splitting hydrogen
production under visible light irradiation can be achieved when the following conditions are
met:

Semiconductors should be photocorrosion free

The small band gap semiconductor should be able to be excited by visible light
The CB of the large band gap semiconductor should be more negative than EH2=H2O
12

Electron injection should be fast as well as efficient

The CB of the small band gap semiconductor should be more negative than that of the
large band gap semiconductor

Figure: Electron Injuction in composite semiconducton.

5.3. Noble metal loading

Noble metals, including Pt, Au, Pd, Rh, Ni, Cu and Ag, have been reported to be very
effective for enhancement of TiO2 photocatalysis. As the Fermi levels of these noble metals
are lower than that of TiO2, photo-excited electrons can be transferred from CB to metal
particles deposited on the surface of TiO2, while photo-generated VB holes remain on the
TiO2. These activities greatly reduce the possibility of electron-hole recombination, resulting
in efficient separation and stronger photocatalytic reactions.
5.4. Metal ion-implantation
Metal ion-implantation was recently reported to be an effective method to modify
semiconductor electronic structures to improve visible light response. When TiO 2 is
bombarded with high-energy transitional metal ions (accelerated by high voltage), these highenergy ions are injected into the lattice and interact with TiO 2. This process modifies TiO2
electronic structure and shifts its photo-response to the visible region (up to 600nm).
Presently metal ion implanted TiO2 is believed to be the most effective photocatalyst for solar
energy utilization and is in general referred as the second generation photocatalyst.

13

Takeuchi et al. (2000) implanted Cr-ion into TiO 2 thin film for NO decomposition under
visible light irradiation. The TiO2 thin film was prepared by ionized cluster beam (ICB)
method. In this method, metal Ti was heated up to 2000 K and the Ti vapor was introduced
into a high vacuum chamber in the presence of O2 to produce TiO2 thin film.
The main advantages of ICB method are:
(i) High crystalline TiO2 can be obtained as calcination is avoided
(ii)The properties of thin film, such as thickness of the coating, can be controlled
(iii)
Contamination with impurities can be prevented as this process is usually carried out in a
high vacuum chamber

6. SELECTION OF THE DOPENT

The slection of the dopent for doping of the catalyste, following important factors should
be considered.
1. Electron/Hole Trap Efficiency: The dopant should have higher efficiency to trap exited
electrons and holes. As Cu, Mn and Fe ions can trap both electrons and holes, doping of
these metal ions may work better than doping of Cr, Co and Ni ions. The latter metal ions
can only trap one type of charge carrier.
2. Dopant Content: Enhanced photocatalytic activities and red shift of photo-response
were observed at certain doping content. Suitable amounts of dopants helped to control
the crystallite size of nano-doped-TiO2 while producing a high specific surface area of
nano-doped-TiO2. For example the TiO 2 thin film doped by Mn non-uniformly at the
optimal dopant concentration (0.7 at %) is of the highest activity.
3. Least Structural Defects: Several studies have indicated that doping creates structural
defects that could be sources for charge recombination and in this sense are potentially
negative in their effects. Doping using high-energy sputtering, which provide the
uncommon existence of tetravalent dopants such as Fe4+ and Cr4+ that match the valency
of Ti4+ in TiO2.
4. Surface Doping: Doping the metal ions near the surface was beneficial for charge carrier
transferring, while deep doping led to poor performance. For instance; Be ion doped TiO2
on photocatalytic hydrogen production in the presence of electron donors (ethanol).
Dopants C and P were found to be less effective as the introduced states were so deep
that photo-generated charge carriers were difficult to be transferred to the surface of the
catalyst
5. Dopant Methods: Solution-based method such as hydrothermal, solgel, and
precipitation method is the most widely used method for doping nonmetal into TiO2.
14

(1) Heat treatment of TiO2 at high temperatures: The method is generally used to prepare
N- or C-doped TiO2. (2) Physical Method: Sputtering TiO2 target in an atmosphere
containing doping species such as N2Ar will incorporate N in the TiO 2 target. (3) Solgel: Cu-, Fe-, and Al-doped TiO2 prepared by the sol-gel have least effect on crysatlinity.
6. Narrow Band Gap: TiO2 was doped with S, the mixing of S 3p states with the VB of
TiO2 increased the width of VB, resulting in band gap narrowing. The efficient
photocatalytic activity of S-doped TiO2 was evaluated by photodecomposition of 2propanol and methylene blue.
7. Reproducibility: Doping with metallic or non-metallic elements, have in common the
difficulty in the reproducibility of the photocatalytic activity from batch to batch of
doped semiconductor and from one laboratory to other.
8. Crystallinity: The difficulty in reproducibility may arise from the different crystallinity
of the materials that makes it generally advisable to anneal the solid at high temperatures
for some time to increase crystallinity. The process of annealing: promote relocation of
the dopant and, eventually, its expelling from the anatase lattice.
9. Recombination centres: The dopant can act as a charge recombination centre that acts
against the separation of excited electron and hole. These problems can be countered by
controlling the dosages of the dopants. Doping of anions (N, F, C, S etc.) in TiO 2
crystalline could shift its photo-response into visible spectrum.

7. METHODS OF DOPING
Doping has been proven to be a great method to enhance the photocatalytic activity. In recent
years, nonmetal-doping has demonstrated great potential to be applied in the photocatalytic
field. There of number of methods are available for doping of photocatalystes. Some of these
are defined below.
7.1. Methods for Metal Ion Doping
1. Micro-emulsion method: Micro-emulsions are transparent, optically isotropic and
thermodynamically stable colloidal dispersions In which two liquids Initially immiscible
typically water and oil coexist.
2. Ambient chemical method: There is disclosed a method of controlling surface dopant
concentration in a semiconductor material in which the dopant is diffused from a doped
oxide source. The method involves the use of an oxidizing ambient during the doping

15

operation which creates a growing interface oxide barrier to moderate the doping of the
substrate.
3. Sol gel Method: Include synthesis of nanosized crystallized powder of high purity at
relatively low temperature, possibility of stoichiometry controlling process.
4. Solution combustion method: Combines features of chemical reaction and high
temperature routes, has become recently of increasing interest as easy and cheap
technique for the synthesis of oxide nanomaterials.

Table: Preparation of photocatalystes using various methods of metal ion doping.

S. No. Method
1.
Microemulsion method
2.
Ambient chemical method

Doped catalyste
Fe3+ cations with TiO2
V-doped TiO2photocatalyst

3.

Sol gel Method

Co3+, Cr3+, Ce3+,Mn2+, Al3+, and Fe3+

4.

Solution combustion method

W, V, Ce, and Cu metal-doped anatase TiO2

7.2. Non metal doping Methods

1. Vapour deposition method: The substrate is exposed to one or more volatile precursors,
which react and/or decompose on the substrate surface to produce the desired deposit.
Frequently, volatile by-products are also produced, which are removed by gas flow
through the reaction chamber.

2. Ion Implantation Technique: Dopant ions such as boron, phosphorus or arsenic are
generally created from a gas source, so that the purity of the source can be very high.
When implanted in a semiconductor, each dopant atom can create a charge carrier in the
semiconductor after annealing.
3. Spray pyrolysis technique: The solution is sprayed by means of glass nozzle on the
hotter substrate with a spray rate of 2ml/min.

16

Table: Preparation of photocatalystes using various methods of non-metal ion doping.

S. No.
1.
2.
3.
4.

Method
Vapour deposition method
Ion implantation technique
Direct hydrolysis method
Spray pyrolysis technique

Doped Catalystes
C-doped TiO2 nanotubes
F-doped TiO2
I-doped TiO2
N, F codoped TiO2

7.3. Sol-Gel Methods

The sol-gel process is a wet-chemical technique widely employed recently in the fields
of materials science and ceramic engineering. Such methods are utilized primarily for the
fabrication of materials (typically a metal oxide) starting from a chemical solution which acts
as the precursor for an integrated network (or gel) of either discrete particles or network
polymers.
Typical precursors are metal alkoxides and metal chlorides, which undergo various forms
of hydrolysis and polycondensation reactions. The formation of a metal oxide involves
connecting the metal centers with either oxo (MOM) or hydroxo (MOHM) bridges, and
generating metal-oxo or metal-hydroxo polymers in solution. Thus, the sol evolves towards
the formation of a gel-like diphasic system containing both liquid and solid phases whose
morphologies range from discrete particles to continuous polymer networks.
In the case of the colloid, the volume fraction of particles (or particle density) may be so
low that a significant amount of fluid may need to be removed initially for the gel-like
properties to be recognized. This can be accomplished through plenty of ways. The simplest
method is to allow time for sedimentation to occur, and then pour off the remaining liquid.
Centrifugation can also be used to accelerate the process of phase separation.
Removal of the remaining liquid (solvent) phase requires a drying process, which is
typically accompanied by a significant amount of shrinkage and densification. The rate
atwhich the solvent can be removed is ultimately determined by the distribution of porosity in
the gel. The ultimate microstructure of the final component will be strongly influenced
bychanges imposed upon the structural template during this phaseof processing. Afterwards,
a thermal treatment, or a firing process, is also necessary in order to favor further poly17

condensation and to enhance the mechanical properties and structural stability via final
sintering, densification, and grain growth. One of the distinct advantages

of this

methodology, as opposed to the more traditional processing techniques, is that densification is

often achieved at much lower temperatures. The general procedure of sol-gel method is
describe in the figure.

Figure: General procedure of Sol-Gel

The precursor sol can be either deposited on a substrate to form a film (e.g., by dip
coating or spin coating), casted into a suitable container with the desired shape (e.g., to obtain
monolithic ceramics, glasses, fibers, membranes, and aerogels), or used to synthesize
powders (e.g., microspheres, nanospheres)
7.3.1. Advantages of Sol-Gel Method
The advantages of sol-gel method are:
1.
2.
3.
4.

No special apparatuses are required, easy to operate

Uniform films can be easily prepared, the purity of the films are high
Phase structure of films can be controlled and
Applied to the industrial production.

18

8. ADVANTAGES AND DISADVANTAGES OF PHOTOCATALYSIS

8.1. Advantages
The photocatalytic process gradually breaks down the contaminant molecules, no
residue of the original material remains and therefore no sludge requiring disposal to landfill
is produced. The catalyst itself is unchanged during the process and no consumable chemicals
are required. This results in considerable savings and a simpler operation of the equipment
involved. Additionally, because the contaminant is attracted strongly to the surface of the
catalyst, the process will continue to work at very low concentrations. Taken together, these
advantages mean that the process results in considerable savings in water production cost and
keeping the environment clean.
8.2. Disadvantages
Althourgh there are number of applications of the photocatalysis, however, there are
some challenges that limits the use this process. Nanoparticle TiO 2 does not only destroy all
organic materials but also the organic matrix in which the nanoparticles are embedded. This
limits its application to inorganic environments. Nanoparticle can accumulate if its use is
widespread and could potentially have health impacts for workers exposed to nanoparticle
TiO2 dust. Another challagne is associated with its limited application in industries and
integration with existing wastewater treatment plant. Similarly, the high cost of some
photocatalyste make the process uneconomical. There are currently no regulations related to
the use of nanoparticle TiO2 for water treatment, but standards on test methods for
photocatalytic water purification are under development. Stricter water treatments standards
would require new treatment methods and could thus further the application of photocatalytic
systems with nanomaterials.

9. CONCLUSION
The widespread application of photocatlysis have beneficial impacts on the health of the
general public and thus on the quality of life. Since nanoparticle TiO 2 particles are
inexpensive and may be integrated into different materials, photocatalytic systems and
surfaces, they are not limited to large-scale applications in water treatment facilities. They
may also be applied in homes, hospitals, or offices for disinfection or the degradation of
water and air pollutants. The use of nanoparticle TiO2 for water treatment and disinfection is
expected to have a positive effect on the environment, as it can replace more toxic substances
19

such as organic biocides. This has a significant implication for developing nations. It can also
improve the quality of the water released from water treatment plantsby assisting traditional
treatment methods to target more substances and thereby obtain a higher efficiency of the
whole process.

10. REFERENCES
Anonymus.

Hetrogeneous

photocatalyst.

https://www.scribd.com/doc/

242565818/

photocatalysis-ppt#download
Choi W.Y., Termin A., Hoffmann M.R. (1994). The role of metal ion dopants in quantumsized TiO2: correlation between photoreactivity and charge carrier recombination
dynamics. J Phys Chem, 84:1366979
Chonga, M.N. Bo Jin, Christopher W.K. Chow, Chris Sain. (2010) Recent developments in
photocatalytic water treatment technology: A review. Water Research, 44: 2997-3027
Colmenares. J.C. Design of functionalized nano(photo)catalysts for the valorization of waste
bio-feedstocks

and

water/air

detoxification

http://photocatalysis.

org/projects/3/attachment/achieved%20results%20and%20future%20plans.pdf
Gamage J. and Zhang, Z. (2010) Applications of Photocatalytic Disinfection. International
Journal of Photoenergy. Article ID 764870
Gole JL, Stout JD, Burda C, Lou YB, Chen XB. Highly efficient formation of visible light
tunable TiO2 xNx photocatalysts and their transformation at the nanoscale. J Phys
Chem B 2004;108:123040.
Gurunathan K. Photobiocatalytic production of hydrogen using sensitized TiO2-MV 2
system coupled Rhodopseudomonas Capsulata. J Mol Catal A: Chem 2000;156:5967.
Haque, M..,Detlef Bahnemann and Mohammad Muneer. Photocatalytic Degradation of
Organic Pollutants: Mechanisms and Kinetics. www.intechopen.com
Hashimoto, K. Hiroshi Irie, and Akira Fujishima. (2007) TiO 2 Photocatalysis: A Historical
Overview and Future Prospects. AAPPS Bulletin December, Vol. 17, No. 6.
Hupka, J., Adriana Zaleska, Marcin Janczarek, Ewa Kowalska, Paulina Grska and Robert
Aranowski. UV/Vis light-enhanced photocatalysis for water treatment and protection.
Soil and Water Pollution Monitoring, Protection and Remediation, 323

20

Ibhadon, A.O. and Fitzpatrick, P. (2013). Heterogeneous

Photocatalysis: Recent Advances

and Applications. Catalysts, 3: 189-218; doi:10.3390/catal3010189.

Jana AK. Solar cells based on dyes. J Photochem Photobiol A: Chem 2000;132:117.
Jo, W. and Kim, J. (2009). Application of visible-light photocatalysis with nitrogen-doped or
unmodified titanium dioxide for control of indoor-level volatile organic compounds.
Journal of Hazardous Materials, 164: 360366
Kamat, P.V. (2010) Graphene-based nanoarchitectures. Anchoring semiconductor and metal
nanoparticles on a two-dimensional carbon support. J. Phys. Chem. Lett. 1, 520527.
Khan SUM, Al-Shahry Jr. M, BI W. Efficient photochemical water splitting by a chemically
modified n-TiO2. Science 2002;297:22435.
Kureti, S.; Weisweiler, W. (2002). A new route for the synthesis of high surfacearea
caluminium oxide xerogel. Appl. Catal. A 2002, 225, 251259
Mrowetz M, Balcerski W, Colussi AJ, Hoffmann MR. Oxidative power of nitrogen-doped
TiO2 photocatalysts under visible illumination. J Phys Chem B 2004;108:1726973.
Ni, M., Michael K.H. Leung, Dennis Y.C. Leung, K. Sumathy. (2007). A review and recent
developments in photocatalytic water-splitting using TiO2 for hydrogen production.
Renewable and Sustainable Energy Reviews, 11: 401425.
Ohno T, Akiyoshi M, Umebayashi T, Asai K, Mitsui T, Matsumura M. Preparation of S-doped
TiO2 photocatalysts and their photocatalytic activities under visible light. Appl Catal A:
Gen 2004;265:11521.
Okada M, Yamada Y, Jin P, Tazawa M, Yoshimura K. Fabrication of multifunctional coating
which combines low-e property and visible-light-responsive photocatalytic activity.
Thin Solid Films 2003;442: 21721.
Primo A. and Garca, H. (2013). Solar Photocatalysis for Environment Remediation.
http://dx.doi.org/10.1016/B978-0-444- 53872-7.00007-8
Primo A. and Hermenegildo Garca. Solar Photocatalysis for Environment Remediation.
http://dx.doi.org/10.1016/B978-0-444-53872-7.00007-8
Radwan A. Al-Rasheed. (2005). Water treatment by heterogeneous

photocatalysis an

overview. 4th SWCC Acquired Experience Symposium held in Jeddah.

21

Takeuchi M, Yamashita H, Matsuoka M, Anpo M, Hirao T, Itoh N, et al. (2000)

Photocatalytic decomposition of NO under visible light irradiation on the Cr-ionimplanted thin TiO2 thin film photocatalyst. Catal Lett 2000;67:1357.
Takeuchi M, Yamashita H, Matsuoka M, Anpo M, Hirao T, Itoh N, et al. (2000)
Photocatalytic decomposition of NO on titanium oxide thin film photocatalysts
prepared by an ionized cluster beam technique. Catal Lett, 66:1857.
Tseng, T. K., Yi Shing Lin, Yi Ju Chen and Hsin Chu (2010). A Review of Photocatalysts
Prepared by Sol-Gel Method for VOCs Removal.

Int. J. Mol. Sci., 11: 2336-2361.

Umebayashi T, Yamaki T, Itoh H, Asai K. (2002) Band gap narrowing of titanium dioxide by
sulfur doping. Appl Phys Lett, 81(3):4546.
Yamashita H, Harada M, Misaka J, Takeuchi M, Ichihashi Y, Goto F, et al. (2001) Application
of ion beam techniques for preparation of metal ion-implanted TiO2 thin film
photocatalyst available under visible irradiation: metal ion-implantation and ionized
cluster beam method. J Synchrotron Radiat, 8:56971.
Ying CUI, Hao DU and Lishi WEN. (2008). Doped-TiO 2 Photocatalysts and synthesis
methods to prepare TiO2 films. J. Mater. Sci. Technol., 24:
Zhang, K. Wei Xu, Xinjun Li, Shaojian Zheng, Gang Xu.
photocatalytic activity of

TiO2

film

doped

Effect of dopant concentration on

by

Mn

non-uniformly.

DOI:

10.2478/s11532-006- 0010-8
Zong, X., Gaoqing (Max) Lu, and Lianzhou Wang (2013) Nonmetal
Toward

Visible-Light-Induced

Photocatalysis.

10.1007/698_2013_249

22

Hdb

Doping in TiO2
Env

Chem,

DOI