Semiconductor photocatalysis for dyes degradation and inactivation

of pathogens
Sathish Mohan Botsa* and Keloth Basavaiah
Water pollution management has become an important necessity in present day
modern living. It is reported that nearly 10–15% of organic dyes are discharged in various
ways into the environment which has an adverse effect on public health as well as on aquatic
life. Various technologies such as membrane filtration, liquid-liquid extraction adsorption are
being used to remove organic dyes from water. But these processes have several
disadvantages such as low adsorption capacity, non-recyclability and complex operations for
recycling. Heavy metals, organic pollutants, inorganic anions, and bacteria have been
reported to be successfully removed by various kinds of nanomaterials. On the basis of
numerous studies, nanomaterials show great promise for applications in water and wastewater
treatment.
Semiconductor photocatalysis
Semiconductors such as TiO2, ZnO, Cu2O, MoO3, CeO2, ZrO2, WO3, CuO, Fe2O3 and
SnO2, etc. used as catalysts in Semiconductor photocatalysis (SP) which comprises a large
variety of reactions and processes, e.g. photocatalytic oxidation (PCO), photocatalytic
18 16
reduction, dehydrogenation, hydrogen transfer, O2 - O2 and deuterium-alkane isotopic
exchange, metal deposition, water detoxification, gas-phase pollutants removal and a host of
other environmental applications.

Photocatalytic oxidation is mostly known within the SP reactions and usually involves
the heterogeneous catalytic activation of a semiconductor by irradiation from a light source of
appropriate wavelength, depending on the band gap energy of the semiconductor. This
activation generates hydroxyl and other highly reactive oxygenated radicals, which facilitate
the oxidative degradation of organic, inorganic and metallic pollutants to get environment-
friendly products such as water, CO2 and mineral acids.This ability to remove contaminants
completely and efficiently combined with low cost, low toxicity and high abundance makes it
an ideal treatment procedure for removing organic pollutants and kill the microorganisms.
However, photocatalysis is an advanced oxidation process (AOP) and has been considered as
an effective green and low-cost method to degrade the dyes.
Keywords:

Semiconductor, photocatalysis, dyes degradation, antimicrobial activity, light irradiation

 Water is the largest part of vital kind of stuffs for all existence on earth and hence
known as the universal solvent and easily dissolves other substances. The world running in
the 21st century is facing a major problem and a challenge as water contamination.
Contaminated water contains unwanted substances and it adversely affects the quality and
makes it unsuitable for use. Water resources become contaminated from various sources such
as residential areas, commercial, industrial practices, agricultural practices, etc. Parameters of
wastewater vary widely and depend upon the source from which it is generated. Commonly
they are pathogenic and non-pathogenic microorganisms, organic or inorganic. If wastewater
is disposed of untreated these constituents create a great threat to living beings and the
environment.
Today most of the countries are facing drinking water problems and conditions are very
severe especially in developing countries. The world is facing formidable challenges in
meeting rising demands of clean water as the available supplies of freshwater are depleting
due to
(i) extended droughts,
(ii) population growth,
(iii) more stringent health-based regulations and
(iv) competing demands from a variety of users [1, 3, 4].

Clean water (i.e., water that is free of toxic chemicals and pathogens) is essential to
human health. In countries such as India, 80% of the diseases are due to bacterial
contamination of drinking water. The World Health Organization [2] recommended that any
water intended for drinking should contain faecal and total coliform counts of 0, in any 100
mL sample. When either of these groups of bacteria is encountered in a sample, immediate
investigative action should be taken. The removal or inactivation of pathogenic
microorganisms is the last step in the treatment of wastewater [3]. The protection of water
treatment systems against potential chemical and biological terrorist acts is also becoming a
critical issue in water resource planning [4-5]. Water pollution and pollutants, creating many
fold problems in human life.

Water Pollution

Any shift in the naturally occurring dynamic equilibrium among the environmental
segments namely hydrosphere, atmosphere and lithosphere gives rise to the threat of
pollution. Water pollution is a state of deviation from the normal properties and function of
pure water. The undesirable taste of drinking water, offensive odours from lakes, rivers and
sea beaches enrichment of toxic chemicals, dyes and heavy metals in water bodies, with scum
formation, oil and greases floating on water surfaces are the obvious signs of water pollution,
which makes the water unfit for public water supply, recreation and aesthetics, aquatic and
wildlife, agriculture and industry.

Water Pollutants

A large number of water pollutants may be classified under the following categories:

(i) Organic pollutants

(ii) Inorganic pollutants
(iii)Sediments (Particles different origin)
(iv) Radioactive materials
(v) Heat
(vi) Physical pollutants
(vii) Biological Pollutants

Dyes
Dyes are organic compounds characterized by the presence of unsaturated groups
(chromophores) in their molecular structures which consist of double and/or triple bonds as –
C=C–, –N=N–, –C≡N–, whose function is to shift the radiation absorption in the visible
range. Other functional groups characterizing this class of compounds are the auxochromes
such as –NH2, –OH, –COOH, –SO3H, which are responsible for the increase of the colour
intensity and affinity with the fibers [6]. Dyes are used in many industries like textile, paper,
plastic, leather, ceramic, cosmetics, ink, food processing etc. [7]. Dyes can be classified on
the basis of structure, function, or both, Table 1.1contains a representative listing of dyes
grouped according to their chemical structure. There can also be classified as acidic, basic,
disperse, reactive, anionic, cationic, etc. [8].
Textile dyes and other industrial dyestuffs constitute one of the largest groups of
organic compounds that represent enhancing environmental pollution. About 10–20% of total
dyes produced in the world goes into the environment during the dyeing process and is
released as the textile effluents [9]. The release of that coloured wastewater on the
environment is a considerable source of water pollution and can originate dangerous by-
products through oxidation, hydrolysis, or other chemical reactions taking place in the
wastewater phase. For the removal of dye pollutants, traditional physical techniques
(adsorption on activated carbon, ultrafiltration, reverse osmosis, coagulation by chemical
agents, etc.) can generally be used efficiently. Nevertheless, they are non-destructive, since
they just transfer organic compounds from one phase to another phase, thus causing
secondary pollution easily. Degradation of dye effluents has therefore received increasing
attention.

Table 1.1: Representation of Organic Dyes

Colour
Type of dye Example index Structure

Xanthene Basic Violet C.I. 45.170

Azo Reactive Orange C.I. 17757

Thiazine Methylene Blue C.I. 52015

Anthraquinone Rective Blue C.I. 61205

Triphenylmethane Basic Violet C.I. 42.600

Phthalocyanine Reactive Blue C.I. 74459

 Indigo Indigo Carmine C.I. 73015

C.I. Acid
Quinoline D&C Yellow Yellow

C.I. Acid
Phenanthrene D&C Green Green
More than 60% of commercial dyes with different chemical structures are used in
textile, food, pharmaceutical, paper and ink industries and usually their wastes are discharged
into water [10]. The toxic and carcinogenic nature of these dyes and their manufacturing
precursors represent a danger to human beings and perturbation in aquatic life. The increased
public concern about these environmental pollutants and the creation of international
environmental standards have prompted the need for the development of novel treatment
methods for converting organic pollutants (such as dye effluents) to harmless compounds.
The maximum dyes utilized in the pigmentation of leather, textiles, ceramics, paper, and
food-processing. About 15% of these dyes are lost with wastewater during synthesis and
processing [11]. This shows a huge hazard to human and environmental health owing to their
potential toxicity [12].
Biological pollutants (contamination)
The species such as algae, fungi, bacteria, viruses, actinomycetes, archaebact,
mycoplasma, protozoans, etc. Disease-producing parasitic worms and aquatic weeds are
some of the major biological pollutants. An antibacterial agent may act by destroying the
organism (bactericidal) or by inhibiting its growth (bacteriostatic). There are many categories
of antibiotics that are available in market such as penicillins, cephalosporins, tetracyclines,
aminoglycosides, sulphonamides, etc. Even though a lot of antibiotics are available in the
market the future effectiveness of antimicrobial therapy is somewhat in doubt.
Microorganisms, particularly bacteria are becoming resistant to extra antimicrobial agents.

Treatment techniques

There are two strategies for the development of appropriate water treatment processes
in order to counterbalance the growing environmental problems. These are,
 a) Treatment of contaminated drinking, ground, and surface water
b) Treatment of wastewaters containing toxic or non-biodegradable compounds.

The wastewater treatment processes and technologies available at present are very
diverse. In general, the conventional processes are often classified as preliminary, primary,
secondary and tertiary treatment [13]. Conventional biological treatment methods for
industrial wastewaters are, in general, ineffective due to their resistance to aerobic
degradation, and in the case of azo dyes results often in an intensively colored discharge from
the treatment process. Chemical destruction may be accomplished using chlorine or ozone.
These chemical treatments may be yielded encouraging results of colour and organics
removal, but the required dosages are often too high to be economically feasible [14].

Reductive cleavage through anaerobic biological treatment generates potentially

carcinogenic intermediates or end products, such as aromatic amines, in the process. Physical
methods such as flocculation, reverse osmosis, air-stripping, absorption on activated charcoal,
combustion and aerobic biological oxidation are non-destructive. These processes merely
transfer the pollutants to from one medium to others, thus causing secondary pollution [15].
Aerobic biological oxidation is limited when the wastewater contains substances either
recalcitrant to biodegradation, or inhibitory or toxic to the bio-culture [16].

Other conversion processes can be limited by economic reasons, oxidative potential,

effluent characteristics, or tendency to form harmful disinfectant by-products, for example
the case of formation of trihalomethanes (THMs) when a chlorination procedure is used for
drinking water treatment, leading to the transfer of pollutants from the aqueous phase to
others, without their destruction [17].

In the present day treatment technologies, Advanced Oxidation Processes (AOP) are
an attractive alternative for the treatment of contaminated ground, surface and wastewaters
containing hardly-biodegradable anthropogenic substances as well as for the purification and
disinfection of drinking water [18-20].

Advanced Oxidation Processes (AOP)

In the last two decades, a lot of research was addressed to a special class of oxidation
techniques defined as Advanced Oxidation Processes (AOP), pointing out its potential
prominent role in the wastewater purification, in which the high oxidizing potential species
like hydroxyl radicals are utilized as an alternative way of treating undesirable organic
pollutants. It has been successfully shown that AOP could solve the problem of bio-
recalcitrant water pollutants working at near ambient temperature and pressure [21].Although
AOP use is different for various reacting systems, all are characterized by the same chemical
feature: production of hydroxyl radicals. These radicals are extraordinarily reactive species,
they attack most part of organic molecules with rate constants usually in the order of 106 –
109 M-1 S-1 [22].

Hydroxyl radicals are also characterized by a low property of attack that may be
useful attribute for an oxidant utilized in effluent and to solve pollution issues. The versatility
of AOP is also enhanced by the fact that they offer different possible ways for hydroxyl
radicals production thus allowing better compliance with the specific treatment requirements.

Table 1 shown that hydroxyl radical has the maximum thermodynamic oxidation
potential. Therefore, many researchers have waged their attention on hydroxyl radical based
oxidation processes. As well, most environmental contaminants react one million to one
billion times faster with hydroxyl radicals than with O3, a conventional oxidant [23].

Table 1: Oxidation potential of several oxidants in water

Oxidant Oxidation Potential (eV) [24]

•OH 2.80
O(1D) 2.42
O3 2.07
H2O2 1.77
Permanganate ion 1.97
Chlorine 1.36
O2 1.23

The oxidation reactions involving hydroxyl radical and substrates (RH or PhX) in
aqueous solutions may be classified, with respect to their character to [25]:

a) Abstraction of hydrogen ion

•OH + RH R• + H2O
b) Addition reactions
•OH + PhXH OPhX•
 c) Electron transfer
•OH + RH [R-H]+ • + HO-

AOP are usually classified into different ways according to the reaction phase
(homogeneous or heterogeneous) or to the hydroxyl radical generation methods (chemical,
electrochemical, sonochemical or photochemical). The main AOP processes are shown in
Fig.1.3 and are briefly described below to provide a brief knowledge on each of them.

H2O2/O3/UV

H2O2/O3 SONOLYSIS

•OH
O3/UV ELECTROLYSIS

+3
UV/TiO 2/H2O2 UV/Fe /H2O2

Fig. 3: Various Advanced Oxidation Processes

Sonolysis:

Sonolysis or sonochemical Oxidation Techniques (SOT) have received considerable

attention as AOP because they lead to the rapid degradation of chemical contaminants in
water [26-27]. SOT involves the use of ultrasonic waves to produce an oxidative environment
via cavitation that yields localized microbubbles and supercritical regions in the aqueous
phase.

Cavitation is the formation, growth and sudden collapse (implosion) of microscopic

gas bubbles in liquids. These bubbles collapse and high local temperatures (2000–50000C)
and pressures (500 atm) are produced [28]. The water vapour and O2 in the cavitation bubbles
undergo thermal dissociation to yield •OH, •OOH and •H radicals as well as O atoms. H2O2 is
formed as a consequence of hydroxyl and hydroperoxyl recombination outside the cavitation
bubbles.
 Though this process has shown to result in the generation of highly reactive species,
the production of extreme conditions like high temperature and ultrasonics, are very short
lived and practically less feasible.

Electrochemical methods

In the last few years, there is a great development in the effective electrochemical
treatments for the destruction of toxic and bio-refractory organics in water [29-30]. Anodic
oxidation and indirect electro-oxidation with H2O2 generation are the most usual techniques
utilized to achieve the mineralization of pollutants, to their final conversion as CO2, water
and inorganic ions. In anodic oxidation, adsorbed hydroxyl radicals (•OH) are formed at the
surface of high-oxygen overvoltage anode from water oxidation:

H2O •OHads + H+ + e-

Radical, as shown above, is a powerful oxidizing agent, with ability to react with
organics giving dehydrogenated or hydroxylated derivatives. Under these conditions,
however, most aromatic solutions are poorly mineralized, because of the generation of hardly
oxidizable carboxylic acids.

Other potent indirect electro-oxidation methods for water remediation involve the
continuous supply of a strong oxidant such as H2O2 to the treated solution from the two-
electron reduction of oxygen on graphite, carbon, mercury pool and O2-diffusion cathodes
[31-34] which involves, continuous monitoring, usage of an important limited source,
electricity and are cost effective.

Advanced Photochemical oxidation processes

An interesting class in AOP is the Advanced Photochemical Oxidation processes

(APO) [23]. APO processes are characterized by a free radical mechanism initiated by the
interactions of photons of a proper energy level with the molecules of chemical species
present in the solution or a catalyst.

The most used APO technologies can be broadly divided into two groups: (1)
homogeneous photocatalysis and (2) heterogeneous photocatalysis. These APO technologies
are briefly described below:

Homogeneous photocatalysis
 Homogeneous photocatalysis is the sequence of reactions that involve the same phase
catalysts and reactants. Most commonly, a homogeneous photocatalyst is co-dissolved in a
solvent with the reactant. The application of homogeneous photodegradation is to treat
contaminated waters with UV/H2O2 and UV/O3. The use of UV light for photodegradation of
pollutants can be classified into two principal areas: (i) direct photodegradation, which
proceeds following direct excitation of the pollutant by UV light and (ii) photooxidation,
where light drives oxidative processes principally initiated by hydroxyl radicals. The latter
process involves the use of an oxidant to generate radicals, which attack the organic
pollutants to initiate oxidation. Three major oxidants used are hydrogen peroxide, ozone and
photo-Fenton system (Fe+3/H2O2).

UV/H2O2: UV oxidation with H2O2 was first applied to waste water treatment by Koubeck
[35]. The most commonly accepted mechanism for the photolysis of H2O2 is the cleavage of
the molecule into hydroxyl radicals with a quantum yield of two •OH radicals formed per
quantum of radiation absorbed. This reaction is observed only at λ < 300 nm for
concentrations of H2O2 of 10-1mol L-1. On the other hand, H2O2 is known to dismute.

H2O2 +hν 2 •OH

H2O2 + HO2- O2 + H2O + OH-

The use of UV/ H2O2 is very common for the treatment of several contaminated
waters [36]. The major drawback of using H2O2 is its low molar extinction coefficient at the
near UV-region [39]. The H2O2/UV photo process needs low pressure mercury lamps
emitting short UV-radiation (254 nm), which is less available in the solar radiation. The high
operating costs of the UV lamps reduce the feasibility of the application of the system in a
large scale [37].

O3/UV: Ozone is widely used as an oxidant in pollution abatement in aqueous media. It has
the advantage that it is an eco-friendly oxidant as its use is residue-free. The photolysis of
ozone dissolved in water leads to the production of hydrogen peroxide and the subsequent
formation of hydroxyl radical, which oxidizes the organic compounds. Sometimes direct
reactions of molecular ozone and the pollutants also take place. However with many
pollutants, it reacts so slowly that for all practical purposes they must be considered ozone-
refractory [38]. For this reason, procedures are being applied where the oxidative power of
the ozone is ‘activated’, i.e., by a combination of ozone with H2O2, with H2O2/UV radiation
[39], with Fe(III)/UV or Cu(I)/UV [50].

The O3/UV process is considered as an advanced water treatment for the effective
oxidation and destruction of toxic and refractory organics [40], bacteria, and viruses in water
but it has the same problem as H2O2 process about the usage of solar energy since O3 also,
does not absorb light at λ > 300 nm.

Photo-Fenton reactions: The photo-Fenton reaction was discovered by H.J.H Fenton in

1894 [41]. Fenton reaction rates are strongly increased by irradiation with UV/visible light,
this type of photo assisted reaction is referred to as the photo-Fenton reaction [42].

Fe+3 + H2O + hν Fe+2 + •OH + H+

The hydroxyl radical, generated once in solution attacks almost every organic compound. The
positive effect of irradiation on the degradation rate is due to the photochemical regeneration
of ferrous ions (Fe+2) by photoreduction of ferric ions (Fe+3). The newly generated ferrous ion
reacts with H2O2 generating a second hydroxyl radical and ferric ion and the cycle continue.
In these conditions, iron can be considered as the real catalyst.

The main advantage of the photo-Fenton process is the light sensitivity up to a

wavelength of 600 nm [43]. The depth of light penetration is high and the contact between
the pollutant and the oxidizing agent is close since homogeneous solution is used. Photo-
Fenton process was used with great success to treat a wide variety of contaminants [44].

Degradation rates increase with an increase in H2O2 and iron concentration, but after a
certain level, the reaction rate levels off and sometimes is negatively affected. This may be
due to auto-decomposition of H2O2 to oxygen, water and recombination of •OH radicals. And
due to the increase of brown turbidity that hinders the absorption of the light required for the
process. The need for acidification of a wastewater stream is one of the major obstacles
towards an industrial application of the photo-Fenton reaction [45].

The limitation inherent to the homogeneous catalysis is that all the reactants including
the catalysts are in solution and the recovery of catalyst is complicated and expensive. Also,
the level of iron in water allowed by environmental legislation [46] is also a problem to
ponder, in the case of photo-Fenton process.
 Among AOPs, heterogeneous photocatalysis is an attractive method because of its
applications in the conversion and storage of light energy, and it has been successfully
employed for the degradation of various families of organic pollutants [47-48].

Heterogeneous photocatalysis

Heterogeneous photocatalysis is a process in which a combination of photochemistry

and catalysis is operable and implies that light and catalyst are necessary to bring out a
chemical reaction. In recent years, there has been a growing interest in the use of
semiconductors as photosensitizers for the complete oxidative mineralization of pollutants by
oxygen [49]. In heterogeneous catalysis, the catalyst is in a different phase to the reactants,
providing a surface for the chemical reaction to take place on. The support materials
(catalysts) employed in these studies can be broadly classified into two categories: (i)
inorganic supports such as SiO2 or Al2O3, which provide an ordered two-dimensional
environment for effecting and controlling photochemical processes more efficiently than can
be attained in homogeneous solutions; (ii) semiconductor supports such as TiO2 or CdS,
which directly participate in photochemical reactions either by absorbing the incident photon
and transferring charge to an adsorbed molecule [18].

Heterogeneously dispersed semiconductor surfaces provide both a fixed environment

to influence the chemical reactivity of a wide range of adsorbates and a means to initiate
light-induced redox reactivity in these weakly associated molecules. Depending on where the
initial excitation occurs, photocatalysis can be generally divided into two classes of
processes. When the initial photoexcitation occurs in an adsorbate molecule which then
interacts with the ground state catalyst substrate, the process is referred to as a catalyzed
photoreaction. When the initial photoexcitation takes place in the catalyst substrate and the
photoexcited catalyst then transfers an electron or energy into a ground state molecule, the
process is referred to as a sensitized photoreaction.

Upon photoexcitation of several semiconductors heterogeneously suspended in either

aqueous or nonaqueous solutions, simultaneous oxidation and reduction reactions occur. The
incident light that initiates this sequence is in a wavelength region absorbed by the
semiconductor rather than by the substrate of interest. These reactions, therefore, involve
photosensitization, i.e., indirect photoactivation of the heterogeneously dispersed particulate
absorber rather than the direct formation of an excited state of the substrate. Furthermore, the
suspended semiconductor particle that acts as the photocatalyst is often stable to the
photolysis conditions and a large number of oxidative conversions per active site on the
catalyst can be attained without significant degradation of the semiconductor’s redox
catalytic capacity.

Semiconductor photocatalysis

Semiconductor photocatalysis has its origin in the substantial research effort in the
seventies and early eighties. Semiconductors (e.g., TiO2, ZnO, Fe2O3, CdS, ZnS, etc.) can act
as sensitizers for light-reduced redox processes due to their electronic structure, which is
characterized by a filled valence band and an empty conduction band, separated by a band
gap, Ebg, a region devoid of energy levels. Activation of a semiconductor photocatalyst is
achieved through the absorption of a photon with an energy hν that matches or exceeds the
band gap energy, Ebg. An electron e-cb, is promoted from the valence band, VB, into the
conduction band, CB, leaving a hole, h+vb. Excited-state conduction-band electrons and
valence-band holes undergo many events after the light absorption by TiO2 particles, which
have been illustrated in Fig. 1.4.

In the absence of a suitable electron and hole scavengers, the stored energy is
dissipated within a few nanoseconds by recombination [50]. If a suitable scavenger or surface
defect state is available to trap the electron or hole, recombination is prevented and
subsequent redox reactions may occur. The valence band holes are powerful oxidants (+1.0 to
+3.5 V vs NHE depending on the semiconductor and pH), while the conduction band
electrons are good reductants (+0.5 to -1.5 V vs NHE) [51].
 Fig: TiO2-semiconductor photocatalytic process.

When a semiconductor is in contact with an aqueous solution, thermodynamic

equilibration takes place at the interface. This may result in the formation of a space-charge
layer within a thin surface region of the semiconductor, in which the electronic energy bands
are generally bent upwards or downwards, respectively, in the cases of n- and p-type
semiconductors. The thickness of the space-charge layer is usually of the order of 1-103 nm,
depending on the carrier density and dielectric constant of the semiconductor. If this
semiconductor receives photons with energies greater than that of the material’s band gap,
Ebg, electron-hole pairs are generated and separated in the space-charge layer.

The purification of water by semiconductor photocatalysis is attracting a great deal of

interest, not only from research workers but also from water purification companies. This
interest arises because:

(i) The mineral ‘effluent’ so produced is harmless to the environment,

(ii)The process of photomineralization can be turned on or off at the

a flick of a switch and

(iii) There is a real possibility that it could be readily incorporated

into existing UV water purification systems.

Choice of semiconductor

There are a lot of different semiconducting materials which are readily available but
only a few are suitable for sensitizing the photomineralization of a wide range of organic
pollutants which can be summarized by the following equation:

Organic + O2 semiconductor CO2 + H2O + mineral acids

pollutant ultra-band gap light

A sensitizer for the above reaction must be:

(i) Economical
(ii) Photoactive
 (iii) Able to utilize visible and/near UV light
(iv) Biologically and chemically inert
(v) Photostable (Ex. nonlabile for photoanodic corrosion)

Among the various photocatalysts developed, TiO2 is undoubtedly the most popular and
widely used photocatalyst since it is of low cost, high photocatalytic activity, chemical and
photochemical stability [52, 53]. However, TiO2 is not ideal for all purposes and performs
rather poorly in processes associated with solar photocatalysis due to its wide band gap (3–
3.2 eV), thus making impractical overall technological processes based on TiO2. To design
visible-light-driven photocatalysts, two strategies have been proposed. One is to modify the
wide bandgap photocatalysts (such as TiO2, ZnS) by doping or by producing hetero-junctions
between them and other materials [52], and the other involves the exploration of novel
semiconductor materials capable of absorbing visible light. Various compounds, such as
BiVO4, Bi2WO6, CaBi2O4, PbBi2Nb2O9, Bi4Ti3O12, and Ag@AgCl, and others have been
reported to be promising photocatalysts under visible light irradiation [54–56]. Despite many
of these photocatalysts being effective for the degradation of organic pollutants and water
splitting, up to date, the present achievements are still far from the ideal goal.

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