Desalination 276 (2011) 13–27

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

An overview on the photocatalytic degradation of azo dyes in the presence of TiO2

doped with selective transition metals
M.A. Rauf ⁎, M.A. Meetani, S. Hisaindee
Chemistry Department, P.O. Box 17551, UAE University, Al-Ain, UAE

a r t i c l e i n f o a b s t r a c t

Article history: This article presents an overview on the degradation of azo dyes using transition metal doped TiO2 as
Received 12 January 2011 photocatalysts in aqueous solutions. Such dopants reduce the recombination of e−cb and h+vb and decrease
Received in revised form 24 March 2011 the band gap or create intra-band gap states, which result in more light absorption. Moreover, the addition of
Accepted 26 March 2011
these dopants can alter the surface properties of TiO2 catalyst such as surface acidity and surface area.
Available online 20 April 2011
Therefore, the photocatalysis on modified TiO2 can be promoted using visible light. An important role in this
Keywords:
process is played by molecular oxygen and other active species such as O•− • •
2 , HO2, H2O2 and OH which are

Azo dyes generated in a sequence of reactions. Besides this, the degradation of dyes depends on several other
Doping parameters such as pH, catalyst concentration, substrate concentration and the nature of the doping
Free radicals substances. Depending on the structure of the azo dye, the major identified intermediates are hydroxylated
Heterogeneous catalysis derivatives, aromatic amines, naphthoquinone, phenolic compounds and several organic acids. This review
Intermediates also presents the literature findings on the available pathways and mechanisms of degradation of some azo
Photocatalysis dyes in the presence of metal doped TiO2 catalysts.
Transition metals
© 2011 Elsevier B.V. All rights reserved.
TiO2

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.1. Classification of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2. Experimental techniques used for studying dye degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3. Principles of photocatalysis and mechanistic pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1. Direct photocatalytic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2. Indirect photocatalytic mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4. Operational factors influencing the photocatalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.1. Effect of dye concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.2. Effect of catalyst amount . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.3. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.4. Effect of light intensity and irradiation time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.5. Dissolved oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5. Effect of dopants on dye degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.1. Doping TiO2 with Cr ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.2. Doping TiO2 with Cu ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.3. Doping with Fe ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5.4. Doping with Mn ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.5. Doping with Zn ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5.6. Doping with V ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.7. Doping with Ag ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.8. Doping with W ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

⁎ Corresponding author. Tel.: + 971 3 7136122; fax: + 971 3 7136944.

E-mail address: raufmapk@yahoo.com (M.A. Rauf).

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.03.071
14 M.A. Rauf et al. / Desalination 276 (2011) 13–27

1. Introduction [18–20], ozonation process [21], sonolysis [22–25], photocatalytic

Synthetic dyes comprise an important part of industrial water
effluents, as they are discharged in abundance by many manufactur-
ing industries. The impact of these dyes on the environment is a major
concern because of the potentially carcinogenic properties of these
chemicals [1]. Besides this, some dyes can undergo anaerobic
decoloration to form potential carcinogens [2,3]. The wastewater
which is colored in the presence of these dyes can block both sunlight
penetration and oxygen dissolution, which are essential for aquatic
life. Thus there is a considerable need to treat these colored effluents
before discharging them to various water bodies. Various approaches
on handling and decontaminating such effluents have been reported
in the literature. Typical techniques include the classical methods
such as adsorption [4–6], coagulation [7,8], ion flotation [9] and
sedimentation [10]. All these techniques are versatile and useful, but
they all end up in producing a secondary waste product which needs
to be processed further. Another set of techniques which are relatively
newer, more powerful, and very promising is called Advanced
Oxidation Processes (AOPs) which has been developed and employed
to treat dye-contaminated wastewater effluents [11]. This methodol-
ogy would normally utilize a strong oxidizing species such as •OH
radicals produced in situ, which causes a sequence of reactions
thereafter to break down the macromolecules into smaller and less
harmful substances. In many cases the macromolecule is completely
mineralized into water and carbon dioxide. The AOP technique has
drawn considerable attention from various quarters of scientific
community as it is easy to handle and produces significantly less
residuals as compared to the classical approaches. Amongst the many
techniques employed in the AOP approach are the UV photolytic
technique [12–14], Fenton process [15–17], photo-Fenton process
approach [26–30], biodegradation [31–33] and the radiation induced
degradation of dyes [34–37].
Various physico-chemical techniques are available for the elimi-
nation of dyes from wastewater and in particular photocatalysis is a
more promising tool. Moreover, photocatalysis can be used to cause
redox transformations and decompose a dye molecule. The use of
photosensitive semiconductors such as TiO2, ZnO, Fe2O3, CdS, ZnS and
V2O5 has been reported in the literature for their use in reducing color
of the dye solutions owing to their environmental-friendly benefits in
the saving of resources such as water, energy, chemicals, and other
cleaning materials [38–42]. Titanium dioxide (TiO2) mediated based
photodegradation has attracted extensive interest owing to its great
advantages in the complete removal of organic pollutants from
wastewater [43]. This is mainly because of its various merits, such as
optical-electronic properties, low-cost, chemical stability, and non-
toxicity [44]. The main aim of this paper is to produce a condensed and
coherent overview on the photocatalytic degradation of azo dyes in
the presence of TiO2 doped with selective transition metals, which can
serve as a ready reference for future scientific endeavors in this area.
1.1. Classification of dyes
Dyes are mainly classified based on their structure, source, color and
method of application in color index (C.I.), which has been continuously
edited since 1924. Depending on the chromophores, dyes can be
classified in various classes. These include the acridine dyes, azo dyes,
arylmethane dyes, anthroqinone dyes, nitro dyes, xanthenes dyes and
quinine–amine dyes etc. Table 1 summarizes the structures of various
classes of dyes along with an example of each class. The investigation of
radiation induced decomposition of dyes and their derivatives due to

Table 1
Classification of dyes based on molecular structure.

Class Structure Representative dye Structure

H H
Acridine Acridine O
N (H3C)2N N N(CH3)2

C C
H H
NaO3S SO3Na

N N
Azo N N Amido B N N
OH NH2
NO2

NH 2
Diarylmethane C Auramine O (H 3C)2N C N(CH 3)2

HO

O O

OH OH O CH 3
Anthraquinone Carmine OH CO 2H
OH
O
HO OH
OH O

C N(CH3)2
C
Triarylmethane Malachite green

N(CH3)2

ONa
OH
HO3S NO2
NO2
Nitro Naphthol

NO2
(C2H5)2N O N(C2H5)2

O
Xanthene Rhodamine B
CO2H

H 3C N CH3

N NH
H 2N N NH2
Quinone-imine Safranin O
N
 M.A. Rauf et al. / Desalination 276 (2011) 13–27 15

Table 2
Representative examples of various types of azo dyes.

Class Representative dye Structure

Monoazo Orange II HO

NaO3S N N

NH2 H2N

Diazo Congo Red N N N N

NaO3S SO3Na

NaO3S HO

N N N N N N
Triazo Direct Blue 71
NaO3S
SO3Na
SO3Na

their environmental hazard is a rather popular subject and many papers
have been published in this field [12–37].
Azo dyes are the largest group of synthetic colorants (60–70%) and
are being used in industry for applications such as textiles, papers,
leathers, gasoline, additives, foodstuffs, cosmetics, laser materials,
xerography, laser printing, etc. and the resulted by-products contain
both dyes and metal ions. Since only 45–47% dyestuffs has been
reported biodegradable, and residual color is mostly due to insoluble
dyes which have low biodegradability [33]. Because of the toxicity and
persistence of azo dyes, their removal from the wastewater has
become an important issue of interest during the last few years.
Azo dyes are characterized by nitrogen to nitrogen double bonds
(–N=N–) that are usually attached to two moieties of which at least one
but usually both are aromatic groups (benzene or naphthalene rings).
Some representative examples of azo dyes are Methyl Orange, Acid
Orange 7, Acid Orange 20, Orange II, Methyl Red, Reactive Red 2,
Reactive Orange 16, Reactive Black 5, Congo Red, Solvent Red 1, Direct
Blue 160, Basic Yellow 15, Basic Blue 41, Disperse Orange 1, Disperse Red
1, Amido Black, Remazol Brilliant Orange 3R, Amaranth, etc. Depending
upon the number of –N=N–groups in the molecule, the azo dyes can be
classified as monoazo (Acid orange 7, Orange G, Methyl red, etc.), diazo
(Congo Red), triazo (Reactive red 120, Naphthol blue black, etc.) and
triazine containing azo dyes (Reactive brilliant red K-2G, Procion red
MX-5B, etc.). Table 2 shows the representative example of each type of
azo dye. The color of azo dyes is determined by the azo bonds and their
associated chromophores and auxochromes. Azo bonds are the most
active bonds in azo dye molecules and can be oxidized by positive hole
or hydroxyl radical or reduced by electron in the conduction band. The
cleavage of –N=N– bonds leads to the decoloration of dyes.
then calculated from the decrease of absorbance of the dye solution at
its maximum absorption wavelength as follows [53]:
 
A
τ = 1− i × 100 ð1Þ
A0
where, A0 and Ai are the absorbance values of the dye solution before
and after irradiation respectively.
A typical laboratory-scale experimental set up includes a vigor-
ously stirred batch photochemical cell, cylindrical flasks or vessels and
glass dishes [29,54,55], whereas, upflow type, membrane based and
coated surfaces have also been reported as photocatalytic reactors for
dye degradation studies [56–59]. Fig. 1 depicts the standard
photochemical reactor used in this type of work.
3. Principles of photocatalysis and mechanistic pathways
Among many known AOPs, photocatalytic degradation has proven
to be a promising technology for degrading organic compounds
[60,61]. The technique is more effective as compared to other AOPs
sampling syringe

2. Experimental techniques used for studying dye degradation

water in
water out
Various experimental techniques have been proposed for both
qualitative and quantitative analysis of various dyes concerning their
degradation. These methods generally involve instrumental analysis UV lamp
such as UV–vis spectrophotometry [45,46], LC/MS [47], HPLC [48], ion
chromatography [49], capillary electrophoresis [50], FTIR [51] and
NMR [52]. In many of these cases, prior procedures of extraction of the
aqueous sample with an organic solvent or filtration are adopted
when a heterogeneous catalyst or solid reactant is employed.
Since dyes are colored in nature, it is relatively easy to monitor
their color change during the course of the experiment. In photo-
catalytic studies, the sample is normally exposed to UV irradiation for magnetic
a given time period and the changes in solution property (such as stirrer
color) are observed by using a spectrophotometer. The solution after
irradiation is then transferred to a cuvette and subjected to absorption
studies on a spectrophotometer. The degree of decoloration (τ) is Fig. 1. Schematic diagram of a photoreactor.
16 M.A. Rauf et al. / Desalination 276 (2011) 13–27

because semiconductors are inexpensive and can easily mineralize

various organic compounds [62].
The basic steps for heterogeneous photocatalysis consist of initially
transferring of the reactants in the liquid phase onto the catalyst
surface followed by adsorption of the reactant on the catalyst surface,
reaction in the adsorbed phase, desorption of the final product and
finally removal of the final products in the liquid phase.
The photocatalytic degradation of an organic compound such as
dye is believed to take place according to the following mechanisms:
When a catalyst is exposed to UV radiation, electrons are promoted
from the valence band to the conduction band. As a result of this, an
electron–hole pair is produced [63]
− þ Fig. 2. Mechanism of generation of oxidative species in a photocatalytic study.
Catalyst þ hν→ecb þ hvb ð2Þ

where, e− +
cb and h vb are the electrons in the conduction band and the
where r is the reaction rate for the oxidation of reactant
electron vacancy in the valence band, respectively. Both these entities can
(mg/L min), kr is the specific reaction rate constant for the
migrate to the catalyst surface, where they can enter in a redox reaction
oxidation of the reactant (mg/L min), ka is the equilibrium
with other species present on the surface. In most cases h+ vb can react
constant of the reactant (L/mg) and C is the dye concentration.
easily with surface bound H2O to produce •OH radicals, whereas, e− cb can
When the chemical concentration Co is a millimolar solution (Co
react with O2 to produce superoxide radical anion of oxygen [59]
is small) the equation can be simplified to an apparent first-order
þ •
H2 O þ hvb → OH þ H
þ
ð3Þ equation:

− −    
O2 þ ecb →O2 ð4Þ C0
ln = kapp t or C = Co exp −kapp t ð10Þ
C
This reaction prevents the combination of the electron and the
hole which are produced in the first step. The •OH and O−2 produced in
the above manner can then react with the dye to form other species A plot of ln Co/C versus time represents a straight line, the slope of
and is thus responsible for the discoloration of the dye. which upon linear regression equals the apparent first-order rate
constant kapp. Generally first-order kinetics is appropriate for the
−• þ •
O2 þ H →HO2 ð5Þ entire concentration range up to few ppm and several studies
•
were reasonably well fitted by this kinetic model. The L–H model
H2 O2 →2 OH ð6Þ was established to describe the dependence of the observed
• 9 10 –1 –1 reaction rate on the initial solute concentrations. Representative
OH þ dye→dyeox ðk ¼ 10 −10 M s Þ ð7Þ
examples of dye degradation adhering to such a process are
−
Dye þ ecb →reduction products ð8Þ reported in the literature [65,66].
(ii) The Eley–Rideal process
In this process, the free charged carriers are initially photo-
It may be noted that all these reactions in photocatalysis are
fragmented followed by subsequent trapping of the holes by
possible due to the presence of both dissolved oxygen and water
surface defects. The surface active centers (S) can then react
molecules. Without the presence of water molecules, the highly
with the dye (chemisorption) to form an adduct species such as
reactive hydroxyl radicals (•OH) could not be formed and inhibit the
(S-dye)+ which can further decompose to produce products or
photodegradation of liquid phase organic molecules.
can recombine with electrons. The reaction scheme is outlined
A schematic presentation of the mechanisms of generation of
below [67]:
oxidative species in a photocatalytic study is shown in Fig. 2. Direct and
indirect photocatalytic pathways are the two suggested mechanisms for − þ
Catalyst þ hν→e þ h ðphotogeneration of free carriersÞ ð11Þ
a given photocatalytic reaction. These are briefly discussed below.
þ þ
S þ h →S ðhole trapping by surface defectsÞ ð12Þ
3.1. Direct photocatalytic pathway
þ −
S þ e →Sðphysical decay of active centersÞ ð13Þ
Two different approaches have been suggested for this type of
mechanism: þ þ
S þ dye→ðS  CPÞ ðchemisorptionÞ ð14Þ
(i) Heterogeneous photocatalysis—the Langmuir–Hinshelwood
þ −
process ðS  dyeÞ þ e →S þ products ð15Þ
Heterogeneous photocatalysis can be generally explained on
the basis of the Langmuir–Hinshelwood process, wherein the 3.2. Indirect photocatalytic mechanism
production of electrons and holes produced by the photoexci-
tation of the catalyst are taken into account. The hole produced In this process, electron–hole pairs are photogenerated on the
is trapped by the adsorbed dye molecule on the catalyst surface surface of the catalyst. The hole is then trapped by water molecules
to form a reactive radical state which can decay as a result of leading to the formation of •OH radicals and H+. These •OH radicals can
recombination with an electron. The catalyst is regenerated in combine to form H2O2 or they can attack the dye to produce
the process. The Langmuir–Hinshelwood (L–H) equation can intermediates and end products. Moreover, the electrons can be trapped
be expressed as follows [64]: by molecular oxygen to form superoxide radical which can enter into a
chain reaction to produce HO•2 and H2O2. Finally, the radicals formed
1 1 1 during this mechanism are responsible for the oxidation of the organic
= + ð9Þ
r kr kr ka C molecule producing intermediates and end products [54].
 M.A. Rauf et al. / Desalination 276 (2011) 13–27 17

The stepwise mechanism is illustrated below: 4.3. Effect of pH

− þ
TiO2 þ hν→e þ h ð16Þ Photodegradation efficiency of dyes is affected by the pH of the
þ • þ solution. The variation of solution pH changes the surface charge of
h þ H2 OðadsÞ→ OHðadsÞ þ H ðadsÞ ð17Þ
TiO2 particles and shifts the potentials of catalytic reactions. As a
O2 þ e
− −•
→O2 ðadsÞ ð18Þ result, the adsorption of dye on the surface is altered thereby causing a
change in the reaction rate. Under acidic or alkaline condition the
−• þ • surface of titania can be protonated or deprotonated respectively
O2 ðadsÞ þ H ↔HO2 ðadsÞ ð19Þ
according to the following reactions [63]:
•
HO2 ðadsÞ→H2 O2 ðadsÞ þ O2 ð20Þ
þ þ
TiOH þ H →TiOH2 ð23Þ
•
H2 O2 ðadsÞ→2HO ðadsÞ ð21Þ
− −
•
TiOH þ OH →TiO þ H2 O ð24Þ
OH þ dye→intermediates→CO2 þ H2 O ð22Þ
Thus titania surface will remain positively charged in acidic
medium and negatively charged in alkaline medium. Titanium dioxide
4. Operational factors influencing the photocatalytic degradation
is reported to have higher oxidizing activity at lower pH, but excess H+
can decrease reaction rate. TiO2 behaves as a strong Lewis acid due to
The oxidation rates and efficiency of the photocatalytic system are
the surface positive charge. The anionic dye on the other hand is a
highly dependent on a number of operational parameters that govern
fused polynuclear aromatic compound with an extensive π electron
the photodegradation of the organic molecule [68]. This section will
conjugation which can easily form a stable complex by donating
briefly discuss the significance of each operational parameter.
electrons to the vacant d orbital of titanium. In other words, the anionic
dye acts as a strong Lewis base and can easily adsorb on the positively
charged catalyst surface. This favors the adsorption of the dye under
4.1. Effect of dye concentration
acidic conditions, while in the alkaline conditions this complexation
process is not favored presumably because of competitive adsorption
The quantity of the dye adsorbed on the surface of the photo-
by hydroxyl groups and the dye molecule in addition to the Coulombic
catalyst is of foremost importance since only this amount contributes
repulsion due to the negatively charged catalyst with the dye molecule
to photocatalytic process and not the one in the bulk of the solution.
[71].
The extent of dye adsorption depends on the initial dye
The extent of dye adsorption depends on the initial dye
concentration. The initial concentration of dye in a given photo-
concentration, nature of the dye, surface area of photocatalyst and
catalytic reaction is an important factor which needs to be taken into
pH of the solution. The pH determines the surface charge of the
account. Generally speaking the percentage degradation decreases
photocatalyst. Adsorption of the dye is minimum when the pH of the
with increasing amount of dye concentration, while keeping a fixed
solution is at the isoelectric point (point of zero charge). The surface of
amount of catalyst [69].
the photocatalyst is positively charged below isoelectric point and
This can be rationalized on the basis that as dye concentration
carries a negative charge above it. Depending on the nature of dye that
increases, more organic substances are adsorbed on the surface of
needs to be adsorbed on the surface of a photocatalyst, the adsorption
TiO2, whereas less number of photons are available to reach the
can be low or high in acidic and basic media.
catalyst surface and therefore less •OH are formed, thus resulting in
At low pH, reduction by electrons in conduction band plays a very
less degradation percentage.
important role in the degradation of dyes due to the reductive
cleavage of azo bonds [72–74]. Acid Orange 7 (an anionic dye) has
shown to degrade more at pH 3 [75]. The rationale behind this is that
4.2. Effect of catalyst amount
at low pH values, more H+ are available for adsorption to mask the
surface of the catalyst thus preventing the photoexcitation of
Dye degradation is also influenced by the amount of the
semiconductor particles, thereby reducing the generation of free
photocatalyst and aggregation of catalyst particles in high amounts
radicals. In alkaline solutions, •OH radicals are easier to be generated
of catalyst. The dye degradation increases with increasing catalyst
by oxidizing more hydroxide ions available on TiO2 surface, thus the
concentration, which is characteristic of heterogeneous photocata-
efficiency of the process is increased [76]. Similar results have been
lysis [11]. The increase in catalyst amount actually increases the
reported in the photocatalysed degradation of diazo and triazo dyes
number of active sites on the photocatalyst surface thus causing an
[77,78]. Fig. 3 shows the trend in % degradation of azo dye at different
increase in the number of •OH radicals which can take part in actual
pH values.
discoloration of dye solution. Beyond a certain limit of catalyst
amount, the solution becomes turbid and thus blocks UV radiation for
the reaction to proceed and therefore percentage degradation starts 4.4. Effect of light intensity and irradiation time
decreasing [70]. A representative example showing the effect of
catalyst amount on % decoloration is presented in Table 3. Both light intensity and time of irradiation affect the dye
degradation [42,79]. It has been shown that at low light intensities
(0–20 mW/cm2), the rate would increase linearly with increasing
Table 3
Effect of V2O5/TiO2 on % decoloration of dye solution in the presence of UV( concentration light intensity (first order), whereas at intermediate light intensities
of TB = SO= 80 μM, CV= 40 μM, irradiation time = 20 min, pH= 6.1) [93]. (25 mW/cm2) the rate would depend on the square root of the light
intensity [80]. At high light intensities the rate is independent of light
Dye Catalyst amount (mg/20 mL)
intensity, because at low light intensity reactions involving electron–
10 20 25 30 40
hole formation are predominant and electron–hole recombination is
Toludine Blue (TB) 15 40 47 41 27 negligible. On the other hand, when light intensity is increased, the
Safranin Orange (SO) 8 11 21 12 – electron–hole pair separation competes with recombination, thereby
Crystal Violet (CV) 6.5 12 – 17 15
causing lower effect on the reaction rate. In many literature studies, it
18
100
80
Degradation %
60
40
20
0 is inactive under visible light due to its wide band gap (3.03 eV for
1 2 3 4 5 7
pH
Fig. 3. Comparison of photocatalytic degradation of Acid Orange 7 and Methyl Orange
by 4.0% WOx/TiO2 composite at different pH values [133].
has been shown that the dye decolorization initially increases as the
light intensity is increased [81,82]. The reaction rate decreases with
irradiation time as it follows the pseudo first-order kinetics and
additionally a competition for degradation may occur between the
reactant and the intermediate products. The slow kinetics of dye
degradation after certain time limit is mainly attributed to the
difficulty in the reaction of short chain aliphatics with •OH radicals,
and the short lifetime of photocatalyst because of active sites
deactivation by strong by-products deposition [83]. Fig. 4 shows the
effect of time on % dye degradation.
4.5. Dissolved oxygen
Oxygen dissolved in solution is commonly employed as an
electron acceptor in photocatalysis reaction to assure sufficient
electron scavengers present to trap the excited conduction band
electron from recombination [39]. The oxygen does not affect the
adsorption on the TiO2 catalyst surface as the reduction reaction takes
place at a different location from where oxidation occurs. Dissolved
oxygen involves in the stabilization of radical intermediates, miner-
alization and direct photocatalytic reactions. Its presence is also
Fig. 4. Effect of irradiation time on % degradation of an azo dye.
M.A. Rauf et al. / Desalination 276 (2011) 13–27
known to induce the cleavage mechanism for aromatic rings in
A07 organic pollutants that are present in the water matrices [39].
MO
5. Effect of dopants on dye degradation
Heterogeneous photocatalysis involving titanium dioxide (TiO2)
appears to be the most promising technology for organic dyes
degradation. However one of the major problems in using TiO2 as a
catalyst is the low photo-quantum efficiency which arises from the fast
recombination of photogenerated electrons and holes. Moreover, TiO2
9 rutile and 3.18 for anatase form). This inherently causes the inability to
make use of the vast potential of solar photocatalysis. Various
techniques have been employed to make TiO2 absorb photons of
lower energy as well. These techniques include surface modification
via organic materials and semiconductor coupling, band gap modifi-
cation by creating oxygen vacancies and oxygen sub-stoichiometry, by
nonmetals including co-doping of nonmetals and metal doping.
Dopants, such as transitional metals have been added to the TiO2
catalyst to improve its response and also reduce the recombination of
photogenerated electrons and photogenerated holes [84–86]. The
main objective of doping is to induce a batho-chromic shift, i.e., a
decrease of the band gap or introduction of intra-band gap states,
which results in more visible light absorption. The effect of metal ion
dopants on the photocatalytic activity is a complex problem. The total
induced alteration of the photocatalytic activity is made up from the
sum of changes which occur in the light absorption capability of the
TiO2 photocatalyst, adsorption capacity of the substrate molecules at
the catalyst's surface and interfacial charge transfer rate. Using
suitable transitional metals as dopants improves the performances
of TiO2 [87–90]. This results in the overlap of the conduction band due
to Ti (3d) with d levels of the transition metals causing red shift of the
band edge of TiO2. It can thus also allow the light absorption to be
widened into the visible region to various extents, depending on the
type of the dopant and its concentration. Therefore the photocatalysis
on modified TiO2 can be promoted using visible light.
Various transition metals, such as Ni2+, Zn2+, Cr3+ and Fe3+ can be
easily incorporated into the crystal lattice of TiO2 because of their similar
ionic radii (The ionic radii of Ni2+ = 0.72 Å, Zn2+ = 0.74 Å, Cr3+ =
0.76 Å and Fe3+ = 0.69 Å are quite similar to that of host Ti4+ = 0.75 Å
ions) [91]. The degradation of dyes is usually faster in mixed systems as
compared to single systems, because the oxidation of dyes consumes
photo-excited holes promptly and efficiently, thus attenuating electron–
hole recombination. In mixed systems this might be because the
recombination is increased by crystallite defects [92–94].
5.1. Doping TiO2 with Cr ions
The incorporation of transition metal ions in TiO2 is interesting for
inducing a batho-chromic shift of the band gap. The band gap energy is
shifted by 2.00 eV in the case of chromium doping [95]. This can be
explained by the excitation of an electron of Cr3+ into the conduction
band of TiO2. For any photocatalytic reaction, the lifetimes of electrons
and holes must be long enough to allow them to reach the surface of
the photocatalyst. The addition of transition metal ions produces new
trapping sites which affect the lifetime of the charge carriers. A lifetime
of 89.3 ms has been reported for pure titania, whereas doping reduces
this lifetime to about 30 ms in the case of Cr3+ [95]. When Cr3+ ions are
present in the matrix, they are initially oxidized by holes (h+):
3þ þ 4þ
Cr þ h →Cr ð25Þ
The beneficial effect of Cr3+ under UV irradiation can be explained
by considering the efficient separation of photo-excited electrons and
holes. Cr3+ can act as photogenerated hole trapper, due to the energy
 M.A. Rauf et al. / Desalination 276 (2011) 13–27 19

level for Cr3+/Cr4+ above the valence band edge of TiO2 [95]. The
trapped holes in Cr4+ can migrate to the surface absorbed hydroxyl
ion to produce hydroxyl radicals:
Cr
4þ −
þ OH ðadsÞ→Cr
3þ •
þ OHðadsÞ
The reaction scheme is well supported by the photocatalytic
chromium cycle which has been reported in the literature [96]. The re-
oxidation of photoreduced chromium species takes place with
molecular oxygen. In the photocatalytic degradation process, organic
matter, molecular oxygen and UV light are consumed in the
chromium cycle, which enables the atmospheric oxygen to oxidize
and thus degrade organic pollutant [97].
Rhodamine B undergoes 25% more degradation in the presence of
10% Cr3+ doped titania as compared to in neat titania [95]. At chromium
concentrations below 1%, both the lifetime and photocatalytical activity
were reported to decrease drastically to a nearly constant low level. This
ð26Þ can be explained on the basis that is that at low concentrations of Cr3+,
these ions can occupy regular lattice sites which act as traps.
At higher ion concentrations of Cr3+ ions, the interstitial sites are
filled up and thus do not contribute to the recombination. In another
study, higher concentration of chromium ions (10%) was used so that
they are completely dispersed into the titania lattice [26]. The 10% of
chromium was selected for two reasons: (a) 10% Cr3+ could be well
dispersed in the titania lattice without the formation of any crystalline
chromium oxide, (b) 10% chromium resulted in higher surface area

Fig. 5. Schematic diagram of various Intermediate formations of Orange G dye as a result of photocatalytic degradation [99].
20 M.A. Rauf et al. / Desalination 276 (2011) 13–27

than other compositions and also that the anatase phase is retained
which is known to be the most catalytically active phase of titania
[98]. Chromium–titanium mixed oxide was used to photodegrade
Orange G dye (azo dye) and the degradation followed the pseudo
first-order kinetics with a degradation efficiency of 70% in 300 min
[99]. The degraded products were analyzed by using the liquid
chromatography tandem mass spectrometry.
The major intermediates were substituted phenols, and aromatic
hydroxyl amines in addition to nitroso compounds and dicarboxylic
aromatic compounds. The degradation pathway scheme (Fig. 5)
suggests that these products were produced by desulfonation and
hydroxylation of the aromatic ring together with oxidative cleavage of
the azo bond and the destruction of the aromaticity and ring cleavage.
Desulfonation was explained by the attack of •OH radicals onto
sulphur followed by its elimination in the form of H2SO4 or NaHSO4.
The remaining aromatic radical species were quenched to produce
phenols and hydroxyl amines. The findings also showed that π bonds
in the azo group are the preferable site for •OH radical attack which
can happen on either of the nitrogen atoms of the azo group thus
leading to a variety of degradation products [26,100]. In another
study, chromium doped titania electrodes were used to degrade Acid
Red G (azo dye) [101]. The photocatalytic efficiency was remarkably
enhanced by the incorporation of Cr3+. The enhanced photocatalytic
degradation rate was attributed to the increase of the charge
separation in these systems.
It was shown that the Cu2+ doped TiO2 catalyst increased the
photocatalytic degradation of two typical azo dyes used in dyeing
industry namely Acid Orange 7 (AO7) and Tartrazine (Tart) [104]. The
behaviour of Cu2+ was explained on the basis that Cu2+ may scavenge
electrons resulting in the formation of Cu+, which in turn enhances
the oxidation of the substrate.
Copper doped TiO2 nanocatalysts have been synthesized by photo-
deposition and sol–gel methods and their activities in the discolor-
ation and mineralization of AO7 were evaluated [105]. The results
indicated that the Cu-doped TiO2 nanocatalysts with a low copper
concentration prepared by the photo-deposition method showed
enhanced photocatalytic activity; TiO2 nanocatalyst doped with 1% Cu
showed the best performance. Complete color removal and 99% of
total organic carbon (TOC) removal were achieved after 150 min of
reaction. TiO2 nanocatalysts doped with more than 1% Cu concentra-
tion blocks the TiO2 from absorbing the incoming photons thereby
showing decreased photocatalytic activities.
Several heterojunctions such as Cu2O/TiO2, Cu/Cu2O/TiO2 and
Cu/Cu2O/CuO/TiO2 were prepared and studied for their potential
application as photocatalysts. They were found to show high perfor-
mance under visible light [106]. Orange II was used as a representative
dye molecule in this study. The highest photocatalytic activity was
observed for the Cu/Cu2O/CuO/TiO2 system under visible light. It is well
known that Cu cannot act as a photosensitizer, but it can mediate the
electron injection from Orange II to the conduction band of TiO2 making
the generation of radical O2•− possible.

5.2. Doping TiO2 with Cu ions

5.3. Doping with Fe ions
In solution, Cu(I) produced from Cu(II) by photoreduction
undergoes relatively fast re-oxidation mostly in reaction with TiO2 particles can be easily doped by iron, forming mixed oxides or
molecular oxygen [96]: mixtures of simple/mixed oxides. Iron cations occupy substitutional
positions because of the similar radius of Fe3+ and Ti4+ which form
þ 2þ •−
Cu þ O2 →Cu þ O2 ð27Þ solid solutions with titania at low concentrations (b1 at Fe%). The
presence of iron catalyzes the anatase to rutile transformation, with
Consequently Cu(I) disappearance in oxic environments is very fast
rutile being detected even at high temperature. The formation of solid
(in milliseconds). In suboxic conditions, the Cu(I) concentration varies
solutions and the existence of solubility limits for Fe ions in TiO2 lead
with solar UV irradiation and can even reach 50% of the dissolved copper
to formation of α-Fe2O3 at higher concentrations.
[102]. Oxygen dissolved in water reduces the Cu(I) concentration and
In the presence of low doping levels of this metal, photo generated
thus O•2− and H2O2 are produced instead. These play an important role in
holes and electrons are well separated thereby increasing the
the Cu cycle as they can act either as an oxidant or a reducing agent with
efficiency of the catalyst. Fe3+ traps photo generated holes and
copper. The oxidation can take place by the following steps [96]:
forms Fe4+ which reacts with the surface adsorbed hydroxyl ions to
þ 2þ • − produce hydroxyl radicals and O2− in the surface lattice of doped TiO2
Cu þ H2 O2 →Cu þ OH þ OH ð28Þ
and tends to trap photogenerated holes and produce hydroxyl
þ
Cu þ OH→Cu
• 2þ
þ OH
−
ð29Þ radicals. Alternatively, Fe4+ can also react with photogenerated
electrons thereby affecting the photocatalytic activity. The reaction
whereas, reduction can occur by the following reactions: mechanism is summarized below [107]:
2þ − þ •− þ − þ
Cu þ HO2 →Cu þ O2 þ H ð30Þ TiO2 þ hν→e þ h ð32Þ

2þ •− þ 3þ þ 4þ
Cu þ O2 →Cu þ O2 ð31Þ Fe þ h →Fe ð33Þ
Thus peroxide and superoxide species are not only formed in the 3þ − 2þ
Fe þ e →Fe ð34Þ
copper cycle, but they also had an influence on the Cu(I)/Cu(II)
interconversion. 2þ 3þ −
Fe þ O2 ðadsÞ→Fe þ O2 ð35Þ
It is now well known that copper can participate in photoredox
cycles and its role cannot be ignored. The most important part of the 2þ 4þ 3þ 3þ
Fe þ Ti →Fe þ Ti ð36Þ
cycle is photoreduction of Cu(II) to Cu(I) induced by solar light and
oxidation of copper bound pollutants to the environmentally benign 3þ 4þ −
Ti þ O2 ðadsÞ→Ti þ O2 ð37Þ
forms. Therefore, the Cu(I) is oxidized easily to Cu(II), which may
4þ − 3þ
coordinate with another molecule. Thus the Cu photocatalytic cycle Fe þ e →Fe ð38Þ
contributes to the environmental cleaning [96].
4þ − 3þ •
Photooxidation of pollutants with participation of Cu(II) complexes Fe þ OH ðadsÞ→Fe þ OHðadsÞ ð39Þ
may also occur in heterogeneous systems on semiconductor surfaces.
Since this system requires presence of other substances such as TiO2 or The presence of high concentration of Fe3+ ions can act as
WO3, it seems to be more useful for wastewater cleaning from recombination centers for the photogenerated electrons and holes,
hazardous species rather than for environmental self-cleaning [103]. resulting in the decrease of photocatalytic activity.
 M.A. Rauf et al. / Desalination 276 (2011) 13–27 21

The excitation behavior of Fe–TiO2 (under visible irradiation) arises
from electronic transition from the dopant energy level (Fe3+/Fe4+) to
the conduction band of TiO2. Due to the fact that the t2g level of 3d orbital
of Fe3+ ion is above the valence band of TiO2, Fe3+ ion can absorb a
photon with a wavelength exceeding 400 nm to produce a Fe4+ ion and
a TiO2 conductive band electron [107]. The conductive band electron
further reacts with adsorbed O2 to form O2 −, while Fe4+ reacts with
surface hydroxyl group to produce hydroxyl radical.
The photogenerated electrons preferentially go to Mn ion rather
than oxygen as the transfer time to oxygen is reported to be of the
order of milliseconds [109]. Since Mn3+ and Mn+ ions are relatively
unstable as compared to Mn2+ ions, (d5), therefore there is tendency
for the transfer for the trapped charges from Mn3+ and Mn+ to the
interface to initiate the following reactions [110].
þ 2þ •−
Mn þ O2 →Mn þ O2 ðelectron releaseÞ ð53Þ

3þ 4þ −
Fe þ hν→Fe þe ð40Þ 3þ − 2þ •
Mn þ OH → Mn þ OHðhole releaseÞ ð54Þ
−
e þ
−
O2 ðadsÞ→O2 ð41Þ The photogenerated superoxide ion (O•−
2)
and hydroxyl radical
(•OH) are highly reactive and can effectively degrade the dye.
The photocatalytic activity of Fe–TiO2 catalysts was evaluated from In the case of Mn2+ doping, the rates of detrapping of the charge
the photodegradation of Methyl orange (azo dye) aqueous solution carriers are high which accounts for its higher activity. Additionally,
both under UV and visible light irradiation [107]. Fe3+ doping the induced oxygen vacancies in Mn2+–TiO2 samples can efficiently
effectively improved the photocatalytic activity under both UV light capture the photo generated electrons thereby reducing the recom-
irradiation and visible light irradiation with an optimal doping bination rate. These oxygen vacancies enhance the process of
concentration of 0.1 and 0.2% respectively. The results were explained adsorption of oxygen and increase the interaction between photoin-
on the basis that appropriate Fe3+ doping can efficiently separate the duced electrons of oxygen vacancies and adsorbed oxygen favoring
photogenerated electrons and holes and consequently improves the the photo catalytic reactions which increases the adsorption of dye
photocatalytic activity, however, no product formation was reported molecules [111].
in this work. In the presence of visible light irradiation, Fe3+ doping TiO2 was doped with Mn2+ and its photocatalytic activity was
introduces a new energy level (Fe3+/Fe4+) above the valence band, studied under solar light for the degradation of Methyl Orange and
resulting in the enhancement of light absorption in visible light Amaranth azo dye [60,112]. Mn2+–TiO2 (0.06%) showed highest
regions and the improvement of photocatalytic activity. photocatalytic activity due to the synergetic effect observed in the
In another study using the iron modified TiO2, 0.1 wt.% was found mixed phase and also due to its unique half filled electronic
to be the optimum dopant concentration for the maximum removal of configuration.
Reactive Brilliant X-3B azo dye [108]. It was found that if excessive Methyl Orange (azo dye) has been degraded by using Mn-doped
iron was deposited on TiO2, more Fe(OH)2+ would be formed. The TiO2/SiO2 matrix [113]. It was shown that the photocatalytic activity
light energy falling on the surface of TiO2 decreased due to greater of TiO2/SiO2 enhanced after manganese doping. The photocatalytic
absorption of the incidence light in the range of 290–400 nm by Fe activity of Mn-doped TiO2/SiO2 increased with Mn content and then
(OH)2+. As a result, the removal efficiency of Reactive Brilliant X-3B diminished when the Mn-doped content was increased to 0.5%. When
was found to decrease. Mn-doped content reached 0.8%, the photocatalytic reactivity was
similar to that of TiO2/SiO2. Compared to TiO2/SiO2, the high
5.4. Doping with Mn ions photocatalytic activity of Mn-doped TiO2/SiO2 is due to the variable
valences of manganese. Since Mn2+ and Mn3+ coexist on the surface
Photodegradation on Mn-doped TiO2 surface can be represented of Mn/TiO2/SiO2 photocatalyst, metal ions are the acceptors of
by the following mechanism: electrons, and Mn3+ can trap electrons in TiO2 conduction band.
Thus Mn3+ should trap electrons and prohibit electron–hole
þ −
TiO2 þ hν→hvb þ ecb ð42Þ recombination. Moreover, the electrons trapped in Mn3+ site are
subsequently transferred to the adsorbed O2, and decrease the
4þ − 3þ
Ti þ ecb → Ti ð43Þ recombination rate of the electron–hole pair.
2− − −
O þ hν→O þ e ð44Þ
5.5. Doping with Zn ions
2+
In the presence of Mn ion, the following reactions are possible
[109]: The ionic radii of Zn2+ (0.74 Å) is similar to that of host Ti4+
2þ − þ
(0.75 Å) ions. Hence this ion can easily substitute Ti4+ ion in TiO2
Mn þ ecb →Mn ð45Þ lattice without distorting the crystal structure, thereby stabilizing the
þ 2þ •−
anatase phase over a range of dopant concentrations.
Mn þ O2 ðadsÞ→Mn þ O2 ð46Þ The presence of Zn2+ as a dopant can act as follows [91]:
2þ þ 3þ
Mn þ hvb →Mn ð47Þ
2þ − þ
Zn þ e →Zn ð55Þ
3þ − 2þ •
Mn þ OH →Mn þ OH ð48Þ þ 2þ −•
Zn þ O2 ðadsÞ→Zn þ O2 ð56Þ
Alternatively, the Mn 3+ can also trap conduction band electron or þ þ 2þ
Mn+ can trap valence band hole to retain half filled electronic Zn þ h →Zn ð57Þ
structure of Mn2+ 2þ þ 3þ
Zn þ h →Zn ð58Þ
þ þ 2þ
Mn þ hvb →Mn ð49Þ −
þ• OH
3þ 2þ
Zn þ OH →Zn ð59Þ
3þ − 2þ
Mn þ ecb →Mn ð50Þ 3þ − 2þ
Zn þ e →Zn ð60Þ
2þ 3þ þ 4þ
Mn þ Ti →Mn þ Ti ðelectron trapÞ ð51Þ
The inclusion of Zn2+ ions as dopants in TiO2 can thus generate O−•
2

2þ − 3þ 2−
and •OH radicals which can then take part in subsequent reactions to
Mn þ O →Mn þ O ðhole trapÞ ð52Þ effectively increase the dye degradation.
22 M.A. Rauf et al. / Desalination 276 (2011) 13–27
The 0.1% Zn–TiO2 nanocatalysts exhibited the best photodegradation
of Acid Orange 52 [41]. The appearance of an optimal dopant
concentration was figured out to be a result of the delicate balance of
an increase in trap sites leading to efficient trapping and fewer trapped
carriers leading to longer lifetimes for interfacial charge transfer.
The photocatalytic degradation of Congo Red (CR) has also been
reported in the presence of Zn doped TiO2 [114]. It was found that Zn2+–
TiO2 showed 100% dye degradation of Congo Red when Zn2+ was 0.06%.
The higher activity in the case of Zn2+ (0.06%) –TiO2 was attributed to
the generation of excess hydroxyl radicals due to the prolonged
separation of charge carriers. At this optimum concentration of Zn2+,
the surface barrier becomes higher and the space charge region gets
extended, leading to the efficient separation of electrons and holes.
Although literature findings on the degradation of azo dyes using
zinc doped titania are limited, there are quite a few studies on using
the ZnO/TiO2 composites as potential catalysts for degrading azo dyes.
The coupling of different semiconductor oxides seems useful in order
to achieve a more efficient electron–hole pair separation under
irradiation and, consequently, a higher photocatalytic activity.
In the TiO2/ZnO composite, the electron transfer occurs from the
conduction band of light-activated ZnO to the conduction band of
light-activated TiO2 and, conversely, hole transfer can take place from
the valence band of TiO2 to the valence band of ZnO [115]. This
efficient charge separation increases the photocatalytic activity of
TiO2/ZnO composite. The nanosized TiO2/ZnO powders were found to
display high photocatalytic activity towards the decolorization of
Basic Blue 41(azo dye) in water under solar irradiation and a Ti/Zn
molar ratio of 1:1, and approximately 100% color removal was
achieved in 1 h [116]. Likewise Acid Red 14 and Methyl Orange (both
azo dyes) were effectively degraded using a nanosized powder of
TiO2/ZnO composite [117,118].
Treatment of Acid Orange 7 (azo dye) with UV/ZnO, UV/[(TiO2 +
ZnO)] led to complete decolorization [119]. The catalytic effect of
UV/(TiO2 + ZnO) was found to be higher than UV/ ZnO and UV/TiO2.
5.6. Doping with V ions
Most catalysts based on vanadium oxide consist of a vanadium oxide
phase deposited on the surface of an oxide support, such as SiO2, Al2O3,
TiO2 and ZrO2. Supporting a metal oxide on the surface of another oxide
improves the catalytic activity of the active metal oxide phase due to a
gain in surface area and mechanical strength. Supported vanadium
oxides show chemical and electronic properties, which are entirely
different from those found for unsupported vanadium pentoxide
(V2O5), in aqueous media and in the solid state. The most important
oxidation states in aqueous solution are V5+ and V4+. The specific
vanadium oxide species that can exist depend on the solution pH and
the vanadium oxide concentration.
V5+ is known to undergo the following mechanism [114]:
5þ − 4þ
V þ e →V ð61Þ
4þ 5þ •−
V þ O2 ðadsÞ→V þ O2 ð62Þ
5þ þ 6þ
V þ h →V ð63Þ
V
6þ
þ OH →V
− 5þ
þ OH
•
ð64Þ
5þ 4þ •
V þ dyeðadsÞ→V þ dye ð65Þ
3þ 4þ •−
V þ O2 ðadsÞ→V þ O2 ð66Þ
The V4+ traps holes and electron and forms V5+ and V3+
respectively [120]. Subsequently, the trapped electrons and holes
are released and migrate to the surface of TiO2. By accepting an
electron, the adsorbed O2 on the surface of TiO2 is reduced to O•2−,
while surface hydroxyl group translates into hydroxyl radical (•OH) by
accepting a hole. Both O•2− and •OH can further degrade the dye
molecule. As a result, the introduction of appropriate amount of V4+
ions in TiO2 lattice can restrain the recombination rate of photo-
generated electrons and holes, enhancing the photocatalytic activity
of TiO2.
In the case of vanadium doped catalyst, it was found that Congo
Red degraded to almost 53% in the presence of V5+–TiO2 against to
only 6% in neat TiO2 [114]. Vanadium doped TiO2 nanocrystalline was
prepared and used to degrade Methyl Orange (azo dye) in solution
[121]. The dye degraded 55% more by using the doped catalyst as
compared to the neat TiO2. The photocatalytic activity of vanadium
doped TiO2 film was evaluated through degradation of Reactive
Brilliant Red(azo dye) under visible light, and was compared to pure
titania [122]. Results showed that the photocatalytic degradation of
the dye was 60% in the case of doped catalyst as to only 7% in pure TiO2
film. This was explained in terms of narrowing the band gap which
causes the red shift of the absorption band edge by vanadium doping
as shown in other studies [123,124].
5.7. Doping with Ag ions
Molecular oxygen is the only electron accepting species in
undoped titania. However, in Ag doped titania, two additional
electron accepting species are introduced, namely silver ions (Ag+)
and metallic silver (Ag0). Since the Fermi level of titania is higher, the
electrons would migrate from the titania film to the metallic Ag
particles resulting in a space charge layer at the boundaries between
Ag and titania. The electric field would eventually drive the electrons
to the interior and abstracts holes to the interfacial region of the
titania film. In this situation, silver particles act as electron traps [125].
This results in the efficiency of the charge carrier separation thereby
resulting in the inhibition of recombination.
The most significant advantage of the Ag doping process is
improving the charge separation efficiency of the titania. Due to
improved separation efficiency, the lifetime of charge carriers will
increase and higher number of holes will reach the interfacial region
of the titania film and produce more superactive radicals such as HO•2,
OH• and H2O2 [125].
Another explanation for the role of metal silver on the catalyst
surface is that the noble metal improves the quantum yields by
accelerating the removal and the transfer of electrons from catalyst to
molecular oxygen [126]. Therefore, molecular oxygen can trap
photogenerated electrons to form superoxide radicals and conse-
quently enhance the oxidation of organic molecule such as Methyl
Orange (azo dye) by as much as 30% [127].
In another study, the photocatalytic degradation of Direct Red 23
(azo dye) by nano-Ag doped TiO2 has also been investigated [128].
Photodeposition of 1.5% Ag on the surface of TiO2 enhanced its
photoactivity in Direct Red 23 degradation. The higher photoactivity
of Ag–TiO2 than TiO2 under UV irradiation was ascribed to the effect of
silver deposits acting as electron traps on the Ag–TiO2 surface.
Likewise, Methyl Red (azo dye) was found to degrade by 99% in the
presence of Ag doped TiO2 as against to 85% in neat TiO2 [129].
Methyl Orange (azo dye) was subjected to photodegradation in
the presence of Ag/TiO2 [130].The results showed that the final
concentration of the dye solution in the presence of Ag/TiO2 powder
was much less than that with TiO2. This was explained on the basis
that Ag on the surface of TiO2 acts as photogenerated electron trap,
which accelerates the rate of electron transfer to molecular oxygen,
and thus inhibits the recombination of photogenerated electrons and
holes [131]. On one hand, photogenerated holes produce •OH radicals
which oxidize the dye molecular adsorbed on the surface of Ag/TiO2 ,
while on the other hand, photogenerated electrons accumulate on the
Ag particles by conduction band, and react with the sorbed oxygen
molecular to produce free oxygen radicals, such as O•2−, HO•2− , •OH,
etc. [132]. Moreover, the decrease of the band-gap energy contributed
 M.A. Rauf et al. / Desalination 276 (2011) 13–27 23

2-hydroxy-1,4- phenol
naphthoquinone O
OH

OH

maleic acid
NaO3S
O
HO2C CO2H
phthalide O benzoic acid
CO2H

O
N
N
2-hydroxy
propanoic acid
OH
2-naphthol
2,5-cyclohexadiene
OH CO2H
-1,4-dione
O HO

Acid Orange 2-formyl-benzoic

acid

O
O

CO2H

Fig. 6. Degradation mechanism proposed on the basis of GC/MS analysis during photo degradation of Acid Orange 7 [66].

by the Ag loaded on the TiO2 induces red shift of the photo-absorption
band, and expands the responding photo-spectra to the longer spectra
region.
5.8. Doping with W ions
Complementary to metal/TiO2 photocatalysts, TiO2 has been
coupled with other semiconductors such as WO3 for the degradation
of azo dyes [66,133–137]. A combination of WO3/TiO2 can induce
effective charge separation by trapping photogenerated electrons.
Moreover, the addition of WO3 to TiO2 will increase the Lewis surface
acidity of the catalyst. Thus the WO3/TiO2 particles can adsorb more
•
OH or H2O on the surface and generate a greater amount of •OH
radicals. At the same time, WOx/TiO2 particles have a higher
adsorption affinity toward the reactant molecules [133]. In W/Ti
catalysts, the presence of tungsten in the TiO2 lattice produces local

benzene sulfonic N-(Dimethylamino) phenol

acid
N(CH3)2 SO3H N(CH3)2

(CH3)2N NH2

OH

N
N
NH2 NHCH3

HO3S NH2

SO3Na
aniline N-methylaniline
Methyl orange

Fig. 7. Degradation mechanism proposed on the basis of GC/MS analysis during photo degradation of Methyl Orange [66].
24 M.A. Rauf et al. / Desalination 276 (2011) 13–27

levels in the forbidden band inducing the formation of recombination The above oxidation reduction reactions are in competition with
centers for e−–h+ pairs [134]. The recombination occurs according to the redox processes that could occur at the solid/liquid interface and
the following reactions could play a significant role for the lighter doped samples, negatively
− 6þ 5þ
influencing their photoactivity.
eðTiO2Þcb þ WðbulkÞ →WðbulkÞ ð67Þ By increasing the tungsten content, tungsten oxide species with an
þ 5þ 6þ octahedrally coordination could be produced on the particle surfaces,
hðTiO2Þcb þ WðbulkÞ →WðbulkÞ ð68Þ some interface acceptor states mainly formed by tungsten species can

NH2 NH2

N N N N

(M=700.0)
SO3Na SO3Na
OH
NH2 NH2

N N N N + SO42- + Na+

OH

NO2 NO2

N N N N

(detected (M+H) = 553.9)

OH
H NO2 NO2
C +
O N N N N

(detected (M+H) = 331.4)

OH

OH NO2
C
O N N N N

(detected (M+H) = 347.4)

-COO- OH

NO2
HO
N N N N + CO2

OH
NO2
HO + NO2- + NH4+
NO2 O2N NO2 O2N

NO3-, N2
OH

OH

Cn acids CH3COOH + HCOOH CO2 + H2O

HO
(n<6)
OH

Fig. 8. Photodegradation pathway of CR in the presence of the PW11/TiO2 film [137].

 M.A. Rauf et al. / Desalination 276 (2011) 13–27
be produced on the surface and for higher amounts the so-called
isotypic heterojunctions can appear [133]. The presence of interfer-
ence acceptor states and/or localized heterojunctions allows electron
transfer from the conduction band of TiO2 to W5+(surface) and/or to the
conduction band of WO3 islands. Consequently, the separation of the
photoproduced pairs would improve and the rate of electron transfer
to O2 (which is used as a bubbling gas) would increase.
Tungsten (4%) doped titania was used to photodegrade Acid
Orange 7 and Methyl Orange dyes (azo dyes) and the degradation
followed the pseudo first-order kinetics with a degradation efficiency
of 80% in 300 min [66]. The degraded products were analyzed by using
the liquid chromatography tandem mass spectrometry and degrada-
tion mechanism was proposed as shown in Figs. 6 and 7.
Another example of the photocatalytic degradation of an azo dye
using a tungsten/ titanium oxide composite film was reported by Li et
al. [137]. Intermediates and final products generated during the Congo
Red degradation were analyzed by mass spectrometry and ion
chromatography. Fig. 8 shows the successive degradative pathway
as a result of OH radical attack on the diazo dye compound. The
degradation events included cleavage of C–S bonds, aromatic ring
opening, cleavage of –N=N– double bonds, cleavage of various C–N
and C–C bonds in addition to the decarboxylation.
6. Conclusion
Photodegradation of azo dyes using transition metal doped TiO2 has
been found to be very effective for the remedial of dye-contaminated
solutions. The basis of the reaction is a photoredox process. An
important role in this process is played by molecular oxygen and
other active species, such as O•2−, HO•2, H2O2, •OH and HO•2−, which are
generated in a sequence of reactions. They make the photocatalytic
processes more efficient resulting in enhanced dye degradation via the
formation of intermediates such as aromatic amines, phenolic com-
pounds and several organic acids.
Although azo dyes are one of the most commonly used class of
dyes in industrial applications, limited literature is available on their
remediation from effluents using TiO2 doped with transition metals.
Different papers citing the use of the doped semiconductors seems to
have no connectivity between them as to the amount of catalyst,
reactor set up, reaction time and type, concentration of substrates, and
intensity of UV/Vis radiation. It might be critical at this point to
standardize the conditions of reactions instead of reporting data on
different azo dyes. Another limitation which was observed during this
survey was the lack of suggestive degradation mechanisms of various
azo dyes. This aspect should not be overlooked while reporting any
future work. A demonstrated ability to use transition metal doped
titanium oxide systems at a pilot scale for effluent purification
processes would certainly benefit the environment.
References
[1] S. Parsons, Advanced Oxidation Processes for Water and Wastewater, IWA
Publishing, London, UK, 2004.
[2] M. Zubair Alam, S. Ahmad, A. Malik, M. Ahmad, Mutagenicity and genotoxicity of
tannery effluents used for irrigation at Kanpur, India, Ecotoxicology and
Environmental Safety 73 (2010) 1620–1628.
[3] C. O'Neill, A. Lopez, S. Esteves, F.R. Hawkes, D.L. Hawkes, S. Wilcox, Azo-dye
degradation in an anaerobic-aerobic treatment system operating on simulated
textile effluent, Applied Microbiology and Biotechnology 53 (1999) 249–254.
[4] N. Nasuha, B.H. Hameed, A.T.M. Din, Rejected tea as a potential low-cost
adsorbent for the removal of methylene blue, Journal of Hazardous Materials 175
(2010) 126–132.
[5] M.J. Martin, A. Artola, M.D. Balaguer, M. Rigola, Activated carbons developed
from surplus sewage sludge for the removal of dyes from dilute aqueous
solutions, Chemical Engineering Journal 94 (2003) 231–239.
[6] M.A. Rauf, S.M. Qadri, S. Ashraf, K.M. Al-Mansoori, Adsorption studies of
Toluidine Blue from aqueous solutions onto gypsum, Chemical Engineering
Journal 150 (2009) 90–95.
25
[7] A.L. Ahmad, S.W. Puasa, Reactive dyes decolourization from an aqueous solution
by combined coagulation/micellar-enhanced ultrafiltration process, Chemical
Engineering Journal 132 (2007) 257–265.
[8] M. Riera-Torres, C. Gutiérrez-Bouzán, M. Crespi, Combination of coagulation–
flocculation and nanofiltration techniques for dye removal and water reuse in
textile effluents, Desalination 252 (2010) 53–59.
[9] K. Shakir, A.F. Elkafrawy, H.F. Ghoneimy, S.G. Elrab Beheir, M. Refaat, Removal of
rhodamine B (a basic dye) and thoron (an acidic dye) from dilute aqueous solutions
and wastewater simulants by ion flotation, Water Research 44 (2010) 1449–1461.
[10] S. Zodi, O. Potier, F. Lapicque, J.-P. Leclerc, Treatment of the industrial
wastewaters by electrocoagulation: optimization of coupled electrochemical
and sedimentation processes, Desalination 261 (2010) 186–190.
[11] M.A. Rauf, S.S. Ashraf, Application of Advanced Oxidation Processes (AOP) to dye
degradation—an overview, in: Arnold R. Lang (Ed.), Dyes and Pigments: New
Research, Nova Science Publishers, Inc, 2009.
[12] T.M. Elmorsi, Y.M. Riyad, Z.H. Mohamed, H.M.H. Abd El Bary, Decolorization of
Mordant red 73 azo dye in water using H2O2/UV and photo-Fenton treatment,
Journal of Hazardous Materials 174 (2010) 352–358.
[13] S. Gül, Ö. Özcan-YildIrIm, Degradation of Reactive Red 194 and Reactive Yellow
145 azo dyes by O3 and H2O2/UV-C processes, Chemical Engineering Journal 155
(2009) 684–690.
[14] F.H. AlHamedi, M.A. Rauf, S.S. Ashraf, Degradation studies of Rhodamine B in the
presence of UV/H2O2, Desalination 239 (2009) 159–166.
[15] A. Masarwa, S. Rachmilovich-Calis, N. Meyerstein, D. Meyerstein, Oxidation of
organic substrates in aerated aqueous solutions by the Fenton reagent,
Coordination Chemistry Reviews 249 (2005) 1937–1943.
[16] E. Chamarro, A. Marco, S. Esplugas, Use of Fenton reagent to improve organic
chemical biodegradability, Water Research 35 (2001) 1047–1051.
[17] C. Bouasla, M.E.-H. Samar, F. Ismail, Degradation of methyl violet 6B dye by the
Fenton process, Desalination 254 (2010) 35–41.
[18] J.M. Monteagudo, A. Durán, I.S. Martín, M. Aguirre, Catalytic degradation of
Orange II in a ferrioxalate-assisted photo-Fenton process using a combined UV-
A/C-solar pilot-plant system, Applied Catalysis B: Environmental 95 (2010)
120–129.
[19] A.K. Abdessalem, N. Bellakhal, N. Oturan, M. Dachraoui, M.A. Oturan, Treatment
of a mixture of three pesticides by photo- and electro-Fenton processes,
Desalination 250 (2010) 450–455.
[20] N. Modirshahla, M.A. Behnajady, F. Ghanbary, Decolorization and mineralization
of C.I. Acid Yellow 23 by Fenton and photo-Fenton processes, Dyes and Pigments
73 (2007) 305–310.
[21] A.R. Tehrani-Bagha, N.M. Mahmoodi, F.M. Menger, Degradation of a persistent
organic dye from colored textile wastewater by ozonation, Desalination 260
(2010) 34–38.
[22] S. Song, H. Ying, Z. He, J. Chen, Mechanism of decolorization and degradation of CI
Direct Red 23 by ozonation combined with sonolysis, Chemosphere 66 (2007)
1782–1788.
[23] H. Ghodbane, O. Hamdaoui, Intensification of sonochemical decolorization of
anthraquinonic dye Acid Blue 25 using carbon tetrachloride, Ultrasonics
Sonochemistry 16 (2009) 455–461.
[24] S. Merouani, O. Hamdaoui, F. Saoudi, M. Chiha, Sonochemical degradation of
Rhodamine B in aqueous phase: effects of additives, Chemical Engineering
Journal 158 (2010) 550–557.
[25] X. Wang, Z. Yao, J. Wang, W. Guo, G. Li, Degradation of reactive brilliant red in
aqueous solution by ultrasonic cavitation, Ultrasonics Sonochemistry 15 (2008)
43–48.
[26] M.A. Rauf, M.A. Meetani, A. Khaleel, A. Ahmed, Photocatalytic degradation of
Methylene Blue using a mixed catalyst and product analysis by LC/MS, Chemical
Engineering Journal 157 (2010) 373–378.
[27] R. Xu, J. Li, J. Wang, X. Wang, B. Liu, B. Wang, X. Luan, X. Zhang, Photocatalytic
degradation of organic dyes under solar light irradiation combined with Er3+:
YAlO3/Fe- and Co-doped TiO2 coated composites, Solar Energy Materials and
Solar Cells 94 (2010) 1157–1165.
[28] W. Zhang, J. Zhang, Z. Chen, T. Wang, Photocatalytic degradation of methylene
blue by ZnGa2O4 thin films, Catalysis Communications 10 (2009) 1781–1785.
[29] M.H. Habibi, N. Talebian, Photocatalytic degradation of an azo dye X6G in water:
a comparative study using nanostructured indium tin oxide and titanium oxide
thin films, Dyes and Pigments 73 (2007) 186–194.
[30] S.B. Bukallah, M.A. Rauf, S.S. Ashraf, Photocatalytic decoloration of Coomassie
Brilliant Blue with titanium oxide, Dyes and Pigments 72 (2007) 353–356.
[31] L. Ayed, K. Chaieb, A. Cheref, A. Bakhrouf, Biodegradation and decolorization of
triphenylmethane dyes by Staphylococcus epidermidis, Desalination 260 (2010)
137–146.
[32] X. Zhao, I.R. Hardin, H.-M. Hwang, Biodegradation of a model azo disperse dye by
the white rot fungus Pleurotus ostreatus, International Biodeterioration &
Biodegradation 57 (2006) 1–6.
[33] Ö. ÇInar, S. Yasar, M. Kertmen, K. Demiröz, N.Ö. Yigit, M. Kitis, Effect of cycle time
on biodegradation of azo dye in sequencing batch reactor, Process Safety and
Environmental Protection 86 (2008) 455–460.
[34] A. Vahdat, S.H. Bahrami, M. Arami, A. Motahari, Decomposition and decoloration
of a direct dye by electron beam radiation, Radiation Physics and Chemistry 79
(2010) 33–35.
[35] K.A. Mohamed, A.A. Basfar, A.A. Al-Shahrani, Gamma-ray induced degradation of
diazinon and atrazine in natural groundwaters, Journal of Hazardous Materials
166 (2009) 810–814.
[36] Y.-P. Chen, S.-Y. Liu, H.-Q. Yu, H. Yin, Q.-R. Li, Radiation-induced degradation of
methyl orange in aqueous solutions, Chemosphere 72 (2008) 532–536.
26 M.A. Rauf et al. / Desalination 276 (2011) 13–27
[37] K. Dajka, E. Takács, D. Solpan, L. Wojnárovits, O. Güven, High-energy irradiation
treatment of aqueous solutions of C.I. Reactive Black 5 azo dye: pulse radiolysis
experiments, Radiation Physics and Chemistry 67 (2003) 535–538.
[38] L. Andronic, A. Enesca, C. Vladuta, A. Duta, Photocatalytic activity of cadmium
doped TiO2 films for photocatalytic degradation of dyes, Chemical Engineering
Journal 152 (2009) 64–71.
[39] A. Fujishima, X. Zhang, D.A. Tryk, TiO2 photocatalysis and related surface
phenomena, Surface Science Reports 63 (2008) 515–582.
[40] M.M. Mohamed, M.M. Al-Esaimi, Characterization, adsorption and photocataly-
tic activity of vanadium-doped TiO2 and sulfated TiO2 (rutile) catalysts:
degradation of methylene blue dye, Journal of Molecular Catalysis A: Chemical
255 (2006) 53–61.
[41] C. Chen, Z. Wang, S. Ruan, B. Zou, M. Zhao, F. Wu, Photocatalytic degradation of C.I.
Acid Orange 52 in the presence of Zn-doped TiO2 prepared by a stearic acid gel
method, Dyes and Pigments 77 (2008) 204–209.
[42] Z.M. El-Bahy, A.A. Ismail, R.M. Mohamed, Enhancement of titania by doping rare
earth for photodegradation of organic dye (Direct Blue), Journal of Hazardous
Materials 166 (2009) 138–143.
[43] U. Diebold, The surface science of titanium dioxide, Surface Science Reports 48
(2003) 53–229.
[44] Y.B. Xie, X.Z. Li, Interactive oxidation of photoelectrocatalysis and electro-Fenton
for azo dye degradation using TiO2–Ti mesh and reticulated vitreous carbon
electrodes, Materials Chemistry and Physics 95 (2006) 39–50.
[45] M. Saquib, M. Abu Tariq, M. Faisal, M. Muneer, Photocatalytic degradation of two
selected dye derivatives in aqueous suspensions of titanium dioxide, Desalina-
tion 219 (2008) 301–311.
[46] F.H. Abdullah, M.A. Rauf, S.S. Ashraf, Kinetics and optimization of photolytic
decoloration of carmine by UV/H2O2, Dyes and Pigments 75 (2007) 194–198.
[47] M.A. Meetani, S.M. Hisaindee, F. Abdullah, S.S. Ashraf, M.A. Rauf, Liquid
chromatography tandem mass spectrometry analysis of photodegradation of a
diazo compound: a mechanistic study, Chemosphere 80 (2010) 422–427.
[48] A. Bianco Prevot, D. Fabbri, E. Pramauro, C. Baiocchi, C. Medana, High-
performance liquid chromatography coupled to ultraviolet diode array detection
and electrospray ionization mass spectrometry for the analysis of intermediates
produced in the initial steps of the photocatalytic degradation of sulfonated azo
dyes, Journal of Chromatography. A 1202 (2008) 145–154.
[49] J.-M. Herrmann, C. Guillard, J. Disdier, C. Lehaut, S. Malato, J. Blanco, New
industrial titania photocatalysts for the solar detoxification of water containing
various pollutants, Applied Catalysis B: Environmental 35 (2002) 281–294.
[50] S.G. Huling, R.G. Arnold, R.A. Sierka, P.K. Jones, D.D. Fine, Contaminant adsorption
and oxidation via Fenton reaction, Journal of Environmental Engineering 126
(2000) 595–600.
[51] D. Solpan, O. Güven, E. Takács, L. Wojnárovits, K. Dajka, High-energy irradiation
treatment of aqueous solutions of azo dyes: steady-state gamma radiolysis
experiments, Radiation Physics and Chemistry 67 (2003) 531–534.
[52] C. Galindo, P. Jacques, A. Kalt, Photochemical and photocatalytic degradation of
an indigoid dye: a case study of acid blue 74 (AB74), Journal of Photochemistry
and Photobiology A: Chemistry 141 (2001) 47–56.
[53] M.A. Rauf, S. Ashraf, S.N. Alhadrami, Photolytic oxidation of Coomassie Brilliant
Blue with H2O2, Dyes and Pigments 66 (2005) 197–200.
[54] B. Yue, Y. Zhou, J. Xu, Z. Wu, X. Zhang, Y. Zou, S. Jin, Photocatalytic degradation of
aqueous 4-chlorophenol by silica-immobilized polyoxometalates, Environmen-
tal Science & Technology 36 (2002) 1325–1329.
[55] C.-H. Wu, H.-W. Chang, J.-M. Chern, Basic dye decomposition kinetics in a
photocatalytic slurry reactor, Journal of Hazardous Materials 137 (2006) 336–343.
[56] J. Saien, A.R. Soleymani, Degradation and mineralization of Direct Blue 71 in a
circulating upflow reactor by UV/TiO2 process and employing a new method in
kinetic study, Journal of Hazardous Materials 144 (2007) 506–512.
[57] S. Mozia, Photocatalytic membrane reactors (PMRs) in water and wastewater
treatment. A review, Separation and Purification Technology 73 (2010) 71–91.
[58] A. Danion, J. Disdier, C. Guillard, N. Jaffrezic-Renault, Malic acid photocatalytic
degradation using a TiO2-coated optical fiber reactor, Journal of Photochemistry
and Photobiology A: Chemistry 190 (2007) 135–140.
[59] N.M. Mahmoodi, M. Arami, N.Y. Limaee, N.S. Tabrizi, Kinetics of heterogeneous
photocatalytic degradation of reactive dyes in an immobilized TiO2 photo-
catalytic reactor, Journal of Colloid and Interface Science 295 (2006) 159–164.
[60] E. Forgacs, T. Cserháti, G. Oros, Removal of synthetic dyes from wastewaters: a
review, Environment International 30 (2004) 953–971.
[61] A. Fujishima, T.N. Rao, D.A. Tryk, Titanium dioxide photocatalysis, Journal of
Photochemistry and Photobiology C: Photochemistry Reviews 1 (2000) 1–21.
[62] M. Stylidi, D.I. Kondarides, X.E. Verykios, Pathways of solar light-induced
photocatalytic degradation of azo dyes in aqueous TiO2 suspensions, Applied
Catalysis B: Environmental 40 (2003) 271–286.
[63] I.K. Konstantinou, T.A. Albanis, TiO2-assisted photocatalytic degradation of azo
dyes in aqueous solution: kinetic and mechanistic investigations: a review,
Applied Catalysis B: Environmental 49 (2004) 1–14.
[64] A.E.H. Machado, J.A. de Miranda, R.F. de Freitas, E.T.F.M. Duarte, L.F. Ferreira, Y.D.T.
Albuquerque, R. Ruggiero, C. Sattler, L. de Oliveira, Destruction of the organic
matter present in effluent from a cellulose and paper industry using photo-
catalysis, Journal of Photochemistry and Photobiology A: Chemistry 155 (2003)
231–241.
[65] C.G. da Silva, J.L. Faria, Photochemical and photocatalytic degradation of an azo
dye in aqueous solution by UV irradiation, Journal of Photochemistry and
Photobiology A: Chemistry 155 (2003) 133–143.
[66] A.K.L. Sajjad, S. Shamaila, B. Tian, F. Chen, J. Zhang, Comparative studies of
operational parameters of degradation of azo dyes in visible light by highly
efficient WOx/TiO2 photocatalyst, Journal of Hazardous Materials 177 (2010)
781–791.
[67] M. Pera-Titus, V. García-Molina, M.A. Baños, J. Giménez, S. Esplugas, Degradation
of chlorophenols by means of advanced oxidation processes: a general review,
Applied Catalysis B: Environmental 47 (2004) 219–256.
[68] M.N. Chong, B. Jin, C.W.K. Chow, C. Saint, Recent developments in photocatalytic
water treatment technology: a review, Water Research 44 (2010) 2997–3027.
[69] C.-C. Wang, C.-K. Lee, M.-D. Lyu, L.-C. Juang, Photocatalytic degradation of C.I.
Basic Violet 10 using TiO2 catalysts supported by Y zeolite: an investigation of
the effects of operational parameters, Dyes and Pigments 76 (2008) 817–824.
[70] J. Sun, L. Qiao, S. Sun, G. Wang, Photocatalytic degradation of Orange G on
nitrogen-doped TiO2 catalysts under visible light and sunlight irradiation,
Journal of Hazardous Materials 155 (2008) 312–319.
[71] H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard, J.-M. Herrmann,
Photocatalytic degradation of various types of dyes (Alizarin S, Crocein Orange G,
Methyl Red, Congo Red, Methylene Blue) in water by UV-irradiated titania,
Applied Catalysis B: Environmental 39 (2002) 75–90.
[72] W. Baran, A. Makowski, W. Wardas, The effect of UV radiation absorption of
cationic and anionic dye solutions on their photocatalytic degradation in the
presence TiO2, Dyes and Pigments 76 (2008) 226–230.
[73] V. Augugliaro, C. Baiocchi, A. Bianco Prevot, E. García-López, V. Loddo, S. Malato,
G. Marcí, L. Palmisano, M. Pazzi, E. Pramauro, Azo-dyes photocatalytic
degradation in aqueous suspension of TiO2 under solar irradiation, Chemosphere
49 (2002) 1223–1230.
[74] K. Soutsas, V. Karayannis, I. Poulios, A. Riga, K. Ntampegliotis, X. Spiliotis, G.
Papapolymerou, Decolorization and degradation of reactive azo dyes via
heterogeneous photocatalytic processes, Desalination 250 (2010) 345–350.
[75] M.A. Behnajady, N. Modirshahla, M. Shokri, Photodestruction of Acid Orange 7
(AO7) in aqueous solutions by UV/H2O2: influence of operational parameters,
Chemosphere 55 (2004) 129–134.
[76] M. Qamar, M. Saquib, M. Muneer, Photocatalytic degradation of two selected dye
derivatives, chromotrope 2B and amido black 10B, in aqueous suspensions of
titanium dioxide, Dyes and Pigments 65 (2005) 1–9.
[77] B. Zielinska, J. Grzechulska, B. Grzmil, A.W. Morawski, Photocatalytic degradation
of Reactive Black 5: a comparison between TiO2-Tytanpol A11 and TiO2-Degussa
P25 photocatalysts, Applied Catalysis B: Environmental 35 (2001) L1–L7.
[78] C. Guillard, H. Lachheb, A. Houas, M. Ksibi, E. Elaloui, J.-M. Herrmann, Influence of
chemical structure of dyes, of pH and of inorganic salts on their photocatalytic
degradation by TiO2 comparison of the efficiency of powder and supported TiO2,
Journal of Photochemistry and Photobiology A: Chemistry 158 (2003) 27–36.
[79] N. Daneshvar, D. Salari, A.R. Khataee, Photocatalytic degradation of azo dye acid
red 14 in water: investigation of the effect of operational parameters, Journal of
Photochemistry and Photobiology A: Chemistry 157 (2003) 111–116.
[80] J.-M. Herrmann, Photocatalysis fundamentals revisited to avoid several mis-
conceptions, Applied Catalysis B: Environmental 99 (2010) 461–468.
[81] T. Sauer, G. Cesconeto Neto, H.J. José, R.F.P.M. Moreira, Kinetics of photocatalytic
degradation of reactive dyes in a TiO2 slurry reactor, Journal of Photochemistry
and Photobiology A: Chemistry 149 (2002) 147–154.
[82] C.M. So, M.Y. Cheng, J.C. Yu, P.K. Wong, Degradation of azo dye Procion Red MX-
5B by photocatalytic oxidation, Chemosphere 46 (2002) 905–912.
[83] Y. Li, S. Sun, M. Ma, Y. Ouyang, W. Yan, Kinetic study and model of the
photocatalytic degradation of rhodamine B (RhB) by a TiO2-coated activated
carbon catalyst: effects of initial RhB content, light intensity and TiO2 content in
the catalyst, Chemical Engineering Journal 142 (2008) 147–155.
[84] M. Asiltürk, F. SayIlkan, E. Arpaç, Effect of Fe3+ ion doping to TiO2 on the
photocatalytic degradation of Malachite Green dye under UV and vis-irradiation,
Journal of Photochemistry and Photobiology A: Chemistry 203 (2009) 64–71.
[85] F. SayIlkan, M. Asiltürk, P. Tatar, N. Kiraz, S. Sener, E. Arpaç, H. SayIlkan,
Photocatalytic performance of Sn-doped TiO2 nanostructured thin films for
photocatalytic degradation of malachite green dye under UV and VIS-lights,
Materials Research Bulletin 43 (2008) 127–134.
[86] M. Bettinelli, V. Dallacasa, D. Falcomer, P. Fornasiero, V. Gombac, T. Montini, L.
Romanò, A. Speghini, Photocatalytic activity of TiO2 doped with boron and
vanadium, Journal of Hazardous Materials 146 (2007) 529–534.
[87] P. Bouras, E. Stathatos, P. Lianos, Pure versus metal-ion-doped nanocrystalline
titania for photocatalysis, Applied Catalysis B: Environmental 73 (2007) 51–59.
[88] T.K. Ghorai, D. Dhak, S.K. Biswas, S. Dalai, P. Pramanik, Photocatalytic oxidation of
organic dyes by nano-sized metal molybdate incorporated titanium dioxide
(MxMoxTi1-xO6) (M = Ni, Cu, Zn) photocatalysts, Journal of Molecular Catalysis
A: Chemical 273 (2007) 224–229.
[89] X. Yang, F. Ma, K. Li, Y. Guo, J. Hu, W. Li, M. Huo, Y. Guo, Mixed phase titania
nanocomposite codoped with metallic silver and vanadium oxide: new efficient
photocatalyst for dye degradation, Journal of Hazardous Materials 175 (2010)
429–438.
[90] S. Rehman, R. Ullah, A.M. Butt, N.D. Gohar, Strategies of making TiO2 and ZnO
visible light active, Journal of Hazardous Materials 170 (2009) 560–569.
[91] L.G. Devi, N. Kottam, B.N. Murthy, S.G. Kumar, Enhanced photocatalytic activity
of transition metal Mn2+, Ni2+ and Zn2+ doped polycrystalline titania for the
degradation of Aniline Blue under UV/solar light, Journal of Molecular Catalysis
A: Chemical 328 (2010) 44–52.
[92] S. Liu, J.-H. Yang, J.-H. Choy, Microporous SiO2–TiO2 nanosols pillared
montmorillonite for photocatalytic decomposition of methyl orange, Journal of
Photochemistry and Photobiology A: Chemistry 179 (2006) 75–80.
[93] M.A. Rauf, S.B. Bukallah, A. Hamadi, A. Sulaiman, F. Hammadi, The effect of
operational parameters on the photoinduced decoloration of dyes using a hybrid
catalyst V2O5–TiO2, Chemical Engineering Journal 129 (2007) 167–172.
 M.A. Rauf et al. / Desalination 276 (2011) 13–27
[94] F. Han, V.S.R. Kambala, M. Srinivasan, D. Rajarathnam, R. Naidu, Tailored titanium
dioxide photocatalysts for the degradation of organic dyes in wastewater
treatment: a review, Applied Catalysis A: General 359 (2009) 25–40.
[95] K. Wilke, H.D. Breuer, The influence of transition metal doping on the physical
and photocatalytic properties of titania, Journal of Photochemistry and
Photobiology A: Chemistry 121 (1999) 49–53.
[96] P. Ciesla, P. Kocot, P. Mytych, Z. Stasicka, Homogeneous photocatalysis by
transition metal complexes in the environment, Journal of Molecular Catalysis A:
Chemical 224 (2004) 17–33.
[97] P. Ciesla, A. Karocki, Z. Stasicka, Photoredox behaviour of the Cr–EDTA complex
and its environmental aspects, Journal of Photochemistry and Photobiology A:
Chemistry 162 (2004) 537–544.
[98] M. Al-Shamisi, M.Sc Thesis, Environmental Science, United Arab Emirates
University, Al-Ain, 2009.
[99] M.A. Meetani, M.A. Rauf, S. Hisaindee, A.A. Khaleel, A. AlZamly, A. Ahmed,
Mechanistic studies of photoinduced degradation of Orange G using LC/MS,
unpublished results.
[100] M. Karkmaz, E. Puzenat, C. Guillard, J.M. Herrmann, Photocatalytic degradation of
the alimentary azo dye amaranth: mineralization of the azo group to nitrogen,
Applied Catalysis B: Environmental 51 (2004) 183–194.
[101] E.B. Gracien, J. Shen, X. Sun, D. Liu, M. Li, S. Yao, J. Sun, Photocatalytic activity of
manganese, chromium and cobalt-doped anatase titanium dioxide nanoporous
electrodes produced by re-anodization method, Thin Solid Films 515 (2007)
5287–5297.
[102] R. Glazewski, G.M. Morrison, Copper(I)/copper(II) reactions in an urban river,
Science of The Total Environment 189–190 (1996) 327–333.
[103] D. Chen, A.K. Ray, Removal of toxic metal ions from wastewater by
semiconductor photocatalysis, Chemical Engineering Science 56 (2001)
1561–1570.
[104] K.V.S. Rao, B. Lavédrine, P. Boule, Influence of metallic species on TiO2 for the
photocatalytic degradation of dyes and dye intermediates, Journal of Photo-
chemistry and Photobiology A: Chemistry 154 (2003) 189–193.
[105] R.S.K. Wong, J. Feng, X. Hu, P.L. Yue, Discoloration and mineralization of non-
biodegradable azo dye Orange II by copper-doped TiO2 nanocatalysts, Journal of
Environmental Science and Health A 39 (2004) 2583–2595.
[106] N. Helaïli, Y. Bessekhouad, A. Bouguelia, M. Trari, Visible light degradation of
Orange II using xCuyO2/TiO2 heterojunctions, Journal of Hazardous Materials 168
(2009) 484–492.
[107] T. Tong, J. Zhang, B. Tian, F. Chen, D. He, Preparation of Fe3+-doped TiO2
catalysts by controlled hydrolysis of titanium alkoxide and study on their
photocatalytic activity for methyl orange degradation, Journal of Hazardous
Materials 155 (2008) 572–579.
[108] X.-H. Qi, Z.-H. Wang, Y.-Y. Zhuang, Y. Yu, J.-l. Li, Study on the photocatalysis
performance and degradation kinetics of X-3B over modified titanium dioxide,
Journal of Hazardous Materials 118 (2005) 219–225.
[109] S.D. Sharma, K.K. Saini, C. Kant, C.P. Sharma, S.C. Jain, Photodegradation of dye
pollutant under UV light by nano-catalyst doped titania thin films, Applied
Catalysis B: Environmental 84 (2008) 233–240.
[110] C.-y. Wang, C. Bottcher, D.W. Bahnemann, J.K. Dohrmann, A comparative study of
nanometer sized Fe(III)-doped TiO2 photocatalysts: synthesis, characterization
and activity, Journal of Materials Chemistry 13 (2003) 2322–2329.
[111] L.G. Devi, S.G. Kumar, B.N. Murthy, N. Kottam, Influence of Mn2+ and Mo6+
dopants on the phase transformations of TiO2 lattice and its photo catalytic
activity under solar illumination, Catalysis Communications 10 (2009) 794–798.
[112] Y. Mu, H.-Q. Yu, J.-C. Zheng, S.-J. Zhang, TiO2-mediated photocatalytic
degradation of Orange II with the presence of Mn2+ in solution, Journal of
Photochemistry and Photobiology A: Chemistry 163 (2004) 311–316.
[113] Y. Xu, B. Lei, L. Guo, W. Zhou, Y. Liu, Preparation, characterization and
photocatalytic activity of manganese doped TiO2 immobilized on silica gel,
Journal of Hazardous Materials 160 (2008) 78–82.
[114] L.G. Devi, B.N. Murthy, S.G. Kumar, Photocatalytic activity of TiO2 doped with
Zn2+ and V5+ transition metal ions: Influence of crystallite size and dopant
electronic configuration on photocatalytic activity, Materials Science and
Engineering: B 166 (2010) 1–6.
[115] V. Sukharev, R. Kershaw, Concerning the role of oxygen in photocatalytic
decomposition of salicylic acid in water, Journal of Photochemistry and
Photobiology A: Chemistry 98 (1996) 165–169.
27
[116] Y. Jiang, Y. Sun, H. Liu, F. Zhu, H. Yin, Solar photocatalytic decolorization of C.I.
Basic Blue 41 in an aqueous suspension of TiO2–ZnO, Dyes and Pigments 78
(2008) 77–83.
[117] S.K. Asl, S.K. Sadrnezhaad, M.K. rad, The seeding effect on the microstructure and
photocatalytic properties of ZnO nano powders, Materials Letters 64 (2010)
1935–1938.
[118] D.L. Liao, C.A. Badour, B.Q. Liao, Preparation of nanosized TiO2/ZnO composite
catalyst and its photocatalytic activity for degradation of methyl orange, Journal
of Photochemistry and Photobiology A: Chemistry 194 (2008) 11–19.
[119] W.A. Sadik, Decolourization of an azo dye by heterogeneous photocatalysis,
Process Safety and Environmental Protection 85 (2007) 515–520.
[120] B. Tian, C. Li, F. Gu, H. Jiang, Y. Hu, J. Zhang, Flame sprayed V-doped TiO2
nanoparticles with enhanced photocatalytic activity under visible light irradi-
ation, Chemical Engineering Journal 151 (2009) 220–227.
[121] H. Li, G. Zhao, Z. Chen, G. Han, B. Song, Low temperature synthesis of visible light-
driven vanadium doped titania photocatalyst, Journal of Colloid and Interface
Science 344 (2010) 247–250.
[122] J. Xu, Y. Ao, M. Chen, D. Fu, C. Yuan, Photocatalytic activity of vanadium-doped
titania-activated carbon composite film under visible light, Thin Solid Films 518
(2010) 4170–4174.
[123] J.C.S. Wu, C.-H. Chen, A visible-light response vanadium-doped titania
nanocatalyst by sol-gel method, Journal of Photochemistry and Photobiology
A: Chemistry 163 (2004) 509–515.
[124] D. Masih, H. Yoshitake, Y. Izumi, Photo-oxidation of ethanol on mesoporous
vanadium–titanium oxide catalysts and the relation to vanadium(IV) and (V)
sites, Applied Catalysis A: General 325 (2007) 276–282.
[125] C. He, Y. Yu, X. Hu, A. Larbot, Influence of silver doping on the photocatalytic
activity of titania films, Applied Surface Science 200 (2002) 239–247.
[126] H. Gerischer, A. Heller, Photocatalytic oxidation of organic molecules at TiO2
particles by sunlight in aerated water, 1992.
[127] A. Alem, H. Sarpoolaky, The effect of silver doping on photocatalytic properties of
titania multilayer membranes, Solid State Sciences 12 (2010) 1469–1472.
[128] N. Sobana, K. Selvam, M. Swaminathan, Optimization of photocatalytic
degradation conditions of Direct Red 23 using nano-Ag doped TiO2, Separation
and Purification Technology 62 (2008) 648–653.
[129] C. Sahoo, A.K. Gupta, A. Pal, Photocatalytic degradation of Methyl Red dye in
aqueous solutions under UV irradiation using Ag+doped TiO2, Desalination 181
(2005) 91–100.
[130] H. Wang, J. Niu, X. Long, Y. He, Sonophotocatalytic degradation of methyl orange
by nano-sized Ag/TiO2 particles in aqueous solutions, Ultrasonics Sonochemistry
15 (2008) 386–392.
[131] P.D. Cozzoli, E. Fanizza, R. Comparelli, M.L. Curri, A. Agostiano, D. Laub, Role of
metal nanoparticles in TiO2/Ag nanocomposite-based microheterogeneous
photocatalysis, The Journal of Physical Chemistry. B 108 (2004) 9623–9630.
[132] J. Yu, J. Xiong, B. Cheng, S. Liu, Fabrication and characterization of Ag–TiO2
multiphase nanocomposite thin films with enhanced photocatalytic activity,
Applied Catalysis B: Environmental 60 (2005) 211–221.
[133] A.K.L. Sajjad, S. Shamaila, B. Tian, F. Chen, J. Zhang, One step activation of WOx/
TiO2 nanocomposites with enhanced photocatalytic activity, Applied Catalysis B:
Environmental 91 (2009) 397–405.
[134] M.A. Saepurahman, F.K. Abdullah, Chong, Preparation and characterization of
tungsten-loaded titanium dioxide photocatalyst for enhanced dye degradation,
Journal of Hazardous Materials 176 (2010) 451–458.
[135] H. Song, H. Jiang, X. Liu, G. Meng, Efficient degradation of organic pollutant with
WOx modified nano TiO2 under visible irradiation, Journal of Photochemistry
and Photobiology A: Chemistry 181 (2006) 421–428.
[136] T. Hathway, E.M. Rockafellow, Y.-C. Oh, W.S. Jenks, Photocatalytic degradation
using tungsten-modified TiO2 and visible light: kinetic and mechanistic effects
using multiple catalyst doping strategies, Journal of Photochemistry and
Photobiology A: Chemistry 207 (2009) 197–203.
[137] D. Li, Y. Guo, C. Hu, C. Jiang, E. Wang, Preparation, characterization and
photocatalytic property of the PW11O397-/TiO2 composite film towards azo-dye
degradation, Journal of Molecular Catalysis A: Chemical 207 (2004) 183–193.