~"

r~

DESALINATION
ELSEVIER

Desalination 155 (2003) 255-263

www.elsevier.com/locate/desal

Titanium dioxide mediated photocatalyzed degradation of a

textile dye derivative, acid orange 8, in aqueous suspensions
Mohd Saquib, Mohd Muneer*
Department of Chemistry, Aligarh Muslim University, Aligarh 202002, India
Tel. +91 (571) 270-3515; Fax +91 (571) 270-2758; email: chtl2mm @ainu.hie.in

Received 8 January 2002; accepted 9 December 2002

Abstract

Titanium dioxide mediatedphotocatalyseddegradation of a textile dye derivative, acid orange 8 ( 1), was investigated
in aqueous suspensions of titanium dioxide by mordtoting the depletion of total organic carbon (TOC) content as a
function of irradiation time under a variety of conditions. The degradation kinetics were studied under different
conditions such as pH, catalyst concentration, substrate concentration, different types of TiO2 and in the presence of
electron aeceptors such as hydrogen peroxide (1-I20z) and potassium bromate (KBrO3) besides molecular oxygen. The
degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was
found to be more efficient compared with other photocatalysts. The dye was found to be adsorbed on the surface of the
photocatalyst at acidic pH.
Keywords: Photocatalysis; Textile dye; Acid orange 8; Titanium dioxide

I. I n t r o d u c t i o n

The environmental problem associated with

textile dyeing and finishing activities mainly
originate from the extensive use of a wide variety
of organic dyestuffs, the chemical characteristics
of which vary greatly [1,2]. Azo dyes, characterized by the presence of the N=N linkage,
comprise about half of all textile dyes used today
[3]. One major source of these effluents is the
*Corresponding author.

waste arising from industrial processes which

utilize dyes to color paper, plastics and natural
and artificial fibers [4]. A substantial amount of
dyestuff is lost during the dyeing process in the
textile industry [4], which poses a major problem
for the industry as well as a threat to the environment [4-8]. Decolourization of dye effluents has
therefore acquired increasing attention. Decolourization of dye effluent by bisulfite-catalysed
borohydride reduction has also been reported [9].
During the past two decades, photocatalytic
processes involving TiO2 semiconductor particles

0011-9164/03/$- See front matter 2003 Elsevier Science B.V. All rights reserved
PII: S 0 0 1 1 - 9 1 6 4 ( 0 3 )00303-5

256

M. Saquib, M. Muneer / Desalination 155 (2003) 255-263

under UV light illumination have been shown to

be potentially advantageous and useful in the
treatment of waste water pollutants. Earlier
studies [ 10-13] have shown that a wide range of
organic substrates such as alkanes, alkenes,
aromatics, surfactants, and pesticides can be
completely photomineralized in the presence of
TiO 2 and oxygen.
There are several studies related to the use of
semiconductors in the photomineralization of
photostable dyes [14-20]. Photoexcitation of
semiconductors leads to the formation of an
electron hole pair, which can eventually bring
about a redox reaction from organic substrates
dissolved in water. Alternatively, direct absorption of light by the dye, adsorbed on the semiconductor surfaces, can lead to charge injection
from the excited state of the dye to the conduction band of the semiconductor. It has been
shown earlier [ 14-20] that such processes can be
used for removing colouring material from dye
effluents in the presence of visible light.
No major efforts have been made to study the
degradation kinetics of an azo dye derivative
such as acid orange 8. Thus, we have undertaken a detailed study on the photodegradation of
this textile dye derivative, sensitized by TiO2 in
aqueous solution.

/CH3
NaO3S ~

N--N

2. Experimental
2.1. Reagents and chemicals

Acid orange 8 (1) was obtained from Aldrich

and used without any further purification. The
water used in all the studies was double distilled.
While the photocatalyst titanium dioxide, P25

(Degussa AG), was used in most of the experiments, other catalyst powders - - namely
Hombikat UV100 (Sachtleben chemic GmbH),
PC500 (Milenium inorganic chemicals) and TTP
(Travancore titanium products, India) - - were
used for comparative studies. P25 consists of
75% anatase and 25% rutile with a specific BETsurface area of 50 m2g-~ and a primary particle
size of 20 nm [21]. Hombikat UV100 consists of
100% anatase with a specific BET-surface area
>250 m2g-~ and a primary particle size of 5 nm
[22]. The photocatalyst PC500 has a BET-surface
area of 287 m2g-~ with 100% anatase and a
primary particle size of 5-10 nm [23], whereas
TTP has a BET-surface area of 9.82 mEg-1. The
other chemicals used in this study such as NaOH,
HNO3, H202 and KBrO 3, were obtained from
Merck.
2.2. Procedure

Stock solutions of the dye containing the

desired concentration were prepared in double
distilled water. An immersion well photochemical reactor made of Pyrex glass equipped
with a magnetic stirring bar, a water circulating
jacket and an opening for supply of molecular
oxygen was used. For irradiation experiments
250 mL of the stock solution were taken into the
photoreactor and the required amount of photocatalyst was added; the solution was stirred and
bubbled with molecular oxygen for at least
30 min in the dark to allow equilibration of the
system so that the loss of compound due to
adsorption could be taken into account. The zero
time reading was obtained from a blank solution
kept in the dark but otherwise treated similarly to
the irradiated solution. The suspensions were
continuously purged with molecular oxygen
throughout each experiment. Irradiations were
carried out using a 125 W medium-pressure
mercury lamp. IR-radiation and short-wavelength
UV-radiation were eliminated by a water jacket.
Samples (10 mL) were collected before and at

M. Saquib, M. Muneer/ Desalination 155 (2003) 255-263

regular intervals during the irradiation. They
were centrifuged by a Janetzki T-24 laboratory
centrifuge before analysis.

2.3. Analysis
The degradation was monitored by measuring
the total organic carbon (TOC) content with a
Shimadzu TOC 5000A analyzer by directly
injecting the aqueous solution. For each experiment the degradation rate of the model pollutant
was calculated from the initial slope obtained by
linear regression from a plot of the natural
logarithm of the TOC of the dye as a function of
irradiation time, i.e., first-order degradation
kinetics. It was calculated in terms of [mole Lmin-l].

3. Results

3.1. Photolysis of Ti02 suspensions containing

acid orange 8
Fig. 1 shows the depletion in TOC on irradiation of an aqueous solution of acid orange 8
(0.25 mM) in the presence and absence of TiO2
by the Pyrex-filtered output of a 125 W medium-

257

pressure mercury lamp. It was found that 75%

mineralization of the model compound took place
after 90 min of illumination, whereas no observable loss of the dye occurred in the absence of the
photocatalyst. The degradation curves can be
fitted reasonably well by an exponential decay
curve, suggesting first-order kinetics. The resulting first-order rate constant was used in all
subsequent plots to calculate the degradation rate
using the formula below:
- d [TOC]/dt = kc"
where k is the rate constant, c the concentration
of the pollutant, and n is the order of reaction.
Control experiments were carried out in all
cases using unirradiated blank solutions. It has
been found that the dye is adsorbed significantly
in the dark at pH 3 and 5.3. The zero irradiation
time readings were obtained from blank solutions
kept in the dark, but otherwise treated similarly to
the irradiated solutions.

3.2. Comparison of different photocatalysts

The influence of four different photocatalysts
(Degussa P25, Hombikat UV100, PC500 and
TTP) on the degradation kinetics of acid orange
8 (1) is shown in Table 1. It was observed that

1,3.
1
-,,,,m--.~

I,-

rsoeoca~dya

Table 1
Comparison of degradation rate for the mineralization of
acid orange 8 under different photocatalysts
Type of photocatalyst

O,4

Degradation rate
(mole L-1 min-j 10-3)

02
0

:30

1
40

t
!0

80

400

Irradiation time (rain)

Fig. 1. Influence of photocatalysts on the degradation of

acid orange 8. Experimental conditions: dye concentration (0.25 mM), V = 250 mL, immersion well photoreactor, 125 W medium-pressure Hg lamp, photocatalyst:
Degussa P25 (1 gL-~), cont. 02 purging and stirring,
irradiation time = 1.5 h.

P25
0.00392
UV100
0.00265
PC500
0.00173
TTP
0.00043
Experimental conditions: dye concentration (0.25 mM),
V= 250 mL, P25 (1 gL-l), Sachtleben Hombikat UV 100
(1 gL-t), PC 500 (1 gL-t), TTP (1 gL-~), immersion well
photoreactor, 125W medium-pressure Hg lamp, cont. 02
purging, irradiation time = 1.5 h.

258

M. Saquib, M. Muneer/ Desalination 155 (2003) 255-263

4"00JOOS

~
,'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

' . 1.

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

'

"=n O~
iS

f,

-'~

pH-5.3

On04

a
tm

o2
{}
,

6
pit

'

'

Fig. 2. Influence of pH on the degradation rate for the

mineralizationof acid orange 8. Experimentalconditions
as in Fig. 1.
the degradation of dye proceeds much more
rapidly in the presence of Degussa P25 compared
with other photocatalysts. In all of the following
experiments, Degussa P25 was used as the
photocatalyst since this material exhibited the
highest overall activity for the degradation of the
model compound.

3.3. p H effect
Using Degussa P25 as the photocatalyst, the
photomineralization of acid orange 8 (1) in the
aqueous suspensions of TiO 2 was studied in the
pH range between 3 to 11. The degradation rate
for the mineralization of acid orange 8 (1) as a
function of reaction pH is shown in Fig. 2. The
degradation rate for the TOC depletion is found
to gradually increase from pH 3 to 9 followed by
a sudden decrease as the pH rises to pH 11. A
significant adsorption of the dye on the surface of
the photocatalyst was observed at pH 3 and 5.3 as
seen by the typical TOC V amount of TiO 2 at
different pH (Fig. 3). The adsorption study ofazo
dye 1 was investigated by stirring the aqueous
solution in the dark for 24 h in a round-bottomed
flask containing varying amounts of TiO2 such as
0,0.5, 1, 2 and 5 gL-] at pH 3, 5.3, 9 and 11.
It is pertinent to mention here that the pH of
the solution was adjusted before irradiation and
it is not maintained throughout the reaction. A

2
3
4
Amou.t of TiO 2 (gL'l)

Fig. 3. Depletion in TOC Vs amount of the T i O 2 at

different pH showing the adsorption of acid orange 8 in
the dark. Experimental conditions: dye concentration
(0.25 mM), V = 250 mL, Photocatalyst: Degussa P25
(0.5, 1, 2 and 5 gL-l), stirring in the dark for 24 h.

decrease in the pH of the reaction mixture was

observed at the end of illumination.

3.4. Effect of substrate concentration

It is important both from a mechanistic and an
application point of view to study the dependence
of photocatalytic reaction rates on the substrate
concentration. Hence the effect of substrate
concentration on the degradation of acid orange
8 (1) was studied at different concentrations:
0.12, 0.25, 0.35 and 0.5 mM. Fig. 4 shows the
degradation rate for the mineralization of acid
orange 8 as a function ofsubstrate concentration
using Degussa P25 as the photocatalyst. It is
interesting to note that the degradation rate
increased with the increase in substrate concentration from 0.12 to 0.25 mM. A further
increase in the substrate concentration from 0.25
to 0.5 mM led to a decrease in the degradation
rate.

3.5. Effect of catalyst concentration

The effect of photcatalyst concentration on
the degradation kinetics of acid orange 8 (1) was
investigated using different concentrations of
Degussa P25 varying from 0.5 to 5 gL-L As

o
~

259

M. Saquib, M. Muneer / Desalination 155 (2003) 255-263

ao0s

'~D

0Din

00W

oom

'~ ooa
,

+ i I I ,
O1

I i I i i I , i ,
O2

, , ,

O3

~1

, ,

, , i
O,5

06

+,,ill
1

Substrate Concent ration ( r a M )

Fig. 4. Influence of substrate concentration on the

degradation rate for the mineralization of acid orange 8.
Experimental conditions: dye concentrations (0.12, 0.25,
0.35, and 0.5 mM), V= 200 mL, Photocatalyst: Degussa
P25 (1 gL-t), immersion well photoreactor, 125 W
medium-pressure Hg lamp, cont. O5 purging and stirring,
irradiation time = 1.5 h.

expected, the degradation rate of the acid

orange 8 has been found to increase with the
increase in catalyst concentration from 0.5 gLto 2 g L - I A further increase in the catalyst
concentration from 2 to 5 gL- t leads to a decrease
in the degradation rate (Fig. 5) due to the adsorption of the dye on the surface of the photocatalyst. This observation indicates that beyond
this optimum concentration, other factors affect
the degradation of model compound. At high
TiO2 concentrations, particles aggregate, which
reduces the interfacial area between the reaction
solution and the catalyst; thus, they decrease the
number of active sites on the surface. Light
scattering by the particles and the increase in
opacity may be other reasons for the decrease in
the degradation rate.
3.6. Effect o f electron acceptors

Since hydroxyl radicals appear to play an

important role in photocatalysis, electron acceptors such as hydrogen peroxide and potassium
bromate were added to the solution in order to
enhance the formation of hydroxyl radicals and
also to inhibit the (e-/h +) pair recombination. The

Calalyst

concent~t~n

( g L "1)

Fig. 5. Influence of catalyst concentration on the degradation rate for the mineralization of acid orange 8 at different photocatalyst concentrations. Experimental conditions: dye concentration (0.25 mM), V= 250 mL. Photocatalyst: Degussa P25 (0.5, 1, 2 and 5 gL-l), immersion
well photoreactor, 125 W medium-pressure Hg lamp,
cont. O2 purging and stirring, irradiation time =1.5 h.

_tm
J

}o

I~.~TH:O z

P2Y~'KBrO j

P25

Electron a c c e p t o r s

Fig. 6. Degradation rate for the mineralization of acid

orange 8 in the presence of different electron acceptors.
Experimental conditions: dye concentration (0.25 mM),
V = 250 mL, P25 (1 gL-]), electron acceptors: KBrO3
(5 mM), HzO2 (10 mM), immersion well photoreactor,
125 W medium-pressure Hg lamp, cont. 02 purging and
stirring, irradiation time = 1.5 h.

degradation rates for the mineralization of acid

orange 8 in the presence of these electron
acceptors are shown in Fig. 6. Both the additives
such as hydrogen peroxide and potassium
bromate had a beneficial effect on the degradation of the model compound.

260

M Saquib, M. Muneer / Desalination 155 (2003) 255-263

4. Discussion

The photocatalysed degradation of various

organic systems using irradiated TiO2 is well
documented [10]. The initial step in the TiO2
mediated photocatalysed degradation is proposed
to involve the generation of the (e-/h ) pair
leading to the formation of a hydroxyl radical and
superoxide radical anion [Eqs. (1)-(3)]:
TiO 2 + ho --~ e~b+ h~b

(1)

02 + e~b ~

(2)

H20 + h~b ~

0"2OH" + H

(3)

It has been suggested that the hydroxyl

radicals and superoxide radical anions are the
primary oxidizing species in the photocatalytic
oxidation processes. These oxidative reactions
result in the bleaching of the dye, and the efficiency of the degradation depends upon the
oxygen concentration, which determines the efficiency with which the conduction band electrons
are scavenged and the (e-/h ) recombination is
prevented. Alternatively, the electron in the conduction band can be picked up by the adsorbed
dye molecules, leading to the formation of a dye
radical anion; subsequent reaction of the radical
anion can lead to degradation of the dye. In the
present case both mechanisms can operate in an
oxygen-saturated solution.
The results on the photodegradation of the
model compound using different kinds of TiO2
photocatalysts with different bulk and surface
properties, i.e., BET-surface, impurities, lattice
mismatches or density of hydroxyl groups on the
catalyst's surface, are apparently responsible for
the photocatalytic activity since they affect the
adsorption behavior of a pollutant or intermediate
molecule and the lifetime and recombination rate
of electron-hole pairs.
An earlier study [24] has shown that Degussa
P25 owes its high photoreactivity to a slow

recombination of electron and holes whereas

Sachtleben Hombikat UV 100 has a high photoreactivity due to its fast interfacial electron
transfer rate. In these studies it was found that
Degussa P25 showed better photocatalytic activity for the degradation of a model compound.
Earlier studies have shown that Degussa P25 was
found to show better activity for the photocatalytic degradation of a large number of
organic compounds [25-28]. On the other hand,
Lindner et al. [29] showed that Hombikat UV 100
was almost four times more effective than P25
when dichloroacetic acid was used as the model
pollutant. The photocatalyst Hombikat UV 100
was found to be better for the degradation of
benzidine and 1,2-diphenyl hydrazine as shown
in a recent study [30].
These results indicate that the activity of the
photocatalyst also depends on the type of the
model pollutant. Another reason for the better
efficiency of the Degussa P25 photocatalyst can
be explained by the fact that Degussa P25 is a
mixture of 25% rutile and 75% anatase.
An important parameter in the photocatalytic
reactions taking place on the particulate surfaces
is the pH of the solution since it dictates the
surface charge properties of the photocatalyst and
size of aggregates it forms. For TiO2 the with
Degussa P25 being the photocatalyst, the zero
point of charge (pH~pc) is at pH 6.25. Hence, at
more acidic pH values, the particle surface is
positively charged, while at pH values above
6.25, it is negatively charged [31 ]. In this study it
was shown that the degradation rate for a model
compound under investigation is strongly influenced by the reaction pH, which increases with
the increase in pH from 3 to 9 followed by a
sudden decrease as the pH rises to 11.
Due to the low pKa value of the sulphonic
group, acid orange 8 was fully in the anionic
form within the pH range studied. With
increasing pH, the negative charges on TiO2 are
expected to repel the dye, and a decrease in the
efficiency of photo-degradation with increasing

M. Saquib, M. Muneer / Desalination 155 (2003) 255-263

pH is expected. However, it was observed that

the rate increased with an increase in pH. Similar
results were reported earlier for the acetate ion
and acid blue 40 [32,33]. This effect may be
attributed to more efficient generation of
hydroxyl radicals by TiO2 with an increasing
concentration of OH-. At the alkaline pH values,
the hydroxyl radicals have to diffuse away and
degrade the dye in the bulk solution.
The dye was found to be significantly
adsorbed in the dark at pH 3 and 5.3 as shown in
Fig. 3. It is interesting to note that at pH 9 where
the adsorption of the dye on the surface of the
photocatalyst is negligible, the degradation rate
for the mineralization of the dye is maximum,
which suddenly decreases at pH 11. This effect
can be attributed to the fact that the molecule
may be undergoing structural changes in the
double-bond character leading to the oxo form,
which normally happens at higher pH values.
The effect of substrate concentration on the
degradation rate for the mineralization of 1
(Fig. 4) was studied, as it is important both from
a mechanistic and the application point of view.
As oxidation proceeds, less and less of the
surface of the TiO2 particle is covered as the
pollutant is decomposed. Evidently, at total
decomposition, the rate of degradation is zero
and a decreased photocatalytic rate is expected
with increasing illumination time. It has been
agreed, with minor variations, that the expression
for the rate of photomineralization of organic
substrates with irradiated TiO2 follows the
Langmuir-Hinshelwood (L-H) law for the four
possible situations, i.e., (a) the reaction takes
place between two adsorbed substances, (b) the
reaction occurs between a radical in solution and
an adsorbed substrate molecule, (c) the reaction
takes place between a radical linked to the
surface and a substrate molecule in solution, and
(d) the reaction occurs with both species being in
solution. In all cases, the expression for the rate
equation is similar to that derived from the L-H
model, which has been useful in modeling the

261

process, although it is not possible to find out

whether the process takes place on the surface, in
the solution or at the interface.
Our results on the effect of the initial concentration on the degradation rate of the model
compound, shown in Fig. 4, indicate that the rate
increases with the increase in the substrate concentration from 0.125 to 0.25 mM. A further
increase in substrate concentration leads to a
decrease in the degradation rate. This may be due
to the fact that, as the initial concentrations of the
dye increase, more and more dye molecules are
adsorbed on the surface of the catalyst. Hence,
the penetration of light to the surface of the
catalyst decreases and the relative amount of OH"
and 02- on the surface of the catalyst do not
increase as the intensity of light and illumination
time is constant. Conversely, their concentrations
decrease with the increase in concentration of the
dye as the light photons are largely absorbed and
prevented from reaching the catalyst surface by
the dye molecules. Consequently, the degradation
efficiency of the dye decreases as the dye
concentration increases.
One practical problem in using TiO2 as a
photcatalyst is the undesired electron/hole recombination, which, in the absence of proper electron
acceptor or donor, is extremely efficient and thus
represents the major energy-wasting step, which
limits the achievable quantum yield. One strategy
to inhibit the electron-hole pair recombination is
to add other (irreversible) electron acceptors to
the reaction, which could have several different
effects, i.e., (1) to increase the number of trapped
electrons and, consequently, avoid recombination, (2) to generate more radicals and other
oxidizing species, (3) to increase the oxidation
rate of intermediate compounds and (4) to avoid
problems caused by low oxygen concentration. It
is pertinent to mention here that in highly toxic
wastewater where the degradation of organic
pollutants is the major concern, the addition of
inorganic ions to enhance the organic degradation
rate may often be justified. In this connection, we

262

M. Saquib, M. Muneer / Desalination 155 (2003) 255-263

studied the effect of electron acceptors such as

hydrogen peroxide and bromate on the photocatalytic degradation of the model compound
under investigation. These acceptors are known
to generate hydroxyl radicals according to the
Eqs. (4)-(6):

H202 + ecB ~

O'H + OH-

BrO3 + 2H + + ecB

---}

BrO'2 + H20

BrO~ + 2H +6 eca -~ [BrO 2, HOBr] -~

(4)
(5)
(6)

BY + 3H20
As expected, both additives, hydrogen peroxide and potassium bromate, showed a beneficial
effect on the photocatalytic degradation of model
compound as shown in Fig. 6. The enhanced
degradation rate in the presence of H202 can be
explained by several reasons. Firstly, it increases
the rate by removing the surface-trapped
electrons, thereby lowering the electron-hole
recombination rate and increasing the efficiency
of hole utilization for reactions such as (OH- + h +
--, O'H). Secondly, H202 may split photolytically
to produce OH radicals directly, as cited in
studies of homogeneous photooxidation using
UV/(H202 + 02) [34]. Thirdly, the solution phase
may at times be oxygen starved because of either
oxygen consumption or slow oxygen mass
transfer; peroxide addition thereby increases the
rate towards what it would have been had an
adequate oxygen supply been provided.

5. Conclusions
T i O 2 c a n efficiently photocatalyse textile dye
derivatives such as acid orange 8 using artificial
radiation sources. The observations of these
investigations clearly demonstrate the importance
of choosing the optimum degradation parameters
to obtain a high degradation rate, which is
essential for any practical application of photo-

catalytic oxidation processes. The best degradation condition depends strongly on the kind of
pollutant.

Acknowledgements
Financial support by the Department of
Science and Technology (DST), Government of
India (New Delhi), and the Third World
Academy of Sciences (Trieste, Italy) is gratefully
acknowledged. The total organic carbon analyzer
used for the analyses of the samples was a gift
from the Alexander Von Humboldt Foundation
(Germany).

References
[ 1] A. Reifeand H.S. Freeman,Environmental Chemistry
of Dyes and Pigments, Wiley, New York, 1996.
[2] C. O'Neill, F.R Hawkes, D.L Hawkes, N.D
Lourenco, H.M Pincheiro and W. Deice, J. Chem.
Technol. Bioteehnol., 74 (1999) 1009.
[3] J.R Easton, Colour in Dye,house Effluent, P. Cooper,
ed., SDC, Bradford, 1995, p. 9.
[4] H. Zollinger, in: Colour Chemistry, H.F. Eblel and
C.D. Brenzinger,eds., 1st ed.,VCH,NewYork, 1987,
Chap. 16.
[5] C.E. Searle, Chemical Carcinogenesis, ACS Monograph, Amer. Chem. Sot., Washington, DC, 1976.
[6] C.T. Helmes, C.C. Sigman, Z.A. Fund, M.K.
Thompson, M.K. Voeltz, M. Makie, P.E. Klein and
J.B. Lent, J. Environ. Sci. Health A, 19 (1984) 97.
[7] M. Boeninger, Carcinogenicity and metabolism of
azo dyes, especially those derived from benzidine,
DHI-IS(NIOSH), PublicationNo. 80-119, July, 1980.
[8] J.J. Roxon, A.J. Ryan and S.E. Wright, Food Cosmet.
Toxicol., 5 (1967) 367.
[9] M.M. Cook, J.A. Ulman and A. Iraelidis,Abstracts of
Papers, 203 National Meeting of the Amer. Chem.
Soc., San Francisco, 1992, and references therein.
[10] D.M. Blake, Bibliography of work on the photocatalytic removal of hazardous compounds from
water and air, National Renewal Energy Laboratory,
USA, 1999.
[11] J.M. Hermann, Catalysis Today, 53 (1999) 115-129.

M. Saquib, M. Muneer / Desalination 155 (2003) 255-263

[12] M.I. Litter, Applied Catalysis B: Environmental, 23

(1999) 89-114.
[ 13] A. Fujishima, T.N. Rao and D.A. Tryk, J. Photochem.
Photobiol. C: Photochem. Rev., 1 (2000) 1-21.
[14] K. Vinodgopal, I. Bedja, S. Hotechandani and P. V.
Kamat, Langmuir, 10 (1994) 1767-1771.
[15] K. Vinodgopal and P. V. Kamat, J. Photochem.
Photobiol. A: Chem., 83 (1994) 141-146.
[16] A. Mills, A. Belghazi, R.H. Davies, D. Worsley and
S. Morris, J. Photochem. Photobiol. A: Chem., 79
(1994) 131-139.
[17] M. Vautier, C. Guillard and J.M. Hermann, J. Catal.,
20 (2001) 46-59.
[18] I. Arsalan, I.A. Balcioglu and D.W. Bahnemann,
Dyes and Pigments, 47 (2000) 207-218.
[19] S. Sakthivel, B. Neppolian, B. Arabindo, M. Palanichamy and Murugesan, Ind. J. Engineering Mat.
Sci., 7 (2000) 87-93.
[20] J. Zhao, T. Wu, K. WU, K. Oikawa, H. Hidaka and
N. Serpone, Environ. Sci. Technol., 32 (1998) 23942400.
[21] R.I. Bickley, T.G. Carreno, J.S. Lees, L. Palmisano
and R.J.D. Tilley, J. Solid State Chem., 92 (1991)
178-190.
[22] M. Lindner, D.W. Bahnemann, B. Hirthe and W.D.
Griebler, J. Sol. Energy Eng., 119 (1997) 120-125.
[23] S. Rauer, Untersunchung von kommerziell erhaltlichen Titandioxiden hinsichtlich ihrer photokatalytischen Aktivtat, Diplomarbeit, fachhochschule
Hannover, Fachbereich Maschinenbau Vertiefung
Umwelt-und Verfahrenstechnil, Hannover, 1998.

263

[24] S.T. Martin, H. Hermann, W. Choi and M.R. Hoffmann, J. Chem. Soc. Faraday Trans., 90 (1994) 33153322.
[25] M. Muneer, J. Theurich and D. Bahnemann, J.
Photochem. Photobioi. A: Chem., 143 (2001) 213219.
[26] M. Muneer and D. Bahnemann, Water Sci. Technol.,
144 (2001) 331-337.
[27] M. Muneer, J. Theurich and D. Bahnemann, Res.
Chem. Intermed., 25 (1999) 667-683.
[28] M. Saquib and M. Muneer, Dyes and Pigments, 53
(2002) 237-249.
[29] M. Lindner, D.W. Bahnemann, B. Hirthe and W.D.
Griebler, Novel TiO2 powders as highly active
photocatalysts, in: Solar Water Detoxification; Solar
Engineering, W.B. Stine, T. Tanaka and D.E.
Claridge, eds. ASME, New York, 1995, pp. 339-408.
[30] M. Muneer, H.K. Singh and D. Bahnemann, Chemosphere, 49 (2002) 193-203.
[31] H. Hiegendorff, Untersuchungen zur Bedeutung der
Adsorption in der Photokatalyse,PhD Thesis, Department of Chemistry, University ofHannover, Hannover, Germany, 1996.
[32] C. Koval, Proc. Symp. on Photoelectrochemistry,
Electrochemical Society, Pennington, NJ, 1991.
[33] M. Muneer, R. Philip and S. Das, Res. Chem.
Intermed., 23 (1997) 233-246.
[34] G.R. Peyton and W.H. Glaze, Environ. Sci. Technol.,
22 (1988) 761-767.