Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 77:102116 (online: 2001)

DOI: 10.1002/jctb.532

Photocatalytic degradation for environmental

applications a review
Dhananjay S Bhatkhande,1 Vishwas G Pangarkar1* and
Anthony ACM Beenackers2
1
Department of Chemical Technology, University of Mumbai, Matunga, Mumbai - 400 019, India
2
Dept of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands

Abstract: Photocatalysis is a rapidly expanding technology for wastewater treatment. In this review the
chemical effects of various variables on the rate of degradation of different pollutants are discussed in
detail. The effects of adsorption, temperature, intensity of light, pH, and the presence of anions,
cations, etc have been specically covered. A critical analysis of the available literature data has been
made and some general conclusions have been drawn concerning the above mentioned effects. The
need for more work on specic points has been brought out.
# 2001 Society of Chemical Industry

Keywords: photocatalysis; TiO2; cation effect; anion effect; pH effect; temperature effect

NOTATION review is limited to chemical effects and does not cover

a Constant
hn Photon of light
I Plain light intensity
Kl PCD reaction rate constant
x,y,z Stoichiometric coefcients
X Halogen
1 INTRODUCTION
The photocatalytic degradation (PCD) process is
gaining importance in the area of wastewater treat-
ment; especially for wastewater containing small
amounts of refractory organic substances.14 The
process has several advantages over competing pro-
cesses.2 These are: (1) complete mineralization, (2) no
waste disposal problem, (3) low cost, and (4) only mild
temperature and pressure conditions are necessary.
Considerable information is available on the photo-
catalytic mineralization process in terms of reactions
and mechanism, degradation of individual com-
pounds, comparison of different photocatalysts,
etc.38 In their review, Peral et al 9 have explained the
use of photocatalysis for purication and decontami-
nation, and deodorization, of air. Mills et al have also
reviewed semiconductor-sensitized photosynthetic
and photocatalytic processes for removal of organics,
destruction of cancer cells and bacteria and viruses.10
The objective of this review is to critically assess the
available information on these aspects in the light of
actual commercial implementation of the process. The
the hardware required.
In a heterogeneous photocatalytic system, photo-
induced molecular transformations or reactions take
place at the surface of a catalyst. A general stoichio-
metry for the heterogeneous photocatalytic oxidation
can be written as follows:5
 y z hg
Cx Hy Xz X O2 !xCO2 zH
4
 y z
zX H2 O 1
2
2 PHOTOCATALYSTS
Solids that can promote reactions in the presence of
light and are not consumed in the overall reaction are
referred to as photocatalysts. These are invariably
semiconductors. A good photocatalyst should be (i)
photoactive, (ii) able to utilize visible and/or near UV
light, (iii) biologically and chemically inert, (iv) photo-
stable (ie not prone to photocorrosion), (v) inexpen-
sive and (vi) non-toxic. In order for a semiconductor to
be photochemically active as a sensitizer for the above
reaction the redox potential of the photogenerated
valence band hole must be sufciently positive to
.
generate OH radicals, which can subsequently oxidize
the organic pollutant. The redox potential of the
photogenerated conductance band electron must be
sufciently negative to be able to reduce adsorbed O2
to superoxide.2

* Correspondence to: Vishwas G Pangarkar, Department of Chemical Technology, University of Mumbai, Matunga, Mumbai - 400 019, India
E-mail: vgp@udct.ernet.in

Deceased 19 April 2001

(Received 6 March 2001; revised version received 28 August 2001; accepted 16 September 2001)

# 2001 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2002/$30.00 102

 Photocatalytic degradation for environmental applications

Photocatalyst Bandgap energy (eV) Photocatalyst Bandgap energy (eV)

Si 1.1 ZnO 3.2
TiO2 (rutile) 3.0 TiO2 (anatase) 3.2
WO3 2.7 CdS 2.4
ZnS 3.7 SrTiO3 3.4
SnO2 3.5 WSe2 1.2
Fe2O3 2.2 a-Fe2O3 3.1
Table 1. Bandgap energy of various photocatalysts

Si, TiO2, ZnO, WO3, CdS, ZnS, SrTiO3, SnO2,
WSe2, Fe2O3, etc can be used as photocatalysts. Table
17 and Fig 12 give band gap energies and band gap
positions of these catalysts. Figure 1 also gives the
. .
redox potentials of the H2O/OH and O2/HO2
couples.
Oxidation of many pollutants, especially organic
species, requires high potentials with the result that the
valence band location at the semiconductorelectro-
lyte interface has to be rather positive, as exemplied
by TiO2 and CdS. In these instances, the photo-
generated holes will have sufcient energy to oxidize
the organics via the generation of hydroxyl radicals.
Nonetheless some of the candidates listed in Table 1
do not have long-term stability in aqueous media,
notably CdS and ZnO. Photooxidation kinetics are
also poor in some instances, as for example, for n-Si.
Metal sulde semiconductors are unstable since they
undergo photoanodic corrosion, while a-Fe2O3 under-
goes photocathodic corrosion.11 The redox potential
must lie within the band gap position of the photo-
catalyst. As can be seen from Fig 1 this happens only in
the case of TiO2 and SrTiO3.
Generally, the pollutant is organic and the semi-
conductor is TiO2. The range of organic pollutants
that can be completely photomineralized by oxygen,
using TiO2 as the sensitizer, is very wide and includes
many aliphatics, aromatics, detergents, dyes, pesti-
cides, and herbicides. TiO2 in the anatase form
appears to be the most efcient semiconductor for
environmental application. Dagan and Tomkiewicz12
used the solgel method to produce TiO2 aerogel and
used it for the photoassisted oxidation of salicylic acid
and compared it with commercial (P-25) TiO2. The
results showed a much higher photoactivity for the
aerogel. In recent years Degussa P-25 TiO2 has set the
standard for photoreactivity in environmental applica-
tions. There is a wide range of photoreactivity within
specimens of mixtures containing variable contents of
anatase and rutile. Rutile may be active or inactive
according to the preparation method. Thus, the origin
and the method of preparation affect the physico-
chemical properties of the specimen.13 Many re-
searchers concluded that rutile is catalytically
inactive or a much less active form of TiO2.2,14 Khalil
et al 15 have shown that Hombikat UV100 was better
than Degussa, P-25 in the case of the photocatalytic
reduction of Cr(VI) whereas Theurich et al 16 showed
that in the case of photocatalytic degradation of 4-
chlorophenol Degussa P-25 was better than Hombikat
UV100. Degussa P-25 is a non-porous 70:30%
(anatase to rutile) mixture with a BET surface area
of 55  15 m2 g 1 and has a crystallite size of 30 nm in
0.1 mm diameter aggregates.
The photocatlyst derives its activity from the fact
that when photons of a certain wavelength are incident
upon its surface, electrons are promoted from the
valence band and transferred to the conductance
band. This leaves positive holes in the valence band,
which react with the hydroxylated surface to produce
.
OH radicals which are the most potent oxidizing
agents. The relative rates of oxidation reactions with
.
ozone and OH are given in Table 2; these rates

Table 2. Relative rate constants (k, in dm3 mol 1s 1)

of ozone and hydroxyl radicals

Compound O3 OH
Chlorinated Alkenes 10 1103 1091011
Phenols 103 1091010
N-containing organics 10102 1081010
Aromatics 1102 1081010
.
Figure 1. Bandgap position of various photocatalysts and O2/HO2 and Ketones 1 1091010
H2O/OH. pair. (Reproduced from Water purification by Semiconductor Alcohols 10 21 108109
Photocatalysis by Mills A, Davies RH and Worsley D, pp 417425 (1993).
Alkanes 10 2 106109
Reproduced by permission of the Royal Society of Chemistry.)

J Chem Technol Biotechnol 77:102116 (online: 2001) 103

DS Bhatkhande et al
.
conrm the potency of the OH radical. The minimum
wavelength required to promote an electron depends
upon the band gap energy of the photocatalyst and is
given by:2
Ebg 1240=lmin 2
In the absence of suitable electron and hole scavengers,
the stored energy is dissipated within a few nanose-
conds by recombination. If a suitable scavenger or a
surface defect state is available to trap the electron or
hole, their recombination is prevented and a subse-
quent redox reaction may occur. In Degussa P-25 the
conduction band electron of the anatase part jumps to
the less positive rutile part, reducing the rate of
recombination of electrons and positive holes in the
anatase part.17 Thus, Degussa P-25 TiO2 is the most
suitable photocatalyst.18,19
3 MECHANISM
Wet air oxidation (WAO) and advanced oxidation
processes (AOP) using Fenton's reagent and H2O2/
UV are competing processes for photocatalysis. WAO
accomplishes oxidation at elevated temperature (150
325 C) and oxygen pressures (120  103 kN m 2). It
has been suggested that the process proceeds by a free
radical mechanism. In the case of phenol degradation
hydroquinone and catechol are formed initially fol-
lowed by p-benzoquinone and o-benzoquinone. Then
the ring breaks and various C5, C4, and C3 acids are
formed (eg muconic acid, butenoic acid, glyoxalic
acid, succinic acid, 3-oxo-propionic acid), leading to
the formation of acetic acid.20
In the case of advanced oxidation processes using
Fenton's reaction hydrogen peroxide reacts with
ferrous sulfate (Fenton's reagent) to produce hydroxyl
radicals, which destroy organics, eventually producing
water and carbon dioxide. The radicals are formed
according to the following equations:
.
Fe2 H2 O2 !Fe3 OH OH 3 Back reaction
3 2 .
Fe H2 O2 !Fe H HOO 4 e h ! Heat
2H2 O2 !H2 O OH. HOO. 5
In the classical example of phenol degradation using
Fenton's reagent, carboxylic acids and dicarboxylic
acids are produced and, if the oxidation is carried to
completion, CO2 and water are formed. Substituted
aromatic ring compounds can be also oxidized with
Fenton's reagent to carboxylic and dicarboxylic acids
all the way to CO2 and water.21
An advanced oxidation method using H2O2/UV also
proceeds by the formation of OH radicals. Yawalkar et
al have compared photochemical and photocatalytic
processes in the case of phenol degradation.22 In the
case of photochemical degradation using H2O2/UV
(from sunlight) with phenol as the model pollutant,
intermediates such as benzoquinone, hydroquinone,
104
pyrocatechol, and resorcinol were detected. The major
difference between the photochemical and photocata-
lytic degradation is that the intermediates detected in
the case of the photocatalytic process were in very
small amounts; whereas in the case of the photo-
chemical degradation the intermediates were detected
in substantial amounts.22 These authors have also
compared the economics of the photochemical (H2O2/
solar) and photocatalytic (TiO2/solar) processes and
shown that the latter is more economical. Thus it may
be concluded that photocatalysis is a better process,
leading to complete mineralization with smaller
amounts of intermediates being generated.
The mechanism and the reaction scheme for
photocatalysis are described below. Figure 2 depicts
the processes taking place at the catalyst surface. The
initiating step in photocatalysis is the excitation of the
semiconductor (TiO2) by radiation sufciently ener-
getic (l < lmin) to produce an electron-hole pair.
Turchi and Ollis23 have shown that when water
dissociates on a pure TiO2 surface, two distinctive
hydroxyl groups are formed. The experimental evi-
.
dence supporting the concept of OH as the primary
oxidizing species include:
.
(1) ESR (Electron Spin Resonance) detection of OH
as the most abundant radical species.
(2) Necessity of photocatalyst surface hydroxylation
for organic degradation.
(3) Kinetic isotope effect demonstrating the kinetic
.
importance of the OH formation step.
(4) Formation of highly hydroxylated reaction inter-
mediates.
The schematic representation of the bond energetic
model of the overall process of semiconductor photo-
catalysis is shown in Fig 2.
The reaction scheme can be written as.23
Excitation
TiO2
hn >3:2eV
!e h 6
7
Figure 2. Schematic representation of the processes taking place at the
catalyst surface.
J Chem Technol Biotechnol 77:102116 (online: 2001)
 Photocatalytic degradation for environmental applications

Trapping Turchi and Ollis23 as described above is widely

. acceptable.
TiIV OH =H2 O h ! TiIV OH 8
.
TiIV OH ! TiIV OH =H2 O h 9
4 THE DEGRADATION SCHEMES
Ti IV
e ! Ti III
10 The photocatalytic degradation schemes for some
aromatic compounds, eg benzene, chlorophenol and
TiIII O2 $ TiIV O2 11 atrazine, suggested by researchers are given below.
The degradation of any organic substance proceeds via
Adsorption of organic pollutant (S) and photogener- .
the formation of intermediates following OH attack.
ated intermediates (Qj) The suggested pathway for benzene degradation as
given by Turchi and Ollis23 is presented in Fig 3.
site S $ Sads 12
Degradation of chlorophenol has been extensively
site Qj $ Qjads 13 studied.27,28 Indeed, 4-chlorophenol has been used as
a model compound to test the efciency of various
Hydroxyl radical attack on the initial organic pollutant catalysts.28 Mills et al 28 have proposed the reaction
generating intermediates pathway in the case of the PCD of 4-chlorophenol in
.
the presence of ClO3 , as given in Fig 4 (ClO3 was
TiIV OH. Sads ! TiIV Qjads 14 used to adjust the pH).
. The degradation path of s-atrazine herbicides which
TiIV OH S ! TiIV Qj 15
are more complex molecules occurs through a com-
Hydroxyl radical attack on intermediates generating plex series of competitive-consecutive reactions. A
other intermediates simplied scheme portraying the more relevant steps
and intermediates formed, as suggested by Pelizzetti et
TiIV
.
OH Qjads
kQjads
!TiIV Qj1ads 16 al,4 is given in Fig 5.
.
In the case of aromatic substances two to three OH -
. kQj containing substances have been observed as inter-
TiIV OH Qj !TiIV Qj1 17
mediates. Further, no aliphatic acids/compounds have
Other reactions been detected which indicates that after loading of the
ring by two to three hydroxyl groups, the ring opens
.
e TiIV O2 2H $ TiIV H2 O2 18 up.29,22 The intermediates detected by Yawalkar et
. al 22 in the case of phenol conrms the degradation
.
TiIV O2 H $ TiIV HO2 19 scheme suggested by Turchi and Ollis.19 The opened
ring is rapidly converted to CO2 and H2O, etc. The
. .
TiIV H2 O2 TiIV OH $ TiIV HO2 TiIV H2 O absence of aliphatic products is a clear indication of
20 the very rapid mineralization of the opened benzene
ring. Our unpublished work on the PCD of nitroben-
.
The above mechanism reasonably depicts the degra- zene indicates that when OH attack takes place
. .
dation process while maintaining enough simplicity. initially NO2 is not replaced by OH but OH replaces
Other types of mechanisms include reactions in which H at various positions in the ring as phenol and other
oxidation may occur indirectly via the surface-bound intermediates found in the case of phenol were not
hydroxyl radical (ie a trapped hole on the particle detected but m, o, and p-nitrophenol were detected.28
surface) or directly via the valance-band hole before it In the case of benzoic acid degradation phenol and its
is trapped either with the particle or at the particle intermediates were not detected conrming that the
.
surface.5 It was shown by Okamoto et al 24 that OH group does not replace the COOH group till the
hydroxyl radicals are formed not only via holes but ring opens up.30
also via H2O2 from the superoxide ion O2 . Besides
this, according to Fujishima and Rao,25 reduction of
oxygen in aerated aqueous solution to form O2 and 5 WHAT CAN BE DEGRADED?
H2O2 enables charge neutrality to be maintained and From Table 3 it is seen that almost all types of organic
drive the photocatalytic reaction. According to Tunesi and inorganic substances can be degraded using
and Anderson26 H2O2 may also be produced and is photocatalysis. Even streams containing inorganic
.
photodecomposed to OH which reacts with the pollutants such as heavy metals can also be treated
substrate. using this method.
Table 3 gives a summary of various model pollutants
degraded by various researchers, the source of UV
light used, the photocatalyst used, the intermediates 6 INTERMEDIATES DETECTED
detected, etc. The study of intermediates (Table 3) The reaction on the surface is a redox reaction. In
and the applicability of LangmuirHinshelwood general, oxidation of the substrate takes place via OH
.
kinetics suggests that the mechanism proposed by radical attacks while oxygen supplied from air is

J Chem Technol Biotechnol 77:102116 (online: 2001) 105

DS Bhatkhande et al

Table 3. Summary of compounds degraded by various researchers using photocatalysis including information about the UV source used, photocatalyst used,
intermediates detected and comments

Intermediates
Compound degraded Photocatalyst used Source of light detected Comments References

Aliphatic compounds
Gaseous formaldehyde TiO2 lm on glass HgXe lamp None Formaldehyde PCD is greater than Noguchi et al 36
acetaldehyde
Formic acid TiO2 Degussa P-25 on 40W Hg lamp KATADYN LR- Not analysed The method is useful for removal of Mazzarino and Piccinini65
stainless steel 40A aliphatic acids
CHCl3 Degussa P-25 TiO2 1000W Xe arc lamp C2Cl6, C2Cl4 High conc of substrate and low O2 Choi and Hoffmann45
conc
CHBr3 Degussa P-25 TiO2 1000W Xe arc lamp C2Br4 High conc of substrate and low O2 Choi and Hoffmann45
conc
CCl4 Degussa P-25 TiO2 1000W Xe arc lamp CO,CO2 High conc of substrate and low O2 Choi and Hoffmann45
conc
Chloroform TiO2 (anatase) Solar light None Chloroform degradation rate was Ahmed and Ollis32
faster than trichloroethylene
Chloroform Degussa P-25 Ozone-free 450W Xe lamp None Studied the effect of Cl and HClO3 Kormann et al 50
Gaseous formaldehyde TiO2 lm on glass HgXe lamp Formaldehyde Formaldehyde PCD is greater than Noguchi et al 36
acetaldehyde
Dichloromethane Bentonite clay pillared by 1000W Xe arc lamp Not analysed Bentonite clay pillered is better Tanguay et al 66
TiO2 and titanium catalyst
exchanged clays
Trichloroethylene TiO2 (anatase) Solar light None Chloroform degradation rate was Ahmed and Ollis32
faster than trichloroethylene
Ethanol Degussa P-25 attached to 20W, NEC blacklight Not analysed Effect of pH and anions was studied Abdullah et al 40
glass spiral uorescent tube, solar Maximum rate was observed for
parabolic trough pH between 2.8 and 3.8
2-Propanol Degussa P-25 attached to 20W, NEC blacklight Not analysed Effect of pH and anions was studied Abdullah et al 40
glass spiral uorescent tube, solar Maximum rate was observed for
parabolic trough pH above 3.4
Perchloroethylene Degussa P-25 Seven 15 W blacklight-blue None Presence of benzene inhibits the Turchi and Ollis19
uorescent bulbs PCD
Perchloroethylene Anatase TiO2 75W mercury lamp SHL- None Negligible effect of pH was found Gupta and Tanaka43
UVQ
Perchloroethylene, Anatase TiO2 GE BLB-15W Not analysed The chlorinated hydrocarbons can Ollis et al 67
dichloroethane, mono- be completely mineralized except
and di- and trichloroacetic acid, which was
trichloroacetic acid dehalogenated at a negligible rate
Trichloroethylene TiO2 Sunlight Not analysed Cost for solar process could be Mehos and Turchi35
similar to those of more
conventional technologies
Methyl-tert-butyl ether TiO2 Degussa P-25 450W medium pressure Tert-butyl formate, tert-butyl MTBE is readily and rapidly Barreto et al 68
mercury lamp alcohol, acetone, a- degraded photocatalytically
hydroperoxy methyl-tert-
butyl ether, acetic and
formic acid
Glycolic acid TiO2 Degussa P-25 on 40W Hg lamp KATADYN LR- Not analysed The method is useful for removal of Mazzarino and Piccinini65
stainless steel 40A aliphatic acids
Citric acid TiO2 Degussa P-25 on 40W Hg lamp KATADYN LR- Not analysed The method is useful for removal of Mazzarino and Piccinini65
stainless steel 40A aliphatic acids
Monocrotophos Degussa P-25 TiO2 20W blacklight uorescent Detected and identied Anions had detrimental effect Hua et al 51
tube some whereas low conc of Cu2
enhanced the PCD rate slightly
Inorganic compounds
AgNO3 TiO2 anatase and rutile 400 W high pressure None Anatase is better than rutile; rate of Ohtani et al 38
mercury lamp deposition of Ag is grater at high
pH; adsorption is also more at
high pH
HgCl2 Degussa P-25 TiO2 Simulated solar light None HgCl2 and CH3HgCl can be Serpone et al 69
CO.FO.MEGRA, Italy successfully removed
CH3HgCl Degussa P-25 TiO2 Simulated solar light None PCD is more in the absence of Serpone et al 69
CO.FO.MEGRA, Italy oxygen
Reduction of Cr(VI) to Degussa P-25 TiO2 Medium pressure mercury None Hombikat UV100 is better than Khalil et al 15
Cr(III) Hombikat UV100, WO3, lamp Degussa P-25; ZnO is the best
ZnO among the four used
Aromatic compounds
Malic acid Degussa P-25 TiO2 on Philips HPK125W UV lamp Not analysed AgTiO2 gave better results Herrmann et al 70
quartz
Benzene Degussa P-25 Seven 15 W blacklight-blue Phenol and 1,4- Presence of benzene inhibits the Turchi and Ollis19
uorescent bulbs benzoquinone as major PCD
intermediates
Chlorobenzene Anatase TiO2 UV lamp (Spectronics) Not analysed Signicant increase in PCD rate was Butler and Davis55
observed in presence of 10 5 M
Cu(II) and Mn(II) at pH3
Nitrobenzene TiO2 1500 W xenon lamp 2-,3-,4-nitrophenol as With TiO2 rates are 100 times faster Pelizzetti et al 4
intermediates than ZnO
Nitrobenzene Degussa P-25 Sunlight p-nitrophenol, o- PCD rates are faster than phenol, Bhatkhande et al 31
nitrophenol,2- PHBA, benzoic acid
nitroresorcinol, 4-
nitrocatechol
Phenol Degussa P-25 attached to 20W, NEC blacklight Not analysed Spiral reactor was better in the case Matthews18
glass mesh or spiral uorescent tube, solar of articial light; solar degradation
parabolic trough was fastest; PCD rates follow the
trend; salicylic acid > 2-
chlorophenol > 4-
chlorophenol > phenol
Phenol Degussa P-25 attached to 20W, NEC blacklight Not analysed Effect of pH and anions was studied Abdullah et al 40
glass spiral uorescent tube, solar Maximum rate was observed
parabolic trough above pH 3.4

106 J Chem Technol Biotechnol 77:102116 (online: 2001)

 Photocatalytic degradation for environmental applications

Table 3. continued

Intermediates
Compound degraded Photocatalyst used Source of light detected Comments References

Phenol Degussa P-25 as freely Natural sun light Not analysed PCD rates for free suspension was Matthews and McEvoy71
suspended, coated on three times faster than
sand and silica gel immobilized TiO2 Silica supported
gave higher rates
Phenol TiO2 Degussa P-25 UV-B and UV-C 15W Not analysed PCD rates are higher at 254 nm than Matthews and McEvoy32
at 350 nm
Phenol TiO2 Degussa P-25 UV-B and UV-C 15W Not analysed SolutionpHbetween3.5and8.5didnot Matthews and McEvoy41
have a great effect on PCD rates
Phenol TiO2 Degussa P-25 125W Philips HPK mercury Hydroquinone, p- Supported TiO2 can be used to Trillas et al 44
immobilized on glass vapour lamp benzoquinone, and degrade phenol
pearls hydrohydroquinone
(neg)
Phenol Degussa P-25 Sunlight Benzoquinone, Concentrated sunlight can be used Yawalkar et al 22
pyrocatechol, resorcinol, for phenol degradation
hydroquinone
Toluene Anatase TiO2 UV lamp(Spectronics) Not analysed Signicant increase in PCD rate was Butler and Davis55
observed in presence of 10 5 M
Cu(II) and Mn(II) at pH3
Salicylic acid TiO2 Degussa P-25 UV-B and UV-C 15W Not analysed PCD rates are higher at 254 nm than Matthews and McEvoy33
at 350 nm
Salicylic acid Degussa P-25 attached to 20W, NEC blacklight Not analysed Spiral reactor was better in case of Matthews18
glass mesh or spiral uorescent tube, solar articial light; solar degradation
parabolic trough was fastest; PCD rates follow the
trend: Salicylic acid > 2-
chlorophenol > 4-
chlorophenol > phenol
Salicylic acid Degussa P-25 and aerogel 85W Hg lamp Not analysed The aerogel showed much higher Dagan and Tomiewicz12
photocatalytic activity
Salicylic acid TiO2 Degussa P-25 and 2.5 KW medium pressure Intermediates were reported Degussa P-25 is better than tioxide Yatmaz et al 3
tioxide as thin lm in Hanovia-UVV as formed but not
falling lm reactor analysed
Benzoic acid Degussa P-25 Concentrated sunlight Salicylic acid, p-hydroxy Benzoic acid can be degraded using Ajmera et al 30
benzoic acid, etc photocatalysis
p-hydroxybenzoic acid Degussa P-25 Sunlight No intermediates were PHBA can be degraded using Subramaniam et al 29
detected concentrated sunlight; anions
have detrimental effect on
degradation
2-Chlorophenol Degussa P-25 attached to 20W, NEC blacklight Not analysed Spiral reactor was better in case of Matthews18
glass mesh or spiral uorescent tube, solar articial light; solar degradation
parabolic trough was fastest; PCD rates follow the
trend: salicylic acid > 2-
chlorophenol > 4-
chlorophenol > phenol
4-Chlorophenol Degussa P-25 attached to 20W, NEC blacklight Not analysed Spiral reactor was better in case of Matthews18
glass mesh or spiral uorescent tube, solar articial light; solar degradation
parabolic trough was fastest; PCD rates follow the
trend: salicylic acid > 2-
chlorophenol > 4-
chlorophenol > phenol
4-Chlorophenol TiO2 Degussa P-25 Hydroquinone, 1,4- Sayyed et al 74
benzoquinone, 4-chloro-
1,2-hydroxybenzene
4-Chlorophenol TiO2 Degussa P-25 and 2.5 KW medium pressure Intermediates were reported Degussa P-25 is better than tioxide Yatmaz et al 73
tioxide as thin lm in Hanovia-UVV as formed but not
falling lm reactor analysed
4-Chlorophenol TiO2 Degussa P-25 Two halves of 6 Nos, 8W 4-Chlorocatechol, The experiments were performed at Mills et al 28
Blacklight UVA lamps hydroquinone, pH2
benzoquinone, 4-
chlororesorcinol
4-Chlorophenol TiO2 Degussa P-25 coated Articial UV light Not analysed Effect of pH and temp was studied Hofstadler et al 27
on optical bres
4-Chlorophenol TiO2 Degussa P-25 High pressure mercury lamp Hydroquinone, The photonic efciencies decrease Theurich et al 16
benzoquinone, with rising pH, and a slight
hydroxyhydroquinone, increase is observed above pH 9
hydroxybenzoquinone,
phenol, 4-
chlorocatechol, 4-
hydroxyphenyl
benzoquinone, 2,5,4-
trihydroxybiphenyl, 5-
chloro-
2,4dihydroxybiphenyl
4-Chlorophenol TiO2 Hombikat UV100 High pressure mercury lamp Same as above Degussa P-25 is better than Theurich et al 45
Hombikat UV100
2,4-Dichlorophenol Anatase TiO2 UVP XX-155 low pressure Not analysed Slight increase in PCD with pH was Ku and Hsieh42
mercury lamp observe
3,5-Dichlorophenol TiO2 Degussa P-25 125W high pressure lamp 2,5-dichloro-1,4- 3,5-Dichlorophenol can be degraded Jardim et al 74
(Philips) hydroquinone using photocatalysis
2,4-Dichlorophenol TiO2 Degussa P-25 125W Philips HPK mercury Chlorohydroquinone, Immobilized catalyst on glass pearls Trillas et al 44
immobilized on glass vapour lamp chlorophenol can be used for photocatalysis of
pearls 2,4-dichlorophenol
2,4,6-Trichlorophenol Anatase TiO2 High pressure mercury UV Not analysed Studied the effect of adsorption and Tanaka and Saha39
lamp pH on PCD
2,3,5-Trichlorophenol TiO2 Degussa P-25 125W high pressure lamp 2,3,5-trichloro-1,4- 2,3,5-Trichlorophenol can be Jardim et al 75
(Philips) hydroquinone degraded using photocatalysis
Pentachlorophenol TiO2 Degussa P-25 125W high pressure lamp 2,3,5,6-Tetrachloro-1,4- Pentachlorophenol can be degraded Jardim et al 75
(Philips) hydroquinone, 2,3,5,6- using photocatalysis
tetrachloro-
benzoquinone, 2,3,5,6-
tetrachlorophenol

J Chem Technol Biotechnol 77:102116 (online: 2001) 107

DS Bhatkhande et al

Table 3. continued

Intermediates
Compound degraded Photocatalyst used Source of light detected Comments References

Pentachlorophenol TiO2 Degussa P-25 125W high pressure lamp 2,3,5,6-Tetrachloro-1,4- Pentachlorophenol can be degraded Jardim et al 75
(Philips) hydroquinone, 2,3,5,6- using photocatalysis
tetrachloro-
benzoquinone, 2,3,5,6-
tetrachlorophenol
4-Nitrophenol TiO2 from Eurotitania 125 W high pressure lamp Not analysed Effect of pH and temperature was Andreozzi et al 47
studied
Phenoxyacetic acid TiO2 Degussa P-25 125W Philips HPK mercury Phenol, hydroquinone Phenoxyacetic acid can be Trillas et al 44
immobilized on glass vapour lamp degraded using immobilized TiO2
pearls
2,4-Dichlorophenoxy TiO2 Degussa P-25 125W Philips HPK mercury Dichlorophenol 2,4-Dichlorophenoxyacetic acid can Trillas et al 44
acetic acid immobilized on glass vapour lamp be easily degraded using
pearls immobilized TiO2
Octaphenylcyclo, Degussa P-25 TiO2 1500W xenon Lamp Silicate and polysilicate Photoactivity does not change with Minero et al 76
tetrasiloxane (OPCTS) layer formed time
Surfactants dyes etc
Textile dye Reactive Degussa P-25 TiO2 15 W blacklight CO2, NO3 , SO42 ions ZnO and TiO2 are efcient Poulios and Tsachpinis48
Black 5 photocatalysts for PCD of the dye
Commercial azo dyes Degussa P-25 TiO2 500W super high pressure Not analysed Monoazo is more degradable than Tanaka et al 37
mercury lamp the diazo
Sodium dodecyl sulfate, Anatase TiO2 75W mercury lamp Not analysed Analysed for Photocatalysis using TiO2 was very Tanaka and Ichikawa77
sodium dodecyl (Toshiba, SHL-UVQ) toxicity and TOC effective at enhancing the
benzene sulfonate, p- biodegradability and reducing the
nonylphenyl poly toxicity; combined system may be
(oxyethylene) ether applicable
Methylene Blue, Degussa P-25 coated sand 100W medium pressure Not analysed The method can be useful and Matthews78
Rhodamine B, Methyl mercury lamp addition of small amount of H2O2
Orange increases the rate considerably
Methylene Blue Ultrane TiO2 prepared 300W mercury lamp Not analysed Assize is decreased; adsorption and Xu et al 61
degradation increased
Fungicide metalaxyl Degussa P-25 125W medium pressure Analysed and given the PCD Fungicide can be completely Topalov et al 79
lamp pathway mineralized
Degradation using other photocatalysts
Phenol and substituted CdS 300W ELH visible light Not analysed Low pH and adsorption favours the Davis and Huang80
phenols degradation but stability of CdS at
low pH and photocorrosion are the
problems
Salicylic acid ZnO Philips TLAD 15W05 2,5-DHBA, 2,3-DHBA, Salicylic acid can be degraded using Richard and Boule81
uorescent lamp pyrocatechol ZnO as photocatalyst
Potassium cyanide ZnO Phillips HPK 125W CN gives OCN as It is good catalyst even in the case of Domenech and Peral82
intermediate solar irradiation; greater yield was
obtained at pH 11 at which it is
most stable
Reduction of Cr(VI) to ZnO, Hombikat UV100, WO3 Medium pressure mercury Not analysed ZnO is better catalyst Khalil et al 15
Cr(III) lamp
PCD with modified TiO2
Methanol TiO2 with 1% Pt Black uorescent light GE Not analysed Adsorption dependence and surface Chen et al 83
BLB-15W mechanism is proposed
Ethanol TiO2 with 1% Pt Black uorescent light GE Not analysed Adsorption dependence and surface Chen et al 83
BLB-15W mechanism is proposed
Malic acid AgTiO2 Philips HPK 125W UV lamp Not analysed AgTiO2 gave better results Herrmann et al 70
Chloroform urea Anatase TiO2 and Ag- 125 W medium pressure Not analysed Catalyst activity can be increased by Kondo and Jardim84
loaded TiO2 lamp loading silver
Phenol 2,4- Anatase TiO2 and Ag- 125W high pressure Not analysed Ag-loaded TiO2 gave slightly better Alberici and Jardim85
Dichlorophenol, 2,3,5- loaded TiO2 mercury lamps results
trichlorophenol,
pentachlorophenol
Destruction of bromate Platinized TiO2 6*8W germicidal lamp Not analysed Platinized titanium dioxide can be Mills et al 86
ions to bromide used for bromate distruction
Methanol, ethanol, Pt/TiO2 Pd/TiO2 Blacklight Acetaldehyde and acetic Compared with Pt, Pd has less effect Chen et al 83
chloroform, acid in the case of on TiO2
trichloroethylene, ethanol
dichloropropionic acid
Phenol Mn/TiO2 xed on glass bres 125W medium pressure Hydroquinone and catechol Presence of CO3, Ce3, Cr3, Mn2, Brezova et al 87
using solgel technique mercury lamp Al3, and Fe3 ions in the TiO2
layers had a detrimental effect;
with Pt/TiO2 the rate of phenol
degradation was high but
hydroquinone (intermediate)
degradation was slower

reduced. Intermediates are formed during the process
of degradation. As can be seen from Table 3, some of
the researchers did not analyse for the intermediates
and have concentrated on the degradation rates of the
parent substance. Some of them had analysed for
TOC while others only mentioned the intermediates.
From the study of degradation of aromatic substances;
the attack of OH radicals takes place on the ring at the
ortho, para or meta positions depending upon the
existing functional group attached to the ring. The
intermediates containing ortho-, para- and meta-
substituted derivatives are produced with varying
ratios. In the case of halogens OH replaces the halide
before the ring breaks. Generally compounds with two
OH groups attached to the ring or at the most three
were observed; after which the cleavage of the ring
takes place. The lower compounds containing C5, C4,
C3, etc were not observed since after the ring cleavage

108 J Chem Technol Biotechnol 77:102116 (online: 2001)


Figure 3. Photocatalytic degradation scheme for benzene.
the species produced must be highly reactive. If the
ring contains atoms other than carbon, eg nitrogen as
in the case of atrazine, then the degradation takes place
till all the hydrogen atoms attached to the ring are
replaced by OH groups but the further ring cleavage
was not observed.4 In the case aliphatic compounds,
aldehydes, alcohols and acids containing fewer carbon
atoms have been detected as intermediates. In all the
cases, in the presence of a sufcient amount of air or
oxygen and in the absence of hydroxyl radical
scavengers small quantities of intermediates were
detected. It can thus be concluded that the miner-
alization goes to completion. In the presence of salts
and at various pH values, other than neutral pH,
intermediates were detected in larger quantities. The
biphenyl derivatives observed by some of the research-
ers are due to on insufcient supply of oxygen.
7 EFFECT OF LIGHT INTENSITY AND
WAVELENGTH
UV light provides the photons required for the
electron transfer from valence band to conduction
band of the photocatalyst. The energy of a photon is
related to its wavelength and the overall energy input
Figure 4. Photocatalytic degradation scheme for 4-chlorophenol.
J Chem Technol Biotechnol 77:102116 (online: 2001)
Photocatalytic degradation for environmental applications
Figure 5. Photocatalytic degradation scheme for s-atrazine.
to a photocatalytic process is dependent upon the light
intensity. Therefore, the effect of both intensity and
wavelength are important.
Ahmed and Ollis32 studied the PCD of trichlor-
oethylene and chloroform over anatase TiO2 in natural
sunlight. They observed that the initial rate of
decomposition was constant over the central period
of the day. This may be due to the fact that in that
period the variation in intensity is relatively small.
These authors mentioned that in California for a clear
`desert' sky, there is only about a 10% variation in the
total scattered sunlight over the middle 6 h of the day.
In their study of the PCD of phenol over anatase
powder Okamoto et al 24 found that both initial PCD
rate and apparent rate constant were proportional to I
(Intensity of light) below PCD rate of ca 1  10 5mol
m 2 s 1 and to I1/2 above a PCD rate of 2  10 5mol
m 2 s 1 (UV light in their case was substantially
composed of 336, 334 and 313 nm wavelengths).
Matthews and McEvoy33 showed that shorter
wavelength (254 nm) radiation is considerably more
effective in promoting degradation than radiation
centred at 350 nm and the optimum rate occurred
with a lower catalyst loading than required at 350 nm.
Hofstadler et al 27 also showed that shorter wave-
lengths resulted in higher PCD rates of 4-chlorophe-
nol with small amounts of intermediates being formed.
This is due to the fact that shorter wavelength is
associated with greater photon energy.
Ollis et al 1 reviewed the effect of light intensity on
PCD and stated that at low intensities the rate
increased linearly with light intensities. At intermedi-
ate light intensities, the rate depended on the square
root of light intensity. At high light intensities, the rate
is independent of light intensity, conrming the results
of Okamoto et al. 24
Crittenden et al 34 reported that the apparent PCD
rate constant increased as the light intensity increased
for all the catalyst dosages. However, the rate increase
with light intensity depends on catalyst dosage. The
109
DS Bhatkhande et al
dependence of the rate constant KI on the intensity I,
was Ki = I/[a I] where a is constant.
Yawalkar et al 22 showed that for the PCD of phenol
the PCD rate was proportional to I0.5. They used
concentrated solar radiation so that I was relatively
high. This is in agreement with the above observa-
tions.1,23
From their eld tests of the PCD of trichloroethylene.
Mehos and Turchi35 showed that the one sun system
uses sunlight eight times more efciently than the
concentrating system. This is probably due to the fact
that when sunlight is concentrated a much higher
intensity is obtained. At this high intensity although
the generation of positive holes increases, the recombi-
nation of holes and electrons is probably more dominant
than generation of positive holes. Also reection of light
is associated with the loss of energy and the one sun
system can utilize diffused sunlight more efciently.
However, concentrated sunlight gives higher rates. This
observation of Mehos and Turchi35 further supports the
results of Okamoto et al 24 and Ollis et al 1.
In the case of degradation using concentrated solar
light it has been observed that the amounts of
intermediates detected were negligible in the absence
of salts.21 In the case of articial light the intermediates
generated depend on the intensity and wavelength as
well.33 Lower wavelengths give higher rates, which
may be attributed to the fact that they carry higher
energy.
A more systematic investigation of the effect of
wavelength particularly with respect to the PCD and
TOC consumption rates and type and quantity of
intermediates generated is required.
8 EFFECT OF ADSORPTION
There is some evidence to indicate that the degrada-
tion of a substrate occurs on the surface of the
photocatalyst.4,5,19 It is therefore logical to expect that
the rate of degradation of the substrate will be a
function of the adsorbed substrate concentration.
Thus, the extent of adsorption of the substrate may
be an important factor. Several investigators have
observed that there is a clear relationship between
substrate adsorbability and PCD.29,36,37
In experiments investigating the reduction of an
aqueous solution of silver nitrate, the adsorption effect
was studied by Ohatani et al. 38 The amount of Ag
adsorbed on the anatase TiO2 surface decreased with
decreasing pH, becoming negligible at pH < 2. The
Ag adsorbed onto the rutile TiO2 was negligible at
pH < 5 and increased with an increase in pH at pH > 6.
The adsorption was greater on the anatase surface than
on the rutile surface. The PCD rates showed a similar
trend. This observation supports the contention that
adsorption plays an important role in PCD.
In the case of the PCD of gaseous formaldehyde and
acetaldehyde, Noguchi et al 36 showed that the PCD
rate of formaldehyde was greater than that of
acetaldehyde. This was attributed to the differences
110
in their adsorption. In the case of the PCD of
commercial azo dyes, Tanaka et al 37 found that
adsorption of the dye on TiO2 was an important factor
in determining the degradation rate. In the case of p-
hydroxy benzoic acid degradation (PHBA) Subrama-
niam et al 29 showed that the adsorption and PCD rates
bear a direct relationship and as adsorption increased
the PCD rate also increased.
Our work with PHBA, phenol, benzoic acid and
nitrobenzene PCD degradation using solar concen-
trated light also showed that nitrobenzene, being a
more strongly adsorbed species, showed the highest
PCD rates. The PCD rates followed the adsorption
trend.22,30,31
Tanaka and Saha39 studied the PCD of 2,4,6-
trichlorophenol (TCP). They found that although a
signicant amount of adsorption was observed at
lower pH values (3.1,4.2), at higher pH values no
adsorption was noted. At low pH (pH < 6) the
undissociated species TCP was predominant, while
the dissociated chlorophenolate anion predominated
at high pH. An Increase in the rate of PCD was
observed at high pH. It was concluded that the role of
adsorption of TCP on the surface of TiO2 was
insignicant and the process of oxidation takes place
in the bulk solution. This observation contradicts the
ndings of other researchers.22,29,31
Dagan and Tomkiewicz12 showed that adsorption of
salicylic acid was indicated by a bright yellow colour on
the TiO2 surface. Under illumination the yellow
colour changed gradually to dark brown. This clearly
indicates that the adsorption and the reaction are
occurring on the surface, followed by decolorization of
the surface when the reaction was complete.
Overall, based on the information available it is
reasonable to conclude that the degradation of the
substance depends on the adsorption of the substance
on TiO2. The substances which are adsorbed strongly,
degrade faster. This is a clear indication that the
reaction must be taking place on the catalyst surface
itself. Also, the dependence of the reaction rate on the
surface area is supportive of this hypothesis, as
mentioned in Section 13.
9 EFFECT OF pH
The pH may affect the surface charge on the
photocatalyst and also the state of ionization of the
substrate and hence its adsorption. Also, industrial
efuents may be basic or acidic and therefore this pH
effect needs to be considered.
Ohatani et al 38 studied the effect of pH on the
reduction of aqueous AgNO3 solutions on anatase and
rutile TiO2 and showed that pH had some effect on
adsorption and the PCD rate followed a similar trend
to that of adsorption. Abdullah et al 40 studied the
effect of pH on adsorption and on PCD for phenol, 2-
propanol and ethanol and found similar results
although the deviations in all the cases was marginal.
Matthews and McEvoy41 on the other hand observed a
J Chem Technol Biotechnol 77:102116 (online: 2001)

negligible pH effect on the PCD of phenol in the pH
range 3.58.5 with the rate increasing marginally with
increasing pH. This was attributed to the increase in
.
the concentration of OH ions.
42
Ku and Hsieh studied the effect of pH on the
degradation of 2,4-dichlorophenol over anatase TiO2
and showed that in alkaline solutions the PCD rate was
slightly greater than that at neutral and acidic pH with
less intermediates being formed. This might be due to
the possible effect of solution pH on the decomposi-
tion of 2,4-dichlorophenol in water, which probably
changes its reactivity and distribution over the photo-
catalyst. Tanaka and Saha38 studied the effect of pH
on the PCD of 2,4,6-trichlorophenol (TCP). Due to
.
an increase in the concentration of OH radicals, and
the presence of dissociated chlorophenolate anions,
the PCD rate was greater in the alkaline solution.
Hofstadler et al 27 studied the effect of initial pH
from 5.8 to 3.0 on the PCD rate of 4-chlorophenol
using TiO2 coated on optical bres and found that
lowering the pH resulted in a slight increase in the
PCD rate. However, TOC measurements indicated
that pH had a negligible effect. Gupta and Tanaka43
studied the effect of pH on the PCD of perchlor-
oethylene and found that the initial pH had no
signicant effect.
Trillas et al 44 stated that in the case of the PCD of
phenol and dichlorophenol, higher efciencies were
observed at high pH values although the adsorption in
alkaline media was very low but TOC removal rates
remained almost the same.
In the case of the PCD of 4-chlorophenol Theurich
et al 16 showed that the change in the PCD rates due to
pH change was very small with Degussa P-25 and
Hombikat UV100. Apparently, a larger amount and a
higher concentration of intermediates were formed at
higher pH values. Some differences were observed
with different types of catalysts, which may be
attributed to the difference in crystal structure and
average particle size, which may be affecting adsorp-
tion, and hence PCD rates.
Choi and Hoffmann45 studied the effect of pH on
the PCD of CHCl3, CHBr3, and CCl4 and showed
that the rate dramatically increases at pH >11. This
enhancement was ascribed to photoenhanced hydroly-
sis.
Chen et al 46 showed with their experiments using
metallized TiO2 in the PCD of methanol and ethanol,
that the PCD rate is seriously retarded in the alkaline
pH, based on measurement of CO2 evolved. The CO2
produced in the PCD is likely to be absorbed by the
alkali at higher pH, yielding an erroneous result. The
inorganic carbon was not analysed in this work and
therefore a conclusion cannot be reached.
Andreozzi et al 47 studied the effect of pH on the
PCD of 4-nitrophenol and found that the rate was high
at acidic pH, which was attributed to its effect on
adsorption.
Poulios and Tsachpinis48 studied the effect of pH on
the PCD of the textile dye Reactive Black 5. They
J Chem Technol Biotechnol 77:102116 (online: 2001)
Photocatalytic degradation for environmental applications
observed a decrease in the PCD rate at acidic pH due
to a very high increase in the adsorption, especially
between pH values 1 and 3, resulting in the decrease in
the absorption of the radiation due to coverage of the
TiO2 surface by the dye; thus decreasing the genera-
.
tion of OH . Above pH 6 they observed a decrease in
the PCD rate with a minimum at pH 9 reecting the
difculty of sulfonic and ethylsulfonic anions in
approaching the negatively charged surface. Above
pH 9 an increase was observed which was explained as
.
being due to the increase of OH anions on the catalyst
surface.
Davis and Huang49 studied the effect of pH on the
PCD of sulfur-containing compounds using CdS as
photocatalyst. They found that both adsorption and
PCD rate were only slightly dependent upon the
solution pH.
Subramaniam et al 29 showed that in the case of p-
hydroxy benzoic acid, adsorption and degradation
attained a maximum close to the zero point charge of
Degussa P-25 TiO2 at pH 7 (approx) and then
decreased again as the pH was further increased.
In their review Fox and Dulay11 mentioned that the
weak dependence of the PCD rate on the solution pH
is expected. The isoelectric point for TiO2 in water is
about pH 6.
In general, the pH has a varied effect on the process
and it is expected that the increase or decrease in the
pH should affect the rate of degradation as adsorption
varies with pH. In general, adsorption is maximum
near the zero point charge pH (zpc), at which point the
PCD rate is also maximum. In the case of substances
which are weakly acidic, the PCD increases at lower
pH because of an increase in the adsorption. Some
substances undergo hydrolysis at alkaline pH, which is
one of the reasons for the increase in the PCD at
alkaline pH values. Also at alkaline pH values, the
.
concentration of OH radicals is relatively higher and
this may also be another reason for the increase in the
PCD rate.39,44 In the case of substances which
dissociate or form radicals in a certain pH range and
which are then adsorbed, there is an increase in the
rate, which is specic to the substance.39 It should be
noted that the overall efcacy of a PCD process is
indicated more clearly by the TOC. Most authors who
observed a higher PCD rate of the substrate in the
alkaline pH range also observed that the decrease in
TOC was not the same but lower. The different
observations made by various investigators may be due
to differences in conditions employed, such as source
of UV, type of catalyst used, etc. These need to be
reconciled by a systematic investigation under care-
fully controlled conditions with simultaneous
measurements of total inorganic and organic carbon.
10 EFFECT OF ANIONS
Industrial efuents contain, apart from the pollutants,
different salts at different concentrations. The salts are
generally ionized under the conditions of PCD. The
111
DS Bhatkhande et al
anion or cation may have an effect on the rate of PCD.
The presence of anions such as chloride, sulfate,
carbonate, and bicarbonate is common in industrial
efuents. These ions affect the adsorption of the
degrading species, act as hydroxyl ion scavengers and
may absorb UV light as well.
Abdullah et al 40 studied the effect of anions on the
PCD of ethanol and 2-propanol. The presence of
sodium chloride decreased the PCD rate considerably
due its effect on adsorption. The other probability is
that the chloride ions act as scavengers of UV light
through the following reaction:
.
OH Cl
.
!Cl OH 21
The presence of NaNO3 had a negligible effect. Sulfate
ions added as Na2SO4 were found to decrease the rate
of degradation due to a decrease in the adsorption
of the substrate. The photocatalytic activity was
markedly inhibited as soon as phosphate anions were
introduced.
Kormann et al 50 studied the PCD of chloroform and
other organic molecules in aqueous TiO2 suspensions.
They found that anions such as Cl and ClO3
signicantly decrease the photoefciency of the
catalyst at low pH, where they may be adsorbed on
the positively charged TiO2 surface. However, they
have negligible effect at high pH. In this case the pH
and the anion have their own effects and simultaneous
changes of these two factors yields a mixed effect
although, as expected, a detrimental effect of chloride
ions was observed.
Mehos and Turchi35 showed that the presence of
bicarbonate has a detrimental effect on the PCD of
trichloroethylene.
Tanaka and Saha39 studied the effect of chloride
ions on the PCD of 2,4,6-trichlorophenol. At pH 7
chloride ions decreased the PCD rates considerably.
Chloride ions did not inhibit the reaction in alkaline
solutions. Hua et al 51 studied the effect of the presence
of chloride, chlorate and nitrate on the PCD of
monocrotophos. They found that chloride, chlorate
and nitrate had a detrimental effect on the degradation
of monocrotophos. This may be attributed to an effect
on adsorption.
Haarstrick et al 52 studied the effect of chloride and
bicarbonate ions on the degradation of 4-chlorophenol
and p-tolunesulfonic acid. They showed that that the
PCD rate dropped by 50% when 170 mmol dm 3 of
chloride was initially present. Another negative effect
was from bicarbonate. The carbonate and bicarbonate
ions are thought to react with HO radicals, as given
below:
. .
CO3 2 HO !CO3 HO
.
22
. The effect of Fe2 was similar. Anatase photoactivity
HCO3 2 HO !CO3 H2 O 23
The carbonate radical anion is a weak oxidizing agent
that hardly reacts with other molecules.
Subramaniam et al 29 studied the effect of anions on
112
the PCD of p-hydroxy benzoic acid. They showed that
the effect obeys the following order:
SO4 2 < HCO3 < NO3 < Cl
Yawalkar et al 22 studied the degradation of phenol in
the presence of various anions. The observed detri-
mental effect on the photocatalytic degradation of
phenol obeyed the following order:
SO4 2 < CO3 2 < Cl < HCO3
Sulfate has only a small effect on the PCD rate in this
case, which was attributed to its minimal effect on the
adsorption. The effect of chloride is mainly due to
adsorption whereas in the cases of carbonate and
bicarbonate it is due to both adsorption and their
ability to act as scavengers of hydroxyl radicals, as
discussed by Haarstrick et al. 52
Thus sulfate, phosphate, and nitrate will have a
smaller effect on the PCD rate and will decrease the
rate as much as they decrease the adsorption of the
substrate. In general, chloride has a greater effect on
adsorption and chloride ions absorb UV light, hence
considerable decreases are expected in the PCD rate in
the presence of chlorides. Carbonate and bicarbonate
have the largest effect on the PCD rates because of a
.
decrease in the adsorption and their reaction with HO
as discussed earlier. The effect of chloride is pro-
nounced in the case of substances which are weakly
adsorbed whereas in the case of strongly adsorbing
species the effect of carbonate and bicarbonate is
predominant.
11 EFFECT OF CATIONS
The presence of various cations is common in
industrial efuents. They may have a positive or
negative effect on the PCD rate. Various researchers
have reported conicting results. Therefore, a sys-
tematic study is required to delineate the effects of
various cations.
Wei et al 53 studied the effect of transition metal ions,
such as Fe3 and Cu2 on the PCD of phenol. They
found that phenol removal increased rapidly as the
concentration of the ferric ion was gradually increased.
It reached a maximum value in the neighbourhood of
4.8 mmol dm 3. However, excessive ferric ions re-
tarded the catalytic effect. The phenol removal
decreased from 26 to 15% as 20 mmol dm 3 cupric
ions were added
Sclafani et al 54 studied the effect of Fe3, Fe2, and
Ag on the PCD of phenol in aqueous polycrystalline
TiO2 dispersions. They observed that the maximum
photoreactivity for TiO2 (anatase) was obtained in the
presence of oxygen and [Fe3] = 5  10 4 mol dm 3
was benecially inuenced in the presence of oxygen
and [Ag] = 1  10 4 mol dm 3.
Hua et al 51 studied the effect of the presence of
Cu2 on the PCD of monocrotophos and found that at
J Chem Technol Biotechnol 77:102116 (online: 2001)

low Cu2 concentrations (<10 5 mol dm 3) slight
enhancement was observed whereas at higher con-
centrations lower PCD rates were observed.
Butler and Davis55 studied the effect of metal ion
concentration on the PCD of toluene and chloroben-
zene. The results indicate that dissolved Cu(II),
Fe(III), and Mn(II) have both concentration and
pH-dependent effects on the rate of toluene and
chlorobenzene oxidation in TiO2 photocatalytic sys-
tems; a two-fold increase in the initial reaction rate was
observed under the optimum conditions
(10 5 mol dm 3 Cu(II) at pH 3). The decrease in the
rate at higher concentrations may also correspond to
the detrimental effect of anions associated with the
above metal ions and solution opacity.
Prairie et al 56 investigated the effect of the presence
of dissolved metals (Ag, Au, Cd, Cr, Cu, Hg, Ni, and
Pt) on the PCD of a variety of organics (eg methanol,
formic acid, salicylic acid, EDTA, phenol, and
nitrobenzene). It was found that only those metals
with standard reduction potentials more positive than
0.3V (vs normal hydrogen electrode) can be treated
using TiO2 as the photocatalyst.
In the case of the PCD of nitrobenzene the effect of
the presence of 0.1 mol dm 3 FeSO4 and
0.01 mol dm 3 FeSO4 was studied by Bhatkhande et
al. 31 Considerable decrease in the PCD of nitroben-
zene was observed at 0.1 mol dm 3 FeSO4 concentra-
tion, which can be attributed to the effect of the
presence of this salt on the adsorption whereas
negligible effect was observed when 0.01 mol dm 3
FeSO4 was present.
Thus the presence of cations in general has a
detrimental effect on the PCD rates; the only excep-
tions being Fe, Ag, and Cu if present in very small
concentrations in the range of 15  10 6 mmol dm 3.
The detrimental effect may be due to the associated
anion and the effect of the salt on substrate adsorption.
In-depth study is needed to determine the effect of the
presence of cations at lower concentrations.
12 EFFECT OF REACTION TEMPERATURE
In the case of PCD using sunlight the temperature of
the stream may increase as the solar radiation contains
a considerable IR (infrared) factor. Hence, a study of
the effect of temperature is important.
Zeltner et al 57 indicated that increasing the reaction
temperature increased the rates of all reactions
occurring in the system, except for the photogenera-
tion of electron-hole pairs. On the other hand,
increasing the reaction temperature lowers the solubi-
lity of oxygen in the solution. A lower concentration of
dissolved oxygen will cause a decrease in the rate of
electron withdrawal from the surface of the photo-
catalyst. In the case of the PCD of phenol, Yawalkar et
al 22 found that temperature had a negligible effect
when using solar radiation.
In their review Fox and Dulay11 have stated that
compared with most photoreactions, photocatalytic
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Photocatalytic degradation for environmental applications
reactions are not dramatically sensitive to small
variations in temperature. The rate of photoassisted
decomposition of aliphatic alcohols was insensitive to
temperature variations. Arrhenius behaviour was
observed (DE = 8.37 kj mol 1) for photodetoxication
of phenol and salicylic acid, although a linear
dependence of reaction rate on temperature was
reported in the photocatalysed decomposition of
chloroform.
Hofstadler et al 58 studied the effect of temperature
on the PCD of 4-chlorophenol using TiO2 loaded on
optical bres. They observed a linear dependence in
the range of 1060 C. Andreozzi et al 47 studied the
effect of temperature on the PCD of 4-nitrophenol at
pH 3 and 8.5. The effect of temperature in the range of
2050 C on the rate constant k0 is linear. A negative
temperature dependence observed in the acidic pH
was attributed to exothermic adsorption. Thus the
process is apparently weakly dependent on tempera-
ture. The presence of oxygen is important to keep high
.
the concentration of photogenerated OH radical on
the surface of the catalyst. Increasing the temperature
though has other positive effects: it decreases the
solubility of oxygen and negatively affects the con-
centration of photogenerated holes.
13 EFFECT OF SURFACE AREA
Since the PCD process is affected by adsorption of the
substrate on the catalyst the effect of surface area is
important in PCD. As already described, anatase has
better photoactivity than rutile TiO2. The combina-
tion of anatase and rutile decreases the recombination
of photogenerated electrons and holes and hence it
shows more activity than anatase, as in the case of
Degussa P-25. Also as the particle size decreases the
surface area increases, and as the process is adsorption
dependent, the PCD rates also increases.
Dagan and Tomkiewicz12 and Tomkiewicz et al 59
showed that TiO2 aerogels with a surface area of
600 m2 g 1 showed greater activity than commercial
Degussa P-25 which has a surface area of 55 m2 g 1.
In their study of the PCD of chlorinated hydro-
carbons in water, Crittenden et al 34 had shown that
Degussa P-25 TiO2 is more active than Aldrich TiO2.
They also reported that the surface area of Degussa P-
25 is ve times that of Aldrich TiO2.
Robert and Weber60 used solgel prepared TiO2
and prepared TiO2 with surface areas of 162 m2 g 1
and 300 m2 g 1. The latter showed higher photoactiv-
ity as they have higher surface areas. Xu et al 61 studied
the effects of particle size on the PCD of methylene
blue (MB) and showed that the PCD of MB also
increased as the particle size of TiO2 decreased.
The Eco Device Co (Tokyo, Japan),62 in coopera-
tion with Kinki University (Higashi-Hiroshima), has
claimed to have developed a new titania catalyst that
can be activated by visible light. This is a signicant
improvement since it allows the use of the major
portion of solar radiation in the visible range. Most
113
DS Bhatkhande et al
other catalysts require wavelengths in the UV/near
UV, which limits the utility of solar radiation, which
has a small component in this range of wavelength.
14 EFFECT OF REUSED CATALYST
Ahmed and Ollis32 showed that in the case of the PCD
of trichloroethylene and chloroform using sunlight and
anatase TiO2 there was no signicant change in the
catalyst activity when the catalyst was ltered and
reused several times. Our results with the ltered
catalysts in the case of degradation experiments with
nitrobenzene also revealed the same ndings,31 how-
ever if salts are present in the feed liquid, these are
adsorbed on the photocatalyst, reducing its activity.
Simple washing with water restores the activity, which
is again affected in further contact with salts.
15 RELATIVE RATES OF DEGRADATION
The different results obtained by the various research-
ers show that the degradation rates of aliphatic
compounds are dependent on the adsorption of the
substrate on the TiO2 surface. From the previous
discussion it is evident that the degradation of organic
compounds proceeds through progressive attachment
of OH groups. Thus, those compounds, which
facilitate the attachment of OH radical, will degrade
faster. The OH radicals can attack at different
positions of the aromatic ring, depending upon the
directing effect of the original functional group. Thus,
some compounds yield predominantly m-hydroxy
intermediates while others yield a mixture of o- and
p-hydroxy intermediates.
The effect of molecular structure and functional
groups on PCD can be illustrated using benzene
substituted with different functional groups as an
example. The groups that contain an unshared pair of
electrons (O , NR2, NHR, OH, OR, NHCOR,
OCOR, SR), and the four halogens, are electron-
donating groups (I group). The (I) inductive effect
decreases from O to halogens in the sequence, listed
above.63 It is expected that the benzene derivative with
O will show the highest PCD rate and the rate will
decrease in the sequence mentioned above till halo-
benzenes. These groups are predominantly ortho and
para directing. This is conrmed from Table 3 in
which the intermediates detected contain o- and p-
hydroxy derivatives and only a very small amount of m-
hydroxy derivatives. In the case of halobenzenes, OH
replaces the halogen itself, as conrmed from the
intermediates detected (Table 3).
Groups that lack an unshared pair on the atom
bound to the ring and having a I inductive effect
comprise, in approximate order of decreasing ( I)
inductive effect, NR 3 , NO2, CN, SO3H, CHO, COR,
COOH, COOR, CONH2, CCl3, NH3 ( I group).63
It is expected that the benzene derivative with NR3
. contaminants. Environ Sci Technol 25:15231528 (1991).
will show the highest PCD rate and the rate will
decrease in the sequence mentioned above. Also these
114
groups are predominantly meta directing. The inter-
mediates detected in these cases are predominantly m-
hydroxy derivatives. Also, as we move from the NR 3 to
the NH3 group the amount of meta products formed
decreases and ortho and para intermediates increase.
Our experiments with nitrobenzene and benzoic acid
indicate that nitrobenzene PCD rates are greater than
these of benzoic acid, which is in agreement with the
above reasoning.30,31
Surfactants such as anionic sodium dodecylbenzene
sulfonate, cationic benzyldodcyl dimethyl ammonium
chloride, and non-ionic p-nonylphynylpoly
(oxyethyene) have been photocatalytically degraded
on TiO2. Those which bear aromatic rings are more
easily degraded than those substrates containing only
alkyl or alkoxylate groups.
The decomposition rates of amphoteric surfactants
are slower than the cationic and non-ionic surfactants.
The amphoteric species having both negative and
positive charges, cause unstable adsorption on the
TiO2 surface.64 The decomposition of the nitrogen
moieties in surfactants is slower, and is in the following
order: pyridine ring > secondary amine > tertiary
amine > peptide > quaternary ammonium.64
If a nitrogen atom is present in the ring, complete
degradation of the substrate does not take place. The
nal degradation product of s-triazine (atrazine) is
cyanuric acid and not CO2 and H2O.4 Mono-azo dyes
are more degradable than diazo.37
Detailed study under carefully controlled conditions
is necessary to delineate the effects of various groups
on the PCD of aromatic compounds to draw concrete
conclusions.
16 CONCLUSION
In this review the photocatalytic degradation process
has been studied in detail. The effect of adsorption
also has been analysed and it has been concluded that
the substances which are readily adsorbed are de-
graded at a faster rate, indicating that the reaction is a
surface phenomenon. The effect of the presence of
anions and cations has been analysed in detail and
effect of temperature and pH have also has been
discussed.
It can be concluded that the effect of pH is negligible
so pH adjustment is not required. Knowledge of
dissolved salts is essential in view of their inhibiting
effects on PCD. The nature of the light source and the
nature of the catalyst (immobilized or powdered TiO2)
also affects the cost of the operation. Solar radiation is
obviously an attractive proposition.
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