Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12

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Journal of Photochemistry and Photobiology C:

Photochemistry Reviews
journal homepage: www.elsevier.com/locate/jphotochemrev

Review

Heterogeneous photocatalytic degradation of organic contaminants over

titanium dioxide: A review of fundamentals, progress and problems
Umar Ibrahim Gaya a , Abdul Halim Abdullah a,b,∗
a
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor D.E., Malaysia
b
Advanced Materials and Nanotechnology Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400 Serdang, Selangor D.E., Malaysia

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

Article history: Even though heterogeneous photocatalysis appeared in many forms, photodegradation of organic pol-
Received 6 August 2007 lutants has recently been the most widely investigated. By far, titania has played a much larger role
Received in revised form in this scenario compared to other semiconductor photocatalysts due to its cost effectiveness, inert
27 September 2007
nature and photostability. Extensive literature analysis has shown many possibilities of improving the
Accepted 15 December 2007
efficiency of photodecomposition over titania by combining the photoprocess with either physical or
Available online 18 March 2008
chemical operations. The resulting combined processes revealed a flexible line of action for wastew-
ater treatment technologies. The choice of treatment method usually depends upon the composition
Keywords:
Semiconductor
of the wastewater. However, a lot more is needed from engineering design and modelling for success-
Titania ful application of the laboratory scale techniques to large-scale operation. The present review paper
Degradation seeks to offer an overview of the dramatic trend in the use of the TiO2 photocatalyst for remediation
Photocatalysis and decontamination of wastewater, report the recent work done, important achievements and prob-
Ecotoxicity lems.
© 2008 Elsevier B.V. All rights reserved.

Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Basic principles of photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Mechanism of titania-assisted photocatalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
4. Titania versus existing photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
5. Effect of operational parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5.1. Light intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5.2. Nature and concentration of the substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5.3. Nature of the photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.4. Photocatalyst concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.5. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.6. Reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
6. Methods of utilization of titania photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7. Trends in improving the activity of titania . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7.1. Novel photocatalyst preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7.2. Combined operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
8. Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
8.1. Ecotoxicity of titania photoprocesses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
8.2. Future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
9. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

∗ Corresponding author at: Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor D.E., Malaysia. Tel.: +60 389466777;
fax: +60 389435380.
E-mail address: halim@science.upm.edu.my (A.H. Abdullah).

1389-5567/$20.00 © 2008 Elsevier B.V. All rights reserved.

doi:10.1016/j.jphotochemrev.2007.12.003
2 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12
1. Introduction
As recalcitrant organic pollutants continue to increase in air and
wastewater streams, environmental laws and regulations become
more stringent [1,2]. As a response, the development of newer
eco-friendly methods of destroying these pollutants became an
imperative task. Ultimately, research activities centred on advanced
oxidation processes (AOPs) for the destruction of synthetic organic
species resistant to conventional methods. AOPs rely on in situ gen-
eration of highly reactive radical species, mainly HO• by using solar,
chemical or other forms of energy [3,4]. The most attractive feature
of AOPs is that this highly potent and strongly oxidizing radical
allows the destruction of a wide range of organic chemical substrate
with no selectivity.
Among AOPs, heterogeneous photocatalysis has proved to be
of real interest as efficient tool for degrading both aquatic and
atmospheric organic contaminants [5]. Heterogeneous photocatal-
ysis involve the acceleration of photoreaction in presence of
semiconductor photocatalyst. One of the major applications of het-
erogeneous catalysis is photocatalytic oxidation (PCO) to effect
partial or total mineralisation of gas phase or liquid phase contam-
inants to benign substances [6]. Even though degradation begins
with a partial degradation, the term ‘photocatalytic degradation’
usually refers to complete photocatalytic oxidation or photomin-
eralisation, essentially to CO2 , H2 O, NO3 − , PO4 3− and halide ions
[7].
Titania photocatalysis also referred to as the “Honda–Fujishima
effect” was first unfolded by the pioneering research of Fujishima
and Honda [8]. These workers revealed the possibility of water split-
ting by photoelectrochemical cell having an inert cathode and rutile
titania anode. Consequently, the application of titania photocatal-
ysis extended to environmental frontiers. Frank and Bard [9] for
the first time reported the application of TiO2 in photocatalytic
oxidation of CN− and SO3 2− in aqueous medium under sunlight.
Subsequent reports of photocatalytic reduction of CO2 by Inoue et
al. [10] attracted more interest to titania photocatalysis.
As part of the dawn, the photo-kolbe decarboxylation route to
butane reported by Izuml et al. [11] and the suggestion of its reac-
tion mechanism based on hydroxyl radical generation opened a
new chapter in organic synthesis. The earliest description of pho-
todecomposition of organic compounds and studies of effects of
reaction parameters was reported by Kraeutler and Bard [12].
Heterogeneous photocatalysis has attracted constant research
since its infancy considering the high number of excellent reviews
and books devoted by many researchers [7,13]. Despite many appli-
cations the basic photophysical principle and physical chemistry in
photocatalysis is largely the same. The present review sheds light on
the fundamentals of the heterogeneous photocatalytic degradation
of organic contaminants and reports the important accomplish-
ments. Although photocatalytic degradation has broad generality
for destruction of both organic and inorganic compounds the focus
of this paper is on organic contaminants.
2. Basic principles of photocatalysis
Heterogeneous photocatalysis is a discipline which includes a
large variety of reactions: organic synthesis, water splitting, pho-
toreduction, hydrogen transfer, O2 18 –O2 16 and deuterium–alkane
isotopic exchange, metal deposition, disinfection and anti-cancer
therapy, water detoxification, gaseous pollutant removal, etc. [7,14].
Among these appearances titania-assisted heterogeneous photo-
catalytic oxidation has received more attention for many years as
alternative method for purification of both air and water streams.
The basic photophysical and photochemical principles underly-
ing photocatalysis are already established and have been reported
in many literatures [15,16]. Vinodgopal and Kamat [17] reported
that the dependence of the rate of 1,3-diphenylisobenzofuran pho-
todegradation on the surface coverage. In other words, only the
molecules that are in direct contact with the catalyst surface
undergo photocatalytic degradation.
Photocatalytic reaction is initiated when a photoexcited electron
is promoted from the filled valence band of semiconductor photo-
catalyst (SC) to the empty conduction band as the absorbed photon
energy, h, equals or exceeds the band gap of the semiconductor
photocatalyst leaving behind a hole in the valence band. Thus in
concert, electron and hole pair (e− –h+ ) is generated. The following
chain reactions have been widely postulated.
Photoexcitation : TiO2 /SC + h → e− + h+ (1)
− •−
Oxygen ionosorption : (O2 )ads + e → O2 (2)
− +
Ionization of water : H2 O → OH + H (3)
•− +
Protonation of superoxides : O2 +H → HOO• (4)
The hydroperoxyl radical formed in (4) also has scavenging
property as O2 thus doubly prolonging the lifetime of photohole:
HOO• + e− → HO2 − (5)
− +
HOO + H → H2 O2 (6)
Both the oxidation and reduction can take place at the surface of
the photoexcited semiconductor photocatalyst (Fig. 1). Recombina-
tion between electron and hole occurs unless oxygen is available to
scavenge the electrons to form superoxides (O2 •− ), its protonated
form the hydroperoxyl radical (HO2 • ) and subsequently H2 O2 .
3. Mechanism of titania-assisted photocatalytic
degradation
Titania has been widely used as a photocatalyst for generating
charge carriers thereby inducing reductive and oxidative processes,
respectively [18]. Generally, for titania-assisted aerobic photocat-
alytic reaction as opposed to a photosynthetic reaction G is
negative [7]. The corresponding acid HA of the non-metal sub-
stituent is formed as by product:
(7)
Many elementary mechanistic processes have been described
in the photocatalytic degradation of organic compounds over TiO2
surface. The characteristic time for each elementary reaction has
been reported in previous literature (Table 1).
The {>TiIV OH•+ } and {>TiIII OH} represent the surface-trapped
valence band electron and surface-trapped conduction band elec-
trons, respectively. The surface-bound OH radical represented by
{>TiIV OH•+ } is chemically equivalent to the surface-trapped hole
allowing the use of the former and latter terms interchangeably
[20]. According to Lawless and Serpone [22] the trapped hole and
a surface-bound OH radical are indistinguishable species.
There exist a good correlation between charge carrier dynam-
ics, their surface densities and the efficiency of the photocatalytic
degradation over TiO2 . In the last two decades, aqueous suspen-
sions of TiO2 have been probed by picosecond and more recently
femtosecond absorption spectroscopies [23,24]. Traditionally, an
electron scavenger has been employed in such study. A femtosec-
ond spectroscopic study of TiO2 /SCN− aqueous system by Colombo
and Bowman [23] indicated dramatic increase in the popula-
tion of trapped charge carriers within the first few picoseconds.
The results also confirmed that for species adsorbed to TiO2 , the
 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12 3

Fig. 1. Schematic photophysical and photochemical processes over photon activated semiconductor cluster (p) photogeneration of electron/hole pair, (q) surface recombi-
nation, (r) recombination in the bulk, (s) diffusion of acceptor and reduction on the surface of SC, and (t) oxidation of donor on the surface of SC particle.

hole-transfer reaction can successfully compete with the picosec- undergo rapid (∼1 ps) recombination immediately after photoexci-
ond electron–hole recombination process. The following interfacial tation. The important consequences of surface trapped holes (h+ TR )
photochemical reactions were described: and electrons (e− TR ) to the photoxidation of organic compounds
have been highlighted by Serpone et al. [28].
Photoexcitation : TiO2 + h → e− CB + h+ VB (8) In most applications, photocatalytic degradation reactions are
− − carried out in presence of water, air, the target contaminant and
Charge carrier trapping : e CB → e TR (9)
the photocatalyst. The presence of water is indispensable in TiO2
Charge carrier trapping : h+ VB → h+ TR (10) photocatalysis. Earlier work on 2-propanol photooxidation indi-
cated that the reaction did not proceed in the absence of water
[29]. Fig. 2 shows the stages in the photoinduced processes of the
Electron–hole recombination : photomineralisation of organic contaminant in presence of TiO2 .
Photoholes have great potential to oxidize organic species
e− TR + h+ VB (h+ TR ) → e− CB + heat (11) directly (although mechanism not proven conclusively [6]) or indi-
Bahnemann et al. [25] provided evidence for the trapped charge rectly via the combination with OH• predominant in aqueous
carriers using flash radiolysis. Primarily, the fission of bonds in solution [15,30]:
organic molecules is due to the interaction of the trapped e− TR
H2 O + h+ → OH• + H+ (12)
(Ti3+ ) and h+ TR (presumably • OH) pairs near TiO2 particle [26].
In agreement with the foregoing, Furube et al. [27] observed that
R–H + OH• → R • + H2 O (13)
trapped carriers mainly exist near the particle surface and do not
R + h+ → R +• → Degradation products (14)
Table 1
Primary processes and time domains in titania-catalyzed mineralisation of organic The mediation of radical oxidative species in photooxidation was
pollutants [19–21] evidenced by photo- and electro-luminescence spectra of TiO2 elec-
Primary process Characteristic time trode in aqueous solutions measured as functions of the electrode
potential and the solution pH [31]. It was found that the radical
Charge carrier generation
TiO2 + h␯ → e− + h+ fs (very fast)
oxidative species originally absent accumulated after illumination
under anodic bias.
Charge carrier trapping
The primary photoreactions (1)–(11) indicate the critical role
h+ + >TiIV OH → {>TiIV OH• + } 10 ns (fast)
e− + >TiIV OH  >TiOHIII } 100 ps (shallowtrap; dynamic of charge carriers (electron–hole pair) in photooxidative degrada-
equilibrium) tion. Essentially, hydroxyl radicals (• OH), holes (h+ ), superoxide
e− + >TiIV → TiIII 10 ns (deep trap) ions (O2 − ) and hydroperoxyl radicals (• OOH) are highly reactive
Charge carrier recombination intermediates that will act concomitantly to oxidize large vari-
e− + {>TiIV OH• + } → >TiIV OH 100 ns (slow) ety of organic pollutants including volatile organic compounds
h+ + >TiIII OH → TiIV OH 10 ns (fast) (VOCs) and bioaerosols [32,33]. It is however argued experimen-
Interfacial charge transfer tally that the oxidative reaction on titania photocatalyst surface
{>TiIV OH• + } + organic molecule 100 ns (slow) occurs mainly via the formation of holes (with quantum yield
→ >TiIV OH + oxidized molecule of 5.7 × 10−2 ) not hydroxyl radicals formation (quantum yield
{>TiIII OH} + O2 → >TiIV OH + O2 • − ms (very slow)
7 × 10−5 ) [34].
4 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12

Fig. 2. Conceptual diagram for the primary processes involved in photomineralisation of organic compounds.

As a photochemical application, TiO2 photocatalysis is invariably in the process, it is scavenged by oxygen to form HO2 • radicals,
affected by the surface properties of the TiO2 particle. The photoin- which finally convert to • OH radicals.
duced phenomenon is affected by quantum size. Anpo et al. [35] The kinetics of photocatalytic degradation of organic com-
observed blue shift and increase in reaction yield and photocat- pounds usually follows the Langmuir–Hinshelwood scheme
alytic activity as the diameter of the TiO2 particles becomes smaller [16,19,20].
especially below 100 Å. This observation was attributed to the sup-
dC kKC
pression of radiationless transfer and the concurrent enhancement r=− = (15)
dt 1 + KC
of the activities of the charge carriers.
The reaction mechanism for the photooxidative degradation of where r represents the initial rate of photooxidation, C the concen-
many organic pollutants over titania particle has been extensively tration of the reactant, t the irradiation time, k the rate constant
reviewed [19,20,36]. The number of intermediates in the reac- of the reaction and K is the adsorption coefficient of the reactant.
tion and ease of decomposition depends upon the nature organic At mM concentrations C  1, the equation can be simplified to the
contaminant studied. The photocatalytic degradation of methanal apparent rate order equation [39,40]:
and phenol are interesting mechanistic examples on the role of
ln C0
hole, superoxide and hydroxyl radicals in titania-assisted pho- = kKt = Kapp t (16)
C
tomineralisation of aliphatic and aromatic organic templates. The
mechanisms are illustrated in Figs. 3 and 4, respectively. or
In the degradation of phenol, several intermediates have been
Ct = C0 e−Kapp t
reported (Fig. 4). The OH• radical attacks the phenyl ring of the
phenol (a), yielding catechol (b), resorcinol (c), benzene-1,2,3-triol where Kapp is the apparent first order rate constant given by the
(d) and hydroquinone (e), then the phenyl rings in these compounds slope of the graph of ln C0 /C versus t and C0 is the initial con-
break up to give maleic acid (f), then short-chain organic acids such centration of the organic pollutant. Consequently under the same
as, 3-hydroxy propyl carboxylic acid (g), 2-hydroxy propanal (i), condition, the initial degradation rate could be written in a form
2-hydroxy-ethanoic acid glycol acid (j), finally CO2 and H2 O. Even conforming to the apparent first order rate law:
though H• produced during the attack of bonds by OH• participates
r0 = Kapp C (17)

A quasi-exhaustive consideration of photodestruction studies

of organic contaminants proved that the first order rate equa-
tion above holds true [41–46]. At any rate, Langmuir–Hinshelwood
model serves as a basis for the photodegradation of organic
compounds even if it could not directly give adequate fitting
[47]. Nevertheless, for suspended titania-mediated photocatalytic
degradation of organic compounds pseudo-zeroth order is reported
[48].

4. Titania versus existing photocatalysts

An ideal photocatalyst for photocatalytic oxidation is character-

ized by the following attributes [7]:

(1) Photo-stability.
(2) Chemically and biologically inert nature.
Fig. 3. Photocatalytic oxidation of formaldehyde over titania [37]. (3) Availability and low cost.
 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12
Fig. 4. Degradation of phenol in wastewater over nanomaterial titania [38].
(4) Capability to adsorb reactants under efficient photonic activa-
tion (h ≥ Eg ).
Many chalcogenide semiconductors such as TiO2 , ZnO, ZrO2 ,
CdS, MoS2 , Fe2 O3 and WO3 have been examined and used as pho-
tocatalysts for the degradation of organic contaminants [49]. The
minimum band gap energy required for photon to cause photogen-
eration of charge carriers over TiO2 semiconductor (anatase form)
is 3.2 eV corresponding to wavelength of 388 nm [50]. Actually with
TiO2 , photoactivation takes place in the range 300–388 nm.
The photoinduced transfer of electrons that take place with
adsorbed species over semiconductor photocatalyst depends on the
band-edge position of the semiconductor and the redox potentials
of the adsorbates [30].
In spite of the constant vigorous research activities over two
decades in search for an ideal photocatalyst, titania in its anatase
modification has remained a benchmark against which any emerg-
ing material candidate will be measured [51]. The anatase form of
titania is reported to give the best combination of photoactivity
and photostability [6]. Nearly all studies have focused on the crys-
talline forms of titania namely anatase and rutile. However, Zhang
and Maggard [52] reported the preparation of hydrated form of
amorphous titania with wider band energy gap than anatase and
significant photocatalytic activity. The schematic diagram of band
positions for various semiconductors is shown in Fig. 5.
5. Effect of operational parameters
5.1. Light intensity
Photocatalytic reaction rate depends largely on the radiation
absorption of the photocatalyst [53]. Refs. [54,55] revealed increase
in the degradation rate with increase in light intensity during pho-
tocatalytic degradation. The nature or form of the light does not
affect the reaction pathway [56]. In other words, the band-gap
sensitization mechanism does not matter in photocatalytic degra-
dation.
Unfortunately, only 5% of the total irradiated natural sunlight has
sufficient energy to cause effective photosensitization [57]. Besides,
energy loss due to light reflection, transmission and energy loss as
heat is inevitable in the photoprocess [58]. This limitation largely
invited more research in the application of TiO2 to decontamina-
5
tion. The overall quanta of light absorbed by any photocatalyst or
reactant is given by ˚overall , the quantum yield:
rate of reaction
˚overall = (18)
rate of absorption of radiation
as metal oxide such as TiO2 in a heterogeneous regime cannot
absorb all the incident radiation due to refraction, it has been
experimentally difficult to determine quantum yield [59]. The
light scattering in solid–liquid regime particularly is significant.
Another factor limits photonic efficiency is the thermal recombina-
tion between electron and hole [60]. For these reasons, it is argued
that reference to quantum yield or efficiency in heterogeneous sys-
tem is ill-advised despite previous use of the term by previous
references [61,62].
A practical and simple alternative for comparing process effi-
ciencies was suggested [63] by defining a relative photonic
efficiency  r . A quantum yield can subsequently be determined
from  r , as ˚ =  r ˚phenol , where ˚phenol is the quantum yield for
the photocatalyzed oxidative disappearance of phenol (a standard
secondary actinometer) using Degussa P-25 TiO2 as the standard
catalyst material.
5.2. Nature and concentration of the substrate
Organic molecules which can adhere effectively to the surface of
the photocatalyst will be more susceptible to direct oxidation [64].
Thus the photocatalytic degradation of aromatics depends on the
substituent group. It is reported that nitrophenol is much stronger
an adsorbing substrate than phenol and therefore degrades faster
[65]. In the degradation of chloroaromatics, Huqul et al. [66] pointed
out that mono-chlorinated phenol degrades faster than di- or
tri-chlorinated member. In general, molecules with electron with-
drawing group such as nitrobenzene and benzoic acid were found
to adsorb significantly in the dark compared to those with electron
donating groups [67].
During photocatalytic oxidation the concentration of organic
substrate over time is dependent upon photonic efficiency [68].
At high-substrate concentrations however, the photonic efficiency
diminishes and the titanium dioxide surface becomes saturated
leading to catalyst deactivation [69].
6 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12
Fig. 5. The conduction and valence band positions of selected metal oxide semiconductors at pH 0. The left hand scale represents the internal energies to the vacuum level.
The right hand scale is the normal hydrogen electrode scale which allows predictions based on reduction and oxidation.
5.3. Nature of the photocatalyst
There is direct correlation between of organic pollutant and sur-
face coverage of TiO2 photocatalyst [70]. Kogo et al. [71] reported
that the number of photons striking the photocatalyst actually
controls the rate of the reaction. The latter is an indication that
the reaction takes place only in the adsorbed phase of the semi-
conductor particle. A very important parameter influencing the
performance of photocatalyst in photocatalytic oxidation is the sur-
face morphology, namely the particle size and agglomerate size
[72].
Numerous forms of TiO2 have been synthesized by different
methods to arrive at a photocatalyst exhibiting desirable physical
properties, activity and stability for photocatalytic application [73].
Evidently, there is a clear connection between the surface proper-
ties, the rational development of improved synthesis routes and the
possible usefulness of the material prepared in application [74,75].
For instance, smaller nano-particle size is reported to give higher
conversion in gaseous phase photomineralisation of organic com-
pounds over nano-sized titanium dioxide [76].
5.4. Photocatalyst concentration
The rate of photocatalytic reaction is strongly influenced by
concentration of the photocatalyst. Heterogeneous photocatalytic
reactions are known to show proportional increase in pho-
todegradation with catalyst loading [77]. Generally, in any given
photocatalytic application, the optimum catalyst concentration
must be determined, in order to avoid excess catalyst and ensure
total absorption of efficient photons [78]. This is because an
unfavourable light scattering and reduction of light penetration into
the solution is observed with excess photocatalyst loading [79].
5.5. pH
An important parameter in the photocatalytic reactions taking
place on particulate surfaces is the pH of the solution, since it dic-
tates the surface charge properties of the photocatalyst and size
of aggregates it forms [80]. In the current update of the points
of zero charge (pzc) by Kosmulski [81] Degussa P-25, 80% anatase
and 20% rutile is reported to have pzc 6.9. Under acidic or alkaline
condition the surface of titania can be protonated or deprotonated
respectively according to the following reactions:
TiOH + H+ → TiOH2 + (19)
− −
TiOH + OH → TiO + H2 O (20)
Thus, that titania surface will remain positively charged in acidic
medium (pH < 6.9) and negatively charged in alkaline medium
(pH > 6.9). Titanium dioxide is reported to have higher oxidizing
activity at lower pH but excess H+ at very low pH can decrease
reaction rate [82].
The effect of pH on the photocatalytic reactions of organic
compounds and adsorption on TiO2 surface has been extensively
studied [83,84]. Change in pH can result in enhancement of the
efficiency of photoremoval of organic pollutants in presence of tita-
nium dioxide without affecting the rate equation [85]. At optimized
conditions better degradation has been reported [86].
5.6. Reaction temperature
Experimental studies on the dependence of the reaction rate
of degradation of organic compounds on temperature have been
carried out since 1970s [12]. Many researchers established exper-
imental evidence for the dependence of photocatalytic activity
on temperature [87–91]. Generally, the increase in temperature
 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12
enhances recombination of charge carriers and desorption process
of adsorbed reactant species, resulting in decrease of photocatalytic
activity. This is in conformity with Arrhenius equation, for which
the apparent first order rate constant Kapp should increase linearly
with exp(−1/T).
6. Methods of utilization of titania photocatalyst
Titania photocatalyst can be used either as free-standing par-
ticulate or as coating on a substrate. Most experiments utilized
finely powdered TiO2 particles suspended in contaminated water,
which provides large surface area and makes recovery easy after
treatment [92]. Larger particulates may prove useful even in the
case of gaseous organic contaminants but are rather commercially
unavailable and may be costly [6].
Coated catalyst configurations, on the other hand, eliminate the
need for catalyst filtration and centrifugation but generally result in
a significant reduction in system efficiency. A reduction of 60–70%
reduction in performance is reported in aqueous systems for immo-
bilized TiO2 as compared to the unsupported catalyst [39].
Many kinds of support have been explored for TiO2 photocat-
alyst which include soda lime glass [93], aluminium [94], ceramic
tiles [95] and coated glass [96]. Since coatings are very thin, the
actual active surface area of the photoreactor compared to the over-
all volume is low. Despite aforementioned drawbacks, more coated
photocatalysts and immobilisation techniques are still investigated.
In many of these cases TiO2 coated on support assumed more effi-
ciency in organic compound removal than uncoated TiO2 [18].
7. Trends in improving the activity of titania
Despite drawbacks of titania photocatalysis many organic com-
pounds have been successfully investigated largely from the
viewpoint of air and water purification. A large number of organic
contaminants have been studied including endocrine disrupting
compounds (EDCs) [97]. By far, the following avenues have been
constantly explored mainly to suppress electron–hole recombina-
tion and to enhance the photosensitivity of titania for successful
application [58].
7.1. Novel photocatalyst preparations
Due to the constraints involved in ensuring effective photoac-
tivation, there has been growing quest to go beyond the threshold
wavelength of 388 nm which corresponds to the band gap of titania.
The principal foci of these activities include [57,98]
• incorporation of energy levels into the band gap of the titania,
• changing the life time of charge carriers,
• substitution of the Ti4+ with cation of the same size and
• shifting the conduction band and/or valence band so as to enable
photoexcitation at lower energies; success of which depends on
the preparation method.
The major practices involve catalyst modification by doping,
metal coating, surface sensitization, increase in surface area or by
design and development of secondary titania photocatalyst. Sur-
face sensitization has been intensively reviewed elsewhere [7].
Recent studies indicate enhancement of photocatalytic degrada-
tion of gaseous organic contaminants such as acetaldehyde and
phenol over fluorinated titania surface. Depending on the kind of
substrate and reaction condition the effect of surface fluorination
can be positive or negative [99].
7
Fig. 6. Modification of titania photocatalyst by metal doping.
Since 1980s TiO2 has been modified mainly by metal loading
or platinization to achieve better photocatalytic activity [100–102].
Successful doping can be achieved with either transition metal ion
or with non-metal resulting in enhanced efficacy of the photocata-
lyst system (Fig. 6). The last 4 years has attracted growing interest
in doping of titania with Pt due to promising improvement in pho-
tooxidation rate especially in gas phase. Pt–TiO2 has been found
to improve the photooxidation rate of ethanol, acetaldehyde and
acetone in gaseous phase [103]. Nitrogen doped into substitutional
sites of TiO2 has proven very efficient for photocatalysis [104]. Fe
doped zirconia has been reported to show lower efficiency than
even titania P-25 [105,106]. The photophysical mechanism of doped
TiO2 is not yet understood but the p-type metal ion dopants (with
valencies lower than that of Ti4+ ) are believed to act as acceptor
centres as opposed to the p-type [7]. Metal ion implantation with
ions such as V, Cr, Mn, Fe and Ni, was found to cause large shift in
the absorption band of titanium dioxide towards the visible region.
There is no red shift in the case of TiO2 implanted with Ar or Ti
[107] which indicates that the bathocromic shift is not due to the
implantation itself.
Unlike many photocatalysts TiO2 can absorb UV-A light in the
form of sun or room light and as reported in this review can
be improved to absorb light beyond the wavelength of 388 nm.
The assertion to use visible light in photoinduced processes by
Nozik [108] has been as old as the phenomenon of photocataly-
sis itself. Numerous researches aimed at investigating solar TiO2
photocatalytic oxidation [109,110] and novel visible responsive
photocatalyst have been prepared by doping the photocatalyst with
metal or non-metal. Table 2 shows promising preparation of TiO2
photocatalyst made in the recent years.
In mixed semiconductor photocatalysts the synthesis procedure
has marked effect on the catalytic activity of the hybrid photocata-
lyst as reported in the case of TiO2 –SiO2 [130,131]. TiO2 –SiO2 binary
oxides have great potential in the removal of VOCs [132]. In the
case of TiO2 –ZrO2 and TiO2 –SiO2 hybrid oxides the crystallite struc-
ture has marked effect on the photoactivity [133] perhaps because
recombination is increased by crystallite defects. Doong et al. [134]
achieved folds of photocatalytic performance in 2-chlorophenol
degradation with mixed suspension of CdS and TiO2 . The following
primary processes leading to inter-particle electron transfer (IPET)
(Fig. 7) were conjectured to describe the phenomenon. Today, IPET
theory has been widely used to describe promotion effect in similar
photocatalysis [135].
CdS + h → CdS(h+ + e− ) (21)
+ −
TiO2 + h → TiO2 (h + e ) (22)
+ − + −
CdS(h + e ) + TiO2 → CdS(h )TiO2 (e ) (23)
CdS(h+ + e− ) + TiO2 (h+ + e− ) → CdS(h+ + h+ ) + TiO2 (e− + e− )
(24)
The excess electrons on the TiO2 can be scavenged by chemisorbed
diatomic molecular oxygen [136].
8 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12

Table 2
Some novel preparations of UV and visible light responsive titania photocatalysts

Photocatalyst Highlights on synthesis and comments on performance Reference

3+
Nd –TiO2 sol The sol prepared by coprecipitation had anatase crystalline structure and showed higher [111]
photocatalytic activity with reactive dye X-3B than titania under visible light illumination
N-doped TiO2 Nitridation of TiO2 extended absorption to visible region. The addition of PdCl2 further extended [112]
absorption to near IR with high-photocatalytic activity
TiO2−x Ny The photocatalyst was prepared by low-temperature process involving mechanical doping and oxygen [113]
plasma treatment
Highly active bicrystalline TiO2 (anatase-brookite) Nanocrystalline TiO2 was prepared at 100 ◦ C by hydrolysis of Ti(C3 H5 O)4 . High specific area of [114]
750 m2 /g and higher photoactivity over Degussa P-25 was obtained
Mesoporous TiO2 Titanium isopropoxide was the Ti source in the sol–gel method. Co-polymer surfactant was used to [115]
direct structure. The polymeric template was removed by solvent extraction
Cr-doped TiO2 Cr doped anatase TiO2 was prepared by the combination of sol–gel and hydrothermal methods. Cr [116]
doping improved photocatalytic activity for the degradation of XRG dye
Ce-doped mesophorous TiO2 Doping inhibited mesophores collapse and anatase–rutile phase transformation. Doped mesophorous [117]
anatase nanoparticles exhibited higher photocatalytic activity than commercial Degussa P-25
Ag-doped nanocrystalline TiO2 order Photocatalyst was prepared by sol–gel method and subsequent ultrasonication. Photocalalytic activity [118]
was evaluated with methylene blue in presence and in absence of NO3 2− , SO4 2− and CH3 COO− . The
anions caused significant increase in the photocatalytic degradation of the dye which followed
pseudo-first order
C-modified nano-TiO2 The photocatalyst was prepared by heating TiO2 at high temperatures in an atmosphere of hexane. [119]
Even though lower photocatalytic activity was obtained than the TiO2 without C deposition the latter
showed less turbidity after photocatalyst sedimentation
Fe3+ -, Cr3+ - and Co2+ -doped nano-crystalline TiO2 Under UV–vis excitation anatase–rutile transformation increased with increasing dopant [120]
concentration
Titanium oxocluster-derived nanocrystalline TiO2 Photocatalyst sourced from Ti7 O4 (OEt)20 precursor had higher activity than the one obtained from [121]
titanium tetraisopropoxide
Zn2+ -doped TiO2 The photocatalyst was prepared by sol–gel and solid phase reaction methods and evaluated with [122]
Rhodamine B. Significant enhancement of the photoactivity of TiO2 resulted
N–F codoped TiO2 Anatase N–F doped TiO2 was prepared by solvothermal method using tetrabutyl titanate precursor. [123]
The photocatalyst showed very high activity towards visible light induced p-chlorophenol
photooxidative degradation
TiO2 /WO3 multilayer thin film Multilayer prepared by pulse laser deposition (PLD) showed high-photocatalytic activity towards [124]
photodecomposition of methylene blue under visible light illumination
V-doped TiO2 Photocatalyst prepared by modified sol–gel method showed high-photocatalytic activity in the [125]
degradation of crystal violet and methylene blue under visible light
TiO2 –SiO2 beads The photocatalyst was prepared from [Ti(iso-OC3 H7 )4 ] and ethyl silicate by dip coating hollow glass [126]
microbeads and calcination preferably at 650 ◦ C for 5 h. The addition of silica inhibited anatase–rutile
transition
TiO2 –ZnO The novel photocatalyst was prepared by modified sol–gel method using citric acid as complexing [127]
agent. By sulfating, the degradation efficiency of the photocatalyst towards methyl orange improved
significantly
TiO2 -carbide Corrugated shapes of carbide were prepared on metal mesh and TiO2 is loaded in the former. This [128]
preparation has commercial potentials for photodegradation at low concentration
Ball-milled TiO2 /SnO2 Photocatalyst was prepared by ball milling through doping of TiO2 . H2 O was used as disperser. The [129]
crystal faces of TiO2 were not changed and new crystal faces were found by ball milling

7.2. Combined operations O3 • + H+ → HO3 • (31)

For deriving an effective decontamination at relatively lower HO3 • → HO• + O2 (32)

cost the UV/TiO2 version of photooxidative degradation process has
been combined with either physical or chemical operation [13].
The rise in the hyphenated methods paved way to the growing
number of novel water treatment technologies thereby overcom-
ing high-treatment costs. The choice of method depends upon the
composition of water in terms of class of the organics [1] and the
pollutant level [38].
In combined TiO2 /inorganic additive photoprocess electron
scavengers such as O3 [137], Fe2+ /Fe3+ + H2 O2 [138], H2 O2 , S2 O8 2−
and BrO3 − [139] are added to trap electrons and generate more • OH
[50].

H2 O2 + e− → • OH + − OH (25)
2− − 2− •−
S2 O8 + e → SO4 + SO4 (26)
•− +
SO4 + H2 O → SO4 2−
+ • OH +H (27)

BrO3 − + 2H+ + e− → BrO2 • + H2 O (28)

BrO3 − + 6H+ + 6e− → [BrO2 − , HOBr] → Br− + 3H2 O (29)

− −
O3 + e → O3 (30) Fig. 7. Band diagram illustrating charge carrier transfer in coupled semiconductors.
Table 3
Photocatalytic degradation of organic compounds by TiO2 under UV irradiation

Class of organic contaminants Target compound Highlights on experimentals and findings Reference

Aldehydes Acetaldehyde Photomineralisation efficiency over TiO2 film exceeds that over F-TiO2 . Surface fluorination causes adsorption [99]
inhibition to a large extent
Formaldehyde 30 W UV lamp (297 ) and silica support were used in the study. CO and CO2 , found as product of degradation
adsorb on the TiO2 photocatalyst. This could cause catalyst deactivation
Carboxylic acids Phenoxy acetic acid and 2,4,5-phenoxyacetic acid The effect of pH, catalyst, BrO3 − and H2 O2 to degradation was significant in all cases. Degussa P-25 was more [145]
efficient photocatalyst than Hombicat UV 100, Millenium Inorganic PC500 and Travancore
Oxalic acid Synergetic effect of combined sonolysis photocatalysis was confirmed in Ar atmosphere. H2 and CO were [146]
obtained in addition to CO2 . H2 O2 played significant role in the process

U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12
Chloroanilines 2-Chloroaniline Slower degradation resulted at low pH in the UV/TiO2 /H2 O2 system. Excess H2 O2 retarded the degradation rate [147]
Chlorocarboxylic acids Monochloro-acetic acid In the ozonation-photocatalysis, O3 showed high-electron affinity thereby improving the removal rate. O3 was [137]
not decomposed by UV light in the system
Chlorophenols 2-Chlorophenol Photoelectrocatalytic degradation carried out in a batch reactor using TiO2 coated Ti sheets as anode and Pt [148]
cathode was more effective in acidic medium and rate increases linearly with light intensity
4-Chlorophenol Photomineralisation studied with different samples of TiO2 . Degussa P-25 proved more effective a [5]
photocatalyst. Both solar pilot plant and laboratory experiment indicated apparent first order kinetics. Fewer
intermediates and faster TOC disappearance was observed in the solar pilot plant which worked with smaller
optimum titania concentration
2,4-Dichlorophenol Two kinetic models for photocatalytic degradation of 2,4-dichlorophenol over Degussa P-25TiO2 suspension [149]
were proposed based on the influence of different variables; pH, radiation and TiO2 concentration
Mixture of 4-chlorophenol, 2,4-dichlorophenol, Sequential photochemical-biological degradation proved useful. There was no removal of chlorophenol with [150]
2,4,6-trichlorophenol and pentachlorophenol H2 O2 or TiO2 alone
Dyes Acid orange 8 and Acid red 1 Sonophotocatalytic degradation was faster than photocatalytic degradation followed by sonolysis [151]
Chrysoidine Y Degussa P-25 was found to be more effective than ZnO in photomineralisation of the dye at laboratory scale. [152]
UV analysis was used in studies
Acridine orange and Ethidium bromide Degussa P-25 showed superior photocatalytic activity than PC300. Degradation rate was affected by inorganic [153]
additives
Methylene blue, methyl orange, indigo carmine, Chicago TiO2 photocatalyst was immobilised on glass and used for dye removal. Chicago sky blue was the most [154]
sky blue, mixed dye (mixture of the four dyes) resistant to the photodegradation. Methyl orange with t1/2 85.6 min was removed faster
Ethers Methyl tert-butyl ether (MBTE) H2 O2 -enhanced photocatalysis had additive effects apart from synergetic effect but hydrogen peroxide [155]
photolysis had higher degradation rate. Acetone, tert-butyl formate and tert-butyl alcohol were determined as
intermediates
Flourophenols 4-Fluorophenol TiO2 -P25 was found to be more efficient than ZnO under the study conditions. The efficiency of anion oxidants [156]
and cations is respectively in the following order IO4 − > BrO3 − > S2 O8 2− > H2 O2 > ClO3 − and
Mg2+ > Fe3+ > Fe2+ > Cu2+
Fungicides Fenamidone Coated optical fibre photoreactor was used in the study. Slow photocatalytic degradation of fenamidone over [157]
TiO2 was observed. COO− and SO4 2− were identified in the reactor
Herbicides Isoproturon Degradation rate over Degussa TiO2 was faster than Hombicat 100 and was increased by the addition of [158]
electron acceptors. Degradation was slower under solar illumination
Ketones Acetone Vibrofluidized and multiple fixed bed photoreactors were compared. The comparison was based on the [159]
quantum efficiency for the photooxidation of acetone using TiO2 (Hombicat UV 100). Vibrofluidized-bed
showed higher activity for photooxidation. Application of ultrasound does not influenced the rate of
photooxidation of acetone
Perflouroaliphatics Triflouroacetic acid, sulfonic acid of nonafluorobutane and Perfluorosulphonic acids were persistent under the experimental conditions studied. However, [160]
heptadecaflourooctane phosphotungstic acid enhanced mineralisation at extreme acidic pH. CO2 evolution was dependent upon
molecular oxygen availability for the process
Phenolics Phenol TiO2 does not favour degradation at concentrations higher than 100 ppm. Active radicals in mechanism were [36]
confirmed to be H• and HO•
Pharmaceuticals Tetracycline Compound was resistant to photolysis. Photocatalysis over 0.5 g/l TiO2 suspension showed rapid rate of [161]
degradation. The irradiated solution inhibits the activity of microorganisms
Lincomycin Solar photocatalysis and membrane separation was used to study the degradation of the antibiotic. [162]
Photocatalysis was coupled with membrane separation to remove catalyst. The photooxidation of lincomycin
followed pseudo-first order rate kinetics
Polymers Polyvinylpyrollidone (PVP) Three major steps were identified in the photomineralisation of PVP; Adsorption, cleavage of main ring and [163]
lactam ring caused by • OH and • OOH attack and finally the conversion of ammine to NH4 + and NO3 − . Degussa
P-25 with particle size 20–30 nm was used for the study. The higher the intensity from 1 to 4 mW cm−2 the
higher the CO2 yield resulting from mineralisation

9
10 U.I. Gaya, A.H. Abdullah / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 9 (2008) 1–12
Fig. 8. Photocatalytic system development cycle.
The UV/TiO2 /O3 version of the TiO2 /inorganic additive pho-
toprocess is based on attractive features of ozone for organic
contaminant removal which include relatively higher scaveng-
ing effect provided by ozone, ability to decrease the rate of
de-excitation of electrons and elimination of residues [133,140].
The combined ozononation-photocatalysis provides double bene-
fit shared in the scenario of disinfection and removal of recalcitrant
organic contaminants. Application of this method could be benefi-
cial to remedy the failure of the ozonation-photolysis in the removal
of recalcitrant N-nitrosodimethylamine (NDMA) from water [141].
Coupled methods of operation have proven their efficacy in air
and water purification. Suryaman et al. [142] considered coupling
biological treatment with photocatalysis degradation method for
the removal of phenol to reduce operational cost on single pho-
tocatalytic process. The mineralisation time shortened compared
to the single biological treatment and the electrical cost saved
compared to the photocatalysis. It is reported that H2 O2 -enhanced
sonophotocatalytic degradation method is efficient in complete
mineralisation of the popular herbicide propyzamide [143]. The
application of photocatalytic membrane reactors designed to com-
bine slurry with membrane filtration is a solution to the problem
of separation of photocatalyst in aqueous systems [144]. Table 3
gives an overview of pollutants successfully photodecomposed
over titania.
8. Miscellaneous
The stages involved in the development of AOPs assume cyclic
form. The cycle, shown in Fig. 8 starts and ends with the analy-
sis of needs by the end-user. Each stage of the development cycle
is critical for successful operation of the next immediate step. A
problem identified with stage (a) and (b) is most of the pollutants
treated are in a form of mixture [1] and only a limited number of
laboratory studies have been carried on mixtures mainly in recent
years [164–168]. Additionally, laboratory studies concentrate only
on degradation kinetics of target organic contaminants disregard-
ing the toxicity of degradation intermediates. Ref. [169] reported
the intermediate of photodegradation more toxic to Escherichia
coli than the starting material. Modelling and design are critical
for successful industrial application. Design efficiency of a reac-
tor configuration is mainly dependent upon its ability to install
as much catalyst per unit volume as possible a factor necessary
for scale-up [170]. Due to the high number of intermediates pro-
duced during the photocatalytic oxidation of even simple organic
contaminants it is difficult to make complete kinetic analysis. More
work is needed in the fundamentals of reactor design and optimiza-
tion of heterogeneous photoreactors [171]. Several reports pointed
out the development of faulty models for photocatalytic oxidation
reactors by many researchers [172,173]. Hernández-Alonso et al.
[140,149] stressed the need to develop accurate kinetic models for
this promising method of decontamination.
8.1. Ecotoxicity of titania photoprocesses
The final products of photocatalytic degradation may not purely
be innocuous substances. Harmful by-products may cause decrease
in reaction rate and secondary pollution [35]. There has been scanty
literature on the toxicity of the photocatalyst or the overall photo-
catalytic process. Although TiO2 is found in toothpaste due to its
safety nano-scale TiO2 water suspension has been reported toxic to
E. coli and antibacterial inhibition increased with particle concen-
tration during photocatalytic experiment [174]. Maness et al. [175]
attributed this toxicity to the attack of polysaturated phospholipids
in the E. coli by radical oxidizing species.
8.2. Future trends
At the present infancy stage of new century future trends for
development would include:
• the preparation of photocatalyst material capable of selective
photocatalytic degradation of organic pollutants;
• novel preparation of ternary mixed oxide systems for photoox-
idative degradation;
• novel photocatalyst preparations from titanium oxo families since
more member of the families became available;
• design of more reliable photocatalyst that can be photoactivated
by visible and solar light or both.
9. Conclusion
• Heterogeneous photocatalytic degradation using TiO2 photocata-
lyst remains a viable alternative for the degradation of persistent
organic contaminants in both air and water. At least this promis-
ing technology solves the problem of transforming recalcitrant
organic contaminants to non-persistent substance.
• Despite its moderate specific area of 50 m2 /g Degussa P-25
remains a very efficient photocatalyst.
• Environmental friendly aerobic photocatalysis or methods which
produce fewer intermediates still need to be developed to allow
accurate development of models and successful application.
• Though this review is non-exhaustive in the scope of photo-
catalytic degradation of organic contaminants, important facets
regarding fundamental principles and application have been
addressed.
Acknowledgement
The authors acknowledge Universiti Putra Malaysia for the fel-
lowship granted to Umar Ibrahim Gaya.
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