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Water Air Soil Pollut (2011) 215:329

DOI 10.1007/s11270-010-0456-3

Advances in Heterogeneous Photocatalytic Degradation


of Phenols and Dyes in Wastewater: A Review
Saber Ahmed & M. G. Rasul & Wayde N. Martens &
Richard Brown & M. A. Hashib

Received: 7 January 2010 / Accepted: 21 April 2010 / Published online: 15 May 2010
# Springer Science+Business Media B.V. 2010

Abstract The heterogeneous photocatalytic water such as type of photocatalyst and composition, light
purification process has gained wide attention due intensity, initial substrate concentration, amount of
to its effectiveness in degrading and mineralizing catalyst, pH of the reaction medium, ionic compo-
the recalcitrant organic compounds as well as the nents in water, solvent types, oxidizing agents/
possibility of utilizing the solar UV and visible electron acceptors, mode of catalyst application,
light spectrum. This paper aims to review and and calcinations temperature can play an important
summarize the recently published works in the field role on the photocatalytic degradation of organic
of photocatalytic oxidation of toxic organic com- compounds in water environment. Extensive re-
pounds such as phenols and dyes, predominant in search has focused on the enhancement of photo-
wastewater effluent. In this review, the effects of catalysis by modification of TiO2 employing metal,
various operating parameters on the photocatalytic non-metal, and ion doping. Recent advances in TiO2
degradation of phenols and dyes are presented. photocatalysis for the degradation of various phenols
Recent findings suggested that different parameters, and dyes are also highlighted in this review.

Keywords Phenols . Azo dyes . Photocatalysis .


S. Ahmed (*) : M. G. Rasul
Faculty of Science, Engineering and Health, CQ University, Water purification
Rockhampton QLD 4702, Australia
e-mail: s.ahmed@cqu.edu.au
1 Introduction
W. N. Martens
Discipline of Chemistry, Faculty of Science and Technology,
Queensland University of Technology, The reuse and recycling of wastewater effluent is
Brisbane, Australia rapidly growing and becoming a necessity for water
utilities both in Australia and in other parts of the
R. Brown
world to augment our limited fresh water supply,
School of Engineering System,
Queensland University of Technology, which is currently under pressure due to rapid
Brisbane, Australia population growth (Radcliff 2006; Mitchell et al.
2002; DEH 2002). Heightened concerns over public
M. A. Hashib health and associated environmental hazards due to
Department of Ecological Engineering,
Toyohashi University of Technology, the presence of toxic organic compounds such as
Toyohashi, Japan phenols and dyes in wastewater have been reported
4 Water Air Soil Pollut (2011) 215:329

(Eriksson et al. 2007). Phenols and azo dyes are well- in the range of 300400 nm with a typical UV flux of
known for their bio-recalcitrant and acute toxicity. 2030 Wm-2.This suggests the feasibility of using
Phenols and azo dyes are being continuously intro- sunlight as an economically and ecologically sensible
duced into the aquatic environment through various light source (Goslich et al. 1997). As a result,
anthropogenic inputs. The presence of toxic organic development of efficient photocatalytic water
compounds in wastewater effluent is still a major purification process for large-scale applications is a
hindrance as regards widespread acceptance of water recent research challenge in order to bring forward
recycling (Mahmoodi et al. 2007; DEC 2006). a new and efficient end-of-pipe technology.
Furthermore, their variety, toxicity, and persistence Compounds studied using photocatalytic oxidations
can directly impact the health of ecosystem and process in aqueous medium belong to various types of
present a threat to humans through contamination of pesticides, phenolic compounds, and cationic and
drinking water supplies, e.g., surface and ground anionic dyes (Shifu and Yunzhang 2007; Echavia et
water. The response has been the drive to achieve al. 2009; Bahnemann et al. 2007). In light of the basic
effective removal of persistent organic pollutants from and applied researches reviewed, photocatalytic
wastewater effluent to minimize the risk of pollution oxidation method appears to be a promising route
problems from such toxic chemicals to enable its for the treatment of wastewater contaminated with
reuse. Consequently, considerable efforts have been phenols and dyes. However, low quantum efficiency
devoted to developing a suitable purification method due to inefficient visible light harvesting catalyst (Sun
that can easily destroy these bio-recalcitrant organic and Bolton 1996), the design of photoreactor
contaminants. Because of incomplete removal during (Mukherjee and Ray 1999), the recovery and reuse
primary and secondary treatment processes, they are of titanium dioxide (Moctezumaa et al. 2007), the
ubiquitous in secondary wastewater effluents at low generation of toxic intermediates (Konstantinou and
concentration. Despite their low concentration, these Albanis 2003), as well as concern over catalyst
contaminants have raised substantial concern in the deactivation (Legrini et al. 1993; Rincon and Pulgarin
public and regulatory agencies due to their extremely 2004; Doll and Frimmel 2005) are reported to be the
high endocrine disrupting potency and geno toxicity major drawbacks. Information from various inves-
(Arques et al. 2007). Moreover, the conventional end- tigations suggest that photocatalytic degradation of
of-pipe techniques also generate wastes during the pesticides, phenols, and dyes is largely dependent on
treatment of contaminated water, which requires the solution pH, types of catalyst and composition,
additional steps and cost. Heterogeneous photo- organic substrate type and concentration, light
catalytic oxidation (HPO) process employing catalyst intensity, catalyst loading, ionic composition of
such as TiO2, ZnO, etc., and UV light has demon- wastewater, types of solvent, oxidant concentration,
strated promising results for the degradation of and calcinations temperature (Shakthivel et al. 2004;
persistent organic pollutants producing more Byrappa et al. 2006). Understanding the impacts of
biologically degradable and less toxic substances various process parameters that govern the photo-
(Garcia et al. 2006; Garca et al. 2007; Garcia et al. catalytic degradation efficiency is of paramount
2008; Hincapie et al. 2006; Maldonado et al. 2007; importance from the design and the operational points
Malato et al. 2002; Oller et al. 2006).This process is of view when choosing a sustainable, efficient
largely dependent on the in situ generation of technique for the treatment of wastewater. This paper
hydroxyl radicals under ambient conditions which aims to review and summarize the role of important
are capable of converting a wide spectrum of toxic operating parameters on the photocatalytic de-
organic compounds including the non-biodegradable gradation of phenolic compounds and dyes together
one into relatively innocuous end products such as with recent achievements. Recent developments in
CO2 and H2O. In HPO process, destruction of TiO2 photocatalysis for the degradation of various
recalcitrant organics is governed by combined action phenols and dyes by means of metal, non-metal, and
of semiconductor photocatalyst, an energetic radiation ion doping are also highlighted in this review.
source and an oxidizing agent. Moreover, the process The existing limitation and future research needs
can be driven by solar UV/visible light. Near the earth associated with the treatment technology are also
surface, the sun produces 0.20.3 mol photons m-2h-1 discussed.
Water Air Soil Pollut (2011) 215:329 5

2 Principle of Photocatalytic Oxidation Process adsorbed water where it is adsorbed as OH-, is the
primary oxidant, and the presence of oxygen can
In the photocatalytic oxidation process, organic prevent the recombination of an electronhole pair. In
pollutants are destroyed in the presence of semi- the photocatalytic degradation of pollutants, when the
conductor photocatalysts (e.g., TiO2 and ZnO), an reduction process of oxygen and the oxidation of
energetic light source, and an oxidizing agent such as pollutants do not advance simultaneously, there is an
oxygen or air. Only photons with energies greater than electron accumulation in the CB, thereby causing an
the band gap energy (E) can result in the excitation increase in the rate of recombination of e- and h+.
of valence band (VB) electrons which then promote the Thus, it is of paramount importance to prevent electron
possible reactions. The absorption of photons with accumulation in efficient photocatalytic oxidation. In
energy lower than E or longer wavelengths usually photocatalysis, TiO2 has been studied extensively
causes energy dissipation in the forms of heat. The because of its high activity, desirable physical and
illumination of the photocatalytic surface with chemical properties, low cost, and availability. Of
sufficient energy leads to the formation of a positive three common TiO2 crystalline forms, anatase and
hole (hv+) in the valence band and an electron (e-) in rutile forms have been investigated extensively as
the conduction band (CB). The positive hole oxidizes photocatalysts. Anatase has been reported to be more
either pollutant directly or water to produce OH active as a photocatalyst than rutile. Similar oxidation
radicals, whereas the electron in the conduction band pathways to those of TiO2 are confirmed in ZnO
reduces the oxygen adsorbed on the photocatalyst photocatalyst including the formation of OH radical
(TiO2). The activation of TiO2 by UV light can be and the direct oxidation by photogenerated holes, etc.
represented by the following steps. ZnO is reported to be as reactive as TiO2 under
concentrated sunlight, since the band gap energy of
TiO2 + h e- + h+ 2:1 ZnO is equal to that of TiO2, i.e., 3.2e V. Different
light sources such as UV lamps and solar radiation
have been used in previous investigations into the
e-+ O2 O2 - 2:2 photocatalysis of various organic contaminants dom-
inant in wastewater effluent. The following sections
In this reaction, h+ and e- are powerful oxidizing describe the influence of parameters on the photo-
and reductive agents, respectively. The oxidative and catalytic degradation of various phenols and dyes.
reductive reaction steps are expressed as,
Oxidative reaction:
3 Influence of Parameters on the Photocatalytic
Degradation of Phenols and Dyes

h+ + Organic CO 2 2:3
3.1 Crystal Composition and Catalyst Type

The photocatalytic activity of TiO2 is dependent on


+
h + H2O .
OH +H + 2:4 surface and structural properties of semiconductor such
as crystal composition, surface area, particle size
distribution, porosity, band gap, and surface hydroxyl
Reductive reaction: density. Average crystal size is of primary importance
in heterogeneous catalysis because it is directly related
to the efficiency of a catalyst through the definition of
OH +Organic CO2 2:5 its specific surface area. A number of commercially
available catalysts have been investigated for the
Hydroxyl radical generation by the photocatalytic photocatalytic degradation of phenolic compounds
oxidation process is shown in the above steps. In the and dyes in aqueous environment. The photocatalyst
degradation of organic pollutants, the hydroxyl titanium dioxide Degussa P25 has been widely used in
radical, which is generated from the oxidation of most of the experimental conditions; other catalyst
6 Water Air Soil Pollut (2011) 215:329

powders, namely, Hombikat UV100, PC 500, and examined the photocatalytic degradation of three
travancore titanium products (TTP) were also used for monoazo anionic dyes (Acid Orane 8, Acid Orange10,
degradation of toxic organic compounds. P25 contains and Acid Orange12) using immobilized TiO2 on glass
75% anatase and 25% rutile with a specific Brunauer- plates and UV light. The photocatalytic degradation
Emmett-Teller (BET) surface area of 50 m2/g and a rates of tested dyes are shown to follow the order:
primary particle size of 20 nm (Bahnemann et al. AO10>AO12>AO8. This is related to the different
2007). Hombikat UV 100 consists of 100% pure and molecular structures of the dyes and their adsorption
smaller anatase with a specific BET surface area of behavior. Alinsafi et al. (2007) tested the efficiency of
250 m2/g and a primary particle size of 5 nm TiO2 supported either on a glass slide or on a non-
(Bahnemann et al. 2007).The photocatalyst PC 500 woven glass fiber fabric for the decolorization of textile
has a BET surface area of 287 m2/g with 100% anatase wastewater under solar light. Decolorization of the
and primary particle size of 510 nm (Bahnemann et tested sample was reported to be 2174% with a range
al. 2007), and TiO2 obtained from TTP, India, has a of chemical oxygen demand (COD) removal rate 0.2
BET surface area of 9.82 m2/g. It has been demon- 0.9 g COD/h/m2. Pare et al. (2008) compared the
strated that the degradation rate of dyes proceeds much efficacy of ZnO, TiO2, and CdS for the photocatalytic
more rapidly in the presence of Degussa P25 as degradation of Acridine Orange. The order of the
compared with other photocatalysts. The efficiency of degradation rate was shown to be as ZnO>TiO2>CdS.
photocatalysts was shown to follow the order: CdS was reported to be less efficient compared with
P25>UV100>PC500>TTP for the degradation of var- ZnO and TiO2, due to its smaller band gaps.
ious dyes (Qamar et al. 2005a, b; Tariq et al. 2005, Muruganandham et al. (2006) studied the effect of
2008; Faisal et al. 2007). In some cases, the order of various photocatalyst on the decolorization and degra-
degradation was found to be UV100>P25>PC500 dation of Reactive Yellow 14 using UV and solar light
(Saquib and Muneer 2002; Saquib et al. 2008a, b). (Muruganandham and Swaminathan 2006a, b). For
The differences in the photocatalytic activity are likely both processes, the order of activities of the photo-
to be related to the variations in the BET surface, catalysts is shown to be ZnO>P25>TiO2 anatase after
impurities, existence of structural defects into crystal- 40 min irradiation. CdS, Fe2O3, and SnO2 were
line frame work, or density of hydroxyl groups on the reported to have negligible activity on the degradation
catalyst's surface. These factors could influence the of RY 14 decolorization and degradation. An order of
adsorption behavior of a pollutant or degradation P25>ZnO>TiO2 anatase has been reported for the
intermediates and the lifetime and recombination rate solar photocatalytic degradation of reactive orange 4
of electronhole pairs (Qamar et al. 2005a, b). Lu et al. (Muruganandham and Swaminathan 2004). Guetta
2007 compared the photocatalytic degradation of and Ait Amar (2005) compared the performance of
methyl orange (MO) using natural rutile (rutile 93%) five catalysts for the degradation of MO. The order
and P25 (20% rutile) under visible light. After 2 h of efficiency was shown to be P25>Pt-UV100>
irradiation, the degradation efficiency was reported to UV100>Mikro anatase>Prtios AV01. The photo-
be 82.33% and 94.85%, respectively. A possible reason catalytic activity of Degussa P25 was reported to be
was the particle size of P25 (30 nm) which is higher due to slow recombination between electron and
significantly smaller compared with the natural rutile holes where as Hombikat UV 100 has a high photo-
sample (7080 m). In suspended form, Lachheb et al. reactivity due to fast interfacial electron transfer rate.
(2008) reported that, in comparison to PC 500, P25 The higher photoactivity of P25 has been attributed to
was more efficient for the degradation of phenols and its crystalline composition of rutile and anatase. The
poly nitrophenols (4-NP, 2,4-DNP,2,4,6-TNP) in the smaller band gap of rutile absorbs the photons and
presence of either artificial or solar light. The photo- generates electronhole pairs. Then, the electron
catalytic degradation of the tested compounds was transfer takes place from the rutile CB to electron traps
shown in the following order: 2,4,6-TNP>2,4-DNP>4- in anatase phase. Recombination is thus inhibited,
NP>phenol. For PC 500 supported on Ahstrom paper allowing the hole to move to the surface of the particle
1048, the order is different: phenol<4-NP<2,4-D,N, and react (Bahnemann et al. 2007). Guillard et al.
P<2,4,6-TNP. The difference was related to the (1999) compared the photocatalytic efficiency of
variation in adsorption behavior. Khataee et al. (2009) different catalyst with various surface areas, crystallite,
Water Air Soil Pollut (2011) 215:329 7

particle size, and their chemical surface for the conversion and degradation efficiency (Pareek et al.
degradation of 4-chlorophenol. The observed order of 2008). Consequently, the dependency of pollutant
efficiency based on the rate of degradation upon solar degradation rate on the light intensity has been
exposure was shown to be: TiONA PC 10>P25>TiL studied in numerous investigations for various organic
COM HC 120>Hombikat UV 100. In the presence of pollutants; while in some cases, the rate of reaction
P25, Selvam et al. (2007) indicated that complete exhibited a square root dependency on the light
degradation of 4-flurophenol with P25 was achieved in intensity, others observed a linear relationship
60 min while complete degradation occurred in 90 min between the two variables (Terzian and Serpone
in the presence of ZnO. Zheng et al. 2007 compared 1991).Ollis et al. (1991) reviewed the effect of light
the photocatalytic degradation of reactive brilliant red intensity on the organic pollutant degradation rate. It
X-3B in water with pure ZnO, ZrO2ZnO, and P25 has been reported (Hermann 1999) that the rate is
TiO2. The degradation of reactive brilliant red over proportional to the radiant flux for <25 mW/cm2,
coupled ZrO2ZnO was shown to be higher compared and above 25 mW/cm2, the rate has been shown to be
with pure ZnO and also slightly better than that of P25 varied as 1/2, indicating a too-high value of the flux
and TiO2. Sobana and Swaminathan (2007) compared and an increase of the electronhole recombination
the efficiencies of various catalysts (ZnO, TiO2 rate. At high intensity, the reaction rate is independent
anatase, ZnS, SnO2, Fe2O3, and CdS for the degrada- of light intensity. This is likely because at low-
tion of Acid Red 18 under UV irradiation. The highest intensity reactions involving electronhole formation
degradation was achieved with ZnO over TiO2 anatase are predominant, and electronhole recombination is
catalyst due to higher surface area of ZnO (10 m2/g) insignificant. Kaneco et al. (2004) investigated the
over TiO2 anatase (8.9 m2/g). SnO2, Fe2O3, CdS, and effect of light intensity on the solar photocatalytic
ZnS have negligible actively on Acid Red 18 decolor- degradation of Bishphenol A in water with TiO2 on
ization due to smaller band gap which permits rapid sunny and cloudy days. The degradation efficiency is
recombination of hole and electron. Talebian and shown to increase rapidly with increase in the light
Nilforoushan 2009 compared the photocatalytic degra- intensity up to 0.35 mW/cm2, and then the efficiency
dation efficiency of methylene blue (MB) under UV increased gradually. Muruganandham et al. (2006)
irradiation. The observed order of photocatalytic effi- examined the effect of UV radiation power on the
ciency was shown to be SnO2<ZnO<TiO2<In2O3. The decolorization and degradation of Reactive Yellow
same trend was also observed at different pH values for 14. Reported results indicated that the decolorization
the photocatalytic activities of different catalysts due to and degradation increases between 16 and 32 W but
their various micro-structures. Zhang et al. 2004 the increase is not significant in the range of 32
compared the efficiency of coupled oxide ZnOSnO2 48 W, and it is independent of light intensity in the
with ZnO or SnO2 for the degradation of MO. The range of 4864 W. Radiation of 30 W was found to be
photocatalytic efficiency of ZnOSnO2 was significant- the optimum intensity. The increase in light intensity
ly higher compared with ZnO or SnO2 alone. from 18.8 to58.5 Wm-2 increases the decolorization of
Cun et al. (2002) compared the efficacy of zinc Acid Red 27 from 25% to 42% and the degradation
sulfide (ZS) and pure SnO2 for the photocatalytic from 13% to 28% in an 80-cm length immobilized
degradation of MO. The degradation efficiency was continuous flow reactor (Behnajady et al. 2007).
reported to follow the order of Z2S>ZS>ZnO>SnO2. Venkatachalam et al. (2007a) compared the mineral-
ization efficiency of 4-CP using the lamps of
3.2 UV Light Intensity wavelength 365 and 254 nm over TiO2. The miner-
alization rate at 365 nm is reported to be slightly
The light intensity determines the extent of light higher than at 254 nm. The degradation rate constant
absorption by the semiconductor catalyst at a given of Acridine Orange was shown to increase from 0.018
wavelength. The rate of initiation for photocatalysis, to 0.0892 min-1 as the light intensity increases from
electronhole formation in the photochemical reaction 5,000 to 45,000 LUX (Pare et al. 2008). Chiou et al.
is strongly dependent on the light intensity (Cassano (2008a) studied the effect of UV light intensity (20
and Alfano 2000). Light intensity distribution within 400 W) on the phenol degradation. In the UV/TiO2
the reactor invariably determines the overall pollutant system, the degradation rate constants with a light
8 Water Air Soil Pollut (2011) 215:329

intensity of 20, 100, and 400 W are 8.310-3, 0.012, concentration from 0.022 to 0.09 mM (Selvam et al.
and 0.031 min-1, respectively. Under the conditions 2007). Similar trends have been observed for the
tested, an acceptably good linear correlation exists photocatalytic degradation of phenol and m-
between the apparent first-order-rate constant and nitrophenol (Chiou et al. 2008b), Acid Red 114
light intensity. The photocatalytic degradation of Acid (Nikazor et al. 2008), methyl red (Sahoo et al.
Red 88 using immobilized ZnO was shown to 2005), Acid Blue 80 under solar irradiation (Su et
increase with increase in light intensity (Behnajady al. 2008), Amido Black (Qamar et al. 2005b), and
et al. 2009). At higher light intensity, the catalyst Acid Orange 7 (Daneshvar et al. 2007). The removal
absorbs more photons producing more electronhole of bisphenol A was reported to decrease from 100% to
pairs in the catalyst surface, and this increases the 97% as the initial substrate concentration increased
hydroxyl radical concentration and consequently from 0.001 to 0.018 mM, and the removal efficiency
increases the degradation rate. decreased from 97% to 67% with further increase in
BPA concentration to 0.044 mM (Tsai et al. 2009).
3.3 Pollutant Type and Concentration Venkatachalam et al. (2007a) observed that the
photocatalytic degradation of 4-CP increases with
The successful application of photocatalytic oxidation increase in initial concentration up to 0.194 mM and
system requires the investigation of the dependence of then decreases with further increase in 4-CP concen-
photocatalytic degradation rate on the substrate tration from 0.194 to 0.233 mM. This effect has been
concentration. A summary of various phenols and associated with the screening effects at 4-CP concen-
dyes studied under different initial concentration is tration greater than 0.194 mM. Consistently similar
presented in Table 1. In the presence of TiO2 and results have been reported for the photocatalytic
ZnO, the degradation rate of 4-flurophenol was degradation of Chromotrope 2B, Xylenol Orange,
shown to decrease with the increase in initial Bromothymol, Acridine Orange, Acid Orange 8,

Table 1 Influence of initial pollutant concentration on the photocatalytic degradation of various pollutants

Pollutant type Light Photocatalyst Range of initial Optimum concentration, Reference


source concentration, mM mM

Phenol UV TiO2 0.130.71 0.13 Chiou et al. 2008b


m-Nitrophenol UV TiO2 0.130.71 0.13 Chiou et al. 2008b
Chrysoidine Y UV TiO2 0.131.0 0.75 Qamar et al. 2004
Acid Orange 7 UV ZnO 0.0030.009 0.003 Daneshvar et al. 2007
Remazol Brilliant Blue R Solar TiO2 0.120.5 0.12 Saquib and Muneer 2002
Disperse Blue 1 UV TiO2 0.130.5 0.125 Saquib et al. 2008b
Amaranth UV TiO2 0.30.6 0.5 Tariq et al. 2005
Bismarck UV TiO2 0.30.6 0.6 Tariq et al. 2005
Reactive Orange 4 UV F-TiO2 0.0150.035 0.3 Vijayabalan et al. 2009
Acid Blue 45 UV TiO2 0.30.6 0.3 Tariq et al. 2008
Xylenol Orange UV TiO2 0.30.6 0.5 Tariq et al. 2008
Acridine Orange UV TiO2 0.10.5 0.25 Faisal et al. 2007
Ethidium bromide UV TiO2 0.10.4 0.1 Faisal et al. 2007
Bromothymol UV TiO2 0.150.5 0.35 Haque and Muneer 2007
Fast green FCF UV TiO2 0.0310.125 0.031 Saquib et al. 2008a
Phenol UV Pr-TiO2 0.111.7 0.11 Chiou and Juang 2007
Acid Blue 80 Solar TiO2 0.030.2 0.03 Su et al. 2008
Acid Red 18 UV ZnO 0.21.0 0.2 Sobana and Swaminathan 2007
Chromotrope 2B UV TiO2 0.250.75 0.35 Qamar et al. 2005b
Amido Black 10B UV TiO2 0.250.75 0.25 Qamar et al. 2005b
Water Air Soil Pollut (2011) 215:329 9

Amaranth, and Remazol Brilliant Blue R (Saquib and concentration, resulting in a reduction in surface area
Muneer 2002). At high pollutant concentration, the available for light absorption and hence, a drop in
adsorbed reactant molecules may occupy all the active photocatalytic degradation rate. Although the number
sties of catalyst surface, and this leads to decrease in of active sites in solution will increase with catalyst
degradation rate (zero-order kinetics). As explained in loading, a point will appear to be reached where light
several investigations that, as the concentration of penetration is to be compromised because of exces-
target pollutant increases, more and more molecules of sive particle concentration. The trade-off between
the compound get adsorbed on the surface of the these two opposing phenomena results in an optimum
photocatalyst. Therefore, the requirement of reactive catalyst loading for the photocatalytic reaction
species (OH and O2-) needed for the degradation of (Adesina 2004). A further increase in catalyst loading
pollutant also increases. However, the formation of beyond the optimum will result in non-uniform light
OH and O2- on the catalyst surface remains constant intensity distribution, so that the reaction rate would
for a given light intensity, catalyst amount, and indeed be lower with increased catalyst dosage.
duration of irradiation. Hence, the available OH Table 2 summarizes the effect of catalyst concentration
radicals are inadequate for the pollutant degradation on the photocatalytic degradation of various phenols
at higher concentration. Consequently, the degradation and dyes in numerous studies. Venkatachalam et al.
rate of the pollutant decreases as the concentration (2007a, b) observed that the degradation rate of 4-CP
increases (Bahnemann et al. 2007). In addition, an increases linearly with catalyst concentration up to 2 g/
increase in substrate concentration can lead to the l and then decreases due to increase in solution
generation of intermediates, which may adsorb on the turbidity. Selvam et al. (2007) indicated that the
surface of the catalyst. Slow diffusion of the generated degradation rate constant of 4-fluorophenol increases
intermediates from the catalyst surface can result in the from 0.0152 to 0.0358 min-1 as the concentration of
deactivation of active sites of the photocatalyst and TiO2 increases from 1 to 3 g/L in the presence of P25.
consequently, a reduction in the degradation rate. In Furthermore, increase in catalyst loading from 3 to 4 g/
contrast, at low concentration, the number of catalytic L results in a decrease in the rate constant from 0.0358
sites will not be a limiting factor, and the rate of to 0.0296 min-1. In the case of ZnO, a similar
degradation is proportional to the substrate concentra- observation has been made. The optimum concentra-
tion, in accordance with apparent first-order kinetics tions were found to be 3 g/L TiO2 and 4 g/L ZnO for
(Selvam et al. 2007). Under the conditions invest- efficient removal of 4-fluorophenol. The highest
igated, the degradation rate of Bismarck was reported decolorization and degradation rate of Reactive Orange
to increase with the increase in substrate concentration 16 was achieved at the concentration of 0.4 g/L of
(Tariq et al. 2005). This is in accordance with the L-H TiO2 (Mahvi et al. 2009).
law. Several investigations adequately described the Sobana and Swaminathan (2007) studied the effect
dependence of photocatalytic degradation rates on the of ZnO concentration on the decolorization and
concentration of various organic compounds by the degradation rate of Acid Red 18. The optimum
L-H kinetics model (Galindo et al. 2000; Wenhua et al. concentration of ZnO was found to be 4 g/l. The
2000; Alaton and Balcioghu 2001). The L-H model observed low degradation rate at high catalyst loading
was established to describe the dependence of the may also be due to deactivation of activated molecules
observed reaction rate on the initial solute concen- by collision with ground state molecules of titania. The
trations (Turchi and Ollis 1990). photocatalytic degradation of Acid Red 88 was found
to increase as the AgTiO2 loading increases from 0.2
3.4 Influence of Catalyst Loading to 1.8 g/l (Anandan et al. 2008). Under the conditions
tested, Muruganandham and Swaminathan (2006a)
A number of studies (Daneshvar et al. 2003, 2004, reported that the decolorization and degradation of
2006) have shown that the photocatalytic rate initially Reactive Orange 4 (RO4) increased as the catalyst
increases with catalyst loading and then decreases at loading increases from 1 to 4 g/l under UVA irradiation.
high dosage because of light scattering and screening Consistent results have been observed for the solar
effects. The tendency toward agglomeration (particle photocatalytic degradation of RO4 (Muruganandham
particle interaction) also increases at high solid and Swaminathan 2004). The degradation rate was
10 Water Air Soil Pollut (2011) 215:329

Table 2 Influence of catalyst loading on the photocatalytic degradation of various pollutants

Pollutant type Light Photocatalyst TiO2 (g/L) Optimum TiO2 Reference


source concentration, g/L

Reactive Yellow 14 UV TiO2 1.06.0 4 Muruganandham and Swaminathan 2006a, b


BPA Solar TiO2 01.0 0.5 Kaneco et al. 2004
Chrysoidine R UV TiO2 0.55.0 5.0 Qamar et al. 2005a
Cibacron Yellow LS-R UV TiO2 0.14.0 4.0 Kositzi et al. 2007
Phenol UV TiO2 04.0 2.0 Chiou et al. 2008a
Supra Blue BRL Visible K+TiO2 0.252.0 1.5 Chen et al. 2007
Reactive Yellow 14 Solar TiO2 1.06.0 4.0 Muruganandham et al. 2006
Acid Red 88 UV ZnO 212 12 Behnajady et al. 2009
Remazol Brilliant Blue R UV/Solar TiO2 0.55.0 5.0 Saquib and Muneer 2002
Disperse Blue 1 UV TiO2 0.54.0 3.0 Saquib et al. 2008b
Acridine Orange Visible ZnO 0.0.35 0.25 Pare et al. 2008
Amaranth UV TiO2 0.54.0 1.0 Tariq et al. 2005
Bismarck UV TiO2 0.54.0 1.0 Tariq et al. 2005
Acid Orange 8 UV TiO2 0.55.0 2.0 Saquib and Muneer 2003
Acid Blue 45 UV TiO2 0.53.0 2.0 Tariq et al. 2008
Xylenol UV TiO2 0.53.0 3.0 Tariq et al. 2008
Acridine Orange UV TiO2 0.53.0 2.0 Faisal et al. 2007
Bromothymol UV TiO2 0.53.0 3.0 Haque and Muneer 2007
Fast green FCF UV TiO2 0.54.0 4.0 Saquib et al. 2008a
Reactive Orange 4 UV FTiO2 1.05.0 4.0 Vijayabalan et al. 2009
Acid Blue 80 Solar TiO2 0.34.0 2.0 Su et al. 2008
Rhodamine B Solar ZnO 0.050.4 0.3 Byrappa et al. 2006
Chromotrope 2B UV TiO2 0.55.0 5.0 Qamar et al. 2005b
Amido Black 10B UV TiO2 0.55.0 5.0 Qamar et al. 2005b

found to increase with increasing catalyst concentration molecule absorbed. Consequently, the degradation
up to a level and, on subsequent addition of catalyst, efficiency will be enhanced with increasing TiO2
leads to the leveling off the degradation rate (Kaneco et concentration due to the increase in total surface area
al. 2004; Tsai et al. 2009). Regardless of static, slurry, available for contaminant adsorption. Excessive TiO2
or dynamic flow reactors, the initial reaction rates were dosage leads to opacity of the suspension, which
demonstrated to be directly proportional to catalyst prevents the catalyst farthest in solution from being
concentration, indicating a heterogeneous regime illuminated (Haque and Muneer 2007; Saquib et al.
(Bahnemann et al. 2007). However, several researchers 2008a, b). At high catalyst concentration, particle
have noticed that, above a certain concentration, the particle aggregation may also reduce the catalytic
reaction rate even decreases and becomes independent activity due to the scattering and screening effects
of the catalyst concentration. Earlier studies indicated (Adesina 2004). When the concentration of TiO2 is
that this limit depends on the nature of the pollutants, increased above a certain level, the number of active
reactor geometry, and operating conditions of the sites on the TiO2 surface may become almost constant
photoreactor and the amount of illuminated surface of because of the decreased light penetration, the increased
TiO2 particles. In the case of high catalyst concentra- light scattering, and the loss in surface area occasioned
tion, turbidity impedes penetration of light within the by aggregation (particleparticle interactions) at high
reactor. It is assumed that the increase in the number of solid surface (Hermann 1999). In an immobilized
TiO2 particles will result in increased number of reactor, McMurray et al. (2006) reported an optimum
photons absorbed and the number of the pollutant TiO2 loading of 1.1 mg/cm2 for the degradation of
Water Air Soil Pollut (2011) 215:329 11

atrazine. For any application, the optimum catalyst The point of zero charge (Pzc) of the TiO2
concentration has to be determined in order to avoid (Degussa P25) is widely investigated/reported at
excess catalyst (Hermann 1999) and to ensure efficient pH6.25 (Zhu et al. 2005). Table 3 presents a
absorption of photons. summary of phenols and dyes investigated under
various solution pH. While under acidic conditions,
3.5 Solution pH the positive charge of the TiO2 surface increases as
the pH decreases (Eq. 5.1); above pH 6.25, the
Organic compounds in wastewater differ greatly in negative charge at the surface of the TiO2 increases
several parameters, particularly in their speciation with increasing pH. Moreover, the pH of the solution
behavior, solubility in water, and hydrophobicity. While affects the formation of hydroxyl radicals by the
some compounds are uncharged at common pH reaction between hydroxide ions and photo-induced
conditions typical of natural water or wastewater, other holes on the TiO2 surface. The positive holes are
compounds exhibit a wide variation in speciation (or considered as the major oxidation steps at low pH,
charge) and physico-chemical properties. At pH below whereas hydroxyl radicals are considered as the
its pKa value, an organic compound exists as a neutral predominant species at neutral or high pH levels
species. Above this pKa value, organic compound (Shifu and Gengyu 2005; Mathews 1986). It would
attains a negative charge. Some compounds can exist be expected that the generation of OH radicals are
in positive, neutral, as well as negative forms in aqueous higher due to the presence of more available
solution. This variation can also significantly influence hydroxyl ions on the TiO 2 surface. Thus, the
their photocatalytic degradation behavior. pH of the degradation efficiency of the process will be logi-
wastewater can vary significantly. pH of aquatic cally enhanced at high pH. The degree of elec-
environment plays an important role on the photo- trostatic attraction or repulsion between the
catalytic degradation of organic contaminants since it photocatalyst's surface and the ionic forms of
determines the surface charge of the photocatalyst and organic molecule can vary with the change in
the size of aggregates it forms( Bahnemann et al. 2007). solution pH, which can result in enhancement or
The surface charge of photocatalyst and ionization or inhibition on the photocatalytic degradation of
speciation (pKa) of an organic pollutant can be organic pollutants in the presence of TiO2. In the
profoundly affected by the solution pH. Electrostatic presence of P25 and ZnO, the effect of pH on the
interaction between semiconductor surface, solvent photocatalytic degradation of 4-fluorophenol was
molecules, substrate, and charged radicals formed observed to be pH7>pH9>pH4 (Selvam et al.
during photocatalytic oxidation is strongly dependent 2007). As shown elsewhere in (Venkatachalam et
on the pH of the solution. In addition, protonation and al. 2007a), that the degradation rate of 4-CP was
deprotonation of the organic pollutants can take place faster in the acidic pH range compared with the
depending on the solution pH. Sometimes, protonated alkaline pH which was attributed to enhanced
products are more stable under UV radiation than its adsorption of 4-CP on the surface of nano-TiO2.
main structures (Saien and Khezrianjoo 2008). There- Minimization of electronhole recombination in the
fore, the pH of the solution can play a key role in the acidic pH was also indicated to be an important
adsorption and photocatalytic oxidation of pollutants. factor for the enhancement of degradation.
The ionization state of the surface of the photocatalyst Mahmoodi and Arami 2009 tested the effect of pH
can also be protonated and deprotonated under acidic (3.510.5) on the photocatalytic degradation of Acid
and alkaline conditions, respectively, as shown in the Blue 25. Under the conditions examined, the optimum
following reactions: pH was reported to be 10.5 for the degradation of Acid
Blue 25. Using Z2S, Cun et al. 2002 examined the
pH<Pzc TiOH + H+ TiOH2+ 5:1 influence of pH (4.2212.57) on the photocatalytic
degradation of MO and noticed an optimum pH of 4.2.
Soutsas et al. (2009) studied the effect of pH (39)
on the decolorization rates and efficiency of Remazol
pH>Pzc TiOH + OH- TiO-+H2O
Red RR, Remazol Yellow, Procion Crimson H-exl, and
5:2 Procion Yellow H-exl. At pH 3, nearly complete
12 Water Air Soil Pollut (2011) 215:329

Table 3 Influence of pH on the photocatalytic degradation of phenols and dyes

Pollutant type Light source Photocatalyst pH range Optimum pH Reference

Phenol UV TiO2 4.112.7 7.4 Chiou et al. 2008a, b


Chrysoidine Y UV TiO2 3.09.0 9.0 Qamar et al. 2004
m-Nitrophenol UV TiO2 4.112.7 8.9 Chiou et al. 2008b
Reactive Blue 4 UV NdZnO 3.013.0 11 Zhou et al. 2009
BPA Solar TiO2 2.010.0 6 Kaneco et al. 2004
Methylene Blue Visible La TiO2
3+
210 10 Parida and Sahu 2008
Supra Blue BRL Visible K+TiO2 4.511.8 7.2 Chen et al. 2007
Reactive Orange 4 UV FTiO2 1.09.0 3.0 Vijayabalan et al. 2009
Acid Red 88 Visible AgTiO2 0.21.8 1.8 Anandan et al. 2008
Remazol Brilliant Blue R Solar TiO2 3.011.0 3.0 Saquib and Muneer 2002
Disperse Blue 1 UV TiO2 311 3.0 Saquib et al. 2008b
Methyl Orange UV PtTiO2 2.511.0 2.5 Huang et al. 2008
Amaranth UV TiO2 3.459.31 7.73 Tariq et al. 2005
Bismarck UV TiO2 3.257.85 3.25 Tariq et al. 2005
Acid Orange 8 UV TiO2 3.011.0 9.0 Saquib and Muneer 2003
Acid Blue 45 UV TiO2 2.0510.05 5.8 Tariq et al. 2008
Acridine Orange Visible ZnO 2.97.1 7.1 Pare et al. 2008
Bromothymol UV TiO2 2.29.0 4.35 Haque and Muneer 2007
Fast green FCF UV TiO2 3.011.0 4.4 Saquib et al. 2008a
Methyl Red UV AgTiO2 3.013.0 310.0 Gupta et al. 2006
Acid Blue 80 Solar TiO2 2.010.0 10.0 Su et al. 2008
Acid Red 29 UV TiO2 310.5 10.5 Qamar et al. 2005a

decolorization (>90%) of all dyes was achieved in only ZnO, TiO2, and In2O3 as catalysts. For all the catalysts
15 min UV irradiation. Sobana and Swaminathan tested, an observed order of pH: pH 8>pH 6>pH 4>pH
(2007) suggested that the decolorization and degrada- 2 was found to exist in the degradation of MB.
tion of Acid Red 18 by ZnO increases as the pH
increases from 3 to 11. At acidic pH, the removal
efficiency is less due to the dissolution of ZnO. AR 4 Co-occurring Substances
18 was efficiently removed at pH 11 due to the
abundance of OH- ions in the particle surfaces as well 4.1 Ionic Components
as in the reaction medium. Using ZnO and solar light,
the degradation of Rodhamine B was reported to favor The amount of UV absorption is influenced by water
at acidic and basic pH (Byrappa et al. 2006). transmittance over the spectral UV range of interest.
Muruganandham and Swaminathan (2004) observed Some common constituents that affect water transmit-
that the photocatalytic decolorization and degradation of tance are dissolved organic matter, nitrate, and ferrous/
RO4 was efficient/faster in alkaline pH in comparison to ferric ions. The presence of spectator's components in
acidic pH range in both UV and solar irradiation. At low water can adversely affect the contaminant degradation
pH value, TiO2 particle agglomeration reduces the dye rates. Inorganic anions, such as phosphate, sulfate,
adsorption as well as photon absorption. In RO4 dye, nitrate, and chloride, have been reported to limit the
the azo linkage (-N=N-) was indicated to be suscep- performance of solar-based photocatalysis (Abdullah et
tible to electrophilic attack by OH radical. Talebian and al. 1990). Bicarbonate, in particular, is detrimental to
Nilforoushan 2009 examined the effect of pH (28) on reactor performance as it acts as hydroxyl radical
the photocatalytic degradation of MB using SnO2, scavenger (Abdullah et al. 1990). Long term experi-
Water Air Soil Pollut (2011) 215:329 13

ence with photocatalytic oxidation system showed that (2007) observed that the presence of humic acid caused
humic substances in contaminated water can adsorb a significant retardation on the photocatalytic degrada-
strongly titanium dioxide particles and reduce activity tion of 4-chlororphenol. The observed retardations of
toward the target substances (Goswami 1997). There- humic acids were related to the inhibition (surface
fore, the incorporation of pre-treatment process has deactivation), competition, and light attenuation
been indicated to have a beneficial effect on the effects. Moreover, the presence of humic acid in the
performance of photocatalytic oxidation process. Gupta reaction mixture has been reported to significantly
et al. (2006) studied the influence of various ionic reduce light transmittal and therefore, the photooxida-
components on the degradation of crystal violate (CV) tion rate. Humic acid can also compete with organo-
and methyl red (MR) dyes using AgTiO2 as photo- halides for the active sites on the TiO2 surface. Mahvi
catalyst. Cl-, NO3-, SO42-, HPO42-, and humic acid et al. (2009) studied the effect of anions on the
were shown to have negligible effect on the degrada- photocatalytic decolorization Reactive Orange 16.
tion rate, whereas Ca2+ and Fe2+ interfered significant- The observed order of negative impact of anions were
ly. In case of the MR, Cl-, Ca2+, and Fe2+ were shown to be as SO42-<NO3-<Cl-<HCO3-<CO32-.
reported to affect the degradation with the exception of Naeem and Feng (2008) studied the inhibition effect
NO3-, SO42-, and HPO42-(Sahoo et al. 2005). The of anions on the photocatalytic degradation of phenol,
effect of transition metal ions on the degradation of which is reported to be Cl->SO42->NO3->CO32-. At
4-flurophenol was shown to be in the order of Mg2+> certain concentration, Fe3+ is reported to improve the
Fe3+>Fe2+>Cu2+, and the inhibition of inorganic anions degradation rate, whereas Ca2+, Cu2+, and Mg2+ hinder
on the degradation of 4-FP was demonstrated to be the degradation process. The effect of surfactants
CO32->HCO3->Cl->NO3->SO42- (Selvam et al. 2007). (0.05 mmol/L) on the degradation rate of phenol was
Muruganandham et al. (2006) observed that the reported to be sodium dodecyl benzene sulfate>sodium
addition of 0.471.89 mM Na2CO3 decreases the dodecyl sulfonate>sodium dodecyl sulfate (SDS). The
degradation of Reactive Yellow 14 from59.2% to presence of anions is reported to alter the ionic strength
48.2% due to hydroxyl radical scavenging property of of the solution, and therefore, influence the catalytic
carbonate ion. activity, and hence the photocatalytic degradation
(Calza and Pelizzetti 2001). The reaction of hvb+ and
CO32-+.OH OH-+CO3.- 6:1 .
OH with anions which behave as scavengers and thus
inhibit the degradation. Pare et al. (2008) investigated
the effect of carbonate ions on the photocatalytic
HCO3-+.OH H2O+CO3.- 6:2 degradation of Acridine Orange for a range of
concentration from 2.010-3 to 810-3 mM. The
As a result, the primary oxidant hydroxyl radical degradation rate constant was shown to decrease from
decreases gradually with the increase in carbonate 0.023 to 0.015 min-1 under the above concentration
ion, and consequently, there is significant decrease in range. In the presence of NaCl, similar degradation
photocatalytic degradation. Addition of Cl- ion from trends have been reported for a certain concentration
0.47 to 1.89 mM Na2CO3 to reaction decreases the range of 2 to 10 mM due to the hole scavenging
degradation from 80.1% to 72.3% by time of 80 min. properties of these ions. The presence of anionic (SDS)
The decrease in degradation efficiency is due to the and cationic surfactants (C16TAB) retarded the rate of
hole scavenging and hydroxyl radical scavenging degradation due to the preferential adsorption of the
properties of chloride ion. amphiphilic surfactant molecules on the photocatalyst
surface. Epling and Lin (2002) examined the inhibition
Cl-+hVB+ Cl. 6:3
effect of humic substances and inorganic anions on the
degradation of several cationic and anionic dyes. Of
the ionic species (Cl-, NO3-, PO43-, and HCO3-)
Cl. +Cl- Cl2.- 6:4 studied, Cl- showed the strongest inhibition effect on
both cationic and anionic dyes, followed by PO43-. The
The inhibitive effect of CO32- ion is shown to be overall retardation has been attributed to the surface
greater than the inhibitive effect of Cl- ion. Lin and Lin deactivation mechanism. A significant retardation on
14 Water Air Soil Pollut (2011) 215:329

the degradation of MB in the presence of either Aldrich have the most inhibitive effect due to the spatial
humic acid or natural humic substances has been hindrance effect of the t-butyl alcohol. In the presence
reported. Guillard et al. (2003) studied the inhibition of of ethanol and methanol, Aarthi et al. (2007) investi-
inorganic salts on the photocatalytic degradation of gated the effect of solvents and mixed-solvents systems
MB at neutral and basic pH. Under the conditions on the photocatalytic degradation of dye Sudan III. As
tested, the order of inhibition was reported to be the ethanol content in the system increases, the
CO32->PO43->SO42->Cl->NO3-. In the presence of degradation rate was reported to decrease. This effect
200 M nitrate salt, the effect of metal ions on the was attributed to the scavenging of OH radicals by
photocatalytic degradation of Azure A was observed to these solvents. Liu et al. (2009) studied the effect of
be Cu2+>Al3+>Co2+>Zn2+, and the order was shown to solvent type on the photocatalytic activity of N-doped
be Cu2+>Co2+>Fe3+ in the presence of 200 M TiO2 under visible light irradiation for the degradation
chloride salt (Aarthi et al. 2007). Papadam et al. of MO. Under the conditions tested, it was observed
(2007) examined the effect of water matrix on the that the anatase gradually changed into rutile with
decolorization of Acid Orange 20. The presence of increase in carbon chain of methanol, ethanol,
17.1 mM NaCl or 7.04 mM Na2SO4 led to decreased 1-propanol, and 1-butanol as the solvent under
decolorization which was attributed to the trapping of solvothermal conditions. The bicrystalline TiO 2
photogenerated valence band holes and the hydroxyl (19.5% rutile and 80.5% anatase) prepared in methanol
radicals by the respective anions. Aarthi and Madras showed the highest photocatalytic activity for the
(2007) investigated the effect of metal ions (Cu2+,Fe3+, degradation of MO. Aarthi and Madras (2007) exam-
Zn2+, and Al3+) on the photocatalytic degradation of ined the effect of solvent effects on the photocatalytic
Rhodamine B and was shown to follow the order of degradation of rodamine B (RB) using combustion-
Cu2+>Al3>Zn2>Fe3+. In the presence of Cu2+ and synthesized TiO2. In the mixture of ethanol and water,
Zn2+, the degradation of Malachite Green was reduced when ethanol was 10% by volume, the rate decreased
by 76% and 66%, respectively. by 91.5%, and when the ethanol increased to 50% by
volume, no photodegradation was observed. Similarly,
4.2 Solvent Types the rate decreased by 76%, 96%, and 100% when
acetonitrile in the mixture of water and acetonitrile was
Organic solvents are mostly present in many industrial increased from 10%, 20%, and 50% by volume,
wastewaters. Therefore, their effects on the photo- respectively. This effect is attributed to the lesser
catalytic degradation system have been investigated in solvation of excited electrons in the organic solvents
several studies. Lin and Lin 2007 examined the effects compared with the aqueous solution.
of acetonitrile or isopropanol on the photocatalytic
oxidation of 4-chlorophenol. The degradation rate of
4-chlorophenol was shown to decrease from 1.0436 to 5 Influence of Oxidants/Electron Acceptor
0.0525 h-1 as the acetonitrile content increases in the
reaction mixture. A similar retardation effect was also The electronhole recombination is one of the main
observed when 5% isopropanol was added into the drawbacks in the application of TiO2 photocatalysis
acetonitrile/water (1:1) reaction mixture. Behnajady et as it causes waste of energy. In the absence of suitable
al. (2009) observed that the pseudo first-order-rate electron acceptor or donor, recombination step is
constants of Acid Red 88 and water ethanol were predominant, and thus, it limits the quantum yield.
0.0257 and 0.0271 min-1, respectively. The use of Thus, it is crucial to prevent the electronhole
ethanol instead of water as a solvent did not show any recombination to ensure efficient photocatalysis.
significant effect on loading morphology of ZnO on Molecular oxygen is generally used as an electron
glass plate. Shohrabi et al. (2009) studied the effect of acceptor in heterogenous photocatalytic reactions.
various solvents on the photocatalytic degradation of Addition of external oxidant/electron acceptors into
Benzidene Yellow. The observed order of solvents a semiconductor suspension has been shown to
effects on the degradation efficiency are reported to be improve the photocatalytic degradation of organic
t-butyl alcohol>n-butanol>2-propanol>acetonitrile>N- contaminants by (1) removing the electronhole
hexane. Of the alcohols, t-butyl alcohol was shown to recombination by accepting the conduction band
Water Air Soil Pollut (2011) 215:329 15

electron; (2) increasing the hydroxyl radical concen- basic medium. Muruganandham et al. (2006) examined
tration and oxidation rate of intermediate compound; the effect of H2O2, KBrO3, and (NH4)2S2O8 addition
and (3) generating more radicals and other oxidizing on the solar photocatalytic degradation of Reactive
species to accelerate the degradation efficiency of Yellow 14 by varying the amount of oxidant con-
intermediate compounds (Qamar et al. 2005a, b; centration. The optimum concentrations of the oxidants
Saquib and Muneer 2002; Saquib et al. 2008a, b; were 15 mM, 0.90 mM, and 0.88 mM for H2O2,
Tariq et al. 2005, 2008; Faisal et al. 2007; Haque and KBrO3, and (NH4)2S2O8, respectively. Of the oxidants
Muneer 2007). Since hydroxyl radicals appear to play studied, (NH4)2S2O8 was found to be efficient to
an important role in the photocatalytic degradation, oxidize the Reactive Yellow 14 azo dye. Under visible
several researchers have investigated the effect of light irradiation, addition of optimum amount of H2O2
addition of electron acceptors such as H2O2, KBrO3, and K2S2O8 was shown to increase the degradation rate
and (NH4)2S2O8 on the photocatalytic degradation of of Acridine Orange in the presence of ZnO photo-
various dyes and phenolic compounds (Qamar et al. catalyst (Pare et al. 2008). Sobana and Swaminathan
2005a, b; Saquib and Muneer 2002; Saquib et al. 2008a, 2007 observed that addition of KBrO3 and (NH4)2S2O8
b; Tariq et al. 2005, 2008; Faisal et al. 2007; Haque and was shown to increase the photocatalytic degradation
Muneer 2007) to enhance the formation of hydroxyl of Acid Red 18 by ZnO. However, the addition of H2O2
radicals as well as to inhibit the electron/hole(e-/h+) pair was reported to decrease the photocatalytic degradation
recombination. In all cases, the addition of oxidants has rate which was attributed to its low adsorption on the
resulted in higher pollutant degradation rate compared ZnO surface. Both decolorization and degradation of
with the molecular oxygen. In most of the cases, the Reactive Yellow 14 by UV/TiO2 system were reported
order of enhancement is reported to be UV/TiO2/ to increase in the presence of H2O2, (NH4)2S2O8, and
H2O2>UV/TiO2/BrO3->UV/TiO2/S2O82-. The enhance- KBrO3, up to a certain dosage beyond which the
ment of degradation rate is due to the reaction between enhancement was negligible (Muruganandham and
BrO3- and conduction band electron. This reaction Swaminathan 2006b). The effect of oxidants on the
reduces the recombination of electronhole pair. degradation of 4-flurophenol was shown to be in the
order of IO4->BrO3->S2O82->H2O2>ClO3- (Selvam et
BrO3-+6e-CB+6H+ Br-+3H2O 7:1 al. 2007). After 15 min irradiation at pH 4, the
degradation of 4-flourophenol were observed to be
S2O82- can generate sulfate radical anion (SO4-) 79.86%, 66.89%, 60.88%, 53.85%, and 46.35% in UV/
both thermally and photolytically in aqueous solution. TiO2/IO4-, UV/TiO2/BrO3-, UV/TiO2/H2O2, UV/TiO2/
SO4- then reacts with H2O to produce .OH radicals. S2O82-, and in UV/TiO2/ClO3- processes, respectively.
IO4- was found to be most efficient oxidants due to
S2O82- 2SO4
.- 7:2 the generation of a number of highly reactive
intermediate radicals such as IO3., OH., and IO4.. The
optimum concentration of H2O2 addition is found to be
about 1.2 mM/L for the degradation of MO in the
.-
SO4 + H2O
. -
OH+ SO42 + H+ 7:3 presence of 0.5 wt.% PtTiO2/Zeolite systems (Huang
et al. 2008). Under visible light irradiation, the
With the addition of H2O2, the enhancement of influence of oxidants on the degradation of Acid Red
degradation is due to the increase in the hydroxyl 88 by AgTiO2 was found to be peroxomonosulfate>
radical concentration as shown by Eqs. 7.4 and 7.5: peroxodisulfate>hydrogen peroxide (Anandan et al.
2008). Chiou et al. (2008a) investigated the effect of
H2O2+eCB- .
OH+OH- 7:4
H2O2 addition from 1.77 to 88.2 mM on the
photocatalytic degradation of phenol. The addition of
H2O2 from 1.77 to 8.82 mM leads to an increase in
7:5 removal efficiency from 58% to 84% within 3 h. In
contrast, phenol is completely degraded within 2.5 and
The degradation efficiency of UV/TiO2/oxidant 1 h when the level of H2O2 increases to 44.1 and
process is slightly more in acidic medium than in 88.2 mM, respectively.
16 Water Air Soil Pollut (2011) 215:329

6 Combined Approach TiO2/UVA process, color removal was 33% after


40 min treatment. For UVA/TiO2/O3 system, color
In recent years, photocatalysis has been combined with removal was greater than 50% with a significant
other physical and chemical means of treatment to removal within first 10 min. The highest color removal
improve the efficiency of photocatalysis. Generally, rate (70.2%) was achieved by the combined treatment of
integration of several methods provides high treatment photocatalytic oxidation and ozonation. The co-
efficiency compared with individual treatment. TiO2 has treatment of ozonation and photocatalytic oxidation
been combined with ozonation, membrane filtration, increased TOC removal rate by nearly 50% compared
and ultrasound technology for the treatment of various with the process when ozone was used as a pre-
organic compounds. Chen and Smirniotis (2002) treatment for photocatalysis. Mozia et al. (2009)
indicated the enhancement of photocatalytic degrada- compared the effectiveness of photocatalysis and hybrid
tion of phenol and chlorophenol by ultrasound, UV process photocatalysis-membrane distillation (MD) for
irradiation with photocatalysis results in 76% destruc- the degradation of Acid Red 18. The degradation rate
tion in 3 h of treatment. Combination of ultrasound and constants were higher for 10% or less than during the
photocatalysis results in almost complete destruction of hybrid process. This effect was attributed to the
phenol in about 150 min. Synergistic effects observed concentration of feed solution during hybrid process.
in combined approach are attributed to desorption of Grzechulska-Damszel et al. (2009) studied the effective-
organic substrate and degradation by products from the ness of TiO2 photocatalysisnanofiltration (NF) mem-
catalyst surface and de-agglomeration of the catalyst. brane system for the degradation of Acid Red 18.
Mrowetz et al. (2005) reported that the degradation rate However, the integration of post-NF membrane system
constant of Acid Orange 8 in ultrasonic irradiation and did not result in complete removal of organic matter
the combined technique was 0.1, 1.81, and 3.329 from solution when catalyst was used in immobilized
10-4 s-1, respectively, clearly indicating the synergistic form. Suspended TiO2/UF/MD system was reported to
effects. For Acid Red 1 and 2 chlorophenol, the rate be efficient for the removal of organic matter from the
constants in same order are 0.038, 1.22, and 2.89 solution treated by TiO2 photocatalysis compared with
(10-4s-1) and 0.59, 0.88, and 1.58(10-4s-1), respec- the TiO2 photocatalysisNF system. The ion rejection
tively. Li et al. (2003) reported that the degradation rate efficiency was reported to be similar for both systems.
constants of reactive Brilliant Red X-3B using TiO2/ Gonzalez and Martinez (2008) compared the efficiency
UV/O3 system is shown to be 2.563.2 times higher in of sonophotocatalytic system using nano-size anatase
comparison to the maximal rate constants of TiO2/UV/ and rutile TiO2 powders with ultrasound alone for the
O2, 4.689.8 times of maximal rate constants with degradation of Methyl Orange. Under the conditions
TiO2/UV. For the degradation of catechol, the order of studied, the pseudo first-order-rate constants of the three
removal efficiency was demonstrated to be O3>UV/TiO2/ cases were shown to be 0.0179, 0.0068, and
O3>UV/TiO2/O2>UV/TiO2. Within 6 min reaction time, 0.0017 min-1, respectively. The sonophotocatalytic
the decolorization efficiency of Reactive Red 2 was activity of nano-size anatase was found to be efficient
significantly higher in the case of UV/TiO2/O3 system compared with nano-rutile TiO2 powder. Bejarano-Perez
compared with UV/TiO2 system (Wu et al. 2008). and Suarez-Herrera (2007) reported that the kinetic
Oyama et al. (2009) indicated significant mineralization constant of the Congo Red oxidation is 2.6 times
of bisphenol A in UV/TiO2/O3 system as compared with higher than the one obtained in the absence of
either ozonation or UV/O3 and to the UV/TiO2/O2 ultrasound and in the presence of UV light and TiO2
system. Fernando et al. (2005) reported that the P25. It was also observed that the degradation rate of
degradation rate constant of photocatalytic ozonation MO in the presence of both ultrasound and UV light
process was higher compared with TiO2 photocatalysis is significantly higher compared with either sonoca-
for phenol, p-chlorophenol, and p-nitrophenol. Photo- talytic or photocatalysis. Zhang et al. (2006) studied
catalytic ozonation process exhibited the highest miner- the combined photocatalytic membrane technique for
alization efficiency of phenols. Zou and Zhu (2008) the removal of Direct Black 168 dye. The removal of
investigated the comparative efficacy of UVA/TiO2 Direct Black 168 with UV irradiation alone was
and UVA/TiO2/O3 system for the removal of color, achieved at 70%, and the retention of the dye with
A254, and total organic carbon (TOC). By means of membrane filtration alone was reached at 67% after
Water Air Soil Pollut (2011) 215:329 17

300 min in the continuous system. However, when dation of malachite green oxalate. The crystallinity
the photocatalysis system was combined with mem- levels of catalysts are found to be largely dependent on
brane techniques, the removal efficiency of the dye both the nature and the concentration of alkaline. The
was increased to 82% after 300 min under the best crystallinity is obtained for Li-doped TiO2 and is
conditions investigated. Wang et al. (2008) compared lowest for K-doped TiO2. For a given alkaline
the sonophotocatalytic degradation of Methyl Orange concentration, the catalyst prepared by the impregna-
using Degussa P25 (55.07 m 2 /g), Yilli TiO 2 tion technique was shown to be more efficient than
(10.45 m2/g), and AgTiO2 (Ag loaded on Yili those prepared by solgel route. For 5% Li-doped TiO2
TiO2). The degradation rate constants obtained with catalyst prepared by impregnation method, the half life
combined approach were reported to be 5.810-3, of malachite green is reported to be twice shorter than
1.1710-2, and 3.5810-2 min-1, respectively for Yill that observed for P25 TiO2. However, the catalyst
TiO2, P25, and AgTiO2. However, the degradation prepared by solgel route, the presence of Li reduces
rate constants were shown to be 3.210-3, 9.810-3, the catalyst photoactivity. Indeed, the photoactivity of
and 2.5910-2 min-1 in photocatalysis in the same undoped catalyst is shown to be better than Li-doped
order. Reported results indicated that the combination TiO2. Structure and size of TiO2 crystallites are
of sonolysis and photocatalysis enhanced the MO significantly dependent on calcinations temperature.
degradation. Comparatively, the photocatalytic activ- Thermal treatment of TiO2 gels at higher temperature
ity of AgTiO2 nanoparticles was much higher than promotes phase transformation from thermodynamical-
that of Degussa P25 and Yilli TiO2. At pH 7, the ly metastable anatase to more stable and condensed
decolorization rates of Reactive Red 2 were shown to rutile phase. As the dehydration process occurs during
follow the order of UV/US/TiO2(0.94 h-1)>UV/ heat treatment, crystallites grow to dimensions larger
TiO2(0.85 h-1)>US/TiO2(0.25 h-1)>US (Wu and Yu than those of the original particles. Pecchi et al. (2001)
2009). studied the effect of calcinations temperature on the
photocatalytic degradation of pentachlorophenol using
solutiongel method under different pH. Increasing
7 Film Fabrication Technique and Calcination calcinations temperature results in reduced surface area
Temperature and increased crystallinity and particle size. The
degradation rate constant was shown to increase as
Nanocrystalline titanium oxide powder for catalytic the calcinations temperature increased from 300C to
purposes can be applied by a variety of techniques 500C for pH values 3 and 5. Nonetheless, the rate
including solgel method, solvothermal process, reverse constant was higher at 300C and 500C compared
miscellar, hydrothermal method, and electrochemical with 400C at pH 9. Peng et al. (2005) noticed that
methods. There have been several investigations on compared with undoped sample and P25, highest
photocatalytic degradation of various dyes by titania degradation of RB was achieved using La-doped
nanoparticles; however, information on the titania film TiO2 at optimum calcinations temperature of 300C.
fabrication routes on the photocatalytic degradation of This effect was ascribed to larger surface area due to
dyes is still desirable. Song et al. (2009) investigated the the presence of lanthanum ion in the high thermal
effect of titania films with different nanostructures of stable mesostructures TiO2. However, the degradation
nanorods (NR), solgel film, nanotubes (NT), and rate was shown to decrease as the calcinations
nanoparticle aggregates on the photocatalytic degrada- temperature increases from 300C to 700C. The
tion of RB, Methylene Blue, and Methyl Orange. In reduction of photocatalytic activity was reported to be
the case of RB degradation, the observed order was related with the decrease in specific surface area from
reported to be NR>DP>SG>NT, and the order was 460.6 to 102.1 m2/g. After calcinations at 900C, it
shown to be NR>SG>DP>NT for the degradation of was also indicated that the anatase crystallites begin to
MB. Nonetheless, an order of NT>DP>SG>NR was grow extensively and transform to rutile phase and
found to observe for the degradation of MO. then segregate from mesostructures. Subsequently, the
Bessekhouad et al. (2004) studied the effect of alkaline whole mesostructure is completely destroyed (Chen et
(Li, Na, and K) doped TiO2 prepared by solgel route al. 2007). The surface areas are in the decreasing order
and impregnation method on the photocatalytic degra- of TiO2>4.6% K+ doped>14.3% K+ doped, 4.6% K+
18 Water Air Soil Pollut (2011) 215:329

doped>TiO2>14.3% K+ doped, 4.6% K+ doped>14.3% decrease of specific surface area from 300C onwards
K+ doped>TiO2, and 14.3%K+ >4.6%K+>TiO2 when is a consequence of crystallization and growth of
the samples were calcined at 400C, 600C,700C, and anatase. At calcination temperature above 700C, the
850C, respectively. Similar trends of the dependence specific surface area was <1 m2/g. No discernible
of pore volume, micropore volume, external surface changes were observed in the visible light activity.
area, and micropore surface area on the K+ content and Baiju et al. (2007) indicated that the crystallite size of
calcination temperature are reported. Of all the samples TiO2 increases as the calcinations temperature increases
tested, 4.6% K+ doped TiO2 calcined at 700C was for both pure and Ta2O5 doped-TiO2. For any given
shown to be efficient for the degradation of Supra Blue temperature, crystallite size TiO2 decreases as the
dye under the conditions studied. Behnajady et al. amount of Ta2O5 increases from 1 to 10 mol%. All
(2009) investigated the effect of furnace temperature the Ta2O5-added titania was shown to have higher
on the photoactivity of immobilized ZnO for the surface area than pure titania. The addition of Ta2O5
degradation of Acid Red 88 for range of 400C to was reported to increase the anatase phase stability
500C. Degradation rate was shown to increase from above 1,000C by inhibiting the increase in crystallite
0.0257 to 0.0208 min-1 with increasing temperature size of titania. The optimum calcinations temperature
from 400C to500C, which is attributed to the was found to be 500C for the degradation of MB.
increase in particle size from 42 to 67 nm and thereby Silveyra et al. (2005) tested the effect of calcinations
reduced availability of surface area. Zheng et al. (2007) temperature (600800C) on the photocatalytic
studied the effect of calcinations temperature on the degradation of phenol using N-doped TiO2. Highest
photocatalytic degradation of reactive Brilliant Red degradation was obtained at 600C and no variation
X-3B for a range of 250550C. Under the conditions was observed at 700C and 800C. Huang et al. (2008)
investigated, the highest degradation was achieved at examined the effect of calcinations temperature on the
350C. Using a carbon doped-TiO2, Xiao and Ouyang decolorization rate of Methyl Orange solution under
(2009) observed that the reduction in surface area from UV irradiation. In case of the undoped TiO2, the
20 to15.5 m2/g is due to the increase in calcination decolorization rate decrease from 73% to 31% as the
temperature from 500800C. This would lead to the calcination temperature increases from 110C to 500C.
decrease of active sites on which reactants could In contrast, the decolorization rate decreases from
adsorb. Under the conditions tested, decolorization of 87.8% to 43.2% with increase in temperature for the
MB was reported to decrease from 49.16% to 39.16% above range in the presence of 1.5% pt-TiO2 catalyst.
with increasing calcination temperature. The order of This effect was related to the formation of TiO2 anatase
photocatalytic activity and the formation rate of .OH phase and conglomeration of catalyst particles which
radicals per unit surface area was shown to be closely reduces the specific surface areas of samples, resulting
related. An optimum temperature of 600C was in the decrease of photocatalytic activity at lower
also noticed for the photocatalytic degradation of calcinations temperature. Wawrzyniak et al. (2006)
Methylene Blue and the formation rate of .OH radicals. studied the effect of calcination temperature (100
Wen et al. (2009) indicated that no significant changes 800C) on the photocatalytic degradation of phenol and
on the photocatalytic degradation of MB were ob- two azo dyes (Reactive Red, Direct Green) by N-doped
served as the calcination temperature increases from TiO2 under visible light irradiation. The highest
500C to 600C. The degradation rates were higher effectiveness of phenol degradation was achieved at
in the case of Co doped TiO2 calcined at 500C and calcinations temperature 700C. In case of degradation
600C, compared with that of one calcined at 700C. of both azo dyes, the highest degradation was observed
This effect was attributed to the presence of larger at 500C and 600C. Temperature of 600C was
surface area. It is well-known from the literature that reported to be the optimum calcinations temperature
calcination temperature is an important factor that for the highest photocatalytic degradation of phenol
probably influences the crystalline sizes, morphology, using 5 mol% La-doped TiO2 (Liqiang et al. 2004). In
and surface area of TiO2 which can clearly affect the the presence of STiO2ZrO2, the optimum calcina-
photocatalytic activity. Lim et al. (2007) reported that tions temperature was 500C for the degradation (85%)
the BET surface area of C-doped TiO2 decreased from of rodhamine B in the visible irradiation. The optimum
200 m2/g (200C) to 80 m2/g (400C). A rapid calcinations temperature was shown to be 400C when
Water Air Soil Pollut (2011) 215:329 19

STiO2 was the visible light catalyst (Tian et al. 2009). At 350C, the higher photocatalytic activity of coupled
Talebian and Nilforoushan (2009) studied the effect of oxides was reported due to variation in phase
annealing temperature (250550C) on the photocata- composition and particle size. Using Z2S, an optimum
lytic activity of In2O3 film for the degradation of MB. temperature of 600C was found for the degradation of
The optimum annealing temperature was 550C, and MO (Cun et al. 2002).
the activity of In2O3 film was directly related to degree
of crystallinity at higher temperature. Gorska et al.
(2009b) studied the effect of calcinations temperature 8 Doping and Mixed Semiconductor
(350750C) on the photocatalytic degradation of
0.21 mM phenol under UV (25<<400 nm) and visible The recombination of photogenerated electrons and
(>400 nm) light irradiation. After 60 min irradiation, holes are believed to be reason for the low photo-
maximum amount of phenol degradation was about activity of TiO2. Structural imperfections in the TiO2
80% when P25 TiO2 calcinated at 350C in visible lattice generate trap sites which may act as recombi-
light. The sample calcined at 350C was shown to have nation centers, leading to a decrease in the levels of
the largest BET surface area (205.8 m2/g), the smallest electrons and holes. In order to enhance the TiO2
crystallite size (8.4 nm) and an average pore diameter photocatalysis as well as the response into the visible
of 8.3 nm of TiO2. This effect was attributed to the spectrum of solar light, TiO2 has been doped with
efficient absorption of light vis region due to the certain transition metals, non-metals, and ionic com-
existence of largest amount of carbon in aromatic C-C ponents. Doped ions can also act as charge trapping
bonds (10.1 at %). However, the photocatalyst calci- sites and thus reduce electronhole recombination.
nated at 450C was found to have the highest activity The effect of doping on the activity of photocatalyst is
in UV light irradiation. Lettmann et al. (2001) observed governed by several factors, e.g., the type and
that, about 30% 4-CP (Co =0.25 mM) was degraded concentration of dopant, preparation method, the
after 100 min irradiation (>400) in the presence of a structure and the initial concentration of the pollutants
catalyst-obtained hydrolysis, followed by calcination at (dyes and phenols), and physico-chemical properties
250C for 3 h. Using a carbon doped TiO2 prepared by of the catalyst. Both positive and negative results
TiCl4 hydrolysis in tetrabutylammonium hydroxide have been reported from doping with metal ions. The
(calcinations at 400C, 1 h), 70% TOC reduction of increase in charge separation efficiency will enhance
0.25 mM 4-CP was reported by Shakthivel et al. the formation of both free hydroxyl radicals and
(2004). Porter et al. (1999) examine the microstructural active oxygen species (Kato et al. 2005). The amounts
changes in Degussa P25 due to heat treatment. The of doping concentration along with a summary of the
TiO2 powder was annealed from 600C to 1,000C. dyes and phenolic compounds degraded using doped
Under UV irradiation, the apparent crystallite size and catalyst are shown in Table 4. Upon 45 min UV
rutile content of catalyst increased with increasing irradiation, >99% degradation of Methyl Red was
calcination temperatures, whereas the specific surface reported with Ag doped TiO2 whereas only 85% was
area and the rate of phenol degradation was reported to degraded in the presence of TiO2 (Sahoo et al. 2005).
decrease. Sonawane and Dongare (2006) tested the Liu et al. (2005) compared the photocatalytic activi-
effect of calcinations temperature (275500C) on the ties of N-doped TiO2 and Degussa P25 for the
photocatalytic activity of 2%-Au/TiO2 for the degrada- degradation of three azo dyes: AO7, MX-5B, and
tion of phenol under solar light. The catalyst calcinated RB5 in the presence of UV and solar light. Some 95%
at 275C exhibited the highest activity compared with decolorization of AO7 was reported to occur in 1 h
the sample calcinated at higher temperature. Using ZnO under UV illumination and the doped TiO2 was
upon solar irradiation, the photocatalytic degradation of reported to be four times more efficient compared
4-nitrophenol increases from 52.9% to 74.4% as the with bare TiO2. In addition, 70% dye removal was
calcinations temperature increases from 110C to 300C achieved within 3 h whereas no detectable dye
due to higher surface area and lowest crystallite sizes decolorization was reported to obtain under solar
(Parida et al. 2006). Zhang et al. (2004) studied the irradiation. Under the tested conditions, 0.2 mmol
effect of calcinations temperature (300900C) on the fluoride ion is shown to be the optimum concentration
photocatalytic degradation of MO using ZnOSnO2. for the efficient removal of Reactive Orange 4
20 Water Air Soil Pollut (2011) 215:329

Table 4 The influence of dopant concentration on photocatalytic activity of photocatalyst

Pollutant Light source Photocatalyst Doping (%) Optimum doping (%) Reference

Methylene Blue Visible C-TiO2 03.2 1.25 Wong et al. 2008


Supra blue BRL dyes Visible K+TiO2 014.3 4.6 Chen et al. 2007
XRG dyes UV/Visible Fe3+/Fe2+TiO2 0.030.15 0.09 Zhu et al. 2004
Methyl Orange Solar Eu2+TiO2 0.51.0 1.0 Yi et al. 2007
Methyl orange Solar Gd3+TiO2 0.11.0 0.5 Yi et al. 2007
p-chlorophenol UV Ag TiO2
+
0.10.5 0.5 Kirilov et al. 2006
p-chlorophenol UV Pd2+TiO2 0.10.5 0.5 Kirilov et al. 2006
Methelyne Blue Visible Pd2+TiO2 05.0 5.0 Chan et al. 2009
Phenol Visible Fe3+TiO2 0.45.1 1.0 Adan et al. 2007
Methyle Orange UV Mo6+TiO2 01.5 1.0 Yang et al. 2004
4-Chlorophenol Visible Ce4+TiO2 01.0 0.6 Silva et al. 2009
Methylyne Blue UV V5+TiO2 0.255.0 0.5 Tian et al. 2009
2,4-Dichlorophenol Visible V5+TiO2 0.255.0 1.0 Tian et al. 2009
Methelyne Orange UV Pt6+TiO2 03.0 1.5 Huang et al. 2008

(Vijayabalan et al. 2009). Ag and Pd modified TiO2 counterpart. The doped TiO2 was reported to show
were shown to have improved photocatalytic activity higher photocatalytic activity for the degradation of
for the degradation of p-chlorophenol compared with RhB compared with undoped TiO2. In comparison to
Degussa P25 which was coupled with better charge undoped TiO2, 0.5% AgTiO2 was shown to achieve
separation and therefore, to slower recombination 1.53 times higher degradation of 2,4,6-trichlorophenol
(Kirilov et al. 2006). Under the conditions tested, by Rengaraj and Li (2006). Nonetheless, Ag content
Gupta et al. (2006) reported that more than 90% beyond the stated level was reported to have a
degradation of CV and MR mixtures was achieved in detrimental effect on the photocatalytic activity of
the presence of Ag doped TiO2 compared with only TiO2. Under the conditions tested, Silva et al. (2009)
about 70% with TiO 2 . Anandan et al. (2008) noticed an optimum Ce content of 0.6% (w/w) into
compared the effectiveness of 8 wt.% AgTiO2 for TiO 2 matrix for enhanced degradation of 4-
the degradation of Acid Red 88 in the presence of chlorophenol in the visible light. In addition to the
electron acceptors such as under visible light retardation of phase transformation, this behavior was
illumination. In comparison to TiO2, the nano-sized related to the shift of TiO2 absorption edge towards
AgTiO2 exhibited seven times higher photodegrada- longer wavelengths, by reducing the band gap of
tion rate in the presence of peroxomonosulfate while original material. Subramanian et al. (2008) examined
2.7 times higher in the case peroxodisulfate. Andronic the effect of Co doping on the structural and optical
and Duta (2007) noticed that optimum photocatalytic properties of TiO2 to obtain a nanocrystalline films of
behavior of Cd doped-TiO2 was found to be at 0.1 at. pure and doped TiO2 with grain size 10 to 25 nm. The
% for cadmium acetate and 0.5 at.% for cadmium films were reported to be transparent in the visible
chloride for the degradation of MO and MB, region, and the absorption edge shifted towards
respectively. Carbon doped TiO2 was reported to be the higher wavelength with increasing Co content.
efficient for the degradation phenol under visible light The observed decrease in band gap was attributed to
irradiation (Lee et al. 2008). This effect was attributed the formation of Co impurity band into the TiO2
to the shifting of absorption edge to a lower energy, energy bands. Venkatachalam et al. (2007a) observed
thus improving the photocatalytic activity in the that under identical and optimal experimental condi-
visible region. tions, 1 mol% Mg2+ and Ba2+ doped nano-TiO2, nano-
Ren et al. (2007) observed a high surface area and TiO2, and P25 required 300,360, and 450 min,
significant absorption in the visible light (>420 nm) respectively, for the complete mineralization of
for a carbon doped TiO2 compared with undoped 4-chlorophenol. The photocatalytic degradation of 4-
Water Air Soil Pollut (2011) 215:329 21

CP over TiO2 and Mg2+ and Ba2+ doped TiO2 with other samples when the doping level of K+ and
indicated the higher activity for doped TiO2. Enhanced calcinations temperature are 0143.% and 400
adsorption of 4-CP on the catalyst surface and smaller 1,000C, respectively (Chen et al. 2007).
particle size due to Mg2+ and Ba2+ loadings are Wong et al. (2008) studied the influence of
indicated to be the cause for higher activity of the crystallinity and carbon content on the photocatalytic
catalysts. The BET surface area of both S-doped TiO2 degradation of MB under visible light by varying the
and undoped TiO2 is shown to decrease significantly as carbon content from 03.2%. Under the conditions
the calcinations temperature increases from 300C to tested, the highest degradation was achieved at 1.25%
500C (Raileanu et al. 2009). The presence of S dopant carbon content. Zhu et al. (2004) observed that TiO2
onto TiO2 matrix slightly improve their photocatalytic doped with 0.09% FeCl3 and 0.09% FeCl2 exhibited
activities and led to better chlorobenzene removal higher photocatalytic activity than undoped TiO2 for
compared with undoped TiO2. The photocatalytic the decolorization of Active Yellow XRG dye diluted
activity is also increased slightly as the sintering in water under both UV and visible light irradiation.
temperature increases. Regardless of the organic Fe2+/Fe3+ doped TiO2 was reported to have high
chloride pollutant, the removal has been reported to specific surface areas and small crystal sizes. TiO2
vary between 96% and 100% under the conditions doped with FeCl3 was found to have better catalytic
studied. Lattice defects induced by dopant were activity for the degradation of XRG than those doped
indicated to strongly influence the photocatalytic with FeCl2. Yi et al. (2007) studied the effect of
activity. Irrespective of the number of coatings and Eu2+/Gd3+-co-doping onto TiO2 for the degradation of
the irradiation times, the Ag and S-doped TiO2 MO under natural sunlight. The suitable doping
exhibited higher removal compared with undoped content is reported to be 0.51.0% for Eu2+ and
TiO2. The S-doped TiO2 were shown to be more 0.11.0% for Gd3+; the optimum doping content for
efficient than the Ag doped-TiO2 which was attributed Eu2+ is 1.0% and for Gd3+ 0.5%. Coleman et al.
to the presence of anatase crystalline phase of TiO2 and (2005) noticed that the addition of Ag or Pt had no
to a more significant surface concentration of dopant. effect on the photocatalytic degradation of endocrine
Xie and Zhao (2008) indicated that increasing reactive disrupting chemicals at levels found in water. This
temperature from 40C to 140C was reported to was attributed to the high concentration of holes and
enhance the crystalline size from 3.8 to 6.0 nm. F-N hydroxyl radicals in the systems compared with the
and S-N co-doping resulted in a new strong absorption low level of organic matters to be degraded. At high
band in the visible range of 400620 nm, and with the concentration, a significant increase in the reaction
decrease in reactive temperature, the absorption edge rate observed for bisphenol A and resorcinol over Pt/
shifted toward higher wavelength. In the visible region TiO2. Under UV and visible light irradiation, the
(420 nm), photocatalytic activity of doped-TiO2 for mesoporous PdTiO2 film with a molar ratio of Pd/Ti=
the degradation of MO was reported to be three times 0.05 exhibited the highest activity for the degradation
more effective than that of bare P25. Sheng et al. of MB due to smaller crystallite size and lower
(2008) noticed that N-Br-codoped TiO2 readily crystallinity in mesoporous TiO2 film that that of
photodegrade MB under visible light irradiation in nonporous TiO2 film (Chan et al. 2009). The photo-
comparison to N-doped TiO2. This behavior was catalytic activity for aqueous phenol degradation of
attributed to its anatase crystalline framework, low anatase titania is shown to be enhanced upon doping
electronhole recombination rate, and high absorbance with Fe3+ up to ca. 1 wt.% (Adan et al. 2007). In
in the visible light. In contrast to P25 TiO2, photo- particular, maximum activity is observed for the
catalytic activity of N, C-doped TiO2 was four times 0.7 wt.% Fe3+ sample; in contrast, doping above ca.
higher for the degradation of phenol under visible light 3 wt.% does not produce any significant enhancement
(>400 nm) irradiation (Gorska et al. 2009a). The in the photocatalytic activity. Under solar radiation,
degradation rate of RB by La-doped-TiO2 was higher La3+-TiO2 containing 0.4 mol % lanthanum showed
compared with undoped TiO2 for all the calcination highest surface area(124.8 m2/g), lowest crystallite
temperature investigated (Peng et al. 2005). TiO2 size (8 nm), and exhibited 50% more degradation of
doped with 4.6% K+ and calcined at 700C was Methylene Blue compared with pure TiO2(Parida and
demonstrated to exhibit higher activity compared Sahu 2008). Zheng et al. (2007) noticed that the
22 Water Air Soil Pollut (2011) 215:329

coupled ZrO2ZnO system with 2.5% Zr was more studied the effect of Fe3+ doping (03.0 mol% Fe3+)
efficient compared with ZnO for the degradation of on the photocatalytic activity of TiO 2 for the
reactive Brilliant Red X-3B. Wen et al. (2009) degradation of phenol under UV light. Fe3+-doped
investigated the effects of I and F codoped TiO2 TiO2 was reported to possess the anatase structure
(prepared by solgel-impregnation method) on the with a range of crystal size 811 nm. The highest
photocatalytic degradation of MB. Co doping with I degradation efficiency was found at 0.5 mol% Fe3+-
and F was shown to enhance the degradation of MB doped TiO2. After 2-h calcination at 600C, the order
under simulated sunlight irradiation. The photocata- of photocatalytic activity of La-doped TiO2 for phenol
lytic activity of as prepared I-F codoped TiO2 was degradation was demonstrated to be 1>1.5>3>0.5>
reported to be much higher than that of pure, I-doped, 5>0 mol% La (Liqiang et al. 2004). Mohammad and
and F-doped TiO2 when the molar ratios of I and F to Al-Esaimi (2006) observed that 98% degradation of
Ti were maintained at 10. The difference in the MB was achieved after 75 min UV light irradiation in
photocatalytic activity was ascribed to larger surface the presence of 2V/TiO2SO4 catalyst, whereas only
area and stronger absorbance in the visible light range 78% degradation was obtained using 2V/TiO2 in the
by doping with I and F. The photocatalytic activity of same time. The variation in degradation efficiency
co-doped TiO2 was higher than pure TiO2 under UV was related to the difference in vanadium and sulfate
and visible lights. content. Under visible light irradiation, the photo-
Bouras et al. (2007) compared the photocatalytic catalytic activity of S-doped TiO2ZrO2 was shown to
degradation of Basic Blue in the presence of pure and be higher compared with unmodified STiO2 and
three cationic doped (Fe3+, Cr3+, and Co2+) TiO2 Degussa P25 for the degradation of Rhodamine B
under UV-vis and visible light irradiation. In all three (Tian et al. 2009). The observed effect has been
studied cases, the efficiency of UV-vis photodegrada- attributed to the larger surface area, smaller crystal
tion dramatically decreased in the presence of size, porous structure, and more surface hydroxyl
dopants. The decrease was faster in the case of Fe3+ groups in the catalyst. Ghasemia et al. (2009)
and Co2+ dopants and slower in the case of Cr3+. Li et tested the effect of transition metal ions on the
al. (2003) indicated that the photocatalytic activity of photocatalytic degradation of Acid Blue 92 under
Carbon-Black-modified nano-TiO2 (CBTiO2) thin UV light. The effect of transition metals ions on the
films was 1.5 times higher than that of TiO2 thin photocatalytic degradation rate and efficiency was
films in degrading Reactive Brilliant Red X-3B. Tian shown to be Fe-TiO 2 >CoTiO 2 >CrTiO 2 >Mn
et al. (2009) studied the photocatalytic activity of V TiO2>CuTiO2>NiTiO2>ZnTiO2>TiO2. The photo-
doped-TiO2 for the degradation of MB and 2, catalytic degradation of MB by various TiO2/SnO2
4-dichlorophenol using UV and visible light. In the thin films photocatalyst was investigated by varying
presence of UV light, 0.5% V-TiO2 was reported to be the amount of tin. For all TiO2/SnO2 thin films, the
efficient for the degradation of MB relative to pure degradation efficiency was higher compared with
TiO2. Under visible light irradiation, the degradation pure TiO2 films, exhibiting the highest for TiO2/
rate of 2,4-dichlorophenol over 1% V-TiO2 is shown SnO2 films with 9% Sn. The behavior was related to
to be two times higher compared with undoped TiO2. greater porosity and smaller band gap energies
Baiju et al. (2007) tested the photocatalytic activity of compared with pure TiO2 films (Martinez et al. 2005).
Ta2O5 doped TiO2 for the degradation of MB by Yuan et al. (2002) studied the influence of
varying the amount of Ta2O5 from 1 to 10 mol %. co-doping of Zn2+ and Fe3+ on the photocatalytic
Under the conditions examined, 2 mol % of tantalum degradation of phenol under solar light irradiation.
was shown to be efficient compared with pure TiO2. The co-doping of 0.5 mol% Zn2+ and 1 mol % Fe3+
Zhou et al. (2009) studied the photocatalytic activity onto TiO2 was found to be two times more efficient
of Nd-doped ZnO for the degradation of Reactive compared with pure TiO2. This behavior was attrib-
Blue 4 in aqueous suspension by varying the dopant uted to the coupled influenced of the co-dopant and
concentration from 13 mol%. Some 2.5 mol % titania energy bands. Qu et al. (2009) studied the
Nd-doped ZnO was demonstrated to be efficient for effects of the co-addition of Zn2+ and sodium
the enhanced photocatalytic activity under the ex- dodecylbenzenesulfonate (DBS) on photocatalytic
perimental conditions. Naeem and Ouyang (2009) degradation of RB relative to the undoped anatase
Water Air Soil Pollut (2011) 215:329 23

TiO2 nanoparticle films. In comparison to undoped irradiation whereas Co was beneficial only under
TiO2 film, the addition of Zn2+ was shown to improve visible light irradiation. This effect was ascribed to
both the photocatalytic activity and the hydrophilicity, an increased charge separation of the photogenerated
which was attributed to surface oxygen vacancies. electronhole pairs.
However, the co-addition of Zn2+ and DBS resulted in
a film with super hydrophilic behavior. The degrada-
tion efficiency was reported to decrease from 43.5% 9 Conclusion
to 35% due to the co-addition of Zn2+ and DBS. Lee
et al. (2005) compared the photocatalytic degradation Based on the recent representative studies, this review
of p-nitrophenol over TiO2 and TiO2/SiO2 nano- focuses on the role of various operating parameters on
particles prepared by the micro-emulsion method the photocatalytic degradation of various dyes and
using PFPE-NH4 surfactant. TiO 2 /SiO 2 (80:20) phenols, and reports the main advances.TiO2 has been
nanoparticles were reported to have a higher photo- suggested to be efficient for the degradation and
catalytic activity than pure TiO2 and the TiO2/SiO2 mineralization of various toxic organic pollutants, e.
(90:10) particles. This effect has been attributed to the g., phenols and dyes in water in the presence of UV,
decrease of crystallite size from 17 to 133 nm with an visible or solar light, and oxygen. The findings also
increase in silica content. Chen et al. (2009) studied suggest that various operating parameters such as type
the effect of Cu2+ doping (00.2 wt.%) on the of photocatalyst, light intensity, pollutant types, and
photocatalytic degradation of Methyl Orange using initial concentration, amount of catalyst, initial pH of
TiO2/SiO2. The optimum dopant content was about the reaction medium, mode of catalyst application,
0.10 wt.%. The photocatalytic activity of Cu2+-doped oxidizing agents/electron acceptors, and presence of
TiO2/SiO2 system was higher than that of TiO2/SiO2. ionic components in solution can significantly influ-
This behavior was attributed to the trapping of both ence the photocatalytic degradation rate of phenols
photogenerated holes and electrons, and inhibition of and dyes. Optimization of degradation parameters is
the electronhole recombination, leading to the crucial from the perspective of efficient design and
increase of photocatalytic activity. Arabatzis et al. application of photocatalytic oxidation process to
(2003) observed a two times faster degradation of ensure sustainable operation. The potential of this
Methyl Orange in the presence of Au/TiO2 compared technique under multi-component pollutants needs
with that obtained with the original TiO2 material. further attention to yield stable pollutant removal
Sonawane and Dongare (2006) tested the effect of through the optimization of process parameters. Metal
Au doping (12% Au/TiO2) on the photocatalytic and non-metal doped TiO2 have been reported to be
degradation of phenol in solar light irradiation of efficient for the improved degradation rate. In spite of
4.55 Wm2/day. In comparison to undoped TiO2, extensive investigations, the commercial exploitation
TiO2 doped with 12% Au showed 22.3 times of photocatalysis has been hindered by the lack of
higher photocatalytic activity. Using solgel method, efficient and low-cost visible light harvesting catalyst,
Venkatachalam et al. (2007b) examined the effect of a relatively poor understanding of the reactor design,
Zr4+ doping(0.55.0 mol % Zr4+) onto TiO2 matrix and inadequate scale-up strategies. Future research
for the photocatalytic degradation of 4-chlorophenol. should focus on the development of a more reliable
The photocatalytic activity of 3.0 mol% doped TiO2 photocatalyst that can be activated by visible and
samples were reported to be higher than that of nano- solar light or both. In addition, more work is required
TiO2 and Degussa P25. Enhanced adsorption of 4- on the modeling of photoreactor to optimize its design
CP over the catalyst surface and decrease in particle for pollutant degradation. In the literature, there is
size are indicated to be the reason for high activity of currently little information on the modeling of photo-
the catalyst. Bellardita et al. (2007) investigated the reactor to optimize its performance. Present research
effect of metal loading (W, Co, and Sm) onto TiO2 activities at CQ University and QUT, Australia focus
matrix on the photocatalytic degradation of 4- on the computational fluid dynamics modeling of a
nitrophenol. In comparison to Degussa P25, TiO2 flat plate reactor to optimize its design and to predict
loaded with 1% W and Sm caused a significant its performance. Although this review is not exhaus-
improvement in the photocatalytic activity under UV tive in the scope of photocatalytic degradation of
24 Water Air Soil Pollut (2011) 215:329

organic pollutants; however, it addresses the funda- Baiju, K. V., Shajesh, P., Wunderlich, W., Mukundan, P.,
Kumar, S. R., & Warrier, K. G. K. (2007). Effect of
mental principles and recent applications in this area.
tantalum addition on anatase phase stability and photo-
activity of aqueous solgel derived mesoporous titania.
Journal of Molecular Catalysis A: Chemical, 276, 4146.
Acknowledgement This study is supported under an Austra- Behnajady, M. A., Modirshahla, N., Daneshvar, N., & Rabbani,
lian Research Council (ARC) linkage grant in collaboration M. (2007). Photocatalytic degradation of an azo dye in
with CM Concrete Private limited and Department of Public atubular continuous-flow photoractor with immobilized
Works, QLD Government. The authors gratefully acknowledge TiO2 on glass plates. Chemical Engineering Journal, 127,
the financial support of ARC project. One author is also 167176.
grateful for the financial support of the Queensland Govern- Behnajady, M. A., Moghaddam, S. G., Modirshahla, N., &
ment through the Smart State fellowship scheme. Shokri, M. (2009). Investigation of the effect of heat
attachment method parameters at photocatalytic activity of
immobilized ZnO nanoparticles on glass plate. Desalina-
tion. doi:10.1016/j.desal.2009.06.021.
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