w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

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Review

An overview on limitations of TiO2-based particles

for photocatalytic degradation of organic pollutants
and the corresponding countermeasures

Haoran Dong a,b,*, Guangming Zeng a,b, Lin Tang a,b, Changzheng Fan a,b,
Chang Zhang a,b, Xiaoxiao He a,b, Yan He a,b
a
College of Environmental Science and Engineering, Hunan University, Changsha, Hunan 410082, China
b
Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education,
Changsha, Hunan 410082, China

article info abstract

Article history: The pollutants classified as “persistent organic pollutants (POPs)”, are being subject to high
Received 6 February 2015 concern among the scientific community due to their persistence in the environment.
Received in revised form TiO2-based photocatalytic process has shown a great potential as a low-cost, environ-
22 April 2015 mentally friendly and sustainable treatment technology to remove POPs in sewage to
Accepted 24 April 2015 overcome the shortcomings of the conventional technologies. However, this technology
Available online 7 May 2015 suffers from some main technical barriers that impede its commercialization, i.e., the
inefficient exploitation of visible light, low adsorption capacity for hydrophobic contami-
Keywords: nants, uniform distribution in aqueous suspension and post-recovery of the TiO2 particles
Adsorption after water treatment. To improve the photocatalytic efficiency of TiO2, many studies have
Surface modification been carried out with the aim of eliminating the limitations mentioned above. This review
Particle separation summarizes the recently developed countermeasures for improving the performance of
Persistent organic pollutants TiO2-based photocatalytic degradation of organic pollutants with respect to the visible-
Photodegradation light photocatalytic activity, adsorption capacity, stability and separability. The perfor-
mance of various TiO2-based photocatalytic processes for POPs degradation and the un-
derlying mechanisms were summarized and discussed. The future research needs for
TiO2-based technology are suggested accordingly. This review will significantly improve
our understanding of the process of photocatalytic degradation of POPs by TiO2-based
particles and provide useful information to scientists and engineers who work in this field.
© 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

* Corresponding author. College of Environmental Science and Engineering, Hunan University, Changsha, Hunan 410082, China. Tel.:
þ86 0731 88822778.
E-mail address: [email protected] (H. Dong).
http://dx.doi.org/10.1016/j.watres.2015.04.038
0043-1354/© 2015 Elsevier Ltd. All rights reserved.
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 129

2. Basic principle of TiO2 photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3. Limitations and countermeasures in TiO2-based photocatalytic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Approaches to enhance the visible-light photocatalytic activity of TiO2 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Doping with metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.2. Doping with non-metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.3. Co-doping technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.4. Surface organic modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.2. Approaches to enhance adsorption of organic pollutants on TiO2 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.1. Surface organic modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.2. Doping with carbon-based nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3. Approaches for the stabilization of TiO2 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.3.1. Stabilization by support structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.3.2. Stabilization by surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4. Approaches for the separation of TiO2 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4.1. Immobilization on support structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.4.2. Magnetic separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.5. Future challenges in TiO2-based photocatalytic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

from some disadvantages such as incomplete removal, high

1. Introduction consumption of chemical reagent, high treatment cost, time-
consuming and generation of toxic secondary pollutants (H.R.
In recent times, the world faces enormous challenges ahead Dong et al., 2011; Oller et al., 2011; Zhou et al., 2014). Effective
as drinkable water runs short due to natural disasters, popu- alternative water treatment technologies are therefore
lation increase, and water pollution. In view to suppress the required to improve treated effluent quality.
worsening of clean water shortage, the possible reuse of Photodegradation process of POPs has attracted increasing
onsite rural wastewater or treated municipal wastewater from attention during the past decades due to its effectiveness in
treatment plants for agricultural and industrial activities may rapidly degrading and mineralizing recalcitrant organic com-
be the best solution for the future of sustainable water man- pounds (Legrini et al., 1993; Chong et al., 2010; Miranda-Garcia
agement in water-deprived countries (Lapena et al., 1995; et al., 2011). Various photocatalysts including CdS, SnO2, WO3,
Bradley et al., 2002; Xu et al., 2012). Since these wastewaters SiO2, ZnO, Nb2O3, Fe2O3 were being studied but the nano-TiO2
constitute one of the largest possible water resources, their photocatalyst is well-known among the metal oxides for its
reuse is anticipated to offset more clean water resource. high efficiency, low cost, physical and chemical stability,
Recycling wastewaters is usually associated with the widespread availability, and noncorrosive property (Carp et al.,
presence of suspended solids, health-threat coliforms and the 2004; Herrmann et al., 2007). It can be used to degrade a variety
so-called persistent organic pollutants (POPs, e.g., pharma- of organic and inorganic pollutants. When nano-TiO2 is irra-
ceuticals, personal care products and endocrine disrupters) diated with ultraviolet (UV) light, electrons are promoted from
that are both tedious and expensive to treat (Viessman and the valence band to the conduction band, resulting in the
Hammer, 1998; Miranda-Garcia et al., 2011; Zeng et al., generation of energized “holes” in the former (Fujishima et al.,
2013a,b). In particular, the POPs are frequently detected in 2000; Chong et al., 2010). Free electrons react with the oxygen to
treated sewage, surface and groundwater and even drinking form superoxide radical anions (O2), while energized holes


water, and have been observed to be capable of long-range react with water (H2O) or hydroxyl ion (OH) to form hydroxyl
transport, bioaccumulate in human and animal tissue, bio- 
radicals ( OH). To date, the main TiO2 applications are focused
magnify in food chains, and to have potential significant im- on air purification (Ao and Lee, 2003; Zhao and Yang, 2003; Li
pacts on human health and the environment (Miranda-Garcia et al., 2005a,b). Studies in wastewater treatment by TiO2 are
et al., 2011). Development of advanced water treatment still mainly in the stage of laboratory experiments because of
technologies with low-cost and high efficiency to treat the some technical barriers. Firstly, the widespread technological
POPs contaminated wastewater is desirable. Currently, avail- use of TiO2 is to some extent constrained by its wide band gap
able water treatment technologies such as adsorption or (anatase, ~3.2 eV), which requires ultraviolet irradiation for
coagulation merely concentrate the pollutants present by photocatalytic activation, giving rise to a very low energy effi-
transferring them to other phases, but they are not completely ciency in utilizing solar light (Yin et al., 2003; Zaleska, 2008;
“eliminated” or “destroyed” (Padmanabhan et al., 2006). Other Chong et al., 2010). Because UV light accounts for only a small
conventional water treatment methods such as sedimenta- fraction (5%) of the sun's energy compared to visible light (45%),
tion, filtration, chemical oxidation and biotechnology suffer the shift in the optical response of TiO2 from the UV to the
130 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

visible spectral range will have a profound positive effect on valence band (VB) to the conduction band (CB). Fig. 1 depicts
the practical applications of the material. Besides the ineffi- the mechanism of the electronehole pair formation when the
cient exploitation of visible light, the practical applications TiO2 particle is irradiated with light of adequate energy. The
were also prohibited due to the following limitations: 1) low light wavelength for such photon energy usually corresponds
adsorption capacity to hydrophobic contaminants; 2) high ag- to l < 400 nm. The photonic excitation leaves behind an empty
gregation tendency; and 3) difficulty of separation and recovery unfilled valence band, and thus generates the electronehole
(Bhattacharyya et al., 2004; Gao et al., 2011; Cui et al., 2013). pair (eehþ) (Eqs. (2.1)e(2.3)).
To improve the photocatalytic efficiency of TiO2, many The eTR and hþTR in Eq. (2.4) represent the surface trapped
studies have been carried out to eliminate the limitations valence band electron and conduction-band hole respectively.
mentioned above. Although some review papers on TiO2 It was reported that these surface-trapped electrons and holes
technologies have been published in recent years, most of recombine much more slowly than they do in the bulk (Furube
them focused on contaminants removal, the reaction mech- et al., 2001). Serpone et al. (1995) have highlighted the impor-
anisms, preparation methods of TiO2-based particles, princi- tant consequences of surface trapped holes (hþTR) and elec-
ples of photocatalysis, and effects of operational parameters trons (eTR) to the photooxidation of organic compounds. In
(Gaya and Abdullah, 2008; Zaleska, 2008; Chong et al., 2010; the absence of electron scavengers (Eq. (2.4)), the photoexcited
Lim et al., 2011; Morales-Torres et al., 2012; Pelaez et al., electron recombines with the valence band hole in nanosec-
2012). None of them extensively summarizes the limitations onds with simultaneous dissipation of heat energy. Hence, the
of TiO2-based technologies and the developed countermea- presence of electron scavengers is vital for prolonging the
sures in the past years. Therefore, this paper aims to review recombination and successful functioning of photocatalysis.
and summarize the limitations of TiO2 technologies and the In most applications, photocatalytic degradation reactions
recent works on the modification of TiO2 photocatalysts with are carried out in presence of water, air, the target contami-
the purpose of improving the photocatalytic degradation of nant and the photocatalyst. Generally, the positive hole reacts
organic pollutants. The existing shortcomings and future with the surface OH groups on the TiO2 particle to produce

research needs to utilize TiO2 photocatalysis for water treat- surface adsorbed hydroxyl radical ( OHads) (Eqs. (2.5) and (2.6))
ment are also summarized and discussed. depicts how the presence of oxygen prevents the recombi-
nation of electronehole pair, while allowing the formation of
superoxide radical anion (O2). This O2 radical can be further
 

2. Basic principle of TiO2 photocatalysis protonated to form the hydroperoxyl radical (HO2) and sub-

sequently H2O2 (Eqs. (2.7)e(2.9)). The HO2 radical formed was
The semiconductor TiO2 has been widely utilized as a photo- also reported to have scavenging property and thus, the co-
catalyst for inducing a series of reductive and oxidative re- existence of these radical species can doubly prolong the
actions on its surface. The mechanisms underlying the recombination time of the hþTR in the entire photocatalysis
heterogenous photocatalysis employing the semiconductor reaction. Photogenerated holes and the formed reactive oxy-


TiO2 catalyst have been intensively reported in many papers gen species (e.g., OH) can participate in the degradation of
(Fujishima et al., 2000; Gaya and Abdullah, 2008; Banerjee organic pollutants (Fujishima et al., 2000; Zhao and Yang,
et al., 2014). Generally, there are five essential key steps in 2003; Banerjee et al., 2014) (Eqs. (2.10) and (2.11)).
the heterogenous photocatalysis on the surface of TiO2, Since the heterogenous photocatalysis reaction mostly
namely, the (1) photoexcitation (light absorption and charge- occurs on the photon activated surface of TiO2, the under-
carriers generation), (2) diffusion, (3) trapping, (4) recombina- standing of the reaction steps involved in the photo-
tion, and (5) oxidation (Gaya and Abdullah, 2008; Chong et al., degradation of organics is essential in the formulation of
2010; Foo and Hameed, 2010). The key reactions involved in kinetic expressions. With increasing irradiation time, the
the photocatalysis are listed in Table 1. Upon irradiation of liquid phase organic compounds are degraded to their corre-
TiO2 with light energy equivalent to or greater than its band sponding intermediates and further mineralized to carbon
gap energy (anatase, ~3.2 eV), the electron is excited from the dioxide, water and inorganic ions (from heteroatoms) (Eq.

Table 1 e The reactions involved in the TiO2 photocatalysis with the presence of organic pollutant (RH).
Reactions Eq. no.
Photoexcitation: TiO2 þ hv / e þ hþ (2.1)
Charge  carrier trapping of e : e
CB /eTR

(2.2)
Charge  carrier trapping of hþ : hþVB /h þ
TR (2.3)
Electron  hole recombination : eTR þ hVB ðhþ
 þ 
TR Þ/eCB þ heat (2.4)
 þ
Oxidation of hydroxyls: (OH )ads þ h / OHads



(2.5)
Photoexcited e scavenging : ðO2 Þads þ e /O2

(2.6)
Protonation of superoxides : O2 þ OH/HOO
 
(2.7)
 
 
Co  scavenging of e : HOO þe /HO2 (2.8)
Formation of H2O2: HOO þ Hþ / H2O2 (2.9)
Photodegradation by OH: RH þ OH / R þ H2O
  
(2.10)
Direct photoholes: RH þ hþ / R / Intermediate(s)/Final Degradation Products

(2.11)
TiO2 =hv (2.12)
RHƒƒƒƒƒƒƒ!intermediateðsÞ/CO2 þ H2 O þ inorganic ions ðfrom heteroatomsÞ
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 131

of incident solar irradiation and indoor light, which results

from its relatively large band gap (anatase, ~3.2 eV) (Yin et al.,
2003). Hence, any improvement of the photocatalytic effi-
ciency of TiO2 by shifting its optical response to the visible
range will have a profound positive effect.
Since photocatalytic degradation mainly occurs on the
surface of TiO2, mass transfer limitation has to be minimized
for effective TiO2 application in water treatment. However,
due to its poor affinity towards organic pollutants (especially
the hydrophobic organic pollutants), the adsorption of
organic pollutants on TiO2 surface is relatively low, resulting
in slow photocatalytic degradation rates. Therefore, how to
concentrate the target pollutants around the TiO2 nano-
Fig. 1 e Schematic diagram illustrating the principle of TiO2 particles to enhance photocatalytic efficiency requires
photocatalysis with the presence of water pollutant (RH). consideration. Besides, during the photocatalytic degrada-
tion process, the TiO2 nanoparticles may undergo aggrega-
tion due to the instability of the nanosized particle, which
(2.12)). The overall photocatalysis reaction as depicted by Eq. may hamper the light incidence on the active centers and
(2.12) can generally be divided into five independent steps consequently reduce its catalytic activity (Gao et al., 2011;
(Herrmann, 1999): 1) mass transfer of the organic contami- Mallakpour and Nikkhoo, 2014). However, it should be
nants in the liquid phase to the TiO2 surface; 2) adsorption of noted that it may well happen that small particles show
the organic contaminants onto the photon activated TiO2 higher scattering, which can reduce their photocatalytic ac-
surface (i.e. surface activation by photon energy occurs tivity compared to larger ones (Minero and Vione, 2006).
simultaneously in this step); 3) photocatalysis reaction for the Furthermore, for the slurry system, one main practical chal-
adsorbed phase on the TiO2 surface; 4) desorption of the in- lenge to overcome is to recover the nanosized TiO2 particles
termediates from the TiO2 surface and 5) mass transfer of the from the treated water in regards to both the economic
intermediates from the interface region to the bulk fluid. In concern and safety concern. The above limitations in the
terms of rate determination, the overall rate of reaction is application of TiO2-based particles for photocatalytic degra-
equal to the slowest step, which could possibly be either the dation of organic pollutants are summarized in Fig. 2.
mass transfer step or the reaction step. Vinodgopal and Kamat To overcome those limitations of TiO2-based photo-
(1992) also reported the dependence of the photodegradation catalysis, the following countermeasures have been adopted
rate of the organic surrogate on surface coverage of the pho- in previous studies: 1) modification of TiO2 catalyst, in order
tocatalysts used. This outlines the importance of molecules to achieve the utilization of visible light (Bannat et al., 2009;
adsorption or surface contact with the catalyst during the F. Dong et al., 2011); 2) optimization of catalyst synthesis, in
photocatalytic degradation. Another factor that greatly re- order to obtain catalysts with a defined crystal structure,
stricts the photocatalytic activities of TiO2 is the low quantum smaller particle sizes, and high affinity to various organic
yield of excitons due to the fast electronehole (eehþ) pollutants (Makarova et al., 2000; Lightcap et al., 2010); and
recombination. The other important factor is the recombina- 3) design and development of second generation of TiO2
tion of radical intermediates on the TiO2 surface. Partially catalyst, with high separation ability, which can be recov-
oxidized species could undergo reduction by electrons (and ered and regenerated effectively (Nakayama and Hayashi,
partially reduced ones undergo oxidation by holes and/or 2007; Gad-Allah et al., 2007; Tang et al., 2013). The pur-

surface OH) to give back the initial substrate (Vione et al., poses of these modifications and developments were to
2005). Besides, there are other operational parameters that improve photocatalytic efficiency, complete degradation of
could influence the process of photocatalytic degradation, organic pollutants, improve visible light absorption,
e.g., light intensity, nature and concentration of substrate (i.e.,
organic pollutants), nature of photocatalyst (e.g., particle size),
concentration of photocatalyst, pH and reaction temperature
(Gaya and Abdullah, 2008).

3. Limitations and countermeasures in TiO2-

based photocatalytic processes

TiO2 photocatalysis is one of the most efficient destructive

technologies among advanced oxidation processes (AOPs),
because it appears to utilize solar energy to lead to the total
mineralization of most of the organic pollutants that exist in
air and aqueous systems (Legrini et al., 1993). However, its Fig. 2 e Limitations in application of TiO2-based particles
application is limited because of its narrow photocatalytic for photocatalytic degradation of organic pollutants.
region (l < 400 nm) and ability to absorb a small fraction (<5%)
 132
Table 2 e The countermeasures to improve the performance of TiO2-based photocatalytic processes and their respective mechanisms and drawbacks.
Countermeasures Improvements/mechanisms Drawbacks Ref.
Enhancing the Doping of metals ✧ Narrowing band gap ✧ Thermal instability Bannat et al., 2009; J. Zhang et al., 2010
visible-light ✧ Retarding electronehole ✧ Dopant concentration dependent
photocatalytic activity recombination
of TiO2 particles ✧ Enhancing adsorption of contaminants ✧ Costly
Doping of non-metals ✧ Narrowing band gap ✧ Formation of oxygen vacancies Q. Li et al., 2008; F. Dong et al., 2011
✧ Enhancing adsorption of contaminants ✧ Short-term efficiency of photocatalysis
✧ Enhance conductivity of TiO2 ✧ High temperature for preparation and
the procedures are somewhat tedious
Co-doping technique ✧ Improved interfacial charge transfer ✧ The dosage level could be an important Gombac et al., 2007; Huo et al., 2009
factor in influencing the photoactivity
✧ Synergistic effect of two elements co- ✧ Need multistep experimental process

w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6
doping for preparation
Surface organic modification ✧ Enhancing visible light absorption ✧ Surface coating tend to partially desorb Zhao et al., 2005; Chen et al., 2009
(dye sensitization/organic ✧ Improving electronehole separation ✧ Be depressed by the competitive
coating) adsorption of other coexisting species
✧ The sensitizers or coatings are toxic
and unstable in aqueous solution
Enhancing adsorption of Surface organic modification ✧ Hydrogen bonding, neп and пeп in- ✧ Concern on the remobilization of sur- Makarova et al., 2000
organic pollutants on teractions result in stronger adsorption face coating during the photocatalysis
TiO2 particles process
Doping of carbon-based ✧ Provide high surface area, well con- ✧ Concern on the remobilization of Williams et al., 2008; Lightcap et al., 2010
nanoparticle ductivity and higher visible light ab- carbon-based material during the
sorption intensity photocatalysis process
✧ Suppression of electronehole recombi-
nation (due to the high electrical
conductivity)
✧ Band-gap narrowing resulting from the
presence of TieOeC bonds
Stabilization of TiO2 Stabilization by ✧ Immobilize the TiO2 photocatalyst to ✧ Lower activity of supported TiO2 than Carp et al., 2004
particles support structures prevent aggregation the unrestricted catalyst
Stabilization by surface ✧ Prevent the particle aggregation and ✧ Stability could be decreased in the Nakayama and Hayashi, 2007
modification disperse homogeneously of TiO2 presence of cations, e.g., Ca2þ
nanoparticles
Separation of Immobilization on ✧ Immobilize the TiO2 photocatalyst for ✧ Lower activity of supported TiO2 than Mascolo et al., 2007
TiO2 particles support structures easy recovery the unrestricted catalyst
Magnetic separation ✧ This type of composite photocatalyst ✧ The photocatalytic activity of magnetic Gad-Allah et al., 2007; Tang et al., 2013
comprises of a TiO2 shell and a mag- TiO2 can be influenced by the magnetic
netic core, making them recoverable core size, calcination temperature, etc.
due to their magnetic properties
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 133

improve stability and reproducibility, and to improve The effect of metal ion dopants on the photocatalytic ac-
recycle and reuse abilities of TiO2. The countermeasures for tivity is a complex problem. The visible light photoactivity of
overcoming these limitations, and the mechanisms and metal-doped TiO2 can be explained by a new energy level
drawbacks of each countermeasure are briefly summarized produced in the band gap of TiO2 by the dispersion of metal
in Table 2 and are discussed in detail in the following nanoparticles in the TiO2 matrix. As shown in Fig. 3, electrons
sections. can be excited from the defect state to the TiO2 conduction
band by photons with energy equal to hv2. An additional
3.1. Approaches to enhance the visible-light benefit of transition metal doping is the improved trapping of
photocatalytic activity of TiO2 particles electrons to inhibit electronehole recombination during irra-
diation (Fig. 3). Deposition of metal nanoparticles with a large
How to improve the photocatalytic activity of TiO2 in the work function, such as Ag (Tran et al., 2006), Pt (Kowalska
visible region is the main focus of the recent TiO2 photo- et al., 2008), and Au (Subramanian et al., 2001; Wang et al.,
catalysis research. Several approaches for TiO2 modification 2008; Bannat et al., 2009), onto TiO2 surface has been found
have been proposed: metal-ion implanted TiO2 (e.g., Au) to efficiently retard the eehþ recombination because of the
(Anpo, 2000; Fuerte et al., 2001), non-metal doped-TiO2 (e.g., N) Schottky barrier formed at the metaleTiO2 interface. Decrease
(Ohno et al., 2003; Yu et al., 2003b; Pelaez et al., 2012), com- of charge carriers recombination results in enhanced photo-
posites of TiO2 with semiconductor having lower band gap activity. Here, the metal nanoparticles act as a mediator in
energy (e.g. sensitizing of TiO2 with dyes) (Chatterjee and storing and shuttling photogenerated electrons from the TiO2
Mahata, 2001) and TiO2 doped with upconversion lumines- surface to an acceptor. Iliev et al. (2006) demonstrated that
cence agent (Zhou et al., 2006; J. Wang et al., 2007). The deposition of Pt or Ag on the surface of TiO2 greatly enhanced
mechanisms of each modification approach and their ad- the photocatalytic degradation of oxalic acid due to the
vantages and drawbacks are discussed in detail in the increased separation of eehþ and higher rate of O2 reduction.
following. Besides the above causes for the enhanced photoactivity of
metal-doped TiO2, there is another factor that should be taken
3.1.1. Doping with metals into account in the photocatalytic process. Since surface sites
Over the past decades, metal-doped TiO2 (e.g., Cu, Co, Ni, Cr, can also be occupied by metal ion dopants, the surface prop-
Mn, Fe, Ru, Au, Ag, Pt) photocatalysts have been widely stud- erties as well as the point of zero charge value of TiO2 may be
ied for improved photocatalytic performance on the degra- altered by doping, depending both on the type and amount of
dation of various organic pollutants under visible light the dopant metal. Consequently, a modification of adsorption
irradiation (Anpo, 2000; Fuerte et al., 2001; Arabatzis et al., properties takes place (Fig. 3). Ranjit et al. (2001a,b) reported
2003; Hu et al., 2006; Zang and Farnood, 2008; Zaleska, 2008; that lanthanide ions can form complexes with various Lewis
Han et al., 2014). TiO2 particles can be simply substitution- bases (e.g., acids, amines, aldehydes, alcohols, thiols, etc.)
ally or interstitially doped with different cations, can form through interaction of these functional groups with the f-or-
mixed oxides or a mixture of oxides. The dominant parame- bitals of the lanthanides. Xu et al. (2002) found that the metal-
ters include the character and concentration of dopants and doped TiO2 (e.g., La3þ, Ce3þ, Er3þ, Pr3þ, Gd3þ, Nd3þ, and Sm3þ)
the applied thermal treatment (Soria et al., 1991; Palmisano presents an improved NO2 adsorption. Li et al. (2004) also re-
et al., 1994). Many controversial results are reported in the ported an enhancement of saturated adsorption capacity and
literature since even the method of doping (e.g., impregnation, adsorption equilibrium constants of La3þ doped TiO2
coprecipitation, and solegel methods) leads to different compared to bare TiO2 for 2-mercaptobenzothiazole.
morphological and crystalline properties of the photocatalyst However, it was found that the photocatalytic activity of
(Zaleska, 2008). metal-doped TiO2 could be influenced by dopant concentra-
tion. Ambrus et al. (2008) and Tong et al. (2008) reported an
improved photocatalytic performance for the optimum Fe
dopant concentration. Beyond the optimum concentration of
dopant, the photodegradation rate decreased. It was
concluded that the dopant ions below an optimum dosage
level can act as electronehole separation centers, and thus
enhance the photocatalytic efficiency, while the dopant ions
with dosage level exceeds optimum value, can act as elec-
tronehole recombination centers which are detrimental to
the photocatalytic activity (Wu et al., 2009). Besides, metal
doping showed other drawbacks: thermal instability of doped
TiO2 and requirement of more expensive ion-implantation
facilities (J. Zhang et al., 2010). In addition, although noble
metals coupling could be efficient in improving the photo-
catalytic reactions, the cost-effectiveness needed by indus-
Fig. 3 e Mechanisms of metal-doped TiO2 photocatalysis: trial application usually causes their replacement by more
①: narrowing band gap (hv1: pure TiO2; hv2: metal-doped economical transition or non-metals doping.
TiO2); ②: retarding electronehole recombination; and ③:
enhancing adsorption of contaminants (RH).
134 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

3.1.2. Doping with non-metals TiO2 doped with substitutional nitrogen has shallow acceptor
Compared with metal dopants, nonmetal dopants, such as C, states above the valence state. In contrast, TiO2 doped with
N, S, B, P, F and I (Chen et al., 2007), may be more appropriate interstitial nitrogen has isolated impurity states in the middle
for the extension of the photocatalytic activity of TiO2 into the of the band gap. These impurity energy levels are mainly hy-
visible region because their impurity states are near the bridized by N 2p states and O 2p states.
valence band edge, but they do not act as charge carriers, and Besides NeTiO2, the carbon doped TiO2 (CeTiO2) has also
their role as recombination centers might be minimized. received special attention (Wu et al., 2013). Sakthivel and
Numerous contributions have been devoted recently to Kisch (2003) reported that CeTiO2 was five times more active
developing effective TiO2 photocatalysts doped with than NeTiO2 in the degradation of 4-chlorophenol by visible
nonmetal elements to extend the light absorbance of TiO2 into light. In the investigation of CeTiO2, similar to the NeTiO2,
the visible region (F. Dong et al., 2011; Likodimos et al., 2013; there was also a debate as to whether the doped type of carbon
Moustakas et al., 2013; El-Sheikh et al., 2014). Among all is substitutional or interstitial (Chen et al., 2007). This was
nonmetal-doped TiO2 materials, N- and C-doped TiO2 nano- accounted for by the crystal form and synthesis method of
materials have been found to exhibit superior photocatalytic TiO2. Valentin et al. (2005) reported that carbon can be doped
activity under visible light irradiation. into TiO2 lattice and then strongly enhance the visible light
Until now, much effort has been focused on the research of absorption of TiO2 via substituting oxygen sites or getting into
N-doped TiO2 (NeTiO2). There have been a large number of the interstitial positions of TiO2, which is due to the intro-
publications that deal with the preparation of NeTiO2 by duction of series of localized occupied states into the band gap
physical or chemical methods, including solegel, sputtering, of TiO2 lattice. In addition, some reports suggested that large
ion implantation, mechanochemical and plasma-enhanced band gap narrowing could also originate from residual carbon-
chemical vapor deposition method (Zaleska, 2008). However, containing species with complex composition, through
different conclusions concerning the state of doped nitrogen incomplete removal of organic compounds in the calcination
in the NeTiO2 lattice and the mechanism of band gap nar- procedure (Lettmann et al., 2001; Sakthivel and Kisch, 2003).
rowing have been derived (Fig. 4). For example, Asahi et al. Besides, carbon doping can significantly stabilize the anatase
(2001) proposed that substitutional-type doping using N was TiO2 and improve the adsorption of organic pollutant mole-
effective for the band gap narrowing of TiO2 due to the mixing cules on the catalyst surface (Kang et al., 2008; Hahn et al.,
of N 2p with O 2p states in the valence band based on spin- 2009). Moreover, carbon doping can enhance the conductiv-
restricted local density approximation calculations on ity of TiO2 (Janus et al., 2006; Xiao and Ouyang, 2009), as it
anatase. The N 2p state hybrids with O 2p states in anatase could facilitate the charge transfer from the bulk of the TiO2
TiO2 doped with nitrogen because their energies are very structure to the surface region where the desired oxidation
close, and thus the band gap of NeTiO2 is narrowed and the reactions take place (Fig. 4).
material becomes able to absorb visible light. However, Irie In spite of the visible-light photocatalytic performance of
et al. (2003) and Lindgren et al. (2003) found that interstitial- nonmetal-doped TiO2, at the same time, there are some
type doping of N atoms was related to the photo-threshold problems with nonmental-doped TiO2: 1) The doping of non-
energy decrease, which induced localized N 2p states within metals into the lattice of TiO2 usually results in the formation
the band gap just above the top of the valence band, facili- of oxygen vacancies in the bulk. These defects can act as
tating the production of oxygen vacancies. Ihara et al. (2003) massive recombination centers of photo-induced electro-
reported that oxygen-deficient sites formed in the grain nehole pairs, which largely limit the visible light photo-
boundaries is important to emerge vis-activity and nitrogen catalysis efficiency of nonmental-doped TiO2 for industrial
doped in part of oxygen-deficient sites are important as a applications (X.Y. Li et al., 2008; F. Dong et al., 2011). In view of
blocker for reoxidation. Zhao and Liu (2008) concluded that practical application, higher photocatalytic reaction efficiency
is required because the photocatalytic efficiency of nonmetal-
doped TiO2 under visible light is still low (Ozaki et al., 2007;
Dong et al., 2010). 2) The stability of nonmental-doped TiO2
is also a concern in regard to the long-term efficiency of
photocatalysis. It is reported that the stability of NeTiO2 be-
comes worse after photoelectrolysis of water under visible
light irradiation due to a decrease in N concentration at the
surface layer (Kitano et al., 2006). Deactivation of N-doped
TiO2 for the oxidation of 2-propanol in aqueous solution under
visible light after a reaction of 150 h was also observed, which
was related to the liberation of doped N atoms (Nosaka et al.,
2005). 3) The preparation method is another crucial factor that
should be considered for applications. The doping process of
Fig. 4 e Mechanisms of non-metal doped TiO2 the nonmetal elements always involves thermal treatment at
photocatalysis: ①: narrowing band gap (hv1: pure TiO2; hv2: high temperatures (400e850  C) or a long time of hydrother-
non-metal doped TiO2); ②: facilitating electron transfer mal treatment, both of which are unfavorable in energy (F.
from the bulk of the TiO2 structure to the surface region Dong et al., 2011). Besides, expensive, toxic, or unstable pre-
(reaction sites); and ③: enhancing adsorption of cursors are used; undesirable gaseous byproducts are usually
contaminants (RH). produced in the preparation process; and the procedures are
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 135


somewhat tedious, which, in all, make the preparation costly possess suitable reduction potential to generate OH radical by
and large-scale application difficult (Dong et al., 2009). the oxidation of H2O (Rengifo-Herrera et al., 2009; Rengifo-
Therefore, development of new and optimization of existing Herrera and Pulgarin, 2010). It has also been reported that
less oxidative superoxide radical anion O 1

photocatalysts exhibiting activity under visible light with 2 , and O2 species are
surface characteristics of improved performance and having predominantly responsible for the photocatalytic bacterial
high chemical and physical stability are crucial for broader inactivation under visible light irradiation, however, highly

scale utilization of photocatalytic systems in commercial oxidizing OH radicals are produced under UV light excitation,
application. which play active roles toward photocatalytic activity (Rengifo-
Herrera et al., 2009; Rengifo-Herrera and Pulgarin, 2010).
3.1.3. Co-doping technique As discussed in the previous section, the dosage level could
More recently, the simultaneous doping of two kinds of also be an important factor in influencing the photoactivity of
atoms into TiO2 has attracted considerable interest (J. Zhang co-doped TiO2. Below an optimum dosage level, the dopant
et al., 2010). These co-doped TiO2 nanomaterials have been ions can act as electronehole separation centers, promote the
demonstrated to have improved photocatalytic activities charge separation, and thus enhance the photocatalytic effi-
compared to those of non-doped TiO2 or single-ion doped ciency. However, as dosage level exceeds optimum value, the
TiO2, especially in the visible light region. For example, dopant ions can act as electronehole recombination centers
monocrystalline TiO2 codoped with Eu3þ and Fe3þ shows which are detrimental to the photocatalytic activity. Wu et al.
synergistic effect, which significantly increases the photo- (2009) found that 4.0 wt% of Au was found to be the optimum
catalytic degradation of chloroform in solution (five times dopant concentration for photodegradation of methyl orange
compared to pure nanocrystalline TiO2 and about two to six by Au/N-doped TiO2 under both UV and visible light irradia-
times compared to Fe3þ or Er3þ doped separately, respec- tion. Higher amounts of gold deposition (>4.0 wt% Au) caused
tively) (P. Yang et al., 2002). It was proposed that Fe3þ serves decreased photocatalytic activities through an electronehole
as a hole trap and Eu3þ as an electron trap, speeding up the recombination process. In addition, the high concentrations
anodic and the cathodic processes, respectively, via of Au may also block the NeTiO2 from absorbing the incoming
improved interfacial charge transfer. Livraghi et al. (2009) photons.
investigated the decomposition of methylene blue by NeF- Besides high catalytic activity for photodegradation of
codoped TiO2 in aqueous phase. It was found that F could organic pollutants, the issue of physiochemical stability and
activate the active site of N by producing extra electrons to reuse of the synthesized photocatalysts is another main

the low energy orbital of Nb (a paramagnetic species). Doping objective in this research area. Unfortunately, only a few pa-
with F and N created a synergism in which F improved the pers have reported on the stability and reuse of co-doped TiO2
incorporation of N photoactive species into TiO2. Cong et al. (Gombac et al., 2007; Huo et al., 2009). Huo et al. (2009) evalu-
(2007) reported that titania co-doped with N and Fe3þ ated the performance of N and F co-doped TiO2 in methylene
(0.5 wt%) decomposed a 50 mL 20 mg L1 rhodamine B solu- blue degradation through ten successive batches. After ten
tion completely in 4 h under visible light irradiation, faster consecutive photocatalytic experiments, the N and F co-doped
than N-doped TiO2 or Fe-doped TiO2. However, under UV TiO2 photocatalyst retained high photocatalytic performance.
light, the photocatalytic activities of FeeN co-doped TiO2 was Gombac et al. (2007) investigated the stability of NeB co-doped
lower than that of undoped TiO2. The nitrogen ions and Fe3þ TiO2 for photodegradation of methyl orange and found that
dopants could act as the recombination center of electrons after four cycles, a relatively small decrease of the catalyst
and holes, thus decreasing the UV photoactivity. Interest- activity was observed. They suggested that the presence of B
ingly, some research reported that co-doped TiO2 photo- allowed a stronger retention of N-containing species.
catalysts exhibited good photoactivities under both UV and Currently, no report on the changing of concentration or
visible light (J. Zhang et al., 2010). For instance, Lin et al. composition of the dopants after long time of reaction is
(2007) found that the phosphorus and nitrogen co-doped available. It is worthwhile to indicate that research on stability
titania showed high photoactivity in the UV illumination and reuse of these co-doped TiO2 catalysts is in high demand
and also in visible light. They suggested that the OePeN in both academic and commercial sectors.
linkage would lead to the high photocatalytic activity.
In the recent studies, the different roles of reactive oxygen 3.1.4. Surface organic modification
species (ROS) were found in doped and co-doped visible-light- As mentioned above, those metal/nonmetal-doped TiO2 ma-
active TiO2 photocatalysts (Rengifo-Herrera et al., 2009; terials were generally somewhat difficult to be prepared with
Rengifo-Herrera and Pulgarin, 2010; Banerjee et al., 2014; the needs of lattice exchange at high temperature and
Zhao et al., 2014). Zhao et al. (2014) showed that NeF co-doped multistep experimental process. In the past decade, surface
TiO2 exhibited the best performance to destroy 6- modification of TiO2 with organic ligands has drawn much
hydroxymethyl uracil (6-HOMU), a model compound for cya- attention.
notoxins. Mechanistic investigations carried out in the pres-
ence of scavengers for O 1 þ
 
2 , O2 (singlet oxygen), OH, and h vb 3.1.4.1. Dye sensitization. Visible light-induced dye-sensitized
 
have shown that O2 is the prime ROS leading to the photo- TiO2 photocatalysts can be readily prepared under a mild
catalytic degradation of 6-HOMU. Rengifo-Herrera and co- condition through interfacial adsorption of dye molecules on
workers proposed that for NeS co-doped TiO2, photo- TiO2 in an ambient environment (Bae et al., 2004; Chen et al.,
generated holes formed under visible light irradiation do not 2005). Thus, much interest has been shown in surface
136 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

modification of TiO2 with organic dyes for construction of dye- process catalyzed by the dye/complex molecule (Fan and Bard,
sensitized photocatalytic systems under visible-light irradia- 1979). The injected electron reacts with surface adsorbed O2 to
yield O2 (Eq. (3.3)), which produces HO2 on protonation (Eq.
 
tion (Jiang et al., 2007). Dyes that are used as sensitizers

include erythrosin B (Kamat and Fox, 1983), thionine (Patrick (3.4)) and subsequently OH (Eqs. (3.5) and (3.6)) leading to the
and Kamat, 1992), substituted and unsubstituted bipyridine degradation of the organic pollutants (Fig. 5).
(O'Regan and Graetzel, 1991; M. Yang et al., 2002) and phtha- Dye-sensitized photocatalysis begins with the light ab-
locyanine (Yu et al., 2003a). sorption of dye and a subsequent electron transfer from the
The absorption of TiO2 sensitized by a proper dye molecule excited dye to the conduction band of TiO2. The electron
can be extended to visible region because the dye can absorb transfer from excited dye to TiO2 usually depends strongly on
the visible light to reach an excited state (Eq. (3.1)) (O'Regan the adsorption efficiency of the dye molecule (Zhao et al.,
and Graetzel, 1991). The dye in the excited state has, in gen- 1998). However, in the case of the dye-sensitized TiO2 photo-
eral, a lower redox potential than the corresponding ground catalyst, the dye molecules are only absorbed onto the TiO2
state. If the redox potential is lower than the conduction band surface by physical/chemical adsorption. No steady chemical
(CB) of TiO2, an electron may be injected from the excited state bond is formed between TiO2 and dye molecules. So the dye
into the CB (Eq. (3.2) and Fig. 5), and consequently the cationic molecules as sensitizers tend to partially desorb, which can
radicals and CB electron are formed. Surface sensitization of decrease photocatalytic activity during the photocatalytic re-
TiO2 by electron transfer via chemisorbed or physisorbed dyes action process; and the activity can be deeply depressed by the
can 1) increase the efficiency of the excitation processes and 2) competitive adsorption of other coexisting species in the so-
expand the used wavelength range through excitation of the lution. Considering that pollutants usually exist at high con-
sensitizer followed by an electron transfer between the centration in actual wastewaters, dye-sensitized
excited dye and the CB of TiO2. Depending on its redox envi- photocatalysis may face difficulties to keep a valuable electron
ronment, the dye is able to donate (in most cases) or receive an transfer efficiency. In addition, while the dye-sensitized TiO2
electron improving electronehole separation (Kiriakidou is efficient in the utilization of visible light, all of the known
et al., 1999). sensitizers are toxic and unstable (i.e., undergo degradation)
in aqueous solution, thus making them unsuitable for appli-
Dye þ hn/Dye* (3.1) cations in photocatalysis (Zhao et al., 2005).

Dye* þ TiO2 /Dye*þ þ TiO2 ðe Þ (3.2) 3.1.4.2. Organic coating. In the past decades, the modification
of TiO2 nanoparticles with organic chelating ligands has been


TiO2 ðeÞ þ O2 /TiO2 þ O2 (3.3) a key research topic because it does not only induce dramatic
changes in the electrical and optical properties of the nano-
 
particles, but it also results in the occurrence of other desir-
O2 þ Hþ /HO2 (3.4)
able properties. For example, Cozzoli et al. (2003) prepared
 organic-capped anatase TiO2 nanorods at 80  C, which can be
2HO2 /H2 O2 þ O2 (3.5) dispersed in organic solvents to form optically clear concen-
trated solutions because of oleic acid surface modification.
H2 O2 þ e /OH þ OH

(3.6) Niederberger et al. (2004) developed a nonaqueous solegel
If the oxidative energy level of the excited dye/complex method to synthesize water-soluble dopamine-functionalized
compound is favorable (i.e., more negative) with respect to the anatase TiO2 nanoparticles. X.Y. Li et al. (2008) developed an in
CB level of the semiconductor, the dye molecule can transfer situ chemical oxidative polymerization method in hydro-
the electron to the CB of the semiconductor. A prerequisite for chloric acid solutions to synthesize TiO2 nanoparticles modi-
this electron transfer is a low quantum yield of the redox fied by polyaniline. These nanoparticles exhibit significantly
higher photocatalytic activity than neat TiO2 on the degrada-
tion of phenol aqueous solution under visible light irradiation.
Jiang et al. (2007) developed a simple surface modification
of TiO2 nanocrystals through a traditional organic reaction
between the surface hydroxyls on TiO2 nanoparticle and the
eNCO groups of tolylene diisocyanate (TDI). It is noteworthy
that a steady chemical bond is formed in the TDI-modified
TiO2 by the chemical reaction. Due to the existence of the
surface complex, the absorption edge of as-prepared TDI-
modified TiO2 nanomaterial extended well into the visible
region. It was found that the TDI-modified TiO2 material could
largely absorb visible light and showed improved photo-
catalytic performance compared with unmodified TiO2.
Chen et al. (2009) proposed the visible light-induced pho-
tocatalytic mechanism of TiO2eTDI photocatalyst. In the case
Fig. 5 e The mechanism of the photocatalytic of TiO2eTDI, a direct electron transfer from the organic ligand
decomposition of organic pollutants (RH) over organic moiety to the conduction band of TiO2 is achieved upon ab-
ligand (OL) modified TiO2 under visible light. sorption of visible light. The conduction band electron then
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 137

reacts with surface adsorbed oxygen to produce superoxide results indicate that surface modification of nanocrystalline
radical, which subsequently induces the degradation of TiO2 with electron-donating chelating agents is an effective
coexisting organics in the solution. The organic ligand moiety, route to enhance both adsorption and decomposition of
however, was not cleaved from the surface of TiO2. It was nitroaromatic compounds.
subsequently recovered by capturing an electron from the In recent years, molecularly imprinted polymers, owing to
environment (e.g. the reductive species generated during the their attractive selectivity, have been introduced to improve
photodegradation of organics), and then carried out another the selectivity of the TiO2 photocatalyst (Xu et al., 2014). By
reaction cycle with the absorption of another visible light using estrone as a template molecule, Xu et al. (2014) prepared
photon. Thus, the whole visible light-induced photocatalytic molecularly imprinted TiO2 hybridized magnetic ferroferric
process of TiO2eTDI can be expressed briefly as follows (Eqs. oxide (Fe3O4) nanoparticles through a semicovalent approach
(3.7)e(3.10)) and Fig. 5. by a liquid phase deposition method, for selective photo-
 * catalytic degradation and removal of target estrone with the
TiO2  TDI þ hnðvisÞ/ TiO2 ðeÞ  TDIþ (3.7) irradiation of UV light. The obtained Fe3O4@SiO2@imprinted
TiO2 displayed high adsorption capacity, fast kinetics and high
 *   

TiO2 ðeÞ  TDIþ þ O2 / TiO2  TDIþ þ O2 (3.8) selectivity. Also, excellent stability during long-time photo-
catalysis was exhibited. More importantly, the Fe3O4@im-

printed TiO2 provided potential application prospective for
O2 þ Organics/degradation products (3.9)
photocatalytic removal of trace target organic pollutants in
  the presence of other high-level pollutants.
TiO2  TDIþ þ MðenvironmentÞ/TiO2  TDI þ Mþ (3.10)
3.2.2. Doping with carbon-based nanoparticles
3.2. Approaches to enhance adsorption of organic It has been confirmed that TiO2/carbon composites or carbon-
pollutants on TiO2 particles modified TiO2 could increase the adsorption capacity and
improve photodegradation performance in the visible region
Adsorption of contaminants in the vicinity of the photo- (Janus et al., 2006; Shao et al., 2010). Composites of TiO2/C have
catalytic sites promotes the photodegradation of contami- also been shown to improve the energy and power density of
nants that normally do not or in low quantities adsorb on the electrochemical cells and enhance the energy-storage capac-
photocatalyst surface. Thus, improving contaminant adsorp- ity (Cheng et al., 2008). Therefore, TiO2 composited with car-
tion by modifying TiO2 surface is another way to enhance its bon of different forms, such as fullerene (Oh et al., 2007),
photocatalytic activity. Modification of TiO2 surface using activated carbon (W.D. Wang et al., 2007), graphene
chelating ligands has been investigated to enhance adsorption (Kamegawa et al., 2010) and carbon nanotubes (CNTs) (Woan
of organic contaminants (Makarova et al., 2000). Moreover, et al., 2009) have been fabricated to obtain novel structures
fullerene or graphene-modified TiO2 particles also have and properties.
shown excellent adsorptive and semiconducting properties Activated carbon was initially used as a support for TiO2 in
(Oh et al., 2007; Zhang et al., 2012). photodegradation studies (Fu et al., 2004). Loading TiO2 on
activated carbon has drawn great attention since the high
3.2.1. Surface organic modification adsorption capability of activated carbon can help to enrich
The coordination sphere of the surface titanium atoms is organic substrate around the catalyst, promoting the
incomplete and thus exhibits high affinity to oxygen- pollutant transfer process and hence increasing the photo-
containing ligands to form chelating structures. Makarova catalytic efficiency (Y. Li et al., 2008; Xu et al., 2008). The
et al. (2000) investigated the effect of three groups of com- synergistic effect of adsorption by activated carbon and pho-
pounds on adsorption of nitrobenzene (NB): a long chain tocatalytic decomposition by TiO2 has been observed in the
carboxylic acid (lauryl sulfate) to make the surface of the TiO2 degradation of several types of organic pollutants (Matos et al.,
particles hydrophobic; an amino acid (L-arginine) with a high 2007; Lim et al., 2011). Matos et al. (1998) determined that there
affinity for hydrogen-bonding and electron-donating proper- is a synergistic effect when using TiO2 mixed with activated
ties; and a benzene derivative (salicylic acid) that may form carbon having a surface area of 775 m2/g. The phenol degra-
пeп donoreacceptor complexes. It was found that the dation enhancement was attributed to the strong adsorption
adsorption of NB increased at all surface-modified TiO2 spec- of phenol and its intermediate species on the activated carbon
imens as compared with bare TiO2. The best adsorption was followed by subsequent mass transfer of the species to the
found for arginine-modified and salicylate-modified TiO2, photocatalytically active TiO2. Wang et al. (2012) synthesized a
while adsorption was smaller in lauryl-modified colloids. This high thermal stability C-doped SiO2/TiO2 coated with acti-
suggests that hydrogen bonding, neп and пeп interactions vated carbon nanoporous composites. The as-synthesized
result in stronger adsorption of NB as compared with its nanoporous composites exhibit both much higher absorp-
physical adsorption due to the presence of a hydrophobic tion capability and better photocatalytic activity for the
environment on the particle surface. Moreover, due to strong photooxidation of methylene blue than pure TiO2. The higher
electron donating properties, arginine provides a stable sur- absorption capability and better photocatalytic activity are
face layer with a controlled reductive degradation pathway for attributed to their high surface area, well conductivity and
NB. Arginine also improves the coupling between NB and TiO2, higher visible light absorption intensity.
and electrons from the conduction band of TiO2 can be Carbon nanotubes (CNTs) also provide a larger specific
transferred to NB without significant activation energy. These surface area similar to activated carbon and thus enhance the
138 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

photocatalytic degradation as explained above. Beyond the adsorption is due to the formation of both pep conjugations
surface area, CNTs may be tailored to enhance specificity to- and the interactions between methylene blue molecules and
ward adsorbents through the modification of their surface oxygenated surface groups at the edges or on the surfaces of
groups (Carp et al., 2004). When purified via acid treatment, GO. Moreover, electron consumption occurs simultaneously,
CNTs formed alcohol, keto, and acid moieties on their sur- in which GO is partially reduced to RGO under UV assistance
faces. These groups can be further modified to improve and electrons are regenerated, resulting in the partial resto-
adsorption of specific species, an advantage over activated ration of the conjugated pep network (Williams et al., 2008;
carbons that are typically nonselective and have a lower Lightcap et al., 2010). This phenomenon leads to an efficient
pollutant-degradation rate due to the degradation of all spe- charge separation and to the possibility of more pep in-
cies (benign and pollutant) present (Carp et al., 2004). Thus, teractions between the composite and the organic
CNTs are also excellent candidates to allow deeper insight compounds.
into the semiconductor junction of TiO2 with metallic or
semiconducting carbons. 3.3. Approaches for the stabilization of TiO2 particles
Among the same types of carbon supports, fullerene is very
promising for synergistic reasons; its energy sensitization A large surface area can be the determining factor in certain
improves the quantum efficiency and there is an increase of photodegradation reactions, as a large amount of adsorbed
charge transfer between the fullerene and TiO2 by acidifica- organic molecules promotes the reaction rate (Carp et al.,
tion of surface groups. Oh et al. (2007) prepared a fullerene/ 2004). However, one problem that needs to be addressed
TiO2 composite and investigated its photocatalytic effect. with nanosized photocatalysts is the difficulty in distributing
Since fullerene has absorptive and semiconducting proper- single particles uniformly and reducing particle aggregation
ties, the fullerene/TiO2 composite revealed a sound photo- (Nakayama and Hayashi, 2007). Two approaches are possible:
degradation activity. The results revealed that the excellent i) embedding them into a support structure or ii) modifying
activity of the fullerene/TiO2 composites for organic dye their surface using organic coating to reduce particle
removal could be attributed to the synergistic effect of pho- aggregation.
tocatalysis of the supported TiO2 and absorptivity of the
fullerene. 3.3.1. Stabilization by support structures
Graphene is recently emerging as one of the most prom- Since photocatalytic degradation mainly occurs on the surface
ising materials to produce next generation photocatalysts of TiO2, mass transfer limitation has to be minimized for
(Morales-Torres et al., 2012), with excellent mobility of charge effective TiO2 application in water treatment. It is well
carriers, large specific surface area, flexible structure, high recognized that the slurry form in which TiO2 powder is well
transparency and good electrical and thermal conduction dispersed in suspension is more effective than the systems
(Geim and Novoselov, 2007). Nguyen-Phan et al. (2011) pre- with fixed support (Mascolo et al., 2007). However, during the
pared TiO2/graphene oxide composites for the photo- photocatalytic degradation process, the TiO2 particles may
degradation of methylene blue. Superior adsorption and undergo coagulation due to the instability of the nanosized
photocatalysis performance under both UV and visible radi- particle, which will hamper the light incidence on the active
ation were achieved in the presence of the composites rather centers and consequently reduce its catalytic activity (Yu and
than in pure TiO2. The good photocatalytic performance on Zhao, 2001; Cho et al., 2005). Furthermore, for the slurry sys-
the TiO2egraphene oxide composite systems irrespective of tem, one main practical challenge to overcome is to recover
light sources could be attributed to a synergy effect including the nanosized TiO2 particles from the treated water (which is
the increase in specific surface area in the presence of gra- discussed in detail in the following section). How to concen-
phene oxide as well as the formation of both pep conjuga- trate the target pollutants around the TiO2 particles to
tions between dye molecules and aromatic rings and ionic enhance photocatalytic efficiency also requires consideration.
interactions between methylene blue and oxygen-containing These challenges may be realized by mounting the nanosized
functional groups at the edges or on the surfaces of carbon- TiO2 particles on much larger particulates which should also
based nanosheets. Graphene oxide plays the roles of adsor- serve as a good pollutant adsorbent to attain synergistic
bent, electron acceptor and photosensitizer in order to accel- pollutant removal and degradation.
erate photodecomposition. In the past decade, an intense effort has been devoted to
The photocatalytic activity of reduced graphene oxide loading TiO2 on different supports (Carp et al., 2004), such as
(RGO)eP25 composites (1 wt% GO) was also evaluated in the glass beads, fiber glass, glass pellets, glass sheets, silica,
degradation of methylene blue (H. Zhang et al., 2010), a higher organo-clays, stainless steel, Al2O3 fiber textile, c-Al2O3,
conversion of methylene blue being found with these com- quartz beads, polyethene and polypropylene films, fabrics
posites in comparison with bare P25. This photocatalytic (cotton and polyester), activated carbon, and zeolites are used.
enhancement was ascribed to (1) the two-dimensional planar Generally, the strategies focused on supported TiO2 are
grapheme structure favoring dye adsorption, (2) the suppres- developed in order to: 1) immobilize the TiO2 photocatalyst; 2)
sion of electronehole recombination (due to the high elec- increase the illuminated specific catalyst area; 3) increase the
trical conductivity), (3) enhanced light absorption in longer adsorption capacity and surface area of the photocatalyst; and
wavelengths of the visible region, and (4) high transparency 4) influence the selectivity of the photocatalytic reaction. The
and band-gap narrowing resulting from the presence of first demand originates from the requirement to use photo-
TieOeC bonds. In general, the carboxylic acid functional catalysts in continuous processes where the utilization of TiO2
group of GO facilitates binding of oxide particles. The high dye powder is technologically impracticable. Unfortunately, a
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 139

small particle size leads to high filtration costs of catalyst pollutants, many studies have been made on surface modifi-
removal, hindering its industrial application. For this reason, cation of TiO2 particles.
the synthesis of photocatalysts with high activity and effec- Carboxylic acids are most widely used as modifiers, with a
tive separation properties simultaneously is a priority topic. coordination of carboxylic groups (COOH) to surface Ti atoms
A photocatalyst surface is active only if it is illuminated. It (Weng et al., 2003). Mallakpour and Nikkhoo (2014) modified
is difficult to illuminate all the catalyst particles in suspended the surface of TiO2 nanoparticles via grafting with amino acid
systems, because the particles further away from the light containing diacids. This surface modification prevented the
sources are shielded from radiation by those near the light aggregation and allowed a homogenous dispersion of TiO2
source. Hence, the penetration depth of light into suspensions nanoparticles. Nakayama and Hayashi (2007) prepared poly(L-
is limited. In immobilized systems, it is possible to obtain a lactic acid)-TiO2 nanoparticle nanocomposite films by incor-
configuration in which all catalyst particles are illuminated, porating surface modified TiO2 nanoparticles into polymer
e.g., a thin layer coated on a tube surrounding a tube light matrices. In the process of preparing the nanocomposite
(Dijkstra et al., 2001). films, severe aggregation of TiO2 nanoparticles could be
Several attempts have been made to obtain hybrid photo- reduced by surface modification by using carboxylic acid and
catalysts, which are expected to induce synergism because of long-chain alkyl amine. As a result, the TiO2 nanoparticles of
the adsorption properties of organic molecules (Carp et al., 3e6 nm in diameter were uniformly dispersed in polymer
2004). The basic concept is based on the physisorption of re- matrices.
actants on inert substrates followed by their surface diffusion to Li et al. (2015) investigated the stability and the sorption of
the interface between the adsorptive sites and photocatalytic phenanthrene on nano-TiO2 coated with humic acid (HA). The
sites (Chen et al., 1999; Tang et al., 2014a). The first step is nano-TiO2 sedimentation experiments indicated that the
achieved by using supports with large surface areas for presence of aromatic-rich HA was more capable of stabilizing
adsorption and high adsorption capacity for the target sub- nano-TiO2 particles than was the presence of aliphatic-rich
stances, while the second is achieved only if the adsorption HA. This result is because the deionized phenolic groups in
strength is moderate enough to allow diffusion of adsorbed the HAs were preferentially adsorbed on the nano-TiO2 sur-
substrates to the loaded TiO2 (Yoneyama and Torimoto, 2000; faces, which generated a higher charge density on the nano-
Ao and Lee, 2003). Adsorbents such as silica (Vohra and TiO2 surfaces and caused stronger repulsive forces among
Tanaka, 2003), alumina (Tanaka et al., 2002), zeolites (Reddy particles. Furthermore, the aromatic-rich TiO2-HA complexes
et al., 2003), mesoporous molecular sieves, clays (Ooka et al., exhibited a greater sorption capacity than the aliphatic-rich
2003) (TiO2 incorporated into the interlayer space of the clays), TiO2eHAs complexes and nonlinear phenanthrene sorption
and activated carbon (Arana et al., 2003) have been used. In the because of their higher affinity and for the substrate.
recent studies, Athanasekou et al. (2012, 2014) and Moustakas Romanello and Fidalgo de Cortalezzi (2013) studied the ag-
et al. (2014) developed a highly efficient hybrid photocatalytic/ gregation rates, aggregate size and aggregate morphology of
ultrafiltration process for water purification using visible light. Nano TiO2 under the presence of inert electrolytes, divalent
The process relies on the development of partially reduced cations, and these two combined with natural organic matter
graphene oxide/TiO2 composite membranes and their incor- (NOM). NOM adsorbed to the nanoparticles and made their
poration into an innovative water purification device that zeta potential more negative, hence stabilizing them by
combines membrane filtration with semiconductor photo- lowering the pH of maximum aggregation (Dong and Lo,
catalysis. Composites consisting of graphene oxide sheets 2013a; Tang et al., 2014). Divalent cations partially neutral-
decorated with TiO2 nanoparticles were deposited and stabi- ized the adsorbed NOM, and at high concentrations aggrega-
lized into the pores of ultrafiltration mono-channel monoliths tion was observed with Ca2þ, suggesting the presence of
using the dip-coating technique. These studies offer an immo- specific Ca2þ-NOM bridges (Dong and Lo, 2013b, 2014). Li and
bilization alternative permitting scale-up ability and photo- Sun (2011) studied the aggregation/sedimentation potentials
reactor based water treatment industrial applications. of TiO2 nanoparticles in the presence of Suwannee River fulvic
However, in spite of so many efforts, it is still unclear acids (SRFA) at different pH values. The results showed that
which supports are most suitable in terms of mechanical SRFA adsorption significantly enhanced the stability of TiO2
stability and selectivity. Besides, the activity of supported TiO2 nanoparticles at pH 4, 6 and 8, mainly due to the dramatic
is normally lower than the unrestricted catalyst. This is most increase in negative surface charges. Note that the organic
likely the immobilization reduces TiO2's active surface area- surface modifiers or NOM, in aquatic environments can not
to-volume ratios and decreased mass-transfer rate, in addi- only increase the stability of nanoparticles but can also in-
tion to the hindrance in light harvesting that is caused by the fluence the adsorption of hydrophobic organic compounds
massive inactive supports (Mascolo et al., 2007). and the number of available reactive sites on TiO2 particles.
Besides, the organic ligands (e.g., humic acids) can be
3.3.2. Stabilization by surface modification degraded by TiO2 (Uyguner and Bekbolet, 2009), so they are not
TiO2 particles suffer from severe aggregation during photo- necessarily stable under photocatalytic conditions. Presum-
catalytic reactions, which would reduce their active sites and ably, not all the methods used to obtain stable particle sus-
light harvesting capability. As a result, the photocatalytic ac- pensions will lead to photoactive TiO2. Therefore, future work
tivity would be decreased (Liu et al., 2012). Moreover, TiO2 should be carried out to investigate the effects of surface
particles have little affinity for organic matrix because of the modifiers or NOM on the stability and photocatalytic activity
low particle size and high surface energy. For useful applica- of TiO2 particles.
tions, especially for the treatment of hydrophobic organic
140 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

3.4. Approaches for the separation of TiO2 particles membrane provides magnetic nanoparticles with a chemi-
cally inert surface, helping to inhibit the oxidation of the Fe3O4
Finely dispersed TiO2 has large reactive surface area, but it is core by the holes photogenerated in the outer layer TiO2 (Fu
difficult to separate and recover these particles from liquid et al., 2006; Wang et al., 2009). However, the photocatalytic
phase. Thus, the recovery and reusability of the TiO2 particles activity of magnetic TiO2 is also influenced by the magnetic
is crucial and decides their further applications. The way to core size, content of the silica layer and calcination temper-
effectively immobilize or separate the TiO2 particles is still a ature (Gad-Allah et al., 2007).
challenge in the photocatalytic system. In order to solve the Recently, research work is devoted to fabricating multi-
problem of separation, two potential approaches have been component photocatalysts with enhanced visible light
studied, i.e., immobilized TiO2 onto various supports and photoactivity and ability to be recycled (Li et al., 2011; Guo
preparation of magnetic photocatalyst for magnetic separa- et al., 2011; Wu et al., 2012). Magnetic visible photo-
tion (Carp et al., 2004; Gad-Allah et al., 2007). catalysts were investigated for overcoming the two funda-
mental drawbacks, i.e. photocatalyst recovery and visible
3.4.1. Immobilization on support structures light utilization, hindering catalyst application and devel-
Some researchers immobilized TiO2 onto various supports, opment in the fields of environmental pollutants and energy
such as glass fibers, glass, quartz, stainless steel, etc. (Carp sources (Li et al., 2011; Wu et al., 2012). Multi-component
et al., 2004). This has been illustrated in detail in Section photocatalysts with magnetic and photoactive properties
3.3.1. As discussed in the previous part, although these studies provide a way of achieving this. Guo et al. (2011) reported
provided a facile way to solve the particle aggregation and that the Ag halides such as AgBr and AgI (which are photo-
separation problem, the photochemical reactivity of sup- active to visible light) immobilized on SiO2@Fe3O4 magnetic
ported TiO2 is normally reduced due to the reduction of TiO2's supports exhibited faster degradation rates for 4-
active surface area-to-volume ratios, the decreased mass- chlorophenol than NeTiO2. However, the Ag halides are
transfer rate, and the inactive support's hindrance in light easily photo-reduced and quickly lose their stability. Liu
harvesting. Thus, although this approach provides a solution et al. (2013) prepared the magnetic AgBreTiO2/SiO2@Fe3O4
to the solideliquid separation problem, slurry-type reactors photocatalyst by solvothermal and solegel methods, in
offer significant advantages over immobilized catalyst-type which photoactive AgBreTiO2 was seeded on the SiO2@Fe3O4
reactors because of the catalyst surface availability and su- shellecore magnetic support. The catalyst exhibited excel-
perior mass-transfer properties (Matthews, 1990). lent photocatalytic degradation of methylene blue under
visible light, and was easily separated and reused in five
3.4.2. Magnetic separation successive runs, using an external magnetic field. Tang et al.
Another solution to the separation problem is the utilization (2013) designed a new photocatalyst, magnetic TiO2e-
of magnetic separation which provides a very convenient graphene, which integrates the functions of: (1) TiO2 pho-
approach for separating, recovering and reusing the fine tocatalysis, (2) excellent electron-capture ability and high
photocatalytic magnetic particles by external magnetic field adsorptivity of graphene, (3) magnetic separation, and (4)
(Gong et al., 2009; He et al., 2012; Tang et al., 2014b). Some high stability through suppressing photodissolution of the
authors prepared composite nanoparticles with magnetic magnetite by SiO2 (Wang et al., 2009). Taking advantages of
core and photoactive shell using magnetic granules and TiO2 graphene and TiO2, the catalyst exhibited strong light ab-
(Wang and Zhou, 2010). They confirmed that magnetic TiO2 sorption in the visible region and high adsorption capacity to
photocatalysts present enhanced separation properties from organic pollutants, resulting in almost 100% photocatalytic
slurry photoreactors when an external field is applied. In removal efficiency of typical herbicide 2,4-
general, this type of composite photocatalyst comprises of a dichlorophenoxyacetic acid (2,4-D) from water under simu-
TiO2 shell and a magnetic core, making it recoverable due to lated solar light irradiation, far higher than 33% on com-
its magnetic properties such as superparamagnetism, high mercial P25. Furthermore, the catalyst can be rapidly
field magnetic irreversibility and high saturation magnetiza- recovered with highly stable photocatalytic performance.
tion (Wang and Zhou, 2010; He et al., 2012). After 8 successive cycles, the removal efficiency of 2,4-D
A number of materials with different elemental composi- maintained 97.7%, and particularly, 99.1% 2,4-D removal
tions have been used as the magnetic core, such as Fe3O4, g- efficiency came back at the ninth recycle when the catalyst
Fe2O3, NiFe2O4, CoFe2O4, FeCo, and Co3O4. Among these, Fe3O4 was re-treated by ultrasonication.
has drawn a lot of attention due to its remarkable magnetic
properties, low toxicity, and biocompatibility (Deng et al., 3.5. Future challenges in TiO2-based photocatalytic
2008; Zhang et al., 2011; Zhang and Zhu, 2012). However, a processes
direct deposition of TiO2 onto the surface of magnetic oxide
particles leads to high levels of photodissolution (i.e., disso- Despite the increased use and development in the past de-
lution under influence of illumination) of the magnetic core. It cades, TiO2-based photocatalytic technology still suffers from
has been proven that the addition of a silica layer between the some technical barriers that impede its commercialization.
magnetic core and the TiO2 shell promotes the photocatalytic Further research and development in this area are necessary
activity of the catalyst by abating the adverse impact of the to overcome or mitigate these shortcomings and to expand
magnetic core and stabilizing the anatase form of TiO2 the use of the TiO2-based particles for photocatalytic degra-
(Martyanov and Klabunde, 2004). The presence of a silica dation. Based on this review, the key areas for future research
are proposed as follows:
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 141

1) Although many investigations have been carried out con- summarized the recently developed countermeasures for
cerning the modification of the TiO2 surface to improve its improving the performance of TiO2-based photocatalytic
photocatalytic activity, little work has been reported on the degradation of organic pollutants with respect to the above
enhancement of photocatalytic activity of magnetic TiO2 limitations. Several approaches for enhancement of visible-
particles under visible light through doping or/and surface light photocatalytic activity of TiO2 have been developed:
modification. Besides, the physicochemical stability and metal-doped TiO2, non-metal doped-TiO2, co-doped TiO2 (i.e.,
sustainability of non-metal doped or surface-modified TiO2 the simultaneous doping of two kinds of elements into TiO2),
particles for repetitive use have not been studied. It is sensitizing of TiO2 with dyes and TiO2 doped with upconver-
necessary to design a multifunctional photocatalyst that sion luminescence agent. To enhance adsorption of organic
integrates the characteristics of excellent visible-light pollutants onto TiO2 particles, two approaches have been
photocatalytic activity, high adsorption capacity, high proposed: surface modification of TiO2 with organic ligands
stability, and magnetic separability. and doping with carbon-based nanoparticles. Two ap-
2) A complete photodegradation of some POPs by the photo- proaches are possible in distributing TiO2 particles uniformly
catalysts is still difficult to achieve. More studies should be in suspension: embedding TiO2 particles into a support
carried out with the aim of enhancing the reactivity of structure or modifying their surface using organic coating to
photocatalysts. Additionally, it is necessary to explore the reduce particle aggregation. The separation of TiO2 particles
possibility of combined use of TiO2-based technologies from aqueous phase can be achieved via immobilization on
with other technologies (e.g., biological means and elec- support structures or magnetic separation. However, each
trodynamics) to expand the scope of application. Besides, countermeasure still suffers from some technical barriers that
the final or the intermediate products of photocatalytic impede its commercialization. Further research and devel-
degradation may not be innocuous substances. The opment in this area are required to overcome these short-
degradation products can be more dangerous than the comings and to expand the application of the TiO2-based
parent compound. Harmful by-products may cause particles for photocatalytic degradation.
decrease in reaction rate and secondary pollution. There
has been scanty literature on the toxicity of the photo-
catalyst or the overall photocatalytic process, especially for
the modified photocatalysts. Fundamental characteriza- Acknowledgment
tion and quantification of the reactivity, toxicity and fate of
different modified photocatalysts are needed. This research was supported by the Fundamental Research
3) TiO2 photocatalyzed reactions are non-selective oxidations. Funds for the Central Universities, the National Natural Sci-
Since they are governed by a free radical mechanism, the ence Foundation of China (51409100, 51378190) and the Pro-
degradation rate of a large variety of molecules is found to be gram for Changjiang Scholars and Innovative Research Team
approximately the same. On the one hand, this lack of in University (IRT-13R17).
sensitivity may be advantageous, but a poor selectivity also
implies that the catalyst does not differentiate between
highly hazardous contaminants and contaminants of low references
toxicity. The low toxicity contaminants can be easily
degraded by biological means, while many of the highly
hazardous materials are non-biodegradable. Therefore, it is Ambrus, Z., Balasz, N., Alapi, T., Wittmann, G., Sipos, P.,
necessary to develop a photocatalyst system that can selec- Dombi, A., Mogyorosi, K., 2008. Synthesis, structure and
tively degrade pollutants utilizing visible and/or solar light photocatalytic properties of Fe(III)-doped TiO2 prepared from
irradiation, acting as a complement to biological techniques. TiCl3. Appl. Catal. B 81, 27e37.
Anpo, M., 2000. Use of visible light. Second-generation titanium
4) The previous work mainly focused on batch scale of pho-
dioxide photocatalysts prepared by the application of an
tocatalytic degradation and magnetic separation for
advanced metal ion-implantation method. Pure Appl. Chem.
pollutant removal and particle recovery, but lack of appli- 72, 1787e1792.
cation in a larger scale. Thus, there is a need for the design Ao, C.H., Lee, S.C., 2003. Enhancement effect of TiO2 immobilized on
of a prototype for the convenience of both photocatalytic activated carbon filter for the photodegradation of pollutants at
degradation of organic pollutants and particles recovery so typical indoor air level. Appl. Catal. B: Environ. 44, 191e205.
that it can be applied in real practice. Arana, J., Dona, R.J.M., Rendon, E.T., Cabo, C.G., Gonzalez, D.O.,
Herrera, M.J.A., Perez, P.J., Colon, G., Navio, J.A., 2003. TiO2
activation by using activated carbon as a support. Part I.
Surface characterisation and decantability study. Appl. Catal.
4. Conclusions B: Environ. 44, 161e172.
Arabatzis, I.M., Stergiopoulos, T., Bernard, M.C., Labou, D.,
Photodegradation process of POPs by TiO2-based particles has Neophytides, S.G., Falaras, P., 2003. Silver-modified titanium
attracted increasing attention during the past decades. How- dioxide thin films for efficient photodegradation of methyl
orange. Appl. Catal. B: Environ. 42, 187e201.
ever, its application is limited due to some main practical
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., Taga, Y., 2001.
challenges: i) the inefficient exploitation of visible light, ii) low
Visible-light photocatalysis in nitrogen-doped titanium
adsorption capacity for hydrophobic contaminants, iii) uni- dioxides. Science 293, 269e271.
form dispersion in aqueous suspension and iv) post-recovery Athanasekou, C.P., Romanos, G.E., Katsaros, F.K., Kordatos, K.,
of the TiO2 particles after water treatment. This review Likodimos, V., Falaras, P., 2012. Very efficient composite
142 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

titania membranes in hybrid ultrafiltration/photocatalysis Cui, J., He, T., Zhang, X., 2013. Synthesis of Fe3O4@SiO2@Ption-
water treatment processes. J. Membr. Sci. 392e393, 192e203. TiO2 hybrid composites with high efficient UVevisible light
Athanasekou, C.P., Morales-Torres, S., Likodimos, V., photoactivity. Catal. Commun. 40, 66e70.
Romanos, G.E., Pastrana-Martinez, L.M., Falaras, P., Deng, Y., Qi, D., Deng, C., Zhang, X., Zhao, D., 2008.
Dionysiou, D.D., Faria, J.L., Figueiredo, J.L., Silva, A.M.T., 2014. Superparamagnetic high-magnetization microspheres with
Prototype composite membranes of partially reduced graphene an Fe3O4@SiO2 core and perpendicularly aligned mesoporous
oxide/TiO2 for photocatalytic ultrafiltration water treatment SiO2 shell for removal of microcystins. J. Am. Chem. Soc. 130,
under visible light. Appl. Catal. B: Environ. 158e159, 361e372. 28e29.
Bae, E., Choi, W., Park, J., Shin, H.S., Kim, S.B., Lee, J.S., 2004. Effects of Dijkstra, M.F.J., Michorius, A., Buwalda, H., Panneman, H.J.,
surface anchoring groups (carboxylate vs. phosphonate) in Winkelman, J.G.M., Beenackers, A.A.C.M., 2001.
ruthenium-complex-sensitized TiO2 on visible light reactivity in Comparison of the efficiency of immobilized and
aqueous suspensions. J. Phys. Chem. B 108, 14093e14101. suspended systems in photocatalytic degradation. Catal.
Bannat, I., Wessels, K., Oekermann, T., Rathousky, J., Today 66, 487e494.
Bahnemann, D., Wark, M., 2009. Improving the photocatalytic Dong, F., Guo, S., Wang, H.Q., Li, X.F., Wu, Z.B., 2011.
performance of mesoporous titania films by modification with Enhancement of the visible light photocatalytic activity of C-
gold nanostructures. Chem. Mater. 21, 1645e1653. doped TiO2 nanomaterials prepared by a green synthetic
Banerjee, S., Pillai, S.C., Falaras, P., O'Shea, K.E., Byrne, J.A., approach. J. Phys. Chem. C 115, 13285e13292.
Dionysiou, D.D., 2014. New insights into the mechanism of Dong, F., Wang, H.Q., Wu, Z.B., 2009. One-step “green” synthetic
visible light photocatalysis. J. Phys. Chem. Lett. 5, 2543e2554. approach for mesoporous C-doped titanium dioxide with
Bhattacharyya, A., Kawi, S., Ray, M.B., 2004. Photocatalytic efficient visible light photocatalytic activity. J. Phys. Chem. C
degradation of Orange II by TiO2 catalysts supported on 113, 16717e16723.
adsorbents. Catal. Today 98, 431e439. Dong, F., Wang, H.Q., Wu, Z.B., Qiu, J.F., 2010. Marked
Bradley, B.R., Daigger, G.T., Rubin, R., Tchobanoglous, G., 2002. enhancement of photocatalytic activity and photochemical
Evaluation of onsite wastewater treatment technologies using stability of N-doped TiO2 nanocrystals by Fe3þ/Fe2þ surface
sustainable development criteria. Clean Technol. Environ. modification. J. Colloid Interface Sci. 343, 200e208.
Policy 4, 87e99. Dong, H.R., Guan, X.H., Wang, D.S., Li, C.Y., Yang, X., Dou, X.M.,
Carp, O., Huisman, C.L., Reller, A., 2004. Photoinduced reactivity 2011. A novel application of H2O2eFe(II) process for arsenate
of titanium dioxide. Prog. Solid State Chem. 32, 33e177. removal from synthetic acid mine drainage (AMD) water.
Chatterjee, D., Mahata, A., 2001. Demineralization of organic Chemosphere 85 (7), 1115e1121.
pollutants on the dye modified TiO2 semiconductor Dong, H.R., Lo, I.M.C., 2013a. Influence of humic acid on the
particulate system using visible light. Appl. Catal. B: Environ. colloidal stability of surface-modified nano zero-valent iron.
33, 119e125. Water Res. 47 (1), 419e427.
Chen, D.M., Jiang, Z.Y., Geng, J.Q., Wang, Q., Yang, D., 2007. Dong, H.R., Lo, I.M.C., 2013b. Influence of calcium ions on the
Carbon and nitrogen co-doped TiO2 with enhanced visible- colloidal stability of surface-modified nano zero-valent iron in
light photocatalytic activity. Ind. Eng. Chem. Res. 46, the absence or presence of humic acid. Water Res. 47 (7),
2741e2746. 2489e2496.
Chen, F., Deng, Z., Li, X.Z., Zhang, J., Zhao, J., 2005. Visible light Dong, H.R., Lo, I.M.C., 2014. Transport of surface-modified nano
detoxification by 2,9,16,23-tetracarboxyl phthalocyanine zero-valent iron (SM-NZVI) in saturated porous media: effects
copper modified amorphous titania. Chem. Phys. Lett. 415, of surface stabilizer type, subsurface geochemistry, and
85e88. contaminant loading. Water Air Soil Pollut. 225, 2107e2118.
Chen, F., Zou, W.W., Qu, W.W., Zhang, J.L., 2009. Photocatalytic El-Sheikh, S.M., Zhang, G.S., El-Hosainy, H.M., Ismail, A.A.,
performance of a visible light TiO2 photocatalyst prepared by a O'Shea, K.E., Falaras, P., Kontos, A.G., Dionysiou, D.D., 2014.
surface chemical modification process. Catal. Commun. 10, High performance sulfur, nitrogen and carbon doped
1510e1513. mesoporous anataseebrookite TiO2 photocatalyst for the
Chen, H., Masumoto, A., Nishimija, N., Tsutsumi, K., 1999. removal of microcystin-LR under visible light irradiation. J.
Preparation and characterization of TiO2 incorporated Y- Hazard. Mater. 280, 723e733.
zeolite. Colloids Surfaces A: Physicochem. Eng. Aspects 157, Fan, F.R., Bard, A.J., 1979. Spectral sensitization of the
295e305. heterogeneous photocatalytic oxidation of hydroquinone in
Cheng, H.S., Chen, L., Cooper, A.C., Sha, X.W., Pez, G.P., 2008. aqueous solution at phthalocyanine-coated TiO2 powders. J.
Hydrogen spillover in the context of hydrogen storage using Am. Chem. Soc. 101, 6139e6140.
solid-state materials. Energy Environ. Sci. 1, 338e354. Foo, K.Y., Hameed, B.H., 2010. Decontamination of textile
Cho, H.I., Park, H.J., Kim, G.Y., 2005. Oxidative degradation and wastewater via TiO2/activated carbon composite materials.
toxicity reduction of trichloroethylene (TCE) in water using Adv. Colloid Interface Sci. 159, 130e143.
TiO2/solar light: comparative study of TiO2 slurry and Fu, P.F., Luan, Y., Dai, X.G., 2004. Preparation of activated carbon
immobilized systems. J. Environ. Sci. Health, Part A 40, fibers supported TiO2 photocatalyst and evaluation of its
1033e1044. photocatalytic reactivity. J. Mol. Catal. A: Chem. 221, 81e88.
Chong, M.N., Jin, B., Chow, C.W.K., Saint, C., 2010. Recent Fu, W.Y., Yang, H.B., Bala, H., Liu, S.K., Li, M.H., Zou, G.T., 2006.
developments in photocatalytic water treatment technology: a Preparation and characteristics of coreeshell structure cobalt/
review. Water Res. 44, 2997e3027. silica nanoparticles. Mater. Chem. Phys. 100, 246e250.
Cong, Y., Zhang, J.L., Chen, F., Anpo, M., 2007. Preparation, Fuerte, M.D.H.A., Maira, A.J., Martinez-Arias, A., Fernadez-
photocatalytic activity, and mechanism of nano-TiO2 co- Garcia, M., Conesa, J.C., Soria, J., 2001. Visible light-activated
doped with nitrogen and iron (III). J. Phys. Chem. C 111, nanosized doped-TiO2 photocatalysts. Chem. Commun. 24,
10618e10623. 2718e2719.
Cozzoli, P.D., Kornowski, A., Weller, H., 2003. Low-temperature Fujishima, A., Rao, T.N., Tryk, D., 2000. Titanium dioxide
synthesis of soluble and processable organic-capped anatase photocatalysis. J. Photochem. Photobiol. C: Photochem. Rev. 1,
TiO2 nanorods. J. Am. Chem. Soc. 125, 14539e14548. 1e21.
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 143

Furube, A., Asahi, T., Masuhara, H., Yamashita, H., Anpo, M., 2001. Janus, M., Inagaki, M., Tryba, B., Toyoda, M., Morawski, A.W.,
Direct observation of a picosecond charge separation process 2006. Carbon-modified TiO2 photocatalyst by ethanol
in photoexcited platinum-loaded TiO2 particles by carbonisation. Appl. Catal. B: Environ. 63, 272e276.
femtosecond diffuse reflectance spectroscopy. Chem. Phys. Jiang, D., Xu, Y., Hou, B., Wu, D., Sun, Y.H., 2007. Synthesis of
Lett. 336, 424e430. visible light-activated TiO2 photocatalyst via surface organic
Gad-Allah, T.A., Kato, S., Satokawa, S., Kojima, T., 2007. Role of modification. J. Solid State Chem. 180, 1787e1791.
core diameter and silica content in photocatalytic activity of Kamat, P.V., Fox, M.A., 1983. Photo-sensitization of TiO2 colloids
TiO2/SiO2/Fe3O4 composite. Solid State Sci. 9, 737e743. by Erythrosin-B in acetonitrile. Chem. Phys. Lett. 102, 379e384.
Gao, B., Yap, P.S., Lim, T.M., Lim, T.T., 2011. Adsorption- Kamegawa, T., Yamahana, D., Yamashita, H., 2010. Graphene
photocatalytic degradation of Acid Red 88 by supported TiO2: coating of TiO2 nanoparticles loaded on mesoporous silica for
effect of activated carbon support and aqueous anions. Chem. enhancement of photocatalytic activity. J. Phys. Chem. C 114,
Eng. J. 171, 1098e1107. 15049e15053.
Gaya, U.I., Abdullah, A.H., 2008. Heterogeneous photocatalytic Kang, I.C., Zhang, Q., Yin, S., Sato, T., Saito, F., 2008. Improvement
degradation of organic contaminants over titanium dioxide: a in photocatalytic activity of TiO2 under visible irradiation
review of fundamentals, progress and problems. J. through addition of NeTiO2. Environ. Sci. Technol. 42,
Photochem. Photobiol. C 9, 1e12. 3622e3626.
Geim, A.K., Novoselov, K.S., 2007. The rise of graphene. Nat. Kiriakidou, F., Kondarides, D., Verykios, X.E., 1999. The effect of
Mater. 6, 183e191. operational parameters and TiO2-doping on the photocatalytic
Gombac, V., De Rogatis, L., Gasparotto, A., Vicario, G., Montini, T., degradation of azo-dyes. Catal. Today 54, 119e130.
Barreca, D., Balducci, G., Fornasiero, P., Tondello, E., Kitano, M., Funatsu, K., Matsuoka, M., Ueshima, M., Anpo, M.,
Graziani, M., 2007. TiO2 nanopowders doped with boron and 2006. Preparation of nitrogen-substituted TiO2 thin film
nitrogen for photocatalytic applications. Chem. Phys. 339, photocatalysts by the radio frequency magnetron sputtering
111e123. deposition method and their photocatalytic reactivity under
Gong, J.L., Wang, B., Zeng, G.M., Yang, C.P., Niu, C.G., Niu, Q.Y., visible light irradiation. J. Phys. Chem. B 110, 25266e25272.
Zhou, W.J., Liang, Y., 2009. Removal of cationic dyes from Kowalska, E., Remita, H., Colbeau-Justin, C., Hupka, J., Belloni, J.,
aqueous solution using magnetic multi-wall carbon nanotube 2008. Modification of titanium dioxide with platinum ions and
nanocomposite as adsorbent. J. Hazard. Mater. 164 (2e3), clusters: application in photocatalysis. J. Phys. Chem. C 112,
1517e1522. 1124e1131.
Guo, J.F., Ma, B.W., Yin, A.Y., Fan, K.N., Dai, W.L., 2011. Lapena, L., Cerezo, M., Garcia-Augustin, P., 1995. Possible reuse of
Photodegradation of rhodamine B and 4-chlorophenol using treated municipal wastewater for Citrus spp. plant irrigation.
plasmonic photocatalyst of AgeAgI/Fe3O4@SiO2 magnetic Bull. Environ. Contam. Toxicol. 55, 697e703.
nanoparticle under visible light irradiation. Appl. Catal. B: Legrini, O., Oliveros, E., Braun, A.M., 1993. Photochemical process
Environ. 101, 580e586. for water treatment. Chem. Rev. 93, 671e698.
Hahn, R., Schmidt-Stein, F., Salonen, J., Thiemann, S., Song, Y., Lettmann, C., Hildenbrand, K., Kisch, H., Macyk, W.F., 2001.
Kunze, J., Lehto, V., Schmuki, P., 2009. Semimetallic TiO2 Visible light photodegradation of 4-chlorophenol with a coke-
nanotubes. Angew. Chem. Int. Ed. 48, 7236e7239. containing titanium dioxide photocatalyst. Appl. Catal. B:
Han, C., Likodimos, V., Khan, J.A., Nadagouda, M.N., Andersen, J., Environ. 32, 215e227.
Falaras, P., Rosales-Lombardi, P., Dionysiou, D.D., 2014. Li, D., Haneda, H., Hishita, S., Ohashi, N., 2005a. Visible-light-
UVevisible light-activated Ag-decorated, monodisperse TiO2 driven NeF-codoped TiO2 photocatalyst. 2. Optical
aggregates for treatment of the pharmaceutical characterization, photocatalysis, and potential application to
oxytetracycline. Environ. Sci. Pollut. Res. 21, 11781e11793. air purification. Chem. Mater. 17, 2596e2602.
He, Z.Q., Hong, T.M., Chen, J.M., Song, S., 2012. A magnetic TiO2 Li, D., Haneda, H., Hishita, S., Ohashi, N., 2005b. Visible-light-
photocatalyst doped with iodine for organic pollutant driven NeF-codoped TiO2 photocatalysts synthesis by spray
degradation. Sep. Purif. Technol. 96, 50e57. pyrolysis and surface characterization. Chem. Mater. 17,
Herrmann, J., Duchamp, C., Karkmaz, M., Hoai, B., Lachheb, H., 2588e2595.
Puzenat, E.G., 2007. Environmental green chemistry as defined Li, F.B., Li, X.Z., Hou, M.F., 2004. Photocatalytic degradation of 2-
by photocatalysis. J. Hazard. Mater. 146, 624e629. mercaptobenzothiazole in aqueous La3þeTiO2 suspension for
Herrmann, J.M., 1999. Heterogeneous photocatalysis: odor control. Appl. Catal. B: Environ. 48, 185e194.
fundamentals and applications to the removal of various Li, Q., Li, Y.W., Wu, P.G., Xie, R.C., Shang, J.K., 2008. Palladium
types of aqueous pollutants. Catal. Today 53, 115e129. oxide nanoparticles on nitrogen-doped titanium oxide:
Hu, C., Lan, Y., Qu, J., Hu, X., Wang, A., 2006. Ag/AgBr/TiO2 visible accelerated photocatalytic disinfection and post-illumination
light photocatalyst for destruction of azodyes and bacteria. J. catalytic “memory”. Adv. Mater. 20, 3717.
Phys. Chem. B 110, 4066e4072. Li, S., Sun, W., 2011. A comparative study on aggregation/
Huo, Y., Jin, Y., Zhu, J., Li, H., 2009. Highly active TiO2xyNxFy sedimentation of TiO2 nanoparticles in mono- and binary
visible photocatalyst prepared under supercritical conditions systems of fulvic acids and Fe(III). J. Hazard. Mater. 197, 70e79.
in NH4F/EtOH fluid. Appl. Catal. B: Environ. 89, 543e550. Li, X.Y., Wang, D.S., Cheng, G.X., Luo, Q.Z., An, J., Wang, Y.H.,
Ihara, T., Miyoshi, M., Iriyama, Y., Matsumoto, O., Sugihara, S., 2008. Preparation of polyanilinemodified TiO2 nanoparticles
2003. Visible-light-active titanium oxide photocatalyst and their photocatalytic activity under visible light
realized by an oxygen-deficient structure and by nitrogen illumination. Appl. Catal. B: Environ. 81, 267e273.
doping. Appl. Catal. B: Environ. 42, 403e409. Li, Y., Dong, X.F., Li, J.P., 2011. Synthesis and characterization of
Iliev, V., Tomova, D., Bilyarska, L., Eliyas, A., Petrov, L., 2006. super para-magnetic composite photocatalystdtitania/silica/
Photocatalytic properties of TiO2 modified with platinum and nickel ferrite. Particuology 9, 475e479.
silver nanoparticles in the degradation of oxalic acid in Li, Y., Ma, M., Sun, S., Wang, X., Yan, W., Ouyang, Y., 2008.
aqueous solution. Appl. Catal. B: Environ. 63, 266e271. Preparation, photocatalytic activity of TiO2ecarbon surface
Irie, H., Watanabe, Y., Hashimoto, K., 2003. Nitrogen- composites by supercritical pretreatment and solegel process.
concentration dependence on photocatalytic activity of Catal. Commun. 9, 1583e1587.
TiO2xNx powders. J. Phys. Chem. B 107, 5483e5486.
144 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

Li, Y.J., Yang, C., Guo, X.T., Dang, Z., Li, X.Q., Zhang, Q., 2015. of emerging contaminants in municipal wastewater
Effects of humic acids on the aggregation and sorption of treatment plant effluents using immobilized TiO2 in a solar
nano-TiO2. Chemosphere 119, 171e176. pilot plant. Appl. Catal. B: Environ. 103, 294e301.
Lightcap, I.V., Kosel, T.H., Kamat, P.V., 2010. Anchoring Minero, C., Vione, D., 2006. A quantitative evaluation of the
semiconductor and metal nanoparticles on a two dimensional photocatalytic performance of TiO2 slurries. Appl. Catal. B:
catalyst mat. storing and shuttling electrons with reduced Environ. 67, 257e269.
graphene oxide. Nano Lett. 10, 577e583. Morales-Torres, S., Pastrana-Martı́nez, L.M., Figueiredo, J.L.,
Lim, T.T., Yap, P.S., Srinivasan, M., Fane, A.G., 2011. TiO2/AC Faria, J.L., Silva, A.M.T., 2012. Design of graphene-based TiO2
composites for synergistic adsorptionephotocatalysis photocatalysts e a review. Environ. Sci. Pollut. Res. 19,
processes: present challenges and further developments for 3676e3687.
water treatment and reclamation. Crit. Rev. Environ. Sci. Moustakas, N.G., Kontos, A.G., Likodimos, V., Katsaros, F.,
Technol. 41, 1173e1230. Boukos, N., Tsoutsou, D., Dimoulas, A., Romanos, G.E.,
Lin, L., Zheng, R.Y., Xie, J.L., Zhu, Y.X., Xie, Y.C., 2007. Synthesis Dionysiou, D.D., Falaras, P., 2013. Inorganiceorganic
and characterization of phosphor and nitrogen co-doped coreeshell titania nanoparticles for efficient visible light
titania. Appl. Catal. B: Environ. 76, 196e202. activated photocatalysis. Appl. Catal. B: Environ. 130e131,
Lindgren, T., Mwabora, J.M., Avendano, E., Jonsson, J., Hoel, A., 14e24.
Granqvist, C.-G., Lindquist, S.-E., 2003. Photoelectrochemical Moustakas, N.G., Katsaros, F.K., Kontos, A.G., Romanos, G.Em.,
and optical properties of nitrogen doped titanium dioxide Dionysiou, D.D., Falaras, P., 2014. Visible light active TiO2
films prepared by reactive DC magnetron sputtering. J. Phys. photocatalytic filtration membranes with improved
Chem. B 107, 5709e5716. permeability and low energy consumption. Catal. Today 224,
Liu, J.J., Zuo, S.L., Yu, L.M., Yu, Y.C., Li, B.S., Chen, P.W., 2013. 56e69.
Visible light photodegradation of methylene blue by Nakayama, N., Hayashi, T., 2007. Preparation and
AgBreTiO2/SiO2@Fe3O4 magnetic photocatalysts. Particuology characterization of poly(L-lactic acid)/TiO2 nanoparticle
11, 728e731. nanocomposite films with high transparency and efficient
Liu, K., Zhu, L.J., Jiang, T.F., Sun, Y.G., Li, H.B., Wang, D.J., 2012. photodegradability. Polym. Degrad. Stab. 92, 1255e1264.
Mesoporous TiO2 micro-nanometer composite structure: Nguyen-Phan, T.D., Pham, V.H., Shin, E.W., Pham, H.D., Kim, S.,
synthesis, optoelectric properties, and photocatalytic Chung, J.S., Kim, E.J., Hur, S.H., 2011. The role of graphene
selectivity. Int. J. Photoenergy 2012, 1e9. oxide content on the adsorption-enhanced photocatalysis of
Livraghi, S., Elghniji, K., Czoska, A.M., Paganini, M.C., Giamello, E., titanium dioxide/graphene oxide composites. Chem. Eng. J.
Ksibi, M., 2009. Nitrogen-doped and nitrogenefluorine- 170, 226e232.
codoped titanium dioxide. Nature and concentration of the Niederberger, M., Garnweitner, G., Krumeich, F., Nesper, R.,
photoactive species and their role in determining the Colfen, H., Antonietti, M., 2004. Tailoring the surface and
photocatalytic activity under visible light. J. Photochem. solubility properties of nanocrystalline titania by a
Photobiol. A 205, 93e97. nonaqueous in situ functionalization process. Chem. Mater.
Likodimos, V., Han, C., Pelaez, M., Kontos, A.G., Liu, G.L., 16, 1202e1208.
Zhu, D.W., Liao, S.J., de la Cruz, A.A., O'Shea, K., Nosaka, Y., Matsushita, M., Nishino, J., Nosaka, A.Y., 2005.
Dunlop, P.S.M., Byrne, J.A., Dionysiou, D.D., Falaras, P., 2013. Nitrogen-doped titanium dioxide photocatalysts for visible
Anion-doped TiO2 nanocatalysts for water purification under response prepared by using organic compounds. Sci. Technol.
visible light. Ind. Eng. Chem. Res. 52, 13957e13964. Adv. Mater. 6, 143e148.
Makarova, O.V., Rajh, T., Thurnauer, M.C., 2000. Surface O'Regan, B., Graetzel, M., 1991. A low-cost, high-efficiency solar
modification of TiO2 nanoparticles for photochemical cell based on dye-sensitized colloidal TiO2 films. Nature 353,
reduction of nitrobenzene. Environ. Sci. Technol. 34, 737e740.
4797e4803. Oh, W.C., Jung, A.R., Ko, W.B., 2007. Preparation of fullerene/TiO2
Mallakpour, S., Nikkhoo, E., 2014. Surface modification of nano- composite and its photocatalytic effect. J. Ind. Eng. Chem. 13,
TiO2 with trimellitylimido-amino acid-based diacids for 1208e1214.
preventing aggregation of nanoparticles. Adv. Powder Ohno, T., Mitsui, T., Matsumura, M., 2003. Photocatalytic activity
Technol. 25, 348e353. of S doped TiO2 photocatalyst under visible light. Chem. Lett.
Martyanov, N., Klabunde, J., 2004. Comparative study of TiO2 32, 364e365.
particles in powder form and as a thin nanostructured film on  nchez-Pe
Oller, I., Malato, S., Sa rez, J.A., 2011. Combination of
quartz. J. Catal. 225, 408e416. advanced oxidation processes and biological treatments for
Mascolo, G., Comparelli, R., Curri, M.L., Lovecchio, G., Lopez, A., wastewater decontaminationda review. Sci. Total Environ.
Agostiano, A., 2007. Photocatalytic degradation of methyl red 409, 4141e4166.
by TiO2: comparison of the efficiency of immobilized Ooka, C., Yoshida, H., Horio, M., Suzuki, K., Hattori, T., 2003.
nanoparticles versus conventional suspended catalyst. J. Adsorptive and photocatalytic performance of TiO2 pillared
Hazard. Mater. 142, 130e137. montmorillonite in degradation of endocrine disruptors
Matos, J., Laine, J., Herrmann, J.M., 1998. Synergy effect in the having different hydrophobicity. Appl. Catal. B: Environ. 41,
photocatalytic degradation of phenol on a suspended mixture 313e321.
of titania and activated carbon. Appl. Catal. B: Environ. 18, Ozaki, H., Iwamoto, S., Inoue, M., 2007. Marked promotive effect
281e291. of iron on visible-light-induced photo-catalytic activities of
Matos, J., Laine, J., Herrmann, J.M., Uzcategui, D., Brito, J.L., 2007. nitrogen-and silicon-codoped titanias. J. Phys. Chem. C 111,
Influence of activated carbon upon titania on aqueous 17061e17066.
photocatalytic consecutive runs of phenol photodegradation. Padmanabhan, P.V.A., Sreekumar, K.P., Thiyagarajan, T.K.,
Appl. Catal. B: Environ. 70, 461e469. Satpute, R.U., Bhanumurthy, K., Sengupta, P., Dey, G.K.,
Matthews, R., 1990. Purification of water with near-UV Warrier, K.G.K., 2006. Nano-crystalline titanium dioxide
illuminated suspensions of titanium dioxide. Water Res. 24, formed by reactive plasma synthesis. Vacuum 80, 11e12.
653e660. Palmisano, L., Schiavello, M., Sclafani, A., Martin, C., Martin, I.,
Miranda-Garcia, N., Suarez, S., Sanchez, B., Coronado, J.M., Rives, V., 1994. Surface properties of iron-titania
Malato, S., Maldonado, M.I., 2011. Photocatalytic degradation
 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6 145

photocatalysts employed for 4-nitrophenol photodegradation highly uniform polyaniline-magnetic mesoporous silica
in aqueous TiO2 dispersion. Catal. Lett. 24, 303e315. composite. Chem. Eng. J. 254, 302e312.
Patrick, B., Kamat, P.V., 1992. Photoelectrochemistry in Tang, Y.H., Zhang, G., Liu, C.B., Luo, S.L., Xu, X.L., Chen, L.,
semiconductor particulate systems. J. Phys. Chem. 96, Wang, B.G., 2013. Magnetic TiO2egraphene composite as a
1423e1428. high-performance and recyclable platform for efficient
Pelaez, M., Nolan, N.T., Pillai, S.C., Seery, M.K., Falaras, P., photocatalytic removal of herbicides from water. J. Hazard.
Kontos, A.G., Dunlop, P.S.M., Hamilton, J.W.J., Byrne, J.A., Mater. 252e253, 115e122.
O'Shea, K., Entezari, M.H., Dionysiou, D.D., 2012. A review on Tang, W.W., Zeng, G.W., Gong, J.L., Liang, J., Xu, P., Zhang, C.,
the visible light active titanium dioxide photocatalysts for Huang, B.B., 2014. Removal of heavy metals from aqueous
environmental applications. Appl. Catal. B: Environ. 125, solutions using nanomaterials affected by humic/fulvic acid: a
331e349. review. Sci. Total Environ. 468e469, 1014e1027.
Ranjit, K.T., Willner, I., Bossmann, S.H., Braun, A.M., 2001a. Tran, H., Scott, J., Chiang, K., Amal, R., 2006. Clarifying the role of
Lanthanide oxide-doped titanium dioxide photocatalysts: silver deposits on titania for the photocatalytic mineralisation
novel photocatalysts for the enhanced degradation of p- of organic compounds. J. Photochem. Photobiol. A 183, 41e52.
chlorophenoxyacetic acid. Environ. Sci. Technol. 35, Tong, T., Zhang, J., Tian, B., Chen, F., He, D., 2008. Preparation of
1544e1549. Fe3þ-doped TiO2 catalysts by controlled hydrolysis of titanium
Ranjit, K.T., Wilner, I., Bossmann, S.H., Braun, A.M., 2001b. alkoxide and study on their photocatalytic activity for methyl
Lanthanide oxide doped titanium dioxide photocatalysts: orange degradation. J. Hazard. Mater. 155, 572e579.
effective photocatalysts for the enhanced degradation of Uyguner, C.S., Bekbolet, M., 2009. Application of photocatalysis
salicylic acid and t-cinnamic acid. J. Catal. 204, 305e313. for the removal of natural organic matter in simulated surface
Reddy, E.P., Davydov, L., Smirniotis, P., 2003. TiO2-loaded zeolites and ground waters. J. Adv. Oxid. Technol. 12, 87e92.
and mesoporous materials in the sonophotocatalytic Valentin, C.D., Pacchioni, G., Selloni, A., 2005. Theory of carbon
decomposition of aqueous organic pollutants: the role of the doping of titanium dioxide. Chem. Mater. 17, 6656e6665.
support. Appl. Catal. B: Environ. 42, 1e11. Vione, D., Minero, C., Maurino, V., Carlotti, M.E., Picatonotto, T.,
Romanello, M.B., Fidalgo de Cortalezzi, M.M., 2013. An Pelizzetti, E., 2005. Degradation of phenol and benzoic acid in
experimental study on the aggregation of TiO2 nanoparticles the presence of a TiO2-based heterogeneous photocatalyst.
under environmentally relevant conditions. Water Res. 47, Appl. Catal. B: Environ. 58, 79e88.
3887e3898. Viessman Jr., W., Hammer, M.J., 1998. Water Supply and Pollution
Rengifo-Herrera, J.A., Pulgarin, C., 2010. Photocatalytic activity of Control, sixth ed. Addison Wesley Longman Inc, California,
N, S co-doped and n-doped commercial anatase TiO2 powders USA.
towards phenol oxidation and E. coli inactivation under Vinodgopal, K., Kamat, P.V., 1992. Photochemistry on surfaces:
simulated solar light irradiation. Sol. Energy 84, 37e43. photodegradation of 1, 3-diphenylisobenzofuran over metal
Rengifo-Herrera, J.A., Pierzchała, K., Sienkiewicz, A., Forro, L., oxide particles. J. Phys. Chem. 96, 5053e5059.
Kiwi, J., Pulgarin, C., 2009. Abatement of organics and Vohra, M.S., Tanaka, K., 2003. Photocatalytic degradation of
Escherichia coli by N, S co-doped TiO2 under UV and visible aqueous pollutants using silica-modified TiO2. Water Res. 37,
light. Implications of the formation of singlet oxygen (1O2) 3992e3996.
under visible light. Appl. Catal. B: Environ. 88, 398e406. Wang, C., Yin, L., Zhang, L., Kang, L., Wang, X., Gao, R., 2009.
Sakthivel, S., Kisch, H., 2003. Daylight photocatalysts by carbon- Magnetic (g-Fe2O3@SiO2)n@TiO2 functional hybrid
modified titanium dioxide. Angew. Chem. Int. Ed. 42, nanoparticles with actived photocatalytic ability. J. Phys.
4908e4911. Chem. C 113, 4008e4011.
Serpone, N., Lawless, D., Khairutdinov, R., Pelizzetti, E., 1995. Wang, J., Ma, T., Zhang, G., Zhang, Z.H., Zhang, X.D., Jiang, Y.F.,
Subnanosecond relaxation dynamics in TiO2 colloidal sols Zhao, G., Zhang, P., 2007. Preparation of nanometer TiO2
(particle sizes Rp ¼ 1.0e13.4 nm). Relevance to heterogeneous catalyst doped with upconversion luminescence agent and
photocatalysis. J. Phys. Chem. 99, 16655e16661. investigation on degradation of acid red B dye using visible
Shao, G.S., Liu, L., Ma, T.Y., Wang, F.Y., Ren, T.Z., Yuan, Z.Y., 2010. light. Catal. Commun. 8, 607e611.
Synthesis and characterization of carbon-modified titania Wang, S.H., Zhou, S.Q., 2010. Titania deposited on soft
photocatalysts with a hierarchical meso-/macroporous magnetic activated carbon as a magnetically separable
structure. Chem. Eng. J. 160, 370e377. photocatalyst with enhanced activity. Appl. Surf. Sci. 256,
Soria, J., Conesa, J.C., Augugliaro, V., Palmisano, L., Sciavello, M., 6191e6198.
Scalfani, A.J., 1991. Dinitrogen photoreduction to ammonia Wang, W.D., Silva, C.G., Faria, J.L., 2007. Photocatalytic
over titanium dioxide powders doped with ferric ions. J. Phys. degradation of Chromotrope 2R using nanocrystalline TiO2/
Chem. 95, 274e282. activated-carbon composite catalysts. Appl. Catal. B: Environ.
Subramanian, V., Wolf, E., Kamat, P.V., 2001. 70, 470e478.
Semiconductoremetal composite nanostructures. To what Wang, X., Mitchell, D.R.G., Prince, K., Atanacio, A.J., Caruso, R.A.,
extent do metal nanoparticles improve the photocatalytic 2008. Gold nanoparticle incorporation into porous titania
activity of TiO2 films? J. Phys. Chem. B 105, 11439e11446. networks using an agarose gel templating technique for
Tanaka, T., Teramura, K., Yamamoto, T., Takenaka, S., photocatalytic applications. Chem. Mater. 20, 3917e3926.
Yoshida, S., Funabiki, T., 2002. TiO2/SiO2 photocatalysts at low Wang, Y.B., Zhang, J.Z., Liu, X., Gao, S.M., Huang, B.B., Dai, Y.,
levels of loading: preparation, structure and photocatalysis. J. Xu, Y.B., 2012. Synthesis and characterization of activated
Photochem. Photobiol. A: Chem. 148, 277e281. carbon-coated SiO2/TiO2xCx nanoporous composites with
Tang, L., Yang, G.D., Zeng, G.M., Cai, Y., Li, S.S., Zhou, Y.Y., high adsorption capability and visible light photocatalytic
Pang, Y., Liu, Y.Y., Zhang, Y., Luna, B., 2014a. Synergistic effect activity. Mater. Chem. Phys. 135, 579e586.
of iron doped ordered mesoporous carbon on adsorption- Weng, Y.X., Li, L., Liu, Y., Wang, L., Yang, G.Z., 2003. Surface-
coupled reduction of hexavalent chromium and the relative binding forms of carboxylic groups on nanoparticulate TiO2
mechanism study. Chem. Eng. J. 239, 114e122. surface studied by the interface-sensitive transient triplet-
Tang, L., Fang, Y., Pang, Y., Zeng, G.M., Wang, J.J., Zhou, Y.Y., state molecular probe. J. Phys. Chem. B 107, 4356e4363.
Deng, Y.C., Yang, G.D., Cai, Y., Chen, J., 2014b. Synergistic
adsorption and reduction of hexavalent chromium using
146 w a t e r r e s e a r c h 7 9 ( 2 0 1 5 ) 1 2 8 e1 4 6

Williams, G., Seger, B., Kamat, P.V., 2008. TiO2egraphene Zang, Y., Farnood, R., 2008. Photocatalytic activity of AgBr/TiO2 in
nanocomposites. UV-assisted photocatalytic reduction of water undersimulated sunlight irradiation. Appl. Catal. B:
graphene oxide. ACS Nano 2, 1487e1491. Environ. 79, 334e340.
Woan, K., Pyrgiotakis, G., Sigmund, W., 2009. Photocatalytic Zeng, G.M., Chen, M., Zeng, Z.T., 2013a. Risks of neonicotinoid
carbon-nanotubeeTiO2 composites. Adv. Mater. 21, pesticides. Science 340 (6139), 1403.
2233e2239. Zeng, G.M., Chen, M., Zeng, Z.T., 2013b. Shale gas: surface water
Wu, C.L., Shen, L., Zhang, Y.C., Huang, Q.L., 2012. Solvothermal also at risk. Nature 499 (7457), 154.
synthesis of Cr-doped ZnO nanowires with visible light-driven Zhang, H., Lü, X.J., Li, Y.M., Wang, Y., Li, J.H., 2010. P25-graphene
photocatalytic activity. Mater. Lett. 65, 1794e1796. composite as a high performance photocatalyst. ACS Nano 4,
Wu, X.Y., Yin, S., Dong, Q., Guo, C.S., Li, H.H., Kimura, T., Sato, T., 380e386.
2013. Synthesis of high visible light active carbon doped TiO2 Zhang, H., Zhu, G.Q., 2012. One-step hydrothermal synthesis of
photocatalyst by a facile calcination assisted solvothermal magnetic Fe3O4 nanoparticles immobilized on polyamide
method. Appl. Catal. B: Environ. 142e143, 450e457. fabric. Appl. Surf. Sci. 258, 4952e4959.
Wu, Y.M., Liu, H.B., Zhang, J.L., Chen, F., 2009. Enhanced Zhang, J., Wu, Y., Xing, M., Leghari, S.A.K., Sajjad, S., 2010.
photocatalytic activity of nitrogen-doped titania by deposited Development of modified N doped TiO2 photocatalyst with
with gold. J. Phys. Chem. C 113, 14689e14695. metals, nonmetals and metal oxides. Energy Environ. Sci. 3,
Xiao, Q., Ouyang, L.L., 2009. Photocatalytic activity and hydroxyl 715e726.
radical formation of carbon-doped TiO2 nanocrystalline: effect Zhang, X., Wu, F., Deng, N., 2011. Efficient photodegradation of
of calcination temperature. Chem. Eng. J. 148, 248e253. dyes using light-induced self-assembly TiO2/b-cyclodextrin
Xu, A.W., Gao, Y., Xu, H.Q., 2002. Preparation, characterization, hybrid nanoparticles under visible light irradiation. J. Hazard.
and their photocatalytic activities of rare earth doped TiO2 Mater. 185, 117e123.
nanoparticles. J. Catal. 207, 151e157. Zhang, Y.C., Zhang, N., Tang, Z., Xu, Y., 2012. Improving the
Xu, J., Ao, Y., Fu, D., Yuan, C., 2008. Synthesis of fluorine-doped photocatalytic performance of grapheneeTiO2
titania-coated activated carbon under low temperature with nanocomposites via a combined strategy of decreasing defects
high photocatalytic activity under visible light. J. Phys. Chem. of graphene and increasing interfacial contact. Phys. Chem.
Solids 69, 2366e2370. Chem. Phys. 14, 9167e9175.
Xu, P., Zeng, G.M., Huang, D.L., Feng, C.L., Hu, S., Zhao, M.H., Zhao, C., Pelaez, M., Dionysiou, D.D., Pillai, S.C., Byrne, J.A.,
Lai, C., Wei, Z., Huang, C., Xie, G.X., Liu, Z.F., 2012. Use of iron O'Shea, K.E., 2014. UV and visible light activated TiO2
oxide nanomaterials in wastewater treatment: a review. Sci. photocatalysis of 6-hydroxymethyl uracil, a model compound
Total Environ. 424, 1e10. forthe potent cyanotoxin cylindrospermopsin. Catal. Today
Xu, S.F., Lu, H.Z., Chen, L.X., Wang, X.C., 2014. Molecularly 224, 70e76.
imprinted TiO2 hybridized magnetic Fe3O4 nanoparticles for Zhao, J., Wu, T., Wu, K., Oikawa, K., Hidaka, H., Serpone, N., 1998.
selective photocatalytic degradation and removal of estrone. Photoassisted degradation of dye pollutants. 3. Degradation of
RSC Adv. 4, 45266e45274. the cationic dye rhodamine B in aqueous anionic surfactant/
Yang, M., Thompson, D.W., Meyer, G.J., 2002. Charge-transfer TiO2 dispersions under visible light irradiation: evidence for
studies of iron cyano compounds bound to nanocrystalline the need of substrate adsorption on TiO2 particles. Environ.
TiO2 surfaces. Inorg. Chem. 41, 1254e1262. Sci. Technol. 32, 2394e2400.
Yang, P., Lu, C., Hua, N., Du, Y., 2002. Titanium dioxide Zhao, J., Yang, X., 2003. Photocatalytic oxidation for indoor air
nanoparticles co-doped with Fe3þ and Eu3þ ions for purification: a literature review. Build. Environ. 38, 645e654.
photocatalysis. Mater. Lett. 57, 794e801. Zhao, J.C., Chen, C.C., Ma, W.H., 2005. Photocatalytic degradation
Yin, S., Zhang, Q., Saito, F., Sato, T., 2003. Preparation of visible of organic pollutants under visible light irradiation. Top. Catal.
light-activated titania photocatalyst by mechanochemical 35, 269e278.
method. Chem. Lett. 32, 358e359. Zhao, Z., Liu, Q., 2008. Mechanism of higher photocatalytic
Yoneyama, H., Torimoto, T., 2000. Titanium dioxide/adsorbent activity of anatase TiO2 doped with nitrogen under visible-
hybrid photocatalysts for photodestruction of organic light irradiation from density functional theory calculation. J.
substances of dilute concentrations. Catal. Today 58, 133e140. Phys. D: Appl. Phys. 41, 1e10.
Yu, J., Zhao, X., 2001. Effect of surface treatment on the Zhou, Y.Y., Tang, L., Zeng, G.M., Chen, J., Cai, Y., Zhang, Y.,
photocatalytic activity and hydrophilic property of the solegel Yang, G.D., Liu, Y.Y., Zhang, C., Tang, W.W., 2014. Mesoporous
derived TiO2 thin films. Mater. Res. Bull. 36, 97e107. carbon nitride based biosensor for highly sensitive and
Yu, J.C., Xie, Y., Tang, H.Y., Zhang, L., Chan, H.C., Zhao, J., 2003a. selective analysis of phenol and catechol in compost
Visible light-assisted bactericidal effect of metal bioremediation. Biosens. Bioelectron. 61, 519e525.
phthalocyanine-sensitized titanium dioxide films. J. Zhou, W., Zheng, Y., Wu, G., 2006. Novel luminescent RE/TiO2
Photochem. Photobiol. A: Chem. 156, 235e241. (RE ¼ Eu, Gd) catalysts prepared by in-situation solegel
Yu, J.C., Zhang, L., Zheng, Z., Zhao, J., 2003b. Synthesis and approach construction of multi-functional precursors and
characterization of phosphated mesoporous titanium dioxide their photo or photocatalytic oxidation properties. Appl. Surf.
with high photocatalytic activity. Chem. Mater. 15, 2280e2286. Sci. 252, 1387e1392.
Zaleska, A., 2008. Doped-TiO2: a review. Recent Pat. Eng. 2,
157e164.