Journal of Environmental Management 198 (2017) 78e94

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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Review

Application of doped photocatalysts for organic pollutant degradation

- A review
Mohammad Reza Delsouz Khaki a, Mohammad Saleh Shafeeyan b, *,
Abdul Aziz Abdul Raman a, **, Wan Mohd Ashri Wan Daud a
a
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603, Kuala Lumpur, Malaysia
b
School of Chemical Engineering, College of Engineering, University of Tehran, 11155/4563, Tehran, Iran

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

Article history: Advanced oxidation process involves production of hydroxyl radical for industrial wastewater treatment.
Received 23 January 2017 This method is based on the irradiation of UV light to photocatalysts such as TiO2 and ZnO for photo-
Received in revised form degradation of pollutant. UV light is used for irradiation in photocatalytic process because TiO2 has a high
27 April 2017
band gap energy which is around 3.2 eV. There can be shift adsorption to visible light by reducing the
Accepted 30 April 2017
band gap energy to below 3.2 eV. Doped catalyst is one of the means to reduce band gap energy. Different
Available online 11 May 2017
methods are used for doped catalyst which uses transition metals and titanium dioxide. The band gap
energy of three types of transition metals Fe, Cd and Co after being doped with TiO2, are around 2.88 ev,
Keywords:
Doped processes
2.97ev and 2.96 ev, respectively which are all below TiO2 energy. Some of the transition metals change
Band gap the energy level to below 3.2 eV and the adsorption shifts to visible light for degradation of industrial
Photocatalytic pollutant after being doped with titanium dioxide. This paper aims at providing a deep insight into
Sol-gel advanced oxidation processes, photocatalysts and their applications in wastewater treatment, doping
processes and the effects of operational factors on photocatalytic degradation.
© 2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2. Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3. TiO2 and ZnO photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4. TiO2 photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.1. Dopants effects on TiO2 photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5. Doping processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.1. Effect of metal doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.2. Effect of non-metal doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.3. Effect of metalloid and halogen doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.4. Effect of Co-doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.5. Coupling of TiO2 with other semi-conductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
6. Operational factors affecting the photocatalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6.1. Effect of calcination temperature of nano-doped-TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6.2. Effect of dopant concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6.3. Effect of initial pollutant concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6.4. Effect of photocatalyst concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6.5. Preparation methods of doped-photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

* Corresponding author.
** Corresponding author.
E-mail addresses: ms.shafeeyan@gmail.com (M.S. Shafeeyan), azizraman@um.
edu.my (A.A.A. Raman).

http://dx.doi.org/10.1016/j.jenvman.2017.04.099
0301-4797/© 2017 Elsevier Ltd. All rights reserved.
 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94 79

6.6. Sol-gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

7. Photocatalytic performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

1. Introduction high voltage pulses of about 10 kV are discharged in water through

two electrodes installed within a short distance, localized heat is
Four different methods are employed in Advanced Oxidation generated, decomposing the water molecules. The same conditions
Processes (AOPs) to generate hydroxyl radicals and treat waste- occur under ultrasound or microwave irradiation, where over-
water, namely (i) ozone treatment, (ii) electrochemical processes, heated regions named hot spots are generated.
(iii) direct decomposition of water, and (iv) photocatalysis (Arslan- Photocatalysis is another OH
generation technology that entails
Alaton, 2007; Rivas et al., 2012; Holkar et al., 2016; Orge et al., the activity of semiconducting metal oxides, e.g. SrTiO3, BiTiO3,
2017). Fig. 1 displays the advanced oxidation technologies for hy- WO3, ZnWO4, ZnO, CuS/ZnS, Bi20Ti20, ZnS, Ag2CO3, Bi2WO6, Nb2O5,
droxyl radical generation. Fe2O3, TiO2, and etc. The process involves a semiconductor as a
Ozone treatment is commonly used for water treatment by photocatalyst, which is activated under light irradiation (Gaya and
directly inserting ozone gas into wastewater. The ozone directly Abdullah, 2008). The Semiconductor Photocatalyst (SP) structure
reacts with organic compounds or indirectly reacts with OH
, contains Valence bands (VB) and Conduction bands (CB) that are
resulting in indirect oxidative decomposition. The organic pollut- separated by Band gap energy (Eg).
ants' properties are a determinant factor of the ozone decomposi-
tion mechanism by either promoting or inhibiting ozone 2. Photocatalysts
decomposition. Therefore, the un-decomposable organic com-
pounds or those that cannot be easily decomposed undergo ozone Among various AOPs, the heterogeneous photocatalytic pro-
treatment. cesses can successfully reduce a broad range of pollutants at
Fenton oxidation technology also generates OH
through ambient temperature and pressure without generating harmful
decomposing H2O2 by Fe2þ in liquid medium with or without light intermediates (Daneshvar et al., 2007; Abdollahi et al., 2011). The
irradiation, or with UV radiation. processes are initiated with the excitation and transfer of an elec-
tron from the VB, which is full of electrons to the empty CB. In
H2O2þFe3þ / HO2
þ Hþþ Fe2 (1) photocatalysis, the photocatalyst absorbs enough energy, which is
nearly equal to its band gap energy level, to become excited. This
HO2 þ Fe2þ / HO
2 þ Fe
3þ


(2) process generates an electron-hole pair that reacts with water and
oxygen molecules or hydroxyl groups to generate highly reactive
HO2 þ Fe3þ / O2þHþ þ Fe2þ


(3) oxygen species, i.e. superoxide anions (
O2) and hydroxyl radicals
(
OH). Then the oxy-radical species attack vital organic components
However, the Fenton oxidation reaction is not applicable for and decompose them through oxidation reactions. Photo-
conditions with pH > 4. Therefore, the pH should be controlled and excitation occurs through the absorption of photon energy (hn),
adjusted for this method, which may increase operational costs which is equal to or higher than the photocatalyst's band gap en-

ski, 2009; Pouran et al., 2015).
(Barbusin ergy (Eg). Therefore, an electron-hole pair (e--hþ) is generated at
Direct decomposition of water molecules through external en- the surface of the photo-excited catalyst. Among different semi-
ergy sources like microwaves, ultrasound, and electromagnetic conductors, titanium dioxide (TiO2) and zinc oxide (ZnO) are the
beams, is also a method of OH
generation. Water molecules are most successful and popular photocatalysts with good photosen-
decomposed into Hþ, OH
and aqueous electrons by irradiation. As sitivity and chemical stability. They are non-toxic and low-cost.

Fig. 1. Advanced oxidation technologies for hydroxyl radical generations.

80 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94
However, they suffer from some limitations pertaining to optical
and electronic properties (Li and Li, 2002; Houshmand et al., 2011).
TiO2 and ZnO are highly active photocatalysts under UV light irra-
diation since their photogenerated electrons and holes are efficient
oxidizing and reducing agents. However, the large band gaps of
TiO2 and ZnO, which are roughly 3.2eV (Khan et al., 2014) and
3.37eV (Ahmad et al., 2013) respectively, restrict their photo-
electrochemical application under visible light irradiation. The easy
recombination of photo-induced holes and electrons also reduces
their efficiency. Adding an oxide to these photocatalysts and sup-
porting them on an oxide are ways to improve their photoactivity
and thermal stability during catalyst preparation.
Among various oxides like TiO2, SnO2, SiO2, CeO2, ZnO, WO3 and
ZrO2, previous works have demonstrated that the heterojunction of
TiO2 and ZnO can have synergic effects due to the injection of
conduction band electrons from ZnO to TiO2, which decreases the
recombination rate and increases the electron-hole pair lifetime.
TiO2 and ZnO, with wide band gaps of 3.2 eV and 3.3 eV, and two
photocatalysts, require excitation light with wavelengths below
400 nm to begin photoreaction. The doping method has been
considered for improving the photoactivity of TiO2 and ZnO. Doping
of two photocatalysts is a method employed for retarding the rapid
charge recombination and enabling visible light absorption by
creating defect states in the band gap. In the former case, the va-
lance band holes or conduction band electrons are trapped in the
defect sites, inhibiting the recombination of photo-induced holes
and electrons and improving the interfacial charge transfer. In the
latter case, electronic transitions from the defect states to the
conduction band or from the valance band to the defect states can
occur under sub-band gap irradiation.
3. TiO2 and ZnO photocatalysts
TiO2 and ZnO are two of the most promising photocatalysts.
However, their wide band gap limits their photocatalytic activity in
the UV wavelength region that contributes to 3e5% of the total
solar spectrum (Zheng et al., 2015; Pouran et al., 2016). The fast
recombination of photogenerated electron-hole pairs is another
limitation of these two semiconductors. This is significant in the
absence of electron donors or acceptors, as it results in major en-
ergy loss and very low photocatalytic reaction yield. Accordingly,
enhancing the photocatalytic activity of TiO2 and ZnO has been
studied by many researchers (Wang et al., 2013a).
Results have indicated that coupling two semiconductors pro-
duces a composite with higher photocatalytic efficiency in most
cases. The synergistic effect between the two semiconductors
modifies the electronic states of the composite, allowing the
transfer of photogenerated charge carriers between the two semi-
conductors, thus promoting electronehole pair separation and
modifying the carrier's lifetime. Compared to TiO2, ZnO has a higher
electron mobility that causes a negative shift in its valence and
conduction band potentials. Accordingly, ZnO is considered suitable
for coupling with TiO2 (Shaheen et al., 2013). Besides, since ZnO and
TiO2 have similar band gap energy, they can effectively improve
each other's photocatalytic performance. In the TiO2eZnO hetero-
junction, the conduction band (CB) of ZnO is positioned above the
CB of TiO2 and the valance band (VB) of ZnO is positioned between
the VB and CB of TiO2, which suppresses the electron-hole pair
recombination and promotes its separation, consequently
improving the photocatalytic activity. As an example, ZnOeTiO₂
binary oxide catalysts were successfully prepared by solid-state
dispersion in a study by Pozan and Kambur (2014). It was then
used in the degradation of 4-chlorophenol and the authors indi-
cated that 20 wt% ZnOeTiO₂ photocatalyst exhibited much higher
photocatalytic activity than pure TiO₂, ZnO and P-25. Zheng et al.
(2015) prepared a ZnO/TiO2 photonic crystal (ZnO/TiO2-PC) heter-
ostructure by pyrolysis. The authors evaluated the performance of
ZnO/TiO2-PC on the degradation of methyl orange. They found that
the synthesized heterostructure had superior photocatalytic ac-
tivity compared to ZnO, TiO2-PC and P25. Amorphous TiO2-modi-
fied ZnO nanorod film was also synthesized to enhance the
photocatalytic activity of ZnO film by Xiao et al. (2014). The pho-
tocatalytic analysis revealed that the TiO2-modified film exhibited
superior photocatalytic efficiency in the decomposition of methyl
orange under ultravioletevisible excitation compared to ZnO
nanorod arrays. Wang et al. (2014a) prepared mesoporous ZnO/
TiO2 hollow microspheres by a facile one-step hydrothermal route
without a template. The authors concluded that the ZnO/TiO2
hollow microspheres had a significant positive effect on photo-
catalytic degradation performance compared to the pristine TiO2
hollow microspheres or ZnO nanosheets.
Other strategies have also been developed for utilizing a wide
spectrum of incident photon energies by tailoring the band gap
absorption of different photocatalysts like TiO2 and ZnO through
metal/non-metal ion doping, co-doping with foreign ions, noble
metal deposition, self-doping, sensitization by inorganic complexes
or organic dyes, and surface complexation. Among the aforemen-
tioned methods, incorporating main group elements (especially
metal and non-metal ions) into TiO2 or ZnO lattices has gained
much attention due to these elements' ability to modify the surface
electronic properties. The redox energy states of transition metal
ions (e.g. Cu, Co, Ni, Cr, Mn, Mo, Nb, V, Fe, Ru, Au, Ag, Pt) mostly lie
within the band gap states of TiO2 or ZnO. This introduces an intra-
band state close to the CB or VB edge, which induces visible light
absorption at sub-band gap energies. Moreover, metal ions affect
the charge carrier equilibrium concentration by serving as electron-
hole traps and increasing the degradation rate. As reported by Yi
et al. (2014), metal species increase the electron capturing capac-
ity of semiconductors. In Yi et al.'s work, iron-doped zinc oxide
nanoflowers were synthesized via a simple hydrothermal process.
These showed enhanced photocatalytic activity under visible light
irradiation.
The photocatalytic visible light activity of titanium dioxide can
be improved by non-metal-doping. In terms of non-metal doping
(e.g. N, S, C, B, P, I, F) (Szkoda et al., 2016), three methods have been
suggested for TiO2 modification: band gap narrowing, (Sun et al.,
2012), impurity energy levels (Di Valentin and Pacchioni, 2013)
and oxygen vacancies (Bharti et al., 2016). Yalçın et al. (2010) pre-
pared a series of N, C and S-doped photocatalysts with different
dopant contents using a simple wet impregnation method. They
explained that band-gap energy level reduction arises from the
contribution of N 2p, C 2p and S 3p orbitals to the O 2p and Ti 3d
states in the valance band of titanium dioxide. Di Valentin and
Pacchioni (2013) doped TiO2 with non-metal boron, carbon, ni-
trogen, and fluorine. Results showed that localized states are
formed in the band gap of the material which allow for electronic
transitions in the visible range. Among all, non-metal nitrogen is
the most beneficial due to the low ionization energy, metastable
centre formation, stability and atomic size comparable to oxygen.
Oxygen vacancies existence in TiO2 doped N can improve the
photocatalysis in visible light (Wu et al., 2013). Substituting nitro-
gen affects both the surface structure and electronic properties of
TiO2, with the former controlling the surface transfer of charge
carriers and the latter determining the light response range and
redox power of carriers (Asahi et al., 2001; Shafeeyan et al., 2015a).
Recently, two methods have been considered in parallel to
further improve the photoactivity of TiO2 and ZnO. Amongst the
aforementioned methods, the heterojunction of two photocatalysts
along with metal or non-metal doping has gained considerable
interest for increasing the photoactivity of different photocatalysts.
 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94
4. TiO2 photocatalyst
Titanium dioxide (TiO2), an n-type semiconductor, is one of the
most applicable photocatalysts that can be used in a wide range of
applications, such as H2 generation, self-cleaning, defogging, water
purification, air purification, sterilization, etc. (Robinson et al.,
2001). TiO2 is non-toxic, abundant, economical, versatile and sta-
ble (Krumme and Boyd, 1988; Aviam et al., 2004). Generally, TiO2 is
a semiconductor with a wide band gap (Eg ¼ 3.0e3.2 eV) that re-
quires excitation light with a wavelength lower than 400 nm
(E ¼ hc l y 1240 l) to begin photoreaction (Fujishima et al., 2000;
Carp et al., 2004). When the surface of TiO2 (or any other photo-
catalyst) is irradiated with UV light, electrons (eCB) and holes
(hCB) are created in the conduction (CB) and valence bands (VB),
respectively (Gaya and Abdullah, 2008). The generated electrons
and holes are subsequently trapped and recombine with each
other. In short, the photo-induced formation procedure follows four
steps, which are photoexcitation (Eq. (4)) charge-carrier trapping of
e (Eq. (5)), charge-carrier trapping of hþ (Eq. (6)) and electron-hole
recombination (Eq. (7)):
TiO2 (aq) þ hn/ e þ hþ (4)
eCB / eTR (5)
hþVB / hþTR (6)
eTR þ hþVB(hþTR) / eCB þ heat (7)
In the next step, the photo-induced electrons in the CB are
trapped by aqueous-adsorbed oxygen and participate in the
reduction process, producing superoxide radical anions (O


2 ) (Eq.
(8)). The superoxide is protonated (Eq. (9)) by Hþ, which is pro-
duced by water ionization in the generated holes (hþ) (Eq. (10)).
HOO
then traps another excited electron to produce HO 2 (Eq. (11)),
followed by the protonation of HO 2 to generate hydrogen peroxide,
as shown in Eq. (12). Finally, hydrogen peroxide is decomposed to
produce hydroxyl radicals (OH$) (Eq. (13)). Meanwhile, the photo-
induced holes in the VB diffuse to the surface of the photocatalyst
and then react with the adsorbed water molecules, generating
another hydroxyl radical (Eq. (14)) (Daneshvar et al., 2007; Kansal
et al., 2008; Abdollahi et al., 2011a; Shafeeyan et al., 2015b).
(O2)ads þ e / O
2

(8)
O
þ
2 þ H / HOO

(9)
H2O / OH þ Hþ (10)
HOO
þ e / HO
2 (11)
HO þ
2 þ H / H2O2 (12)
H2O2 þ e-/ OH þ OH
(13)
H2O þ hþ/Hþ þ OH
(14)
A variety of organisms as well as organic and inorganic pollut-
ants can be deactivated, decomposed or transformed by the syn-
ergistic interaction of hydroxyl radicals, electrons, holes and other
oxidizing radicals (Takeda and Teranishi, 1988).
TiO2 also has a favourable combination of electronic structure,
light absorption properties, charge transport characteristics, and
excited-state lifetime (Benhebal et al., 2013). Furthermore, TiO2 is a
stable compound either photo-chemically or chemically in contrast
81
with other semiconductors such as GaP or CdS, which can easily
solve and produce toxic by-products. Furthermore, TiO2 presents
excellent advantages during environmental purification processes,
including an oxidative reaction that is normally employed to
decompose the polluting materials. Such reaction is improved by
increasing the oxidative power of VB holes. TiO2 with a band gap of
about 3.0e3.2eV and wavelength of about 400 nm presents more
powerful oxidative of the VB holes compared to the reducibility of
photo-induced electrons. Generally, different TiO2 structures have
very strong oxidation power (3.0eV for rutile and 3.2eV for anatase
TiO2) considering approximately 1.2 eV for the oxidation potential
of water and approximately 3.0 eV for the hydrogen reference po-
tential. Furthermore, organic compounds are decomposed
completely into carbon dioxide and water by irradiating TiO2 with
UV light below 400 nm. The reason is the surface temperature of
TiO2, which increases tremendously to almost 300  C. In such
conditions, all materials can be easily oxidized. Fig. 2 shows the
band gap energy level of TiO2 photocatalyst.
For TiO2 photocatalyst, the CB energy level is slightly higher
than the reduction potential of oxygen (ECB ¼ 0.51 V,
EO ¼ 0.33 V), which is a predominant electron acceptor (or
oxidant) and it can ease the transfer of eCB to O2. On the other
hand, its VB energy level (EVB ¼ þ2.69 V) is much lower than the
oxidation potentials of most electron donors (either organic or
inorganic compounds). Accordingly, the highly oxidative holes can
be transferred to the surface-adsorbed hydroxide groups or water
by devising a surface-bound hydroxyl radical. Generally, it can be
concluded that TiO2 encourages the redox transformation of pol-
lutants owing to the positions of its bands.
Fig. 3 displays the TiO2 crystal structure. TiO2 has three main
crystalline structures: anatase (tetragonal), rutile (tetragonal) and
brookite (orthorhombic). Anatase is the phase normally fabricated
in the sol-gel process but brookite is mostly found as a by-product
when precipitation is performed in an acidic medium at low tem-
perature. Rutile is a stable structure while both brookite and
anatase are metastable and usually transfigure to rutile when
heated.
Brookite is generally more reactive than anatase. However,
preparing pure brookite without rutile or anatase is rather difficult,
and therefore it has not been widely investigated (Di Paola et al.,
2013). Besides, anatase presents higher photocatalytic activity
compared to rutile because the higher ECB (~0.2 eV) results in
higher driving force for transferring electrons to O2. This is because
the ECB position affects electron transfer rate and consequently the
Fig. 2. Energy band gap diagram of a TiO2 spherical particle.
82 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94
Fig. 3. TiO2 crystal structure Anatase (a), Rutile (b), Brookite (c).
charge recombination rate. Therefore, it is a determining factor in
the efficiency of photocatalysis. It has always been reported that the
photocatalytic activity of both anatase and rutile structures is
highly influenced by the type of substrate applied (Serpone et al.,
1996; Du and Rabani, 2003; Ryu and Choi, 2007; Tryba et al., 2007).
The surface properties of TiO2, particularly the pH dependence
of the surface charge, are additional determinants of photocatalytic
reaction. TiO2 is known as a diprotic acid due to the amphoteric
nature of the surface hydroxyl groups. Accordingly, the surface
titanol group of this photocatalyst follows the following acidebase
equilibrium reaction:
Ti-OHþ þ
2 4 Ti-OH þ H (pKa1
Ti-OH 4 Ti-O þ Hþ (pKa2)
The average pKa is defined as the pH zero point of charge
(pHzpc), at which the surface charge of the photocatalyst is null. For
the TiO2 photocatalyst, pKa1 ¼ 4.5, pKa2 ¼ 8 and the pHzpc value is
estimated to be 6.2 (Carraway et al., 1994; Yogi et al., 2009).
Therefore, the protonation reaction takes place and the catalyst
surface is positively charged at pH < 6.2, while the catalyst surface
is negatively charged at pH > 6.2 due to the deprotonation reaction.
Apart from the mentioned properties of TiO2, this photocatalyst
is highly reactive during photocatalysis for water treatment and it
has great response even under weak light irradiation. However,
TiO2 is inappropriate for a mass processing system and is inactive
and inapplicable with visible light. Numerous efforts have been
proposed to overcome such limitations and enhance the photo-
catalytic activity of TiO2 through surface modification/complexa-
tion, sensitization, impurity doping, and heterojunction with
semiconductors of similar band gaps, etc.
As the suspension of TiO2 catalyst and water is irradiated with
UV light, the photo-induced electrons in the CB generally react with
dissolved oxygen and produce superoxide radical anions (O2
-).
Besides, the photo-induced holes in the VB diffuse to the TiO2
surface and react with the adsorbed water molecules, forming OH
.
In addition, this photocatalyst can easily be synthesized since it
is an industrially mass-produced material. The ease of applying
TiO2 is another advantage of this photocatalyst that encourages its
industrial application.
Although TiO2 decomposes pollutant compounds even under
weak light easily and fast, it is inactive and unsuitable for a mass
processing system under visible light. Therefore, TiO2 applications
are extremely limited especially with solar energy, since only 3% of
solar light is absorbed from solar energy. Moreover, the
photocatalytic activity of TiO2 depends on the relative degree of
branching of the reactive electronehole pairs into interfacial
charge-transfer reactions. Low surface area is one more limitation
of this photocatalyst.
4.1. Dopants effects on TiO2 photocatalyst
The most important effect of dopants is improved TiO2 elec-
tronic structure to eliminate its light sensitivity and broaden its
effective range from the ultra-violet range to visible light (Jaiswal
(15)
et al., 2012). Although doping techniques are susceptible to ther-
mal instability, they indicate excellent physicochemical properties,
(16)
such as small crystallite size, high specific surface area and high
crystallinity (Pongwan et al., 2016).
The rutile, anatase and brookite phases are the three main
crystalline phases of TiO2 (Reyes-Coronado et al., 2008). The rutile
and anatase phases are common crystallographic phases of TiO2,
with the latter particularly favoured for its exceptional thermody-
namic stability and high photocatalytic activity. The formation of
these phases or transformation from rutile to anatase or vice versa
is extremely dependent on the thermal dehydration mechanism
during which time TieOeTi bonds are formed by the interaction
between the protonated surfaces and eOH groups. Specific surface
area is another important characteristic that determines the
morphology of TiO2 in photocatalysis. The photocatalytic degra-
dation rate of organic pollutants is enhanced by the production of
doped TiO2 with large specific surface area, warranting the avail-
ability of active sites in TiO2. The crystallite size of TiO2 is one of the
aspects affecting the quality of TiO2, with large crystallite sizes up
to a certain limit enhancing the photocatalytic activity of TiO2
(Diebold, 2003).
With the presence of dopants in the formation of TiO2-doped
photocatalyst, the phase transformation from anatase to rutile is
eliminated when the thermal energy can overcome the nucleation
barrier during the dehydration process. In other words, the crys-
tallite size of TiO2 is suppressed by inserting dopants into the
octahedral lattice structure of doped TiO2, enhancing its physico-
chemical characteristics. In addition, the smaller crystals reduce the
recombination of the photogenerated charge carriers, hence, they
are favoured over larger ones. Furthermore, smaller doped TiO2
crystals induce a larger band gap due to the enhanced redox ability
(Jongnavakit et al., 2012). In short, doped TiO2 with a high anatase
percentage, small crystallite size and large specific surface area,
assists high photocatalytic activity.
 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94
5. Doping processes
In doping processes, the rapid charge recombination is retarded
and visible light absorption is enabled by defect states created in
the band gap. In the first case, recombination is inhibited and the
interfacial charge transfer is enhanced by the trapping of VB holes
or CB electrons in the defect sites. In the second case, electronic
transitions from the defect states to the CB or from the VB to the
defect states are allowed under sub-band gap irradiation. Metal
ions (transition metals and noble metals) and non-metal ions are
the two main categories of dopants. Generally, selective metals are
preferred since they have the potential to transfer electrons and
decrease the band gap energy level. For doped catalysts, metal ions
are activated in the presence of a light source, generating electron
holes. Therefore, the presence of metal ion dopant in the photo-
catalyst matrix significantly improves the interfacial electron
transfer and charge carrier recombination rates, which is followed
by greater photoreactivity. Among different metallic doping ele-
ments, copper has proven to be an effective dopant in enhancing
visible light absorption. For example, Park et al. (2013) modified
TiO2 by incorporating Ni2þ, Co2þ, Zn2þ and Cu2þ and reported that
Cu-doped TiO2 was a promising photocatalyst in the photo-
decomposition of methylene blue. Sangpour et al. (2010) modi-
fied TiO2 by doping with Ag, Au, and Cu and found that doping
increased the probability of radical formation. The photoactivity
levels of the investigated photocatalysts were reported to be in the
following order: Cu:TiO2 > Au:TiO2 > Ag:TiO2 > TiO2.
However, in the heterojunction process, the synergic effects of
two semiconductors with similar band gaps can result in low
recombination rate and increased electronehole pair lifetime. The
TiO2 photocatalyst can be potentially coupled with other semi-
conductors, e.g. SiO2, MoO3, CdS, MgO, WO3, SnO2, Cu2O, In2O3 and
ZnO (Wu al. 2006). Among different semiconductors, the photo-
catalytic activity of ZnO is quite similar to TiO2 and appears to be as
reactive as TiO2 under sunlight. Basically, the band gap of ZnO
(around 3.37eV) is close to the energy level of titanium dioxide
(Benhebal et al., 2013). According to the literature, the energy level
and surface area of TiO2 increase when it is mixed with another
photocatalyst. Besides, the light absorption range shifts towards
visible light due to the narrowing band gap energy level as TiO2 is
doped with a semiconductor catalyst (Liu et al., 2006).
TiO2/ZnO has been investigated by a number of researchers for
improving the photodegradation efficiency of TiO2 catalyst (Zhu
et al., 2004; Lakshminarayana et al., 2008). The ability of copper
in modifying the photoactivity of TiO2 (Kim et al., 2013; Pham and
Lee, 2014; Wang et al., 2014) and ZnO (Wu et al., 2012; Ahmad et al.,
2013) has been separately investigated in various works. The hybrid
photocatalyst of TiO2/ZnO with other metals has also been inves-
tigated in some studies (Wang et al., 2010a; Pant et al., 2013).
However, to the best of our knowledge, the hybrid CueZnO/TiO2
photocatalyst has not been studied yet.
5.1. Effect of metal doping
Photocatalytic efficiency generally depends on the generation of
electron-hole pairs that react with the species adsorbed on the
photocatalyst's surface. For doped catalysts, the metal ions are
activated in the presence of a light source, generating electron
holes. Therefore, the presence of metal ion dopants in the photo-
catalyst matrix significantly improves the interfacial electron
transfer rates and charge carrier recombination rates, which is
followed by greater photoreactivity. Metal dopants are also able to
improve the morphology of doped TiO2. To date, different metal
dopants, including iron (Fe) (Pang and Abdullah, 2013), zinc (Zn)
(Zhao et al., 2008), copper (Cu) (Xin et al., 2008), platinum (Pt) (Yu
83
et al., 2013), nickel (Ni) (Jing et al., 2005), manganese (Mn) (Deng
et al., 2011), barium (Ba) (Son et al., 2010) and cobalt (Co)
(Mugundan et al., 2015) have been analysed for their ability to
enhance the photocatalytic performance of nano-doped TiO2. They
improve doped TiO2 performance and increase its industrial ap-
plications by shifting the light absorption wavelength from the UV
to the visible light irradiation spectrum.
The properties of various metal dopants of TiO2 are summarized
in Table 1.
Among different transition metals such, as Cr, Fe, Ni, Zn, Co, (Zhu
et al., 2004a, 2006a,b; Schneider et al., 2014), Cu, copper with redox
potentials of 0.52 V (Cu2þ/Cu) and 0.16 V (Cu2þ/Cuþ) has been used
as a suitable modifier for various visible light-responsive photo-
catalysts (Sagar, 1996). Cu2þ (0.73 Å), Zn2þ (0.83 Å) and Ti4þ
(0.64 Å) have similar ionic radius parameters and therefore Cu2þ
can easily penetrate into TiO2 and ZnO matrices as deep acceptors
in conjunction with neighbouring oxygen vacancy or substituting
the positions of Zn2þ or Ti4þ. In addition, Cu doping shifts the ab-
sorption edges of both photocatalysts towards the visible region
(Mohan et al., 2012). Cu2þ directly traps the electrons generated
from the photocatalyst excitation in CueTiO2 or CueZnO. As such,
doping reduces the electron-hole recombination rate during pho-
tocatalysis by generating charge trapping sites.
Copper has been utilized more extensively as a dopant than
other transition metals. Sreethawong and Yoshikawa (2005)
compared the photocatalytic activity of Aue, Pde and Cu-loaded
mesoporous TiO2 in a single-step sol-gel process with a surfac-
tant template. Zhou et al. (2012) investigated the photocatalytic
activity of meso-tetraphenylporphyrin with different metal centres
(Fe, Co, Mn and Cu) on the surface of TiO2 and reported that
CuPeTiO2 presented the highest activity. In another work, Kaneco
et al. (2012) investigated the photocatalytic hydrogen production
of aqueous alcohol solution with ZnO/TiO2, SnO/TiO2, CuO/TiO2 and
CuO/Al2O3/TiO2, where the maximal hydrogen production was
obtained by using the latter. A few studies have also been con-
ducted on co-doping of TiO2 with copper and another metal/non-
metal dopant (Morikawa et al., 2006; Song et al., 2008; Trejo-
Tzab et al., 2012; Shamiri et al., 2016). Although incorporating a
dopant into the integrated structure of ZnO/TiO2 may yield
improved physical and chemical properties, very few studies have
focused on this. To the best of the author's knowledge, no study has
been conducted on the integration of copper into the TiO2/ZnO
structure to further support semiconductors.
Normally, metal-doped TiO2 products induce a greater anatase
phase presence, crystallite size of about 2.59e12.00 nm and specific
surface area ranging from 100 to 500 m2/g. Among the mentioned
metals, Cu has proven to improve the photocatalytic band gap of
CueTiO2 and CueZnO separately. This is attributed to the presence
of two electrons in the valence layer of Cu that enable electron
transfer (Khaki et al., 2016). Therefore, in the study copper (Cu) was
selected for doping TiO2/ZnO, as it has not been extensively
investigated so far.
5.2. Effect of non-metal doping
Non-metal anion doping has been widely applied to hinder the
recombination of photogenerated electron-hole pairs in nano-TiO2.
This is attributed to the electronic states of non-metals, which are
above the valence band edge of TiO2. Different non-metal dopants
like CeN-Codoped TiO2 (Yu and Jimmy, 2009), S,I-codoped meso-
porous TiO2 (Yu et al., 2010), WO3 Coupled PeTiO2 (Yu et al.,
2010a), F-doped anatase TiO2 (Yu et al., 2010b, 2012), sulfur (S)
(Yu et al., 2010), nitrogen (N) (Wanqin et al., 2013; Foo et al., 2015)
and carbon (C) (Fotiou et al., 2016) have been utilized owing to their
ability to modify the photocatalytic activity and morphology of
84 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94

Table 1
Properties of various metal dopants of TiO2.

Metal Metal/TiO2 (molar Synthesis method Starting material Starting material of metal Crystallite size Phase BET Surface area Ref
Dopant ratio) of TiO2 dopants (nm) (m2/g)

Fe 0.090 Hydrothermal TTB FeCl3,FeCl2 11.40 Anatase 101.40 (Asiltürk et al., 2009)
Fe 0.100 Hydrothermal (Ti(OC4H9n)4 Fe(NO3)3$9H2O 14.50 Anatase 102.00 (Tong et al., 2008)
Fe 1.200 Hydrothermal TiCl3 FeCl3$6H2O 23.70 Anatase 55.50 (Ambrus et al., 2008)
Fe 0.007 Sol gel TTB Fe(NO3)3 e Anatase 175.00 (Hung et al., 2007)
Fe 0.007 Sol gel/microemulsion TTB Fe(NO3)3 12.70 Anatase 83.00 (Ada
n et al., 2009)
Fe 0.980 Sol gel Ti(OPri)4 Fe(NO3)3$9H2O 9.00 Anatase 126.10 (Asiltürk et al., 2009)
Pt 0.800 Impregnation TiO2 Degussa P25 PtCl2 22.28 Anatase 29.17 (Sakthivel et al., 2004)
Pt 1.000 Impregnation TiO2 Degussa P25 H2PtCl6 20.00 Anatase 107.00 (Kozlova and
Photodeposition Vorontsov, 2007)
Pt 1.500 Impregnation TTIP H2PtCl6 31.00 Anatase 19.10 (Abe et al., 2006)
Pt 0.500 Photochemical TBOT H2PtCl6$6H2O 9.15 Anatase 116.10 (Sun et al., 2008)
deposition
Pt 1.500 Photochemical TNBT H2PtCl6$6H2O e Anatase 118.70 (Huang et al., 2008)
reduction
Ce 0.100 Sol gel TiCl4 H2PtCl6$6H2O 14.00 Anatase 68.00 (Ishibai et al., 2008)
Ce 0.010 Hydrothermal Ti(SO4)2 Ce(NO3)4 e Anatase 454.00 (Xiao et al., 2006)
Ce 4.000 Reflux Ti(OBu)4 Ce(NO3)4 8.30 Anatase e (Wang et al., 2010)
V 1.000 Sol gel Ti(OBu)4 VO(OPr)3 12.00 Anatase 107.00 (Bettinelli et al., 2007)

TiO2. The presence of non-metal anions generally enhances the
specific surface area, restrains the growth of crystallite size and
increases the anatase phase percentage in TiO2 photocatalyst. In
addition, non-metal anions influence the redshift in the absorption
spectra of doped TiO2 and broadens its band gap. Therefore, various
photoelectrochemical, photochemical and photocatalytic activities
of TiO2 are improved by transferring its wavelength sensitivity from
the ultraviolet region to the visible light region (Ansari et al., 2016).
A list of properties of various non-metal dopants of TiO2 is sum-
marized in Table 2.
5.3. Effect of metalloid and halogen doping
Recently, halogen doping techniques have attained much
attention due to their ability to substitute in the TiO2 structure as
well as to improve optical and surface properties. This technique is
usually employed to hinder the transformation of anatase to rutile
phase in TiO2edoped photocatalysts. Accordingly, different halogen
dopants, such as fluorine (F) (Yu et al., 2009a; Houshmand et al.,
2013), bromine (Br) (Wang et al., 2017) and iodine (I) (Zhang
et al., 2011) have been investigated in terms of modifying the
morphology and photocatalytic activity of TiO2. Boron (B) (Yu et al.,
2013a) and silicon are two common metalloids used to dope TiO2,
which can be termed either non-metal or metal.
Boron dopants are proven to increase the surface area of B-
doped TiO2, inhibit the growth of TiO2 crystalline structure and
induce the crystalline process. Some researchers contend that sil-
icon dopants increase the thermal stability of anatase and suppress
the transformation of anatase to rutile phase. A list of properties of
various metalloid and halogen dopants of TiO2 is summarized in
Table 3.
5.4. Effect of Co-doping
The highest improvement in TiO2 morphology is obtained by co-
doping technique with double metal or double non-metal dopants
or double metal/non-metal dopants (Zhiyong et al., 2007). Co
doping can affect dopant efficiency, electronic and magnetic
properties. It can improve the stability of desired defects and
enhance the solubility of dopants (Zhang et al., 2016). Co-doping
can increase the surface hydroxyl groups of TiO2 and restrain the
photo-generated electron/hole pair recombination, which results
in a big enhancement in the photocatalytic activity (Yu et al.,
2012a). The co-doping technique shifts the wavelength absorp-
tion of TiO2 from the ultraviolet to the visible light region, enhances
the morphological properties of crystallite size and surface area,
and withstands the anatase-to-rutile phase transformation
(Phattalung et al., 2017). Although TiO2 improvement is achievable
under visible light and an optimal doping level, beyond this level
the TiO2 activity may deteriorate (Huang et al., 2012). In 1994,
Bhargava et al. for the first time synthesized Mn-doped ZnS
nanocrystals (Bhargava et al., 1994). They reported that doped
nanocrystals of semiconductors can yield both high luminescent
efficiencies and lifetime shortening at the same time. In 2011, Segne
et al. studied the photocatalytic activities of visible light sensitive
TiO2 co-doping magnesium (II) and copper (II). The results showed
that co-doping of Mg2þ/Cu2þ into TiO2 shifts the absorbance band
of titanium dioxide from UV to visible region and the band gap

Table 2
Properties of various non-metal dopants of TiO2.

Metal Metal/TiO2 (molar Synthesis Starting material of Starting material of metal Crystallite size Phase BET surface area Ref
Dopant ratio) method TiO2 dopants (nm) (m2/g)

P 0.020 Hydrothermal TNBT H3PO2 14.50 Anatase 104.00 (Jin et al., 2009)
P 0.140 Sol gel TiO2 Degussa P25 H3PO4 8.60 Anatase/ 154.00 (Raj et al., 2009)
rutile
N 0.265 Hydrothermal TiO2 Degussa P25 TEA 15.40 Anatase/ e (Peng et al., 2008)
rutile
N 1.600 Hydrothermal TTIP CH3CH2NH2 25.40 Anatase e (Senthilnathan and
Philip, 2010)
S 1.500 Hydrothermal TiCl4, CS(NH2)2 30.00 Anatase e (Tian et al., 2009)
S 2.800 Hydrothermal TiS2 TiS2 2.80 Anatase e (Ho et al., 2006)
 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94 85

Table 3
Properties of various metalloid-and halogen dopants of TiO2.

Metal Metal/TiO2 (molar Synthesis Starting material of Starting material of metal Crystallite size Phase BET surface area Ref
dopant ratio) method TiO2 dopants (nm) (m2/g)

Metalloid
B 0.001 Hydrothermal Ti(OBu)4 NaBH4 2.59 Anatase 268.31 (Xiao et al., 2006)
B 9.000 Sol gel Ti(OBu)4 VO(OPr)3 6.00 Anatase 127.00 (Xu et al., 2009)
B 0.040 Sol gel TTIP H3BO3 e Anatase 219.00 (Zaleska et al.,
2008)
B 0.148 Sol gel TiO2 (C2H5O)3B 7.00 Anatase 192.00 (Grabowska et al.,
2009)
Si 0.111 Destabilization HFTA HFSA 6.50 e 155.00 (Estruga et al.,
2010)
Si 0.030 Hydrothermal Ti(OC4H9)4 (C2H5)4SiO4 8.20 Anatase 191.70 (Jin et al., 2009a)
Si 0.150 Templating TBOT TEOS 10.00 Anatase 120.00 (He et al., 2010)
Halogen
F 0.050 Hydrothermal Ti(OC3H7)4 NH4F e Anatas 48.00 (Yu et al., 2009a)
F 0.500 Hydrothermal TBOT NH4HF2eH2O 11.20 Anatas 122.00 (Sun et al., 2010)
F 0.770 Hydrothermal TIP NaF 10.00 Anatas 148.00 (Mori et al., 2008)
F 0.039 Sol gel Ti(C2H5O)4 CF3COOH 13.20 Anatas e (Todorova et al.,
2008)
F 0.190 Spray H2TiF6 H2TiF6 e Anatas 27.10 (Li et al., 2005)
pyrolysis
F 0.001 Sol gel Ti(OBu)4 NH4F 3.78 Anatas 169.48 (Xu et al., 2008)
I 0.033 Hydrothermal TTIP HIO3 5.50 Anatase/ 137.60 (Zhang et al., 2011)
brookite
I 0.117 Hydrothermal TNBT KI 4.46 Anatase 184.87 (Wang et al., 2011)
I 0.025 Sol gel Ti(OBu)4 HIO3 5.50 Anatase 259.10 (Ma et al., 2011)

energy is reduced from 3.2 eV to 2.50 eV (Segne et al., 2011). Besides, these semi-conductors share some advantages. TiO2 tends
Different ZnS-doped nanocrystals have been synthesized, including to have higher chemical stability while ZnO tends to have higher
ZnS:Cu (Zio
łczyk et al., 2014), ZnS:Cu, Al (Nguyen et al., 2011), conductivity than TiO2. TiO2 has a much higher dielectric constant
CdS:Mn/ZnS (Yang et al., 2004), ZnS:Mn (Karar et al., 2004), p-type and fewer defect states, which leads to less recombination, whereas
ZnS:N (Wang et al., 2013), ZnS: Cu and Sn (Prabhu et al., 2013), Y3þ ZnO can be easily nanostructured. Heterojunction photocatalyst
doped ZnS (Gayou et al., 2010) and ZnS/Al (Bitri et al., 2017). Among systems improve the photocatalytic behavior of doped photo-
different type of doped ZnS nanocrystals, ZnS activated with Cu catalysts. Heterojunction photocatalyst systems exhibit improved
ions is the most efficient cathodoluminescence phosphors (Zhang charge separations and increased lifetimes of the charge carriers
et al., 2016). In 2008, park et al. investigated cathodoluminescent (Fagan et al., 2016). In 2014 Rawal doped the W ions into the crystal
(CL) and thermal properties of green-emissive carbon nanotube lattice of SnO2 and conduction band was lowered position of SnO2.
(CNT)eZnS:Cu, Al phosphor composites. They found that the Coupling of W-Doped SnO2 and TiO2 can absorb a considerable
cathodoluminescent intensity of ZnS:Cu, Al phosphor coated with portion of visible light (Rawal et al., 2014). Fig. 4 shows the energy
optimal CNT concentrations of 0.75 wt.% with respect to the band diagram describing the photo-generated charge transport in
phosphor was about 1.6 times higher than the pure ZnS:Cu, Al the (W0.05Sn0.95O2, TTO5)/TiO2 heterojunction under visible light
phosphor (Park et al., 2008). irradiation.
Coupling of W-Doped SnO2 and TiO2 heterojunction shows a
significant activity of TTO5/TiO2 which is mainly attributed to the
5.5. Coupling of TiO2 with other semi-conductors inter-semiconductor hole transport mechanism (Rawal et al., 2014).
Fig. 5 shows the visible-light photocatalytic efficiencies of the
Different dopant categories for improving TiO2 morphology, photocatalytic sample 2-propanol (IP).
crystallinity, surface area and photocatalytic activity have been In the TiO2/ZnO heterojunction, the conduction band (CB) of
introduced and investigated. One technique of making TiO2 suitable
for receiving and utilizing visible light and improving its
morphology is to couple it with another semi-conductor such as
SiO2, MoO3, CdS, MgO, WO3, SnO2, Cu2O, In2O3 or ZnO (Wu et al.,
2006). According to the literature, the energy level and surface
area of TiO2 increase by mixing it with another photocatalyst. Be-
sides, the light absorption range shifts towards visible light due to
the reduction of band gap energy level when TiO2 is doped with a
semiconductor catalyst (Liu et al., 2006). Its photoactivity can then
be improved by reducing the recombination rate of the electro-
nehole pairs and by enhancing the interfacial charge transfer ef-
ficiency (Jongnavakit et al., 2012).
Among diverse semiconductors, ZnO is a suitable alternative for
coupling with TiO2 as it has similar band gap energy (around
3.37 eV) and hence similar photocatalytic activity. Moreover, it is
low-cost and satisfies the performance in the degradation of
several organic contaminants (Benhebal et al., 2013). It has addi- Fig. 4. Energy band diagram describing the photo-generated charge transport in the
tionally been found that ZnO is as reactive as TiO2 under sunlight. TTO5/TiO2 heterojunction under visible light irradiation (Rawal et al., 2014).
86 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94

Fig. 5. Visible-light photocatalytic activities of TiO2, TTO5, and several TTO5/TiO2

composites in removing IP (Rawal et al., 2014).

ZnO is positioned above the conduction band of TiO2 and valance

band of ZnO is positioned between the valance band and conduc-
tion band of TiO2, which suppresses the recombination of electron
hole pair and promotes the separation of this pair, improving the
Fig. 6. FT-IR spectra of 3% BeTiO2 samples with different calcination temperature
photocatalytic activity consequently (Khaki et al., 2016). The com-
(Zhang et al., 2012).
bination of TiO2 and ZnO offers a wide range of advantages and is
the most suitable candidate for widespread environmental appli-
cations due to chemical and biochemical inertness, strong oxida- optimal temperature for calcination, beyond which the photo-
tion power, long-term stability against chemical and/or photo- catalytic activity may be reduced due to the agglomeration of
corrosion and cost effectiveness. Doping of Cu in TiO2/ZnO shifts particles that decreases the specific surface area of the photo-
the absorption edges to the visible region. Copper directly traps the catalyst. High calcination temperature induces the replacement of
electrons generated from the excitation of doped CueZnO or nitrogen by oxygen in the air. Therefore, photocatalyst absorption
CueTiO2 catalyst. The doping process with the generation of charge in the visible light region decreases, followed by a decrease in TiO2
trapping sites reduces the electron-hole recombination rate during activity. Zhang et al. studied the effects of calcination temperature
photocatalysis. on Boron-Doped TiO2 samples within a range of temperature from
300 to 600  C. Photocatalytic degradation of methyl orange activity
6. Operational factors affecting the photocatalytic was 96.7% after 90 min of UV-light irradiation (Zhang et al., 2012).
degradation Figs. (6) and (7) show the FT-IR spectra of B doped TiO2 with
different calcination temperature and degradation of methyl or-
Doping of TiO2 with various types of transition metals can ange solution during irradiation in the presence of 3% BeTiO2.
produce impurity states between the valance and conduction
bands, which causes band gap narrowing and increased photo-
6.2. Effect of dopant concentration
efficiency of TiO2 (Lei et al., 2015). The preparation methods in-
fluence the photocatalyst structure and activity. TiO2 doped with
The photocatalytic activity of photocatalysts has been found to
metal ions used in the sol-gel technique offers many advantages,
be directly and extremely proportional to dopant concentration
such as flexibility of introducing dopants in large concentrations,
(Murashkina et al., 2015). However, beyond an optimal amount of
homogeneity and ease of processing (Zhang et al., 2012). Dopant
dopant in the photocatalyst structure, the photocatalytic perfor-
concentration and calcination temperature affect the photocatalyst
mance decreases. Cui et al. (2016) studied photocatalytic activity of
structure by changing the crystal size, particle size, surface area and
Sn1xAgxS2 doped by the degradation of methylene blue under
band gap energy level (Heshan et al., 2008).
solar light irradiation. They found that increasing the amount of Ag
In general, the doping technique is an effective method of
dopant concentration can effectively increase the solar light
improving the morphology and activity of TiO2. However, different
adsorption efficiency of the photocatalyst (Cui et al., 2016). More-
parameters may affect the efficiency of this method and are
over, Eyasu et al. (2013) synthesized photocatalysts Chromium
explained subsequently.
doped ZnS nano-size semiconductor xCr-ZnS (x ¼ 0.05, 0.1, 0.2 &
0.3 mol%). They studied the effect of dopant Cr concentration in
6.1. Effect of calcination temperature of nano-doped-TiO2
CreZnS on photocatalytic degradation of methyl orange dye under
visible radiation. They found degradation of the dye decreased with
Calcination is a thermal process in the presence of oxygen or air
increasing of dye concentration. Highest dye degradation was
that is commonly applied in the formation of photocatalysts in
dopant concentration 0.2 mol % (Eyasu et al., 2013). Dopant con-
order to facilitate phase transition, thermal decomposition, or the
centration at 5 h is shown in Fig. 8.
removal of a volatile fraction (Yu et al., 2009; Changlin et al., 2011).
Accordingly, applying calcination to doped-TiO2 formation can also
improve its photocatalytic activity, morphology, surface area and 6.3. Effect of initial pollutant concentration
crystallinity properties as well as the photocatalyst's optical ab-
sorption (Reli et al., 2012; Zhang et al., 2012). However, there is an The effect of the initial reactant concentration is a determining
 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94
Fig. 7. Absorption spectra of methyl orange solution during irradiation in the presence
of 3% BeTiO2 (Zhang et al., 2012).
Fig. 8. Plot of % degradation of MO vs. dopant concentration (x in mol%) at 5 h over
using xCr-ZnS photocatalyst (Eyasu et al., 2013).
factor in the photocatalytic activity of doped TiO2 in pollutant
degradation. The relationship between the photocatalytic activity
of TiO2 and initial reactant concentration is affiliated with the
adsorption of reactant on the photocatalyst surface and the
screening effect due to reactant overloading. The photocatalytic
activity of TiO2 normally decreases as the initial reactant concen-
tration increases (Eyasu et al., 2013). This may be attributed to the
limited number of active sites available on the photocatalyst sur-
face. Degradation of methyl orange at varying dye initial concen-
tration (10  105 to 75  105 M) using fixed amount (0.5 g/
100 ml) of catalyst (Cr(0.2 mol%)eZnS) are presented in Fig. 9. Apart
Fig. 9. Plots of % photocatalytic degradation of MO under visible radiation as a function
of irradiation time (in hr) at varying dye initial concentration using fixed amount
(0.5 g/100 ml) of catalyst (Cr(0.2 mol%)eZnS) and pH(¼7) (Eyasu et al., 2013).
87
Fig. 10. Photocatalytic degradation at different initial concentration of RR4 using C N
co-doped TiO2eP25 sample (Azami et al., 2016).
from that, the effect of initial dye concentration on the photo-
catalytic efficiency is shown in Fig. 10. Photocatalytic activity of RR4
dye decreased with increasing RR4 dye concentration (Azami et al.,
2016).
6.4. Effect of photocatalyst concentration
Employing an optimum photocatalyst concentration minimizes
cost and energy while maximizing photocatalytic performance
(Saggioro et al., 2011). However, it has frequently been reported
that increasing the photocatalyst concentration enhances the
number of photons absorbed on the photocatalyst surface, and
subsequently increases the generation of electron-hole pairs and
the number of hydroxyl radicals. Nonetheless, the amount of
organic pollutants adsorbed on the photocatalyst surface increases,
which contributes to higher degradation efficiency (Kaur and
Kansal, 2016). Table 4 presents the effects of photocatalyst con-
centration and operational conditions on the degradation of in-
dustrial pollutants.
For a photocatalyst to be highly efficient in pollutant degrada-
tion, it should possess a low band gap energy level and high specific
surface area. The best way to increase the adsorption capacity of
zinc oxide and titanium dioxide is to use a support with reduced
energy, high porosity and high surface area. According to Table 4,
Bi3þ, Bi2WO6, Mn and Cu-doped TiO2 and ZnO display high pho-
tocatalytic efficiency (Bettinelli et al., 2007; Huang et al., 2008;
Karunakaran et al., 2013; Kaur and Kansal, 2016). Degradation re-
sults showed that copper-doped TiO2 enhanced the photoactivity.
Moreover, incorporating Cu2þ into the TiO2 crystal structure as Cu-
doped TiO2 demonstrated high activity under visible light. Nano-
crystal Mn-doped TiO2 displayed high photocatalytic activity under
UV and visible light, where the range of methylene blue degrada-
tion was 99%. Bi3þ-doped TiO2 with the sol-gel process boosted
methyl parathion degradation under UV light by 97%. In the case of
copper-doped TiO2, results indicated that Cu/TiO2 boosted methy-
lene blue degradation by over 95% under visible light. Cu-doped
ZnO calcined at 600  C achieved the highest photoactivity under
UV and visible light.
6.5. Preparation methods of doped-photocatalysts
The effect of doping on photocatalytic activity depends on the
88 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94

Table 4
Effect of photocatalyst concentration and operational condition on degradation of industrial pollutant.

No Doped catalyst Target pollutant Operational condition Out come Ref

UV concentration pH T ( C) TOC COD Photocatalytic degradation

1 CoeTiO2 2-chlorophenol 228 420 nm 22  C 10e50 mg/L _ _ Highest degradation at 600  C (Ad
an et al., 2009)
2 Mn-dopdTiO2 methylene blue 310-400 nm 24e27  C 100 mg _ _ 99% reduction rate (Abe et al., 2006)

3 VeTiO2 2.8 g/l methylene blue 420 5.5 25 C 2.8 g/l _ _ Decrease15-30% (Sun et al., 2008)
4 BeTiO2 2.8 g/l methylene blue 420 5.5 25  C 2.8 g/l _ _ Decrease 2e3% (Sun et al., 2008)
5 TiO2eCu methylene blue 665 6.5 25  C 10 mg _ _ degradation >95% (Liu et al., 2005;
Carvalho et al.,
2013)
6 PreTiO2 phenol 365 577 6.5 6.8 25  C 0.2e1.0 g/L 99 -50% degradation (Huang et al., 2008)
7 TiO2eCu phenol 365 _ 25  C 1 g/l _ _ Best photocatalytic activity (Hung et al., 2007)
calcined at 600  C

8 V5þeTiO2 chlorpyrifos 350e400 5.89 25 C 0.1% _ _ least activity (Ishibai et al., 2008)

9 Th4þeTiO2 chlorpyrifos 350e400 5.89 25 C 0.06% _ _ highest activity (Ishibai et al., 2008)

10 Mo6þeTiO2 chlorpyrifos 350e400 5.89 25 C 0.06% _ _ highest activity (Ishibai et al., 2008)

11 Zn2þeTiO2 Congo Red (CR) 456 _ 25 C 100 mg _ _ 78% (Xiao et al., 2006)

12 V5þeTiO2 Congo Red (CR) 456 _ 25 C 100 mg _ _ 44% (Xiao et al., 2006)

13 NeTiO2 methylene blue 400 _ 25 C 100 mg _ _ 87%, 93% and 95% (Wang et al., 2010)

14 CueZnO methylene blue 200e800 _ 25 C 0.5% mol _ _ highest photocatalytic activity (Bettinelli et al.,
2007)
15 Er3þeTiO2 methylene blue 365 _ 25  C 0.1 g _ _ 50% (Jin et al., 2009)
16 SneTiO2 penicillin solution 365 _ 25  C 0.1 g _ _ 3 mol.% mol of photocatalyst (Raj et al., 2009)
have a high activity
17 Ne TiO2 Azo Dyes 250e450 _ 25  C 10 mg l_1 60% _ 95% (Liu et al., 2005)
18 ZrO2eTiO2 phenol 365 6.2 25  C _ _ _ 54%, 61% and 62% (Senthilnathan and
Philip, 2010)
19 Fe3þeTiO2 phenol 365 5 25  C 0.5 mol% _ _ 55.2%e65.68% (Tian et al., 2009a)
20 Fe3þeTiO2 real textile 35 kHz 3e11 25  C 6 g/L 49.8% 59.4% 79.9% (Ho et al., 2006)
wastewater
21 Bi3þ- TiO2 methylparathion 365 _ 25  C 0.25 g _ _ 97% (Xu et al., 2009)
22 ZneTiO2 Methylene blue 352 _ 25  C _ _ _ 46.3e91.4% (Zaleska et al.,
2008)
23 FeeTiO2 Azo Dyes 400 6.5 35  C 0.5 g L1 _ _ 60% (Grabowska et al.,
2009)
24 Yttrium-TiO2 methyl orange 365 <3>4 25  C 50 ml _ _ 20% (Estruga et al.,
2010)

25 Sm3þeTiO2 Methylene blue 664 _ 25 C 200 mg _ _ 73.90% (Jin et al., 2009a)

26 PdeZnO Methyl orange 365 7 25 C 50 mg _ _ 48.2% (He et al., 2010)

27 FeeTiO2 Dye _ _ 25 C _ _ 33% _ (Li et al., 2010)

28 Ag/FeTiO2 phenol 420 nm _ 25 C _ _ _ 0.50Ag/FeTiO2 highest activity (Peng et al., 2008)

29 (NFeTiO2) 6-hydroxymethyl 350, 420, 3e9 22 C 0.05 g/L _ _ readily degraded under UV (Zhao et al., 2014)
(PFeTiO2) uracil 450 nm
(SeTiO2)
(6-HOMU)
30 TiO2 suspension Aromatic 350 nm 0.1 M 25  C 0.010 0.0082 g/L _ _ Under acidic and neutral (Zheng et al., 2014)
organoarsenic conditions strong adsorption is
compounds observed
31 CueTiO2 bisphenol A visible-light 5.5 25  C 10 mg/L. _ _ CueTiO2 effective photocatalyst (Chiang and Doong,
for degradation of BPA under 2014)
visible light
32 CeTiO2 cyanotoxins 238,262 nm 5.8 25  C 5 ml _ _ The degradation under UV-A, (Fotiou et al., 2016)
followed first-order kinetics
33 TiO2eN DMP 400-600 nm 6.5 22 ± 2  C (0.015 g/L, 100 ml). _ _ high photocatalytic (Wanqin et al.,
degradation activity of N/TiO2 2013)

34 Bi2O3/Bi2MoO6 2,4-dinitrophenol 360 nm 3e11 25 C 2.5 _ 10_5 mol/L _ _ degradation of persistent (Ma et al., 2014)
organic pollutants, and effects
of H2O2
35 Bi2WO6 levofloxacin drug 400e520 nm 3e11 25  C 100 mL _ _ 80% degradation (Kaur and Kansal,
2016)
36 NeTiO2 spiramycin 400e550 nm 6 20-30  C 100 mL _ _ final TOC removal reached a (Vaiano et al., 2015)
value of about 48%,
4þ  3
super oxide radicals (O2 ) was (Carevi



37 Zirconia/Si trichlorophenol 550 nm 7 21 C 40 cm _ _ c et al.,
main source of photocatalytic 2016)
activity

type of compound as well as method employed (Colon et al., 2006).
Preparation methods used for catalyst doping include sol-gel
(Barakat et al., 2005), microemulsion (Ad
an et al., 2007), co-
precipitation (Anandan et al., 2007), hydrothermal process
(Asiltürk et al., 2009) and solvothermal synthesis (He et al., 2013).
Nevertheless, the advantages derived from synthesis of TiO2-
based-photocatalyst by solegel method, which include synthesis of
nano-sized crystallized powder of high purity at atmospheric
pressure, relatively low temperature, possibility of stoichiometry
controlling process have suggested by many researchers.
6.6. Sol-gel method
A lot of research has reported the use of the sol-gel method for
 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94 89

catalyst doping (Alem and Sarpoolaky, 2010; Akpan and Hameed,
2011). The solegel process has been successfully employed in
preparing glassy materials, ceramic powders, and dense or porous
ceramic pieces, as well as for thin film deposition and biosensor
construction (Chiang and Doong, 2014). The materials obtained
from these processes can also be used in selective heterogeneous
catalysis, which represents an area of great economical interest.
Nowadays, solegel methods are well-established, as they allow the
preparation of a broad variety of supported metals, metal oxides,
coatings and composite materials with tailored properties. The
solegel process has been applied in preparing supported metal
catalysts and catalyst supports with higher thermal stability and
resistance to deactivation while providing better flexibility in
controlling catalyst properties, such as particle size, surface area
and pore size distribution. Many authors have suggested solegel as
the best means of dispersing catalytic metals in gels with fine
texture (Goncalves et al., 2006).
Solegel is a wet-chemical technique and one of the most widely
used means of photocatalysts preparation (Bellardita et al., 2010).
This method is mainly used to produce catalyst powders or thin
films. A brief schematic diagram of this process is presented for
TiO2-based photocatalysts in Fig. 11.
Generally, the sol-gel method is inexpensive, easy to operate
and often achievable at low operational temperatures. This process
can easily be used for the deposition of substrates that have large
surface areas or complex surfaces. The sol-gel method is usually
started with a chemical solution that behaves as a precursor for an
integrated gel (or network) of either network polymers or discrete

Water/
Dopant

TiO2-base TiO2- Hydrolyzed Drying/

Sol-gel
reactant alcoholate Sample Calcination

Alcoholic Acidifying
reagent reagent

Fig. 11. Process of Sol-gel method.

Table 5
Sol gel method for preparation doped catalyst.

Doped catalyst Material and conc Parameter Catalyst characteristics Ref

T ( C) pH SA m2 g_1 BG CS nm PS nm

CoeTiO2 Co(III)0.0040.14 mol% TiCl4 98% 200e900 e 39.7 e e 25 (Barakat et al., 2005)
Mn-dopdTiO2 Mn (II) 0.1 M Ti(OCH(CH3)2)4 700 7 38 e 20e30 e (Binas et al., 2012)
VeTiO2 Ti(OBu)4 6.0 ml 500 e 139 e 10.5 e (Bettinelli et al., 2007)
BeTiO2 Ti(OBu)4 17.0 ml 450 e 107 e 12 e (Bettinelli et al., 2007)
TiO2eCu Ti(O-Pr)4 5 ml CuSO4$5H2O 170 mg 400 e _ e 107 e (Carvalho et al., 2013)
500
PreTiO2 (Ti[iso-OC3H7]4 0.12 mol 100 1.8 40 2.80 and 3.10 eV e 10e50 (Chiou and Juang, 2007)
800
TiO2eCu TTIP 10 ml, Cu(NO3)2 0.5 M% 400 e 2 3.00 34 e (Colon et al., 2006)
800
5þ
V eTiO2 TiCl4 25 ml [NH4VO3] 550 7e8 24 2.7 28.42 e (Devi et al., 2009)
Th4þeTiO2 TiCl4 25 ml [Th(NO3)4] 550 7e8 32 3.00 30.28 e (Devi et al., 2009)
Mo6þeTiO2 TiCl4 25 ml (NH4)6Mo7O24$4H2O 550 7e8 22 2.7 29.38 e (Devi et al., 2009)
Zn2þeTiO2 TiCl4 25 ml 550 7e8 31 2.8 15.6 e (Devi et al., 2010)
V5þeTiO2 TiCl4 25 ml 550 7e8 24 2.8 28.4 e (Devi et al., 2010)
NeTiO2 Titanium (IV) Na2EDTA 500 e 58 3.06 e 9.6 (Elghniji et al., 2012)
CueZnO Zn(CH3COO)2$2H2O 0.3 M Cu(CH3COO)2$H2O 400 e e e 3.294 e (Jongnavakit et al., 2012)
Er3þeTiO2 Ti[O(CH2)3CH3]4 3.5 g ErCl3 500 e e 3.09 10.0 e (Lee et al., 2012)
SneTiO2 Ti(OC4H9)4(AR) 5 ml 450 9 399 3.6 e e (Li et al., 2009)
FeeTiO2 Ti(OC4H9)4 Fe(NO3)3 500 7e8 338.7 _ e e (Li et al., 2010)
Ag/FeTiO2 Ti(OBu)4) Ag(NO3) 623 K e 179.6 2.35 5.2 e (Lin et al., 2012)
NeTiO2 Ti[OCH (CH3)2]4 9 ml 400 e e e e 10 (Liu et al., 2005)
ZrO2eTiO2 Ti(OCH2CH2CH2CH3)4 14 ml Ti:acac, (Zr(acac)4) 400 e 140.4 e 1.8 e (McManamon et al., 2011)
1000
Fe3þeTiO2 TBOT 0.1 mol Fe(NO3)3 _9H2O 450 e e e 8.3 e (Naeem and Ouyang, 2010)
Fe3þeTiO2 Ti(OBu)4 Fe(NO3)3$9H2O 500 3 167.6 2.70 e 10 (Pang and Abdullah, 2013)
Bi3þeTiO2 Ti(OeBu)4 21 ml 500 e e e 16e22 e (Rengaraj et al., 2006)
ZneTiO2 TTIP ZnSO4$7H2O 450 e 101.27 e 14.03 e (Nguyen et al., 2012)
FeeTiO2 (Fe(NO3)3$9H2O TTIP 8.87 mL 200 e 118 3.06 8.91 e (Vargas et al., 2012)
Yttrium-TiO2 (Y(NO3)3$6H2O) Ti(OBu)4 10 ml 823 K e 69.0 e 11.5 e (Yajun et al., 2011)
Sm3þeTiO2 (Ti (OPri)4) Sm (NO3) 3 600 6e7 82.94 e 12.80 e (Xiao et al., 2008)
PdeZnO Zn(O2CCH3)2 Pd(NO3)2 773 K e 6.49 e 33 e (bo Zhong et al., 2012)
90 M.R.D. Khaki et al. / Journal of Environmental Management 198 (2017) 78e94
particles (Akpan and Hameed, 2011; Shamiri et al., 2014). Metal
alkoxides such as TiO2 can be precursors. In fact, a gel-like diphasic
system prepared with this method contains both solid and liquid
phases. In the last step, the solvent should be removed from the
produced structure through a drying process, which is accompa-
nied by notable densification and shrinkage. The distribution of
porosity in the gel is a determinant factor in the drying process. The
final microstructure is prominently affected by changes imposed
upon the structural template during drying. Afterwards, a firing
process, or thermal treatment, is applied in order to enhance the
structural stability and mechanical properties. Different types of
solegel and related methods of TiO2 doping include co-doping,
alkaline earth metal ions, rare earth metal ions, transition metal
ions and other metal/non-metal ions. A brief list of applications and
efficiency of TiO2-based photocatalysts prepared through the sol-
gel method is presented in Table 5.
As mentioned, co-doping of TiO2 improves the catalyst's pho-
tocatalytic activity in most cases (Kim et al., 2013). Doping TiO2
with alkaline earth metals through the sol-gel method also pro-
vides better photocatalysis for TiO2 than through the co-
precipitation method. On the contrary, TiO2 doping with transi-
tion metals is not useful for photocatalytic efficiency, except in very
few cases.
Coupled semiconductor photocatalyst of TiO2/ZnO has been
investigated by a number of researchers for improving the photo-
degradation efficiency of TiO2 catalyst (Tian et al., 2009). Besides,
the triple complex of TiO2/ZnO with some metals has also been
investigated in a few studies. However, based on the knowledge of
the author, the triple complex of CueTiO2/ZnO has not yet been
studied. Cu appears to improve the photocatalytic band gap of
CueTiO2 and CueZnO separately. This is attributed to the presence
of two electrons in the valence layer of Cu, which enables electron
transfer. In particular, in a previous study (Khaki et al., 2016), TiO2
was doped with both ZnO and Cu in parallel. The main aim was to
reduce the band gap energy of CueTiO2/ZnO in order to improve its
activity. Therefore, a new hybrid photocatalyst, namely Cu-doped
TiO2/ZnO nano-catalyst was fabricated by entrapping copper ions
in the crystalline matrix of TiO2 and ZnO through the sol-gel syn-
thesis method. The new doped photocatalyst is calcined at two
different temperatures of 500 and 700  C. The photoactivity of Cu-
doped TiO2/ZnO is then evaluated through the degradation of
methyl orange (MO) and methylene blue (MB) under visible light
irradiation (Khaki et al., 2016).
7. Photocatalytic performance
Dopants, such as metals, non-metals, metalloid, and halogens
have been added to the TiO2 photo catalyst to improve its response
and reduce the recombination of photogenerated holes and elec-
trons (Abe et al., 2006; He et al., 2010; Yalçın et al., 2010; Gao et al.,
2011; Aguilar et al., 2013; Wang et al., 2013). The main objective of
doping is decreasing of the band gap energy level, for using of
visible light absorption (Eyasu et al., 2013). Various types of tran-
sition metals, non-metals and metalloid doped, can be easily
incorporated into the crystal lattice of titanium dioxide and zinc
oxide (Zhang et al., 2016). The degradation of organic pollutant is
usually faster in doped systems, because the oxidation of organic
pollutant consumes photo-excited holes efficiently and promptly
and, therefore attenuating electronehole recombination (Saggioro
et al., 2011). As seen in Table 4., nitrogen and fluorine (NF), phos-
phorus and fluorine (PF) and sulfur (S) doped TiO2 for degradation
of 6-hydroxymethyl uracil (6-HOMU) under UV and visible light
follow a pseudo-first-order kinetic model (Zhao et al., 2014; Yusoff
et al., 2014). The results showed a high photocatalytic activity.
Various types of Non-metals doped, such as NeTiO2 and CeTiO2
have been used for degradation of spiramycin (Vaiano et al., 2015),
dimethyl phthalate (Wanqin et al., 2013) and cyanotoxins (Fotiou
et al., 2016). The results showed a high photocatalytic degrada-
tion activity under UV and visible light and also reaching very high
values of TOC removal (approximately 48%). Another explanation
for metal doped titanium dioxide; TiO2 particles can be easily
doped by Cu with sol gel method, affecting the high photocatalytic
activity on degradation of bisphenol An under ultraviolet- and
visible-light (Chiang and Doong, 2014) and organoarsenic com-
pounds, 4-hydroxyl-3-nitrophenylarsenic acid (Roxarsone, ROX)
and 4-aminophenylarsonic acid (p-arsanilic acid, p-ASA) (Zheng
et al., 2014). In another study, 2,4-dinitrophenol and levofloxacin
drug has been degraded by using Bi2O3/Bi2MoO6 composites (Ma
et al., 2014), and Bi2WO6 nanocuboids (Kaur and Kansal, 2016). It
was shown that the photocatalytic activity of Bi2WO6 photocatalyst
enhanced after doping. Approximately 80% degradation of the drug
was achieved in 150 min. The photocatalytic activity of Bi2O3/
Bi2MoO6 increased with the addition of H2O2 (5.0 mmol/L), and
consequently the photocatalytic activity was improved.
8. Conclusion
Non-biodegradable organic waste entails compounds that
cannot be naturally recycled into the life cycle, as they cannot break
down into natural components. Advanced Oxidation Technology
(AOT) is a robust treatment process for wastewater including non-
biodegradable compounds. Four different methods are employed
with AOTs to generate hydroxyl radicals and treat wastewater,
which include (i) ozone treatment, (ii) electrochemical processes,
(iii) direct decomposition of water, and (iv) photocatalysis. Among
the various AOPs, heterogeneous photocatalytic processes are
suitable for eliminating a broad range of pollutants at ambient
temperatures and pressures without generating harmful in-
termediates. The photocatalysis reaction was presented and TiO2
was introduced as one of the most efficient photocatalysts. Subse-
quently, the effects of different parameters (e.g. dopants and
operational parameters) on TiO2 were investigated. Furthermore,
different types of dopant (e.g. metal, non-metal, metalloid and
halogen, co-doping) and coupling of TiO2 with other semi-
conductors were investigated. In terms of operational parameters,
the effects of calcination temperature on nano-doped TiO2, dopant
concentration, initial reactant concentration, and photocatalyst
concentration, and preparation methods of doped photocatalysts
were outlined. TiO2 and ZnO have wide band gaps of around 3.2eV
and 3.3 eV at room temperature, hence they are mainly used under
ultraviolet (UV) irradiation. TiO2 and ZnO photocatalysts also have
the potential to be employed under visible light for greater energy
efficiency. The photocatalytic activity of TiO2 and ZnO can be
improved by reducing the band gap energy level. Metal-doped
TiO2/ZnO nano-size particles such as Ag, Fe, Mo and Cu can
enhance photocatalytic activity. Silver (Ag) is one of the metals with
beneficial influence on photocatalytic activity. According to Table 5,
the Ag/FeTiO2 complex reduces the band gap energy level to
2.35 eV.
Acknowledgement
The authors are grateful to the University of Malaya High Impact
Research Grant (HIR-MOHE- D000038-16001) from the Ministry of
Higher Education, Malaysia which financially supported this work.
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