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Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52

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Journal of Photochemistry and Photobiology A:


Chemistry
journal homepage: www.elsevier.com/locate/jphotochem

Photoelectrocatalytic technologies for environmental applications


R. Daghrir a,1 , P. Drogui a,∗ , D. Robert b,2
a
Institut National de la Recherche Scientifique (INRS-Eau Terre et Environnement), Université du Quebec, 490 rue de la Couronne, Quebec City, Quebec, Canada G1K 9A9
b
Antenne de Saint-Avold du Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse (LMSPC), CNRS-UMR 7515, France

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

Article history: This paper summarizes recent research works dealing with the development of photoelectrocatalytic
Received 31 January 2011 oxidation technologies combining both electrolytic and photocatalytic processes. Photoelectrocatalytic
Received in revised form 27 March 2012 technologies have received particular attention due to their potential and effectiveness in the photodegra-
Accepted 16 April 2012
dation of refractory organic and microbial pollutants present in water and wastewater. Here, titanium
Available online 21 April 2012
dioxide (TiO2 ) plays the most important role compared to other semiconductor photocatalysts (CdS, ZnO,
SnO2 , etc.) due to its excellent chemical and physical properties. The recombination of the photogenerated
Keywords:
electrons and holes is the main factor that generally limits the application of photocatalytic processes
TiO2 photocatalyst
Photoelectrocatalytic degradation
(PCPs) in the environmental field. Considerable efforts have been made to increase the photocatalytic effi-
Catalytic electrode ciency and decrease the charge recombination by means of photoelectrocatalytic processes (PECPs), also
Water purification referred to as electrochemically assisted photocatalytic processes, which consists of applying an external
potential on photocatalysts. This paper deals with the mechanism of photoelectrocatalytic processes,
the characteristics and methods for preparing a TiO2 electrode, the irradiation sources, and the types
of reactors used. Moreover, the key factors affecting the photoelectrocatalytic oxidation efficiency are
discussed, including the applied electrical potential, light intensity, pH, dissolved oxygen concentration,
electrolyte concentration, and temperature. Finally, the paper emphasizes the recent applications of pho-
toelectrocatalytic processes and suggests new research directions for the development of this promising
technology.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction total mineralization of water contaminants. Biological oxidation


is considered to be very economical and widely applicable. How-
Treatment of a range of recalcitrant contaminants derived from ever, the presence of toxic and refractory pollutants in water and
agricultural processes (herbicides, pesticides, etc.), sewage (oestro- wastewaters makes this latter method inappropriate in many cases.
gens, pathogens, etc.), industrial effluents (phenolics compounds, Conventional methods such as ultrafiltration and adsorption using
etc.) and natural runoff (soil and plant derived colorants) is a activated carbon have been applied to remove refractory organic
significant challenge throughout the world. Oxidation processes compounds. The main disadvantage of such methods is that they
(physical, chemical or biological) are one of the main steps in do not destroy the pollutants but rather transfer the pollutant from
water treatment [1]. Chemical oxidation using several oxidants one phase to another [2,3].
such as chlorine, hydrogen peroxide and ozone rarely leads to a Advanced oxidation processes (AOPs) have been proposed as
alternative methods for the elimination of many toxic organic com-
pounds in wastewaters, air and soil. As such, they are used for the
elimination of biorecalcitrant compounds in wastewater [4–7]. The
Abbreviations: AOPs, advanced oxidation processes; CB, conduction band; COD, principle of AOPs (including O3 /H2 O2 , UV/O3 , UV/H2 O2 , H2 O2 /Fe2+ ,
chemical oxygen demand; CTC, chlortetracycline hydrochloride; DP, direct photol- and UV-TiO2 ) is to produce hydroxyl radical in water, a very power-
ysis; EAOPs, electrochemical advanced oxidation processes; E. coli, Escherichia coli; ful oxidant capable of oxidizing a wide range of organic compounds
EO, electrochemical oxidation; PCP, pentachlorophenol; PCPs, photocatalytic
with one or many double bonds [8–11]. Although photocatalytic
processes; PECPs, photoelectrocatalytic processes; PEO, photoelectrocatalytic oxi-
dation; PO, photocatalytic oxidation; PLD, pulsed laser deposition; Pt, platinum; process (UV-TiO2 ) using semiconductor as photocatalyst under UV
PZC, point of zero charge; RVC, reticulated vitreous carbon; SCE, saturated calomel illumination has been extensively studied, its practical exploita-
electrode; TOC, total organic carbon; UV, ultraviolet; VB, valence band. tion for the oxidation of refractory organic pollutant has been
∗ Corresponding author. Tel.: +1 418 654 3119; fax: +1 418 654 2600.
restricted due to the low photonic efficiency [12]. The fast recom-
E-mail addresses: rimeh.daghrir@ete.inrs.ca (R. Daghrir),
bination of the photo-generated electron/hole (e− /h+ ) represents
patrick.drogui@ete.inrs.ca (P. Drogui), drobert@univ-metz.fr (D. Robert).
1
Tel.: +1 418 654 2530; fax: +1 418 654 2600. the major drawback of photocatalytic process applications [13].
2
Tel.: +33 03 87 93 91 85; fax: +33 03 87 93 91 01. Therefore, it is important to retard the recombination of the

1010-6030/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jphotochem.2012.04.009
42 R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52

charge carriers. According to the literature [14–17], a great inter- Table 1


The role and the effect of UV irradiation and current intensity in photoelectrocat-
est in electrochemical advanced oxidation processes (EAOPs) has
alytic mechanism.
been emerging. Combining electrochemical and photo-catalysis
technologies (called photoelectrocatalytic technology) offers the Parameter Reactions Comments
opportunity to separate electron–hole photo-generated (e− /h+ ) UV irradiation TiO2 + h → e− CB + h+ VB • The TiO2 is exposed to the UV
and to prevent their recombination. Photoelectrocatalytic process h+ vb + H2 O → OH• + H+ light with energy greater than
allows not only to increase efficiency and decrease costs, but also h+ vb + OH− → OHad • the band gap energy (>3.2 eV).
e− cb + O2 → O2 • − Electrons are excited from the
to increase the rate of degradation of recalcitrant pollutants [18].
TiO2 valence band into the TiO2
Photoelectrocatalytic oxidation (PEO) in which a small positive conduction band.
potential is applied across the photo-catalyst has proven to be more • In the valence band of the
efficient than photocatalytic process and a better use of the pho- TiO2 photocatalyst, the holes
can react with adsorbed water
togenerated holes [19]. Heterogeneous PEO using semiconductors
(or hydroxyl ions) to produce
as photocatalysts has been largely applied over the last ten years free radicals such as OH• .
for removing organic pollutants [20–22]. This photoelectrocatalytic • The ejected electrons react
technique has received increasing attention in the environmental with electron acceptors such as
field because of its ability to destroy undesirable organic com- oxygen adsorbed to form
superoxide radicals.
pounds in aqueous phase and to remove traces of organic species
that are stable and difficult to oxidize by means of conventional Current intensity e− CB + h+ VB → heat • The current intensity applied
prevents as much as possible
water treatment methods [20,23,24].
the recombination between
The present review aims to provide a comprehensive anal- the photogenerated electrons
ysis of the mechanism of PEO processes, the characteristics of and holes. The recombination
photo-catalyst materials, the source of irradiation, and the dif- between electrons and holes
ferent types of photoelectrocatalytic reactors. The final section of releases the heat.
• Photogenerated electrons in
the manuscript presents some applications of photoelectrocatalytic
the excited TiO2 anode can be
processes in the field of water and wastewater treatment. taken away via the external
circuit, instead of the electron
transfer to molecular oxygen.
2. Mechanism of the photoelectrocatalytic process Consequently, the
photogenerated hole or OH• is
The photoelectrocatalytic technique combines both electrolytic left at the surface of the TiO2
and photocatalytic processes. Recently, the photoelectrocatalytic electrode.
treatment process has received considerable attention in the envi-
ronmental field owing to its ability to retard the recombination of
The electrons ejected to the conduction band can either react
electron–hole pairs (e− CB /h+ VB ) and the possibility to increase the
with electron acceptors such as adsorbed oxygen (O2 ) to form
lifetime of the latter. The applied external potential is a key fac-
superoxide radicals (Eq. (5)) or react with adsorbed water molecule
tor in the photoelectrocatalytic technique because it accelerates
(H2 O) to form oxidative species such as hydroxyl radicals [27].
photocatalytic reaction. The role of UV irradiation and the applied
potential on the photoelectrocatalytic mechanism are indicated in e− CB + O2 → O2 •− (5)
Table 1. The basic process of photocatalysis consists of ejecting an
The photogenerated electrons (e− ) reduce the recombination
electron from the valence band (VB) to the conduction band (CB)
rate of the photogenerated electron–hole pairs and enhance the
of the TiO2 semi-conductor, thereby creating an “h+ ” hole in the
photocatalytic activity [20]. The lifetime of the pairs (e− CB /h+ VB )
valence band. This is due to the UV irradiation of TiO2 with an
is a few nanoseconds. Without electron donors or acceptors these
energy equal or superior to the band gap (>3.2 eV). These charge
electron–hole pairs can recombine to release heat or migrate to the
carriers (e− /h+ ) can migrate to the surface of the catalyst, where
surface of the semiconductor and react with species that have been
they are then available to undergo redox reactions with substrates
adsorbed there.
[25].
e− CB + h+ VB → heat (6)
TiO2 + h → e− CB + h+ VB (1)
The recombination of the photogenerated electron–hole pairs
This is followed by the formation of extremely reactive radi- reduces the quantum efficiency and limits the application of
cals (such as HO• ) at the semi-conductor surface and/or a direct photocatalysis in the field of wastewater treatment [28]. Every
oxidation of the polluting species (R). Table 2 presents the redox recombination means a loss of a hole that might otherwise have
potential of different oxidants. Therefore, pollutants in wastewater promoted the degradation reaction. In order to achieve good pho-
can be degraded directly on the surface of the semiconductor [8] toelectrocatalytic efficiency, recombination between electrons and
or indirectly by reacting with hydroxyl radicals. The photogener- holes must be avoided. This is possible by trapping of free charges
ated hole in the valence bond can react with an adsorbed water at intermediate energy levels [23]. Further reactions can lead to
molecule (or surface hydroxyl) to form oxidative species such as
OH• which subsequently attack the pollutant. It was reported by
Table 2
Chong et al. [26] that in the absence of water molecules, the pow- Redox potential of oxidants used for water treatment.
erful oxidant hydroxyl radicals could not be formed and impedes
Redox couples E◦ , (V) at 25 ◦ C References
the photodegradation of liquid phase organics.
OH• /H2 O 2.81 [115]
h+ VB + H2 O → OH• + H+ (2) O3 /O2 2.07 [116]
S2 O8 2− /SO4 2− 2.05 [117]
h+ VB + OH− → OH• ads (3) H2 O2 /H2 O 1.77 [117]
MnO4 − /Mn2 + 1.51 [117]
h+ VB + R ads → R + (4) HClO/Cl− 1.49 [117]
Cl2 /Cl− 1.36 [117]
R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52 43

Fig. 1. Mechanism of photoelectrocatalytic process using TiO2 photocatalyst and the reactions that occur at the surface.

other oxidant species such as HO2 • , HO2 − , and H2 O2 that can in 0.5 M of Na2 SO4 using a current intensity varying from 0.25 to
promote oxidizing conditions that are not described here. Fig. 1 0.50 A. When pollutant concentration is fixed at the highest level
shows the general mechanism of the photoelectrocatalytic process (50 mg L−1 ), current intensity has a significant influence on the
and the main reaction that occurs at the surface of TiO2 . Accord- removal of CTC. The degradation rate passed from 34.9% to 61.3%
ing to the literature [29,30], potential applied is a key factor that when the current intensity passed from 0.25 to 0.50 A. The effi-
improves photoelectrocatalytic efficiency. In fact, when a positive ciency of photoelectrocatalytic degradation of some contaminants
bias is applied to the Ti/TiO2 photoanode, the thereby generated such as humic acid [29,31] and 4-chlorophenol [30] is maximized
electrons can be transferred into the external circuit instead of by applying an optimal value of external potential (0.6 and 1.5 V
to the oxygen molecule. As a result, the photogenerated hole or is an optimal potential for the photoelectrocatalytic degradation of
OH• will be left at the surface of the TiO2 electrode. Therefore, 4-chlorophenol and humic acid, respectively). The increase of the
the rate of photogenerated electron–hole recombination is limited applied potential above the optimal value may decrease the degra-
while a possibility exists to improve the efficiency oxidation at the dation efficiency but it may also have no effect on the degradation.
semiconductor–electrolyte interface [4,5]. In the photoelectrocat- By applying an external potential, the gradient of the electro-
alytic process, the rate of conversion does not depend directly on chemical potential could be increased to an extent that ensures
the applied potential but depends on several factors: (i) the specific complete separation of all charge carriers (depletion conditions)
feature of the semiconductors, (ii) diffusion light, (iii) adsorption [35]. In electrically biased system (full depletion conditions), the
and desorption of the reactant and products, and (iv) the intensity majority of the electron are drawn inside the semiconductor and
of the electric field in the space charge region [29]. are extracted at the back contact. Under these conditions, the cur-
rent under UV radiation cease to increase and the kinetics of the
reaction is only limited by the photon flux. This phenomenon was
3. Parameters affecting the photoelectrocatalytic process
discussed in detail by [35]. Under biased conditions, the whole reac-
tion sequence involving reduced oxygen species will be absent and
3.1. Effect of external potential applied on TiO2 or effect of
the degradation efficiency of pollutant will be reduced. According
current intensity
to Maeda et al. [36], the oxidation and reduction reactions could be
occurred simultaneously on the illuminated TiO2 photo-catalyst in
Applying an external potential on TiO2 (photo-anode) con-
an electrically unbiased system, where the consumption of photo-
tributes to the separation of the photo-generated electrons and
excited electrons is slow in the conduction band (reduction site).
holes and prevents as much as possible the recombination between
them [13,31]. In the photoelectrocatalytic process, applying an
external potential prevents charge recombination and increases
the lifetimes of the active holes The electrons and holes have more 3.2. Effect of light intensity
opportunities to either oxidize the pollutants directly on the sur-
face of Ti/TiO2 photo-anode (adsorption) or react indirectly with Electron–hole recombination is a limiting step in photocat-
active species (such as hydroxyl radicals) [32]. The effect of elec- alytic reactions [37]. The photocatalytic degradation rates depend
trical potential on hydroxyl radical production has been studied by strongly on the light intensity applied on the surface of the cata-
Jiang et al. [33]. That study showed that the total concentration of lyst. According to Wang et al. [38], the light intensity influences
hydroxyl radicals (higher than 20 ␮mol L−1 ) generated under UV on the extent of the electron–hole pairs photo-generated and
irradiation (20 W) was effectively enhanced with a small applied consequently on the progress of the photocatalytic reaction. By
potential (0.6 V). Consequently, higher efficiency in the degrada- increasing the intensity of the incident light, the probability of
tion of pollutants is recorded. The influence of current intensity excitation of the catalyst and the re-excitation of recombined elec-
was also put into evidence by Daghrir et al. [34] while studying trons can be increased [30]. Moreover, with the increase of UV light
photoelectrocatalytic degradation of chlortetracycline hydrochlo- intensity, the decomposition of organic compounds or the inacti-
ride (CTC) using TiO2 nano-structured photo-anode and a mercury vation rate of bacteria (especially under UVC irradiation) increases
lamp ( = 254 nm). The degradation experiments were carried out due to the increasing concentration of reactive oxygen species and
at different initial concentrations of CTC (from 25 to 50 mg L−1 ) hydroxyl radicals formed on the TiO2 surface [14,39]. The steady
44 R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52

concentration of HO• on the TiO2 surface is described by Chen et al. possible reaction mechanisms can contribute to the degradation
[39] and Cho et al. [40] as follows: of pollutants in photoelectrocatalytic processes: (i) direct attack of
 hydroxyl radicals, (ii) direct photo-oxidation by the positive hole in
(1 − ˛)Ia ˚ the valence band, and; (iii) direct photo-reduction by the electron
[HO• ]S = (7)
kD in the conduction band. Each of these depends on the pH value and
the nature of the substrate.
where Ia is the number of light quanta absorbed per second; ˚ the
quantum yield; kD the diffusion-limited rate constant and ˛ the
3.4. Effect of dissolved oxygen
parameter depending on the pH. Some authors studied the relation-
ship between light intensity and photoelectrocatalytic oxidation
In the photoelectrocatalytic degradation of organic pollutants,
used for degradation of humic acid [31]. It has been proven that
the dissolved oxygen avoids the recombination of photo-generated
the degradation reaction rate is proportional to the light inten-
electron–hole pairs by acting as electron acceptors and participates
sity (k◦ = k2 Ib , where k◦ is the degradation reaction rate; I the
in the formation of reactive oxygen species as the superoxide rad-
light intensity and k2 and b the kinetic constants). In the field of
ical O2 • [25,49,50]. A sufficient amount of O2 promotes oxidizing
water treatment, Chong et al. [26] indicated that a relatively high
conditions. The oxygen is well-known for its effective role in the
light intensity is required to achieve a high photocatalytic reaction
oxidation/reduction reactions of pollutants. The dissolved oxygen
rate. Some authors [41–43] argued that under low light intensi-
source is the aeration system and/or the H2 O molecule electrooxi-
ties (lower than 250 W m−2 ), the reaction rate is proportional to
dation at the anode (Eq. (8)). In the photo-electrocatalytic process,
the light intensity, while under moderate light intensities (above
the electron ejected in the conduction band reacts with electron
250 W m−2 ) the reaction rate is proportional to the square root
acceptors such as O2 to form superoxide radicals O2 •− and subse-
of the light intensity. Nevertheless, under high light intensities,
quently other oxidant species such as H2 O2 , HO2 • and HO2 − (Eqs.
the reaction rate is independent of the light intensity. Limit val-
(9)–(15)) [51]. Moreover, hydrogen peroxide H2 O2 (oxidant) can be
ues range between 22 and 44 kW m−2 [44]. Pareek et al. [45] show
electrogenerated by the cathodic reduction of dissolved oxygen on
that the degradation efficiency of pollutants is strongly linked to
the electrode.
the light intensity distribution within the reactor. According to
the same authors, it is very difficult to maintain a uniform light 2H2 O → O2 + 4H+ + 4e− (8)
intensity distribution within the reactor. For this reason, it is very
important to determine the appropriate light intensities to min- e− + O2(ads) → O2 •− (9)
imize energy consumption and to increase the rate of pollutant
O2 •− + H+ → HO2 • (10)
degradation. For practical application (i.e. large-scale application),
it could be interesting to use the natural UV irradiations emitted by •
2HO2 → H2 O2 + O2 (11)
the solar spectrum in the presence of a TiO2 photocatalyst material
in order to minimize treatment costs. However, if the natural UV O2 •− + HO2 • → O2 + HO2 − (12)
irradiations emitted by the solar spectrum are insufficient, these HO2 − + H+ → H2 O2 (13)
can be combined with artificial UV lamp irradiation.
+
O2 + 2eCB + 2H → H2 O2 (14)
3.3. Effect of pH
2H2 O + 2H+ VB → H2 O2 + 2H+ aq (15)

According to the literature [30,46], in the field of wastewater The presence of reactive oxygen species in high quantity can
treatment, pH is one of the most important parameters that influ- limit the recombination of photo-generated electron–hole and
ence the removal of pollutants. It affects the capacity of adsorption improve the efficiency oxidation at the semiconductor interface.
and dissociation of the target compounds, the charge distribution The performance of the photoelectrocatalytic cell in term of pollu-
to photocatalyst surface, and the oxidation potential of the valence tant degradation could be evaluated using Faradayic efficiency (Eq.
band [26,30,46]. Many authors [26,28–30,47] used the point of zero (16)). A simple relationship between photocurrent density and the
charge (PZC) to study the performance of photocatalytic oxidation amount of pollutant removal could be derived from Faraday’s law
using TiO2 as photocatalyst. The PZC has a pH value of approxi- [13].
mately 6 (pHPZC ) for TiO2 [29]. Under these conditions, the surface
(−dc/dt) × V × F
charge of TiO2 is neutral and the electrostatic interaction between f = (16)
the pollutant and TiO2 is absent. For pH values higher than the PZC i
of TiO2 , the surface becomes negatively charged and an electro- where (−dc/dt) represents the disappearance rate of pollutant, V is
static repulsion toward anionic compounds dominates. However, the working volume (m3 ) of the reactor, F is the Faraday constant
the surface of the catalyst becomes positive when the pH is lower (coulombs) and i is the photocurrent density (A cm−2 nm−1 ).
than the PZC of TiO2 . For a pH value between 3 and 10, the distri- Some authors [26,52] suggest that the presence of dissolved
bution of TiOH is greater than or equal to 80%, whereas for a pH oxygen provides the cleavage mechanism for aromatic pollutants
value above 10 or below 3 the distribution of TiO− and TiOH2 + , present in water. The pressure of oxygen applied during the reac-
respectively, is greater than or equal to 20% [26]. tion is also important. A higher organic photomineralization rate
In the photoelectrocatalytic process, the maximum degradation was obtained by applying a higher pressure of oxygen [52]. For
rate of certain pollutants such as pentachlorophenol [46], humic instance, by increasing the airflow in the photoelectrocatalytic
acid [31], benzotriazole [28] and dye [48] is much faster in an process, Liang et al. [53] demonstrated that the oxidation of 2,3-
acidic solution than in an alkaline solution. Nonetheless, Wang dichlorophenol can be increased. When the oxygen molecule is in
et al. [30] have proven that the degradation rate of 4 chlorophe- excess in the medium, the transfer rate of photogenerated elec-
nol was enhanced in both alkaline and acid solutions. However, trons from the surface of the titania to the molecular oxygen will
the effect of pH in photocatalytic reactions cannot be general- be maximized. However, according to Almquist and Biswas [54], in
ized. Laboratory experiments are required in order to determine the photocatalytic process, the electron transfer rate depends on
optimum pH conditions, unless data are available from previous the type and characteristics of the titania as well as the rate of the
studies conducted under similar operating conditions [4]. Three charge transfer.
R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52 45

3.5. Effect of electrolytes was proven by the Van’t Hoff–Arrhenius equation (Eq. (17)), where
the rate constant k is linearly proportional to the exp(−1/T).
In an electrolytic process, the conductivity of the solution affects k  Ea
1 1

the efficiency of current intensity, voltage, and the consumption of 1
ln =− − (17)
electrical energy. The conductivity must be high in order to ensure k2 R T2 T1
good ion transfer in the effluent. If the conductivity is too low, the where k1 and k2 are the constants of temperature T1 and T2 , respec-
resistance is too high and consequently, an increase of the applied tively; Ea is the energy activation; and where R is the universal gas
voltage is observed. NaCl and Na2 SO4 are the two electrolytes most constant.
often used. The type of electrolyte and its concentration affect the
photoelectrocatalytic degradation process [30]. The results of a 4-
chlorophenol degradation study showed that photoelectrocatalytic 3.8. Effect of mass transfer
efficiency improved in the presence of sodium sulfate and that
the degradation process increased with the concentration of elec- It is well-known that, hydrodynamic conditions (or mass trans-
trolyte (from 0.05 to 0.2 M). In the photoelectrocatalytic process, fer coefficient) inside reactors are greatly linked to the cell
the electrolyte Na2 SO4 is the electrolyte that has been widely used configuration or cell design [66–68]. Indeed, in the PECP, the oxi-
by several authors [8,28,29,55–58]. For instance, pentachlorophe- dation of pollutants can occur heterogeneously. Pollutants must
nol degradation was improved when Na2 SO4 was added to the be transported to the photo-anode surface first, and then be oxi-
solution. The removal rate of pentachlorophenol was accelerated dized there as a result of hydroxyl radical formation (OH• ) [69–71]
by increasing the electrolyte concentration (from 6.0 mg pen- or owing to the photogenerated hole [25,72,73]. Experiments are
tachlorophenol/L at 0.005 M Na2 SO4 to 3.0 mg pentachlorophenol/L required to determine the value of the mass transfer coefficient
at 0.01 M Na2 SO4 ) [46]. During the photoelectrocatalytic process, and to study the hydrodynamic conditions of the reactor prior to
the addition of an electrolyte improves treatment efficiency since the development of practical applications.
it modifies the conductivity of the solution and facilitates the pas-
sage of the electrical current in solution, which in turn prevents 4. TiO2 electrodes: characteristics and specificities
the fast recombination between photo-generated electrons and
holes. 4.1. Preparation of TiO2 electrodes

Several methods can be used to prepare TiO2 electrodes for


PECPs. The anodizing method has been widely used by several
3.6. Effect of counter electrode (or cathode electrode)
authors to prepare Ti/TiO2 electrodes [46,59,74,75]. Anodizing
titanium metal can be carried out in acid [76] or alkaline [77]
Another interesting advantage of the photo electrocatalytic pro-
solution. Commercial titanium foils with appropriate dimensions
cess (compared to conventional photocatalytic process) could be
(25 mm × 50 mm) were used to prepare TiO2 films by anodization.
the use of a cathode material, such as vitreous carbon (VC) on which
The initial surface was polished with abrasive papers and rinsed in
hydrogen peroxide (H2 O2 ) can be electrochemically generated by
an ultrasonic bath containing cold distilled water. Prior to anodiza-
cathodic reduction of dissolved oxygen [59]. This peroxide induces
tion, the titanium plate was first immersed in an HF/HNO3 /H2 O
non offensive by-products contrarily to chlorine. Under UV irradi-
solution and then cleaned with alcohol and distilled water. The
ation, hydrogen peroxide can be decomposed into hydroxyl radical
treated Ti served as an anode and a platinum (Pt) foil served as a
(in addition to hydroxyl radical produced on the surface of photo-
cathode. Both were placed in acid or alkaline solution and an electri-
catalyst). This should contribute to enhance pollutant degradation.
cal current was applied at a constant voltage and for an appropriate
Likewise, the addition of an electron acceptor (e.g. H2 O2 ) should
time. The anodization process was accompanied by a significant
prevent the electron–hole recombination and increase the photo-
generation of heat [74]. The freshly generated TiO2 electrode was
catalyst efficiency [60]. According to previous studies [28,37,59],
then rinsed in distilled water, and then dried first in the atmosphere
such an oxidant agent (H2 O2 ) is beneficial for photocatalytic reac-
and then at 105 ◦ C for 2 h [75]. The sol–gel method has also been
tion by trapping the conduction band electron in order to generate
used by many authors [13,55,78] to prepare the TiO2 /Ti electrode.
more hydroxyl radical.
Sol–gel electrodes were fabricated by coating a layer of TiO2 sol
onto the titanium substrates via repetitive heat treatments. The
plate titanium substrate formed was dip-coated into a TiO2 sol solu-
3.7. Effect of temperature tion prepared by the method according to Xu et al. [55], and dried
for 10 min at 500 ◦ C. The coating and drying process was repeated
According to our knowledge, the effect of temperature on PECPs several times and the resulting materials were heated between 500
has not been studied in the literature. However, its effect has been and 550 ◦ C for 1 h [49] or 2 h [55]. The TiO2 electrode can be pre-
widely studied on photocatalytic processes [26,61,62]. The increase pared with chemical deposition methods. Sun et al. [79] used nickel
in photocatalytic temperature (T > 80 ◦ C) promotes and enhances plates coated with a 500 nm thick titanium film as a substrate. The
the charge recombination. Under these conditions, adsorption of titanium film was deposited on nickel plates by means of arc ion
organic compounds on TiO2 surface decreases [26]. According to plating. The deposition of film was conducted at a temperature of
Malato et al. [63], a temperature range between 20 and 80 ◦ C 200 ◦ C and a rate between 50 and 60 nm/s. After deposition, the
is considered as optimum for photomineralization. In a photo- substrate formed was cooled to temperature at 3 ◦ C/min, dipped in
disinfection reaction, an increase in temperature enhances the the solution, and pulled out with a constant speed. During each
inactivation rate of microorganisms [64]. Based on studies car- dip-coating procedure, the gel film was dried at 300 ◦ C during
ried out by Chen and Ray [65], the degradation rate constants of 15 min. An electrophoretic deposition method was also used for
4-nitrophenol increased with increasing temperature from to 288 TiO2 preparation [8]. A TiO2 film was deposited on the pre-treated
to 323 K (at an initial concentration of 4-nitrophenol = 20 ppm; pH fibers coated with SnO2 :Sb (optical fiber with a 600 ␮m silica core
4.3; TiO2 = 2 g L−1 , flow rate = 250 mL min−1 , and O2 saturated). By and a polymer optical cladding). The fiber was immersed at room
increasing temperature, the collision frequency of molecules in temperature during 1 h in a colloidal suspension of TiO2 powder
solution increases and the reaction rate constant improves. This under a potential difference applied between the optical fiber and a
46 R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52

stainless steel sheet. Afterward, the electrode was placed in an oven Table 3
Characteristics of the anatase and rutile forms of TiO2 .
at 450 ◦ C to sinter the TiO2 film.
Compared to the common synthesis methods described above Parameters Anatase Rutile
for the preparation of TiO2 electrodes, new method using for Crystalline structure Quadratic Quadratic
instance a pulsed laser deposition (PLD) process has been Stability Thermodynamically Thermodynamically
investigated by Daghrir et al. [34]. A KrF excimer laser (wave- metastable stable
length = 248 nm, pulse duration = 15 ns) operating at a repetition Elaboration Low temperature High temperature
Structure Nanostructured Grain size greater than
rate of 30 Hz was focused, at an incidence angle of 45◦ , onto the
anatase
TiO2 rotating target (99.95% purity). The on-target laser energy den- Specific surface High Lower
sity was set to 4.5 J/cm2 . For photoelectrocatalytic studies, the TiO2 Band gap (eV) 3.2 3.0
films were deposited on titanium grids. The TiO2 deposits were Absorption edge (nm) 385 405
performed at a deposition temperature 600 ◦ C under an oxygen Ti–Ti distances (Å) 3.04–3.79 2.96–3.57
Ti–O distances (Å) 1.934–1.980 1.949–1.980
background pressure of 1 mTorr. More details on the PLD system Photoconductivity High Lower
and it schematics have been investigated by Desbiens et al. [80]. Activity More active in Less active in
photocatalysis photocatalysis
4.2. Characteristics and specificities of TiO2 electrodes Mobility of charge More mobile charge Less mobile charge
carrier carrier
Density 3.89 4.27
Many researches [43,74,81] have shown that the semiconductor
TiO2 is an excellent photocatalyst that can, under UV light irra-
diation, break down many refractory organic pollutants such as curves gives direct information about what is to be expected if a
pesticides, herbicides, halophenols, dyes and detergents. Titanium selected voltage is applied. In the field of electrochemistry, cyclic
dioxide (TiO2 ) was widely used for the degradation of dyes that voltammetry is a very important analytical characterization. Any
could not be easily oxidized by chemical or biological processes process that includes electron transfer can be investigated using
[82,83]. Several authors [28,30,82,84] show that TiO2 is the most this analytical method. In order to select the appropriate poten-
suitable photocatalyst for environmental applications due to its tial in photoelectrocatalytic process, a voltamperometric study was
excellent chemical and physical properties such as high photosensi- performed by several authors [56,75,83] under and without illumi-
tivity, non-toxicity, long-term stability against photocorrosion and nation. Furthermore, reactors using fixed catalysts need to obtain
chemical corrosion, and strong oxidizing power. Titanium dioxide a stable and active catalyst layer. Irradiation in the reactor must
exits in three different crystal forms: anatase, rutile and brookite. be uniform over the entire surface of the catalyst [90]. The quantity
Anatase and rutile forms have been the most studied phases of and type of catalyst depends mainly on the radiation source, and the
nanostructure TiO2 (Table 3), whereas, brookite forms are still type and concentration of the pollutant and reactor [90]. Accord-
scarce [85–87]. The rutile form of TiO2 begins to adsorb strongly ing to Paschoal et al. [83], the h+ /e− are generated on the layer of
at 405 nm, whereas the anatase form adsorbs until 385 nm [88]. In TiO2 under UV illumination. Besides, oxidation reactions can be ini-
the anatase form, the energy gap between the valence and conduc- tiated owing to the potential gradient between the surface and the
tion bands is slightly larger (3.25 eV) [79]. The anatase form shows a bulk of the semiconductor. As the photocurrent depend on light
higher photocatalytic activity than the rutile form [89]. In photocat- intensity, it could be possible to determine the efficiency of trans-
alytic degradation using TiO2 /UV, a TiO2 catalyst can be utilized in forming light flux into electron flow namely IPCE (incident-photon
two different forms: (1) TiO2 suspended in aqueous medium and to current conversion efficiency) (Eq. (18)) [13].
(2) TiO2 immobilized on support inert materials (TiO2 on robust
i
substrates). By comparison, only the immobilized TiO2 on support IPCE = (18)
F ×P
materials can be used in photoelectrocatalytic processes. The active
surface area available for photocatalytic reactions is much larger in where i represents the photocurrent density (A cm−2 nm−1 ), F is
suspension systems than in film systems [24,90]. The use of TiO2 the Faraday constant (coulombs) and P is the incident light (Ein-
particles in photocatalytic oxidation (PO) has two drawbacks: (i) stein s−1 cm−2 ).
the separation of the suspension of TiO2 from the aqueous phase In order to improve electron–hole separation, De Tacconi et al.
is very difficult and (ii) it involves heat loss due to the recombi- [92] proposed the coupling of the TiO2 semiconductor with another
nation of the electron–hole pairs [13,78]. Recent research works semiconductor such as CdS (coupled nanoparticles CdS/TiO2 ) [93].
tried to immobilize the TiO2 film on support materials such as sand, Other studies [94,95] suggested combined semiconductor powders
glass media, SiC foams [91], ceramic membrane or resins by means such as TiO2 + ZnO and TiO2 + SnO2 . According to Zhang et al. [96],
of coating, soaking, precipitating or spinning methods in order to using different semiconductors simultaneously allows to reduce
solve the problem of TiO2 particle separation from wastewater [74]. electron–holes recombination in individual photoelectrodes. Fig. 2
According to Thiruvenkatachari et al. [87], an immobilized TiO2 presents a semiconductor configuration in which a vectorial trans-
film is preferable compared to dispersed TiO2 because the addi- fer of photogenerated charge carriers between corresponding
tion of a post-treatment (filtration step) is not necessary after the band levels ensures a spatial separation between electrons and
oxidation process. By using the TiO2 film, the quantum efficiency holes [97]. For instance, combining SnO2 /TiO2 photoelectrodes was
will decrease in comparison to TiO2 particulate suspension. The used by several authors [98–101] to oxidize different types of
limit diffusion of the target compounds to the surface of the cat- molecules (Acid Orange 7, to degrade naphthol blue black, formic
alysts and the reduction in the surface area of the catalysts are acid and 1,3,5,7-tetramethylcyclotetrasiloxane). SnO2 /TiO2 cou-
the two factors that are responsible for the decrease of quantum pled with film was found to be more effective than TiO2 film used
efficiency [46]. Photoelectrocatalytic oxidation process in which alone.
a differential potential is applied to photo-catalyst enhances the
quantum efficiency and consequently increases the degradation 4.3. UV radiation of TiO2 electrodes
rate of the pollutant. The potential applied across the immobilized
photo-catalyst is a key factor that prevents the fast recombination In the case of the photocatalysis process, the photoactiva-
of the photo-generated electron–hole and enhances the quantum tion of TiO2 requires irradiations emitted at a wavelength less
efficiency of the process [30]. The analysis of the current–voltage than or equal to 384 nm [87]. UV irradiations are a critical
R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52 47

Fig. 2. Coupling of two different semiconductor configurations.

parameter in photocatalysis and photoelectrocatalysis reactions. quartz cell with a dimension of 25 mm (diameter) × 50 mm (height)
Different types of lamps emitting ultraviolet radiation were used. (Fig. 3). A UV lamp (20 W) with a maximum UV irradiation at
Quasi-monochromatic low pressure lamps transmit at wavelengths 365 nm has also been used outside the photoreactor. The work-
ranging at 254 nm, while polychromatic medium pressure lamps ing volume of this reactor was 10 mL and two Ti/TiO2 and platinum
emit at a wavelengths ranging between 185 and 400 nm [102]. The (Pt) electrodes were connected with a potentiostat were used as
degradation efficiency of certain organic compounds was increased anode and cathode, respectively. A cylindrical quartz cell has also
by applying UV-C radiation (between 200 and 280 nm) followed been used by Xie and Li [59] but with three electrodes (working
by UV-A radiation (between 320 and 380 nm) [103,104]. In the electrode, counter electrode and reference electrode). In this con-
photoelectrocatalysis process, a combination between the catal- figuration (Fig. 4), Ti/TiO2 or Au-TiO2 /Ti (anode) was placed at the
ysis effect as TiO2 , UV illumination and electrochemical process bottom of the reactor to receive UV light irradiation (power: 8 W;
allows enhancing the degradation of emerging contaminants such light intensity: 0.68 mW cm−2 , main emission: 365 nm) by using a
as benzotriazole [28] and 2,4-dichlorophenol [58] and inactiva- medium-pressure mercury lamp. Reticulated vitreous carbon (RVC)
tion of bacteria [57]. In this case, both UV light radiations and or Pt used as a cathode was placed at one side of the cell nearby
the applied potential between anode and cathode are responsi- an air diffuser. A saturated calomel electrode (SCE) was used as the
ble for the photogenerated electron–hole on TiO2 catalysts, and reference electrode. The current applied on the electrode was regu-
consequently for oxidizing the organic substrate. Previous stud- lated by a potentiostat–galvanostat. A further type of configuration,
ies [87,105] have demonstrated the positive effect of UV radiation used by Quan et al. [46], is comprised of a rectangular quartz pho-
on the TiO2 catalyst activation. Rapid electron–hole recombina- toreactor (40 mm × 50 mm × 60 mm with a 2.0 mm wall) with TiO2
tion is the major factor limiting the process when UV light was at the anode and Pt at the cathode. In this type of photoreactor, a
used alone. To enhance the UV radiation effect on TiO2 and to mercury lamp (365 nm) was positioned vertically outside the reac-
improve the quantum yield (˚), the application of current inten- tor. An SCE served as the reference electrode. A schematic diagram
sity on the TiO2 anode electrode is increasingly an object of study of the reactor is shown in Fig. 5. A semi-arc quartz cell of 8.5 cm
[8,75,106,107]. According to Zhang et al. [96] and Rosenfeldt and diameter has been used by Xu et al. [55] to oxidize dye from textile
Linden [108], quantum yield is defined as the ratio of the reactant
molecules consumed or formed to the quantity of absorbed pho-
tons at a given wavelength. By calculating the number of photons
absorbed during the reaction, we can determine the quantum yield
of a reaction (Eq. (19)). Quantum yield depends on pH, wavelength,
pollutant concentration, solvent, temperature, and the concentra-
tion of dissolved oxygen. Quantum yields are determined at specific
wavelengths.
dn/dt
˚= (19)
Iabs
where: ˚ is the quantum yield, n is the number of molecules that
react in this process during time t, and Iabs is the number of photons
absorbed during the same time and in the same volume.

5. Photoelectrocatalytic reactors

The main advantage of using the photoelectrocatalytic process


is the simplicity of the reactor in terms of construction and man- Fig. 3. Photoreactor equipped with two electrodes: Ti/TiO2 as anode and platinum
agement [1]. Several configurations of photoreactors have been electrode as cathode.
described in the literature. Li et al. [63] have used a cylindrical Adapted from [63].
48 R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52

generation of powerful oxidizing species such as H2 O2 and OH•


[110,111]. The direct contact of UV light with polluted water
induced high oxidation of pollutant [34]. Using internal UV config-
uration for laboratory scale applications enhances the distribution
of irradiation across the photo-catalyst and consequently increases
the generation rate of reactive oxygen species. The distance
between the UV source and the working electrode is also an impor-
tant parameter that must be taken into account in the designing of
photo-reactors. It has been reported by Egerton [12] that a large
distance between the light source and the working electrode in a
practical photoreactor reduces the radiation flux and consequently
reduces the efficiency of the process. Besides, mixing in the three
photoreactors (Figs. 3–5) was achieved by a Teflon-covered stirring
bar installed at the bottom of the cell. Nevertheless, high recycling
flow rate of a fraction of treated-water provided by recycling pump
promotes the turbulence near the photocatalyst and increase the
Fig. 4. Photoreactor equipped with three electrodes used for photoelectrocatalytic coefficient of mass transfer at the interface electrode–electrolyte.
oxidation process.
The structure of the electrode could also enhance the mass trans-
Adapted from [62].
fer coefficient. For instance, the electrode in the form of sheet used
by Quan et al. [46] limits the turbulence around the photocata-
lyst and reduces the mass transfer coefficient. The turbulent effect
effluent. A Ti/TiO2 disc (diameter of 7.5 cm and thickness of 1.5 mm) required to promote mass transfer and to minimize fouling can be
and Cu sheet electrodes were respectively used as anode and cath- achieved in the reactor using mesh electrodes and gas sparging with
ode in this photo-reactor-cell. The inter-distance between anode small bubbles [78,109]. It has been shown by Egerton [12] that the
and cathode was 1.0 cm. A mercury lamp (11 W) with a wavelength development of spinning disc and gas sparging inside the reactor
254 nm was placed horizontally in front of the photoanode Ti/TiO2 . influenced the mass transfer.
For the disinfection of water inoculated with Escherichia coli, a ver-
tical cylindrical reactor has been used by Christensen et al. [109]
for photoelectrocatalytic applications. The photo-reactor was fit- 6. Application of photoelectrocatalytic processes (PECPs )
ted with two concentric Pyrex tubes (external diameter 42 mm and
inner diameter 80 mm) and the solution occupied the annular vol- Applications of heterogeneous PECPs using semiconductors as a
ume. The UV source was located in internal configuration along catalyst for the degradation of refractory organic pollutants present
the axis of the reactor. To ensure high mass transfer of reactant to in water and wastewater have received increasing attention in
the electrode inside the photo-reactor, mesh electrodes (100 mm the field of environmental protection. The photoelectrocatalytic
long × 44 mm diameter) and gas sparging with small bubbles have oxidation process has been applied for the treatment of different
been used. effluents containing varied and high amounts of organic com-
With the exception of the photoreactor described by Chris- pounds (dye, phenolic compounds, and humic substances) and
tensen et al. [109], in the experimental units described above, the bacteria (E. coli) that are difficult to oxidize biologically or chem-
UV lamp was installed outside of the photo-reactor and the illu- ically (Tables 4 and 5). A 100% removal of TOC can be reached
mination passed through the window quartz. However, UV lamp depending on the type of organic compounds tested and the exper-
position could influence the efficiency of the photoelectrocatalytic imental condition imposed. The performance of PECPs for the
process. For instance, it has been shown by Daghrir et al. [34] degradation of refractory organic pollutants is best examined on
that UV lamp installed inside the reactor was more effective to the basis of dyes, which are by far the organic compounds that
remove CTC compared to UV lamp installed outside the photore- have been the most studied (Table 5). For instance, when applying
actor. Indeed, UV radiations absorbed by H2 O molecules allow the the photo-electro-catalytic process (using TiO2 anode and carbon

Fig. 5. Rectangular quartz photoreacteur used for photoelectrocatalytic process.


Adapted from [42].
R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52 49

Table 4
Removal of different types of organic pollutants in aqueous solutions using PECPs.

Matrix Type of pollutant Operating conditions Results and comments References

Aqueous solution Bisphenol A 8 W medium pressure mercury lamp (365 nm); AuTiO2 /Ti or % Bisphenol A [59]
TiO2 /Ti (anode); RVC or Pt (cathode); 110 W high pressure removal = 13–99%
sodium vapor lamp (450–650 nm); C0 (bisphenol
A) = 1.12 mg L−1 ; Na2 SO4 = 0.01 M; flow rate of
air = 120 mL min−1 ; initial pH 6.17; current intensity
applied = 0–1.5 mA; treatment time = 180 min
Aqueous solution Benzotriazole (BTA) 15 W UV lamp (253.7 nm); TiO2 (working electrode); Pt EO (0% removal); DP (65% [28]
(counter electrode); SCE (reference electrode); removal); PO (70% removal);
volume = 100 mL; Na2 SO4 = 0.5 M; pH (initial) 6.2; C0 PEO (89.8–90% removal)
(BTA) = 2 × 10−4 M; potential applied = 0–0.8 V; treatment
time = 180 min; pH 2–10; calcinations
temperature = 100–500 ◦ C; Na2 SO4 = 0.05–0.5 M; C
(BTA) = 0.05–0.5 mM
Aqueous solution Pentachlorophenol (PCP) 300 W high pressure mercury lamp (365 nm); C0 EO (0% removal); DP (44% [46]
(PCP) = 20 ppm; pH 7.03; C0 (Na2 SO4 ) = 0.01 M; TiO2 (anode); removal); PO (62% removal);
Pt (cathode); potential applied = 0.0–0.6 V; treatment PEO (82–86% removal)
time = 2 h; pH 3.25–8.00; C (Na2 SO4 ) = 0–0.01 M
Aqueous solution 2,4-dichlorophenol 8 W medium pressure mercury lamp (365 nm); TiO2 /Ti (first 2,4-Dichlorophenol [58]
anode); graphite (cathode); Fe (second anode); degradation (93%);
Na2 SO4 = 0.02 M; oxygen gas flow = 40 mL min−1 ; treatment mineralization of 78%
time = 60 min
Aqueous solution 4-chlorophenol, Oxalic 45 W Hg medium pressure lamp (365 nm); TiO2 film (anode); Oxalic acid: 100% of the total [13]
acid Ag/AgCl (reference electrode; Na2 SO4 = 0.1 M; T < 35 ◦ C; natural organic carbon degradation
pH; treatment time = 5 h 4-chlorophenol: less CO2 was
detected
Aqueous solution Rhodamine B 30 W mercury UVA lamp, Ti/TiO2 (working electrode); Pt Efficient and complete [56]
(counter electrode); SCE (reference electrode); oxidation of Rhodamine B
Na2 SO4 = 0.1 mol L−1 ; potential applied = 0.05–0.5 V; treatment
time = 30 min; pH 2–10
Aqueous solution Humic acid 450 W Xe–Hg UV light lamp (254 nm and 400 nm); TiO2 Color removal (96%); humic [29]
(anode); Pt (counter electrode); SCE (reference electrode); acid removal (98%); TOC
oxygen is bubbled during all experiments; C0 (humic removal (85%)
acid) = 25 mg dm−3 ; potential applied = 0–2 V; treatment
time = 2 h; Na2 SO4 = 0.01 mol dm−3 ; pH (initial) = 7

Table 5
Removal of dye and microbial pollutants using PECPs.

Matrix Type of pollutant Operating conditions Results and comments References

Dye wastewater Textile effluent, Brilliant Blue 11 W mercury lamp (254 nm); radiation 44–83% of RBB (flowing [55]
X-BR (RBB) power = 15 mW cm−2 ; flow rate = 7.7 L h−1 ; TiO2 /Ti aqueous film
sheet: (anode); Cu sheet (cathode); applied photoelectrocatalytic reactor);
potential = 0.6–1.0 V; pH 10; Na2 SO4 = 0.5 g L−1 ; C0 12–75% of RBB removed
(dye) = 20–150 mg L−1 (conventional
photoelectrocatalytic reactor)
Textile wastewater Azo dye Orange II UV lamp (254 nm), TiO2 (anode); carbon cloth Azo dye Orange II removal [8]
(cathode), C0 (azo dye Orange II = 15 mg L−1 ; (100%); TOC removal (57%)
Na2 SO4 = 0.05 M; pH 3; [Fe2+ ] = 0.2 mM;
[H2 O2 ] = 80 mg L−1 ; treatment time = 60 min; reactor
volume = 640 mL; flow rate = 80 L h−1
Textile wastewater Dispersal orange dye (DOD), 125 W medium pressure mercury lamp (254 nm); TiO2 DOD (90% discoloration, [83]
dispersal ruby dye (DRD), (working electrode; Pt gauze (counter electrode); reduction 63% of TOC); DRD
dispersal red dye (DRR), borax, Ag/AgCl (reference electrode); C0 (DOD) = 77 ppm; C0 (94% discoloration, reduction
emulsogen (naphthalene) (DRD) = 72 ppm, C0 (DRR) = 92 ppm; C0 45% of TOC); DRR (100%
(borax) = 1500 ppm; C0 (emulsogen) = 800 ppm; C0 discoloration, reduction 61% of
(Na2 SO4 ) = 0.1 mol Ll− ; potential applied = 1.0V TOC)
Dye solution Rose Bengal 20 W UV lamp (365 nm); Ti/TiO2 (anode); Pt (cathode); Rose Bengal removed = 65% [74]
light intensity = 1.4–2.2 mW cm−2 ; treatment after 0.5 h and 85% after 6 h.
time = 6 h; C0 (Rose Bengal) = 20 mg L−1
Surface water Microcystin aeruginosa 125 W Philips medium pressure mercury lamp UV TOC reduction (90%); Turbidity [118]
light (365–400 nm); Ti/TiO2 (working electrode); Pt removal (100%); color decrease
(counter electrode); bubbling of compressed air, C0 (93%); COD removal (96%);
(chloride) > 0.010 mol L−1 ; pH 4; current bacteria removal (100%)
density = 30 mA cm−2 ; treatment time = 150 min; C0
(NaCl) = 0.05 mol L−1 ; C0 (microcystin
aeruginosa) = 50 ␮g L−1
E. coli colonies solution Escherichia coli XL-1 Blue 9 W/78 UVA lamp (365 nm); TiO2 /Ti, Pt-TiO2 /Ti, EO (removal 5% of E. coli after [57]
R-TiO2 /Ti (anode); Pt (cathode); Ag/AgCl (reference 3 h); PO (removal 80% of E. coli
electrode); potential applied = 1.0 V; C0 after 1 h); PEO (removal 100%
(E. coli) = 103 –107 CFU; C0 (Na2 SO4 ) = 0.1 mol L−1 ; pH of E. coli after 1 h)
5.6; T = 25 ◦ C
50 R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52

cathode electrodes) for the treatment of textile wastewater effluent film photoreactors). This was discussed in detail by Braham and
(containing azo dye Orange), Esquivel et al. [8] obtained 57% of TOC Harris [112] and by McCullagh et al. [113]. Indeed, the indus-
removal. The reactor was equipped with a low pressure mercury trial implementation of the conventional photocatalytic process
lamp of 21 W cm−2 light intensity and operated at 254 nm. By com- must be taken into consideration for practical installations and
parison, 63% of TOC was removed when Paschoal et al. [83] studied the application of the photoelectrocatalytic process for treating
the photoelectrocatalytic method using a medium pressure mer- real wastewater (scale up of photoelectrocatalytic reactors). In
cury lamp operated at the same wavelength for the treatment of fact, in photoelectrocatalytic reactor development, parameters
textile wastewater (containing a Disperse Orange dye). The reac- such as current density, mass transfer, reaction kinetics, catalyst
tor was comprised of TiO2 and Pt electrodes, used as anode and installation and, catalyst illumination (photoanode) are relevant.
cathode, respectively. The current density is obtained by dividing the current intensity
Likewise, PEO could be a good alternative for discoloration and imposed by the surface area of the photoanode (catalyst). Thus, in
mineralization of dispersed dyes. UV irradiations (254 nm) have large-scale application, the imposed current intensity will depend
been applied to treat textile wastewater before and after con- on the size of reactor and the photoanode surface area. On the
ventional treatment (biological method). During the treatment, a other hand, the illumination of the photoanode during electrolysis
potential difference of 1.0 V was applied on the nanoporous pho- determines the amount of water that may be treated per effective
toanode Ti/TiO2 . A degradation rate varying from 53% to 69% of unit area of deployed photoanode. As indicated by several authors
COD could be reached, whereas 80% to 89% of discoloration was [113,114], the main difficulty of this type of reactor is the provision
recorded. of sufficient high specific area of catalyst and the uniform distribu-
Quan et al. [46] also used an electrochemically assisted photo- tion of illumination across this area. Here, it could be interesting to
catalytic method for the degradation of pentachlorophenol (PCP) use the natural UV radiation emitted by the solar spectrum in the
in aqueous solution using a TiO2 nanotube film electrode as well presence of a TiO2 photocatalyst material a measure that would also
as UV irradiation. A degradation rate of 82% was obtained after allow to reduce the treatment costs (solar photoelectrocatalytic
2 h of treatment. PECPs have also been used to remove endocrine reactors). However, if the solar UV irradiations are insufficient, it
disrupting compounds such as bisphenol-A. Xie and Li [59] stud- could be combined with UV lamp irradiation. Likewise, the hydro-
ied PEO of bisphenol-A by using Ti/TiO2 as an anode and RVC as dynamic conditions of the reactor have to be carefully studied and
a cathode. An RVC electrode was used to generate H2 O2 in the optimized. The mass transfer coefficient (kd ) between photoanode
aqueous solution during the treatment. The production of H2 O2 and electrolyte need to be improved to increase the reaction rate
assisted with the TiO2 photocatalysis reaction led to a good per- at the surface of the electrode. For this, the photoanode could be
formance of bisphenol-A degradation (up to 99% of degradation). presented in the form of expanded titanium (Ti) covered with tita-
The residual H2 O2 concentrations recorded (0.2 mM) in the absence nia (TiO2 ). Such an electrode structure provides good mechanical
of bisphenol-A was lower than that measured (0.98 mM) in the strength and, a high surface area (compared to solid plate elec-
presence of bisphenol-A while the same experimental conditions trodes), and could moreover be used as a turbulence promoter near
were applied (current intensity imposed of 1.5 mA for 240 min). The the photoanode for increasing the mass transfer coefficient at the
study conducted by Christensen et al. [78] moreover showed that electrode–electrolyte interface. In addition, a high recycling flow
PEO is able to mineralize 75% of 4-nitrophenol (after 10 h), whereas rate of a fraction of treated-water could be of benefit to decrease
only 30% of 4-nitrophenol was destroyed in the absence of applied the thickness of the diffusion layer near the photoanode electrode,
potential (photocatalytic process). and possibly result in a higher performance of the system. It is
Photoelectrocatalytic technology using TiO2 as a photoanode worth noting that, during electrolysis the photoanode surface may
has been applied by Philippidis et al. [57] and Christensen et al. be covered with organic substances that reduce its electrode active
[109] to ensure the disinfection of a suspension of E. coli. The par- surface. This may affect the treatment performance in long-term
ticular advantage associated with this technology is to avoid the experiments. To circumvent these drawbacks, the use of photoan-
use of chlorine, which has serious negative impacts, among them odes in the form of expanded metal (Ti/TiO2 ) and the application of
the production of toxic compounds, and carcinogenic and muta- a high recycling flow rate during the treatment could be one of the
genic chlorinated organic products and the partial inactivation of easier and more feasible regeneration methods of the photoanode
pathogenic microorganisms. The study of Philippidis et al. [57] surface. Likewise, the polarity reversal could be used to maintain
showed that PEO assured a 100% photoinactivation efficiency when electrode longevity.
applying an anodic potential of 1.0 V. However, electrolysis con-
tributed to the inactivation of less than 5% of E. coli colonies after 3 h
of reaction time, while the photocatalytic process eliminates 80% 7. Current and future development of PECPs
of E. coli. Based on the study of Christensen et al. [109], the rates
of photoelectrochemical disinfection with an illuminated geomet- The photoelectrocatalytic process is considered as a good
ric area of the electrode of 100 cm2 significantly exceed the rate of alternative to conventional photocatalysis for improving the degra-
photocatalytic disinfection for a surface area of 50 m2 g−1 . dation rate of refractory organic pollutants. The introduction of
According to the results presented in Tables 4 and 5, the effi- electrochemical technology into photocatalytic reactions increases
ciency of the photo-electrocatalytic process on the removal of the efficiency of processes and also expands the degradation capac-
pollutant showed a difference. The nature of the pollutant, the ity of the recalcitrant organic pollutants. Due to the successful
operating conditions imposed during the treatment (pH, pollutant results at the laboratory scale, the photoelectrocatalytic process
concentration, irradiation source, current density, mixing inside merits further research, in particular concerning the design of pilot
the photoelectrocatalytic cell, etc.) and the photo-reactor config- units for the treatment of different effluents (industrial, municipal
uration could influence on photoelectrocatalytic efficiency. and domestic effluents). In order to promote the feasibility of pho-
To the best of our knowledge, photoelectrocatalytic applica- totoelectrocatalytic technology for large-scale applications, several
tions have been most often carried out at the laboratory scale. key technical constraints should be addressed. These include: (i) a
By comparison, conventional photocatalytic processes have been better exploitation of solar irradiation to be used as a free energy
tested in large reactors for practical applications by using a wide light source; (ii) development of TiO2 photocatalyst material able
variety of photoreactor designs (e.g. parabolic trough, inclined to operate as much as possible using the solar spectrum (5% of solar
plate, fixed/fluidized bed, packed bed, corrugated plate, and falling energy is emitted as UV irradiation); (iii) research should be focused
R. Daghrir et al. / Journal of Photochemistry and Photobiology A: Chemistry 238 (2012) 41–52 51

on the use of mathematical models for the optimization of param- [18] K. Rajeshwar, J.G. Ibanez, G.M. Swain, Journal of Applied Electrochemistry 24
eters affecting the efficiency of PECPS . It should also be noted that (11) (1994) 1077–1091.
[19] Y. Liu, X. Gan, B. Zhou, B. Xiong, J. Li, C. Dong, J. Bai, W. Cai, Journal of Hazardous
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