Desalination 260 (2010) 51–56

Contents lists available at ScienceDirect

Desalination
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / d e s a l

Electrochemical oxidation of p-aminophenol from water with boron-doped diamond

anodes and assisted photocatalytically by TiO2-supported zeolite
C. Ratiu a,b, F. Manea b,⁎, C. Lazau a, I. Grozescu a, C. Radovan c, J. Schoonman d
a
Department of Condensed Matter, National Institute of Research-Development for Electrochemistry and Condensed Matter, Timisoara, Plautius Andronescu 1, 300224 Timisoara, Romania
b
Department of Applied Chemistry and Engineering of Inorganic Compounds and Environment, “Politehnica” University of Timisoara, P-ta Victoriei no. 2, 300006, Timisoara, Romania
c
West University of Timisoara, Str.Pestalozzi, nr.16, 300115, Romania
d
Delft University of Technology, Faculty of Applied Sciences, DelftChemTech Department, Julianalaan 136, 2628 BL Delft, The Netherlands

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

Article history: In this work, the photocatalytically-assisted electrochemical oxidation for the degradation of 276 mg dm− 3
Received 8 March 2010 p-aminophenol (4-AP) from water with boron-doped diamond (BDD) anodes using TiO2-supported zeolite
Received in revised form 27 April 2010 (TiO2-Z) was investigated. The synergetic effect of this process on the treatment efficiency was assessed in
Accepted 29 April 2010
comparison with the application of each single electrochemical oxidation and photocatalysis process. The
Available online 23 May 2010
process performance was evaluated in terms of 4-AP removal and mineralization efficiencies, electro-
Keywords:
chemical efficiencies, degradation and mineralization rates, mineralization current efficiency and energy
4-AP mineralization consumption. After a reaction time of 120 min, about 23, 90, 56, and 88% of 4-AP was degraded in the
Photocatalytically-assisted electrooxidation photocatalysis, electrooxidation at the current density of 10 mA cm− 2, electrooxidation at the current
BDD anodes density of 5 mA cm− 2 and photocatalytically-assisted electrooxidation at the current density of 5 mA cm− 2.
TiO2-zeolite catalyst Also, for the application of the combined process, an apparent kinetic synergetic effect was achieved for 4-AP
mineralization. The technical and economic assessments suggested the superiority of combined process for
4-AP degradation from water.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction The electrochemical methods are very promising alternatives for

Industrial effluents containing toxic and refractory organic
pollutants cause severe environmental problems and their removal
or degradation is required. The objective of Integrated Pollution
Prevention and Control (IPPC) Directive [1] regarding the industrial
effluent reuse as raw water into production process represents a
challenge for the wastewater treatment technologies. Usually, for the
treatment of the industrial effluents containing refractory organics,
the conventional wastewater treatment for organics removal or
destruction is ineffective to reach the water quality appropriate for its
reusing, and new alternative methods are required.
In recent years, several studies have been focused on the destruction
of recalcitrant organics using different oxidation technologies, such as
advanced oxidation processes (AOPs) [2–6], or electrochemical oxida-
tion [7]. Both processes are based on the in-situ generation of OH
radicals, which allow its non-selective reaction with organics allowing
organics mineralization by its conversion into CO2.
⁎ Corresponding author.
E-mail addresses: cornelia_ratiu@icmct.uvt.ro (C. Ratiu), florica.manea@chim.upt.ro
(F. Manea), l_carmen@icmct.uvt.ro (C. Lazau), grozescu@icmct.uvt.ro (I. Grozescu),
radovan@cbg.uvt.ro (C. Radovan), J.Schoonman@tudelft.nl (J. Schoonman).
organics degradation because of their environmental compatibility,
versatility, simplicity, and easy possibility of automation. The
electrochemical oxidation performance depends strongly on the
electrode material. To generate OH radicals by electrooxidation,
several types of anodes with high overpotential for oxygen potential
are suitable, i.e., DSA-type [8–12], PbO2 [13,14], boron-doped
diamond (BDD) electrodes [15–24] etc. Recently, electrochemical
oxidation with a boron-doped diamond (BDD) electrode is one of the
most promising technologies in the treatment of the industrial
effluents containing organics [20]. BDD electrode exhibited a very
good chemical stability and its application in the electrooxidation of
organics led to complete mineralization into CO2 in relation with
applied potential or current density. A major drawback of the
electrochemical oxidation consists of the high energy consumption
to the mineralization. The presence of a catalyst in the electrical field
[25–30] or combined and direct photoelectrochemical application
[31–36] can enhance the treatment efficiency with lower energy
consumption.
In the present study, the photocatalytically-assisted electrochemical
oxidation using boron-doped diamond (BDD) electrodes was applied to
enhance the treatment efficiency of electrochemical oxidation of
4-aminophenol, which was chosen as a model compound to investigate
the degradation of refractory organics in water. The influence of TiO2-

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.04.068
52 C. Ratiu et al. / Desalination 260 (2010) 51–56
supported zeolite (TiO2-Z) catalyst under UV irradiation in the electric
field was assessed using an undivided electrolytic cell with BDD anodes
and stainless steel cathodes. The synergetic effect of the photocataly-
tically-assisted electrochemical oxidation on the treatment perfor-
mance was determined by comparison with electrochemical oxidation
and photocatalysis using the TiO2-Z catalyst, in terms of 4-AP removal
and mineralization efficiencies, electrochemical efficiencies, degrada-
tion and mineralization rates, mineralization current efficiency, and
energy consumption. In addition, some aspects regarding catalyst
synthesis and characterization are presented.
2. Experimental
2.1. Procedure description
The experiments were carried out by batch processes using an
undivided cell of 1 dm3 capacity, 276 mg dm− 3 p-aminophenol (4-AP)
in 0.1 M Na2SO4 as electrolyte, without pH correction under constant
temperature conditions (room temperature) and 1 g dm− 3 TiO2-
supported zeolite (TiO2-Z) catalyst. The optimum working conditions
regarding the pollutant concentration, pH, current density and catalyst
amount were chosen taking into account the results of preliminary tests
regarding 4-AP degradation by individual photocatalysis and electro-
chemical oxidation. The suspension was illuminated with a 6 W UV
lamp emitting 254–365 nm wavelengths. The BDD/Nb planed-plate
electrodes (100 mm× 50 mm× 1 mm) with an active geometric surface
area of 280 cm2, provided by CONDIAS, Germany, were used as anodes
and stainless steel plates (100 mm × 50 mm× 1 mm) were employed as
cathodes. The solution volume of 0.7 dm− 3 was constantly stirred at
200 rpm using a magnetic stirrer. A regulated DC power supply
(HY3003, MASTECH) was used under the galvanostatic regime at a
current density of 10 and 5 mA cm− 2, respectively. Based on literature
data [18], the values of current densities are selected to assure hydroxyl
radicals generation in relation with low specific energy consumption.
The experimental conditions for each experiment of the electro-
chemical, the photocatalytically-assisted electrochemical degrada-
tion, and photocatalysis are summarized in Table 1.
During the experiments, samples were drawn from the cell at
every 30 min and were analyzed.
2.2. Catalyst preparation and characterization
The TiO2-supported zeolite (TiO2-Z) catalyst was synthesized by a
microwave-assisted hydrothermal method. For the synthesis, natural
zeolites from the Mirşid-Romania area and titanium isopropoxide
(Fluka) were used as precursors.
The zeolite in the natural form (315–500 μm) was activated as the
sodium form (Z-Na) within two stages of acid (HCl) and alkaline
(NaNO3) treatment.
The microwave-assisted hydrothermal method used a mixture of
5 g of natural zeolite in the sodium form (Z-Na) with 45 mL distilled
water under continuous stirring. After a few minutes of stirring, 5 mL
of titanium isopropoxide (Ti precursor) were added as drops. The pH
Table 1
The experimental conditions for each applied oxidation process for 4-AP degradation.
Process Electrochemical TiO2-supported zeolite Presence of
working conditions (g dm− 3) UV lamp
Electrochemical i = 10 mA cm− 2 – No
oxidation (EO-I)
Electrochemical i = 5 mA cm− 2 – No
oxidation (EO)
−2
Photocatalysis-assisted i = 5 mA cm 1 Yes
electrochemical
oxidation (PCEO)
Photocatalysis (PC) – 1 Yes
was adjusted with a nitric acid solution to reach a value of pH 2.5.
After 1 h of stirring, the final solution was introduced into Teflon
autoclaves, tightly closed, and introduced into the professional
microwave oven for 15 min at a temperature of 150 °C.
Finally, the solution was filtered, washed and dried at 60 °C for 2 h.
The structural and morphological characterizations of the catalyst
were carried out by X-ray diffraction (XRD), scanning electron
microscopy (SEM), and cryogenic gas sorption (BET) analysis, using
a X'Pert PRO MPD PANanalytical (The Netherlands) XR diffractometer,
Inspect S Fei Company (The Netherlands) scanning electron micro-
scope, and ASAP 2020 Micromeritics, respectively.
2.3. Analysis and calculation
The solution pH was measured using a WTW inoLAB pH meter. UV
absorbance at 297 nm (UV297) and total organic carbon (TOC) were
chosen as parameters to determine quantitatively 4-AP during the
applied treatment. The UV spectrum was recorded using a Jasco V-530
spectrophotometer and TOC values of the samples were measured
using a Multi N/C 2100/2100 s TOC analyser, provided by Analytik
Jena. The parameters for the assessment of the performance of the
applied processes are described below.
The removal efficiency was determined as the percentage of
removed 4-AP reported at the initial 4-AP concentration.
The mineralization current efficiency (MCE) for each electrolyzed
solution was calculated based in Eq. (1) [24]:
nFVs ΔðTOC Þexp
MCE = × 100ð%Þ ð1Þ
4:32 × 107 mIt
where n is the number of electrons consumed in the mineralization
process of 4-AP, F is the Faraday constant (=96 487 C mol− 1), Vs is
the solution volume (dm3), Δ(TOC)exp is the experimental TOC decay
(mg dm− 3), 4.32 × 107 is a conversion factor for units homogenization
(=3600 s h− 1 × 12 000 mg of carbon mol− 1), m is the number of
carbon atoms in 4-AP, I is the applied current (A), and t is time (h). The
number of electrons consumed is determined based on the overall
mineralization reaction of 4-AP to CO2 (C6H7OH + 11H2O = 6CO2 +
30H+ + 24 e−).
The electrochemical efficiency for 4-AP oxidation was determined
based in Eq. (2) [9]:
ð4AP0 −4APÞ  
E4−AP = × V mg = C·cm
2
ð2Þ
C *S
where 4AP0 − 4AP is the change in the 4-AP concentration deter-
mined by UV297 during experiments for a charge consumption of C
corresponding to various electrolysis times, V is the sample volume
(700 cm3) and S is the area of the electrode surface (cm2).
The electrochemical efficiency for 4-AP mineralization was
determined based in Eq. (2) modified as Eq. (2′) taking into
consideration the change in TOC measurements during experiments,
determining (TOC0 − TOC)
ðTOC0 −TOC Þ  
2
ETOC = × V mg = C·cm ð2′Þ
C *S
The specific energy consumption, Wsp, was calculated with
relation (3):
 
−3
Wsp = Csp × U kWh dm ð3Þ
where Csp represents the specific charge consumption of C corresponding
to 1 dm3 and U is the cell voltage (V).
 C. Ratiu et al. / Desalination 260 (2010) 51–56
3. Results and discussion
3.1. Electrochemical removal of 4-AP from water
Fig. 1a and b shows the results of bulk electrolysis of aqueous
solutions containing 276 mg dm− 3 4-AP in a 0.1 M Na2SO4 electrolyte
under galvanostatic conditions at two different current densities of 5
and 10 mA cm− 2, respectively. It can be observed that both 4-AP
removal efficiencies, expressed by UV297 and TOC, increase with
electrolysis time and with specific electrical charge passed through
the electrochemical oxidation (Fig. 1a). Based on literature data
concerning the phenol-based organics electrooxidation under water
decomposition potential range [18], the 4-AP electrooxidation
occurred in two stages, in the first stage of 4-AP transformation into
Fig. 1. Evolution of the electrochemical treatment process for 4-AP removal at the
current density of 10 mA cm− 2 (square) and 5 mA cm− 2 (circle): a) process efficiency
in relation with UV297 (solid) and TOC (open); b) electrochemical efficiency in relation
with UV297 (solid) and TOC (open); c) cell voltage (solid) and pH (open).
53
carboxylic acids occurs and in the second stage the further oxidation
of carboxylic acid to carbon dioxide occurs. The difference between
UV297 and TOC evolutions with the electrolysis time for both applied
current densities proved the existence of the two oxidation stages.
Improved results were obtained by the application of a higher current
density (10 mA cm− 2) for the same electrolysis time, but it has to take
into consideration that for lower current density lower specific
electrical charge passed in the electrochemical oxidation. The results
of the electrochemical performance presented in Fig. 1b show that the
electrolysis cell operating at a current density of 5 mA cm− 2 leads to
better results for 4-AP oxidation expressed both UV297 and TOC. This
aspect can be explained by a major part of electrical charge consumed
for the abundant oxygen evolution. However, in the all situations it
can be noticed that within 60 min of the bulk electrolysis process, the
best results (in relation to the electrochemical efficiency) are reached.
During electrolysis, the cell voltage remains constant and it can be
observed that the pH of the residual solution first decreases slightly
and later increases to reach a value close to 8 (Fig. 1c). These changes
can be attributed to both anodic and cathodic processes which occur
in the cell. On the cathode the main reaction is the water reduction
with generation of hydroxyl ions, which led to the alkaline pH. At the
same time, on the anode several reactions coexist, i.e., organic
oxidation and oxygen evolution. The oxygen evolution provokes a
pH decrease. The organic oxidation with the carboxylic acids
formation in the first stage and subsequently its oxidation to carbon
dioxide are supported by pH evolution, thus, the presence of the
carboxylic acids lead to a pH decrease and by its conversion the pH is
increased. The resultant balance of cathodic alkalinisation by
predominantly hydrogen evolution process, irreversibility of anodic
oxidation of organics primary and intermediary compounds, and a
smaller anodic pH decrease is an overall pH increase in the cell.
3.2. Photocatalytically-assisted electrochemical degradation of 4-AP
from water
In order to improve the treatment performance of the 4-AP
mineralization, the application of photocatalysis using a TiO2-
supported zeolite (TiO2-Z) catalyst directly in the bulk electrolyte,
the photocatalytically-assisted electrolysis was performed.
3.2.1. The characteristics of TiO2-supported zeolite (TiO2-Z)
Fig. 2a illustrates comparative XRD spectra for TiO2, zeolite, TiO2-
supported zeolite (TiO2-Z), and the peaks corresponding to 2θ ∼ 25.2°,
37.87°, 48.01°, 53.81° can be attributed to the anatase TiO2 phase [37].
In addition, the peaks corresponding to the clinoptilolite component
of zeolite are marked. From Fig. 2b the non-uniform distribution of
TiO2 on the zeolite surface can be seen. The image of zeolite is shown
for comparison in Fig. 2c.
Using BET analysis the specific surface area of TiO2-Z was
compared with that of the zeolite, and it was found that TiO2-Z has
a specific surface area substantially higher than zeolite, i.e., 130.59
versus 58.8 m2 g− 1.
3.2.2. Synergetic removal of 4-AP from water
UV spectra of 4-AP evolution as presented in Fig. 3 were recorded
comparatively with initial 4-AP after the application of each oxidation
process, i.e., electrooxidation at the current density of 10 mA cm− 2
(EO-I), electrooxidation at the current density of 5 mA cm− 2 (EO),
photocatalysis using 1 g dm− 3 TiO2-Z catalyst (PC), photocatalyti-
cally-assisted electrooxidation at the current density of 5 mA cm− 2
using 1 g dm− 3 TiO2-Z catalyst (PCEO). The UV spectra indicated that
the degradation of 4-AP by application of the EO-I and PCEO processes
was more efficient than in the PC and EO processes.
The progression of 4-AP degradation by above-presented processes
indicated different oxidation efficiencies and the profiles are presented
in Fig. 4a and b. The degradation assessment at 60 min showed that the
54 C. Ratiu et al. / Desalination 260 (2010) 51–56

Fig. 3. UV spectrum comparison of 4-AP degradation by PC (2), EO-I (3), EO (4), and
PCEO (5); initial 4-AP (1).

electrooxidation and photocatalysis processes. This can be regarded as

a synergetic effect of the PCEO process.
To assess the 4-AP mineralization by all above-presented processes,
the progression of 4-AP degradation expressed in terms of TOC is shown
in Fig. 4b. After the reaction time of 120 min, about 16, 73, 36 and 72% of
TOC was removed by the application of PC, EO-I, EO, and PCEO,
respectively. The lower values of TOC removal degrees compared with
4-AP removal ones supported the fact that for all applied oxidation
processes the complete mineralization of 4-AP to CO2 occurred via
intermediates, i.e., carboxylic acids.

Fig. 2. a) X-ray diffraction patterns for TiO2 (i), zeolite (ii), and TiO2-Z (iii); b) SEM
image of TiO2-Z; c) SEM image of Z-Na.

lowest 4-AP degradation efficiency was obtained by simple photo-

catalysis. Better results were achieved for the EO-I and PCEO processes.
Thus, after the reaction time of 120 min, about 23, 90, 56 and 88% of
4-AP was degraded in the PC, EO-I, EO, and PCEO, respectively. Taking
into account the same current density of 5 mA cm− 2, it is clear that the Fig. 4. Evolution of 4-AP degradation with the reaction time, expressed in terms of:
net efficiency of the combined process is greater than the sum of both a) UV297,t/UV297,0 and b) TOCt/TOC0; (■) PC; (•) EO-I; (▼) EO; (▲) PCEO.
 C. Ratiu et al. / Desalination 260 (2010) 51–56 55

In general, the dependence of electrochemical reaction rates on

the concentration of organic pollutants has been described by a
pseudo first-order equation. Also, the photocatalysis reaction rate
follows the Langmuir–Hinshelwood kinetic model, which can be
simplified to a pseudo first-order equation [32]. For all applied
oxidation processes the pseudo first-order equation was chosen to
determine the apparent rate constant (kapp), which was calculated
based on the relation ln (C0/Ct) = kapp(t). The kinetic results were
obtained by monitoring changes in 4-AP concentration expressed by
UV297 and TOC analyses as a function of the reaction time. Table 2
shows the apparent rate constants for each applied oxidation process.
The apparent rate constant determined by UV analysis of PCEO was
similar to that of EO-I and by 8.1 and 2.5 times higher than PC and EO,
respectively. Also, the apparent rate constants determined by TOC
analyses are almost similar for EO-I and PCEO, and the latter is higher
by 9.6 and 2.6 times versus PC and EO, respectively. The kinetics of the
Fig. 5. Evolution of the mineralization current efficiency (solid) and the specific energy
TOC reduction in all applied processes showed that TOC reduction was
consumption (open) with the electrolysis time in the electrochemical oxidation of 4-AP
slower in the photocatalytic process, suggesting that the simple in 0.1 M Na2SO4 electrolyte for the application of: 1-EO-I; 2-EO; 3-PCEO.
photocatalysis process was inefficient in the mineralization and
degradation of 4-AP.
Acco0rding to the definition of the synergetic effect SF = kapp,PCEO − In Fig. 5, the evolution of the mineralization current efficiency and
(kapp,PC + kapp,EO) [32], the SF was calculated from the kinetic constants the specific energy consumption with electrolysis time during the
determined by UV and TOC analyses. Thus, (SF)UV of 0.0068 min− 1 and electrochemical treatment and photocatalytically-assisted electro-
(SF)TOC of 0.0063 min− 1 indicated the apparent kinetic synergetic chemical treatment are presented. The specific energy consumption
effects in the PCEO process for both degradation and mineralization of for PC including stirring also was about by 1000 times lower than
4-AP. energy consumption for electrochemical process, and only the last one
For the electrochemical and combined processes, the apparent rate was taken into consideration. For the electrochemical treatment, the
constant determined by UV and TOC analyses was also calculated based values of mineralization current efficiencies are very low after 60 min
on the relation of ln(C0/Ct) = k′app(C), in which C represents the for both current densities, when these become practically constant,
electrical charge passed during electrochemical and combined oxidation and it is apparent that the degradation during the first 60 min of the
of 4-AP. Based on the results gathered in Table 2 can be concluded that electrochemical treatment is responsible for almost the whole
the apparent rate constants determined with UV297 and TOC measure- process. It is well-known that the operating costs of an electrochem-
ments for the PCEO process are the best. Also, the effective minerali- ical oxidation depend strongly on the cell voltage as the specific
zation rate was assessed as the ratio between the apparent rate constant energy consumption (Wsp). Also, as it is logically owing to lower
calculated for the TOC analysis and the apparent rate constant calculated tension value, the energy consumption was lower for the current
for the UV analysis (k′app,TOC/k′app,UV). The value of this ratio close to 1 density of 5 mA cm− 2. By the application of the PCEO process for 4-AP
indicates that the effective mineralization rate was achieved. The value degradation a higher mineralization current efficiency at low specific
of 0.88 compared with 0.86 and 0.82 for EO-I and EO, respectively, energy consumption was reached. Thus, both technical and econom-
confirmed the enhancement effect of the application of photocatalysis ical aspects regarding degradation process of 4-AP from water
on the electrooxidation process of 4-AP to reach the mineralization. suggested the superiority of the PCEO process.
The enhancement effect of the combination of photocatalysis and
electrooxidation processes operating at high voltage or current 4. Conclusions
density may be attributed to two major factors, i.e., reducing the
recombination of electron-hole pairs resulting from photocatalysis, In this work, the electrochemical oxidation and photocatalytically-
and indirect electrochemical oxidation of 4-AP. According to literature assisted electrochemical oxidation using boron-doped diamond
data [32] it is supposed that the degradation mechanism is very (BDD) anodes and a TiO2-supported zeolite catalyst under UV
complex, involving many oxidation steps, e.g., anodic oxidation irradiation were applied for the degradation and mineralization of
involving oxygen evolution, oxidation by electrogenerated H2O2 and 4-aminophenol from aqueous solution.
OH•, oxidation by photogenerated holes and OH•, and the photoelec- The application of the electrochemical oxidation using BDD anodes
trocatalytic synergetic effect. at the two current densities of 10 mA cm− 2 and 5 mA cm− 2 for 4-AP
degradation revealed a better treatment performance at higher current
density. However, the better overall electrochemical performance and
Table 2
energy consumption was achieved at the current density of 5 mA cm− 2.
The pseudo first-order kinetic apparent constant for the degradation of 4-AP
determined by UV297 and TOC analyses. The synergetic effect of the photocatalytically-assisted electrochemical
oxidation operating at the current density of 5 mA cm− 2 on the
Type of 4-AP Applied oxidation Apparent rate constant Correlation
treatment performance was determined in comparison with each
determination process factor, R2
electrochemical oxidation and, in addition, with photocatalysis using
kapp k′app kapp k′app TiO2-Z catalyst. The treatment performance was assessed in terms of
(×10− 3 min− 1) (C− 1)
4-AP removal and mineralization efficiencies, electrochemical efficien-
UV297 PC 1.68 – 0.9118 – cies, degradation and mineralization rates, mineralization current
EO-I 15.52 0.333 0.9917 0.9917
efficiency, and energy consumption. After the reaction time of
EO 5.6 0.240 0.9968 0.9968
PCEO 13.6 0.586 0.9961 0.9961 120 min about 16, 36, and 72% of TOC was removed in the
TOC PC 1.26 – 0.9353 – photocatalysis, electrooxidation at the current density of 5 mA cm− 2,
EO-I 13.37 0.286 0.9633 0.9821 and in photocatalytically-assisted electrooxidation at the current
EO 4.57 0.196 0.9821 0.9633 density of 5 mA cm− 2 and 1 g dm− 3 TiO2-Z, respectively. Also, for the
PCEO 12.1 0.518 0.9886 0.9886
application of the combined process an apparent kinetic synergetic
56 C. Ratiu et al. / Desalination 260 (2010) 51–56
effect, resulted from efficiencies and defined also from conventionally
evaluated rate constants, was achieved for 4-AP mineralization. The
technical and economical assessments suggested the superiority of a
combined process for the degradation and mineralization of 4-AP from
water.
Acknowledgements
Funding for this study was provided by the Romanian National
Research Programs — PNII: ZEONANO — SPP, no. 56/2007, NANO-
ZEOREZID, no. 72-156/2008, and STEDIWAT no. 32-125/2008.
References
[1] *** Directive 2008/1/EC of the European Parliament and of the Council of 15
January 329 2008 concerning integrated pollution prevention and control.
[2] E. Brillas, E. Mur, R. Sauleda, L. Sanchez, J. Peral, X. Domenech, J. Casado, Aniline
mineralization by AOP's: anodic oxidation, photocatalysis, electro-Fenton and
photoelectro-Fenton processes, Appl. Catal. B: Environ. 16 (1998) 31–35.
[3] V. Augugliaro, M. Litter, L. Palmisano, J. Soria, The combination of heterogenous
photocatalysis with chemical and physical operations: a tool for improving the
photoprocess performance, J. Photochem. Photobiol. C: Photochem. Rev. 7 (2006)
127–144.
[4] E.C. Catalkaya, F. Kargi, Color, TOC and AOX removals from pulp mill effluent by
advanced oxidation processes: a comparative study, J. Hazard. Mater. 139 (2007)
244–253.
[5] M. Pera-Titus, V. Garcia-Molina, M.A. Banos, J. Gimenez, S. Esplugas, Degradation
of chlorophenols by means of advanced oxidation processes: a general review,
Appl. Catal. B: Environ. 47 (2004) 219–256.
[6] M. Zhou, J. He, Degradation of azo dye by three clean advanced oxidation processes:
wet oxidation, electrochemical oxidation and wet electrochemical oxidation — a
comparative study, Electrochim. Acta 53 (2007) 1902–1910.
[7] E. Brillas, C. Arias, P.-L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodriguez,
Degradation of organic contaminants by advanced electrochemical oxidation
methods, Portugaliae Electrochim. Acta Review 24 (2006) 159–189.
[8] Y.J. Feng, X.Y. Li, Electro-catalytic oxidation of phenol on several metal-oxide
electrodes in aqueous solution, Water Res. 37 (2003) 2399–2407.
[9] Y.H. Wang, K.Y. Chan, X.Y. Li, S.K. So, Electrochemical degradation of 4-chlorophenol
at nickel–antimony doped tin oxide electrode, Chemosphere 65 (2006) 1087–1093.
[10] R.D. Coteiro, A.R. De Andrade, Electrochemical oxidation of 4-chlorophenol and its
by-products using Ti/Ru0.3 M0.7O2 (M = Ti or Sn) anodes: preparation route
versus degradation efficiency, J. Appl. Electrochem. 37 (2007) 691–698.
[11] M. Panizza, A. Barbucci, R. Ricotti, G. Cerisola, Electrochemical degradation of
methylene blue, Sep. Purif. Technol. 54 (2007) 382–387.
[12] B. Wang, W. Kong, H. Ma, Electrochemical treatment of paper mill wastewater
using three-dimensional electrodes with Ti/Co/SnO2–Sb2O5 anode, J. Hazard.
Mater. 146 (2007) 295–301.
[13] F. Manea, J. Schoonman, C. Radovan, Electrodeposition of PbO2 and Co-doped
PbO2 on stainless steel support and its electrochemical characterization in acidic
media, Rev. Chim. 56 (2005) 266–276.
[14] Y. Liu, H. Liu, Comparative studies on the electrocatalytic properties of modified
PbO2 anodes, Electrochim. Acta 53 (2008) 5077–5083.
[15] N. Katsuki, E. Takahashi, M. Toyoda, T. Kurosu, M. Iida, S. Wakita, Y. Nishiki, T.
Shimamune, S. Wakita, Y. Nishiki, T. Shimamune, Water electrolysis using diamond
thin-film electrodes, Electrochem. Solid State Lett. 145 (1998) 2358–2362.
[16] L. Gherardini, P.A. Michaud, M. Panizza, Ch. Comninellis, N. Vatistas, Electrochemical
oxidation of 4-chlorophenol for wastewater treatment, J. Electrochem. Soc. 148
(2001) D78–D82.
[17] G. Lissens, J. Pieters, M. Verhaege, L. Pinoy, W. Verstraete, Electrochemical
degradation of surfactants by intermediates of water discharge at carbon-based
electrodes, Electrochim. Acta 48 (2003) 1655–1663.
[18] P. Canizares, J. Lobato, R. Paz, M.A. Rodrigo, C. Saez, Electrochemical oxidation of
phenolic wastes with boron-doped diamond electrodes, Water Res. 39 (2005)
2687–2703.
[19] P. Canizares, C. Saez, J. Lobato, M.A. Rodrigo, Detoxification of synthetic industrial
waste-waters using electrochemical oxidation with boron-doped diamond
anodes, J. Chem. Technol. Biotechnol. 81 (2006) 352–358.
[20] P. Canizares, L. Martinez, R. Paz, C. Saez, J. Lobato, M.A. Rodrigo, Treatment of
Fenton-refractory olive oil mill wastes by electrochemical oxidation with boron-
doped diamond anodes, J. Chem. Technol. Biotechnol. 81 (2006) 1331–1337.
[21] Y. Zhang, S. Yoshihara, T. Shirakashi, Novel application of boron-doped diamond
and related material to electrochemical generation of functional water, Electro-
chim. Acta 51 (2005) 1008–1011.
[22] A. Kapalka, G. Foti, C. Comninellis, Investigations of electrochemical oxygen
transfer reaction on boron-doped diamond electrodes, Electrochim. Acta 53
(2007) 1954–1961.
[23] S. Hammami, N. Bellakhal, N. Oturan, M.A. Oturan, M. Dachraoui, Degradation of
acid orange 7 by electrochemically generated •OH radicals in acidic aqueous
medium using a boron-doped diamond or a platinum anode: a mechanistic study,
Chemosphere 73 (2008) 678–684.
[24] E. Guinea, F. Centellas, J.A. Garrido, R.M. Rodriguez, C. Arias, P.-L. Cabot, E. Brillas,
Solar photoassisted anodic oxidation of carboxylic acids in presence of Fe3+ using
a boron-doped diamond electrode, Appl. Catal. B: Environ. 89 (2009) 459–468.
[25] T. An, G. Li, Y. Xiong, X. Zhu, H. Xing, G. Liu, Photoelectrochemical degradation of
methylene blue with nano TiO2 under high potential bias, Mater. Phys. Mech. 4
(2001) 101–106.
[26] J. Chen, M. Liu, J. Zhang, X. Ying, L. Jin, Photocatalytic degradation of organic
wastes by electrochemically assisted TiO2 photocatalytic system, J. Environ.
Manag. 70 (2004) 43–47.
[27] Y. Lei, Z. Shen, X. Chen, J. Jia, W. Wang, Preparation and application of nano-TiO2
catalyst in dye electrochemical treatment, Water. SA. 32 (2) (2006) 205–210.
[28] Z.M. Shen, D. Wu, J. Yang, T. Yuan, W.H. Wang, J.P. Jia, Methods to improve
electrochemical treatment effect of dye wastewater, J. Hazard. Mater. 131 (2006)
90–97.
[29] B. Wang, L. Gu, H. Ma, Electrochemical oxidation of pulp and paper making
wastewater assisted by transition metal modified kaolin, J. Hazard. Mater. 143
(2007) 198–205.
[30] L. Gomathi Devi, N. Kottam, S. Girish Kumar, K.S. Anantha Raju, Mechanism of charge
transfer in the transition metal ion doped TiO2 with bicrystalline framework of
anatase and rutile: photocatalytic and photoelectrocatalytic activity, Catal. Lett. 131
(3-4) (2009) 612–617.
[31] J. Krysa, J. Jirkovsky, Electrochemically assisted photocatalytic degradation of
oxalic acid on particulate TiO2 film in a batch mode plate photoreactor, J. Appl.
Electrochem. 32 (2002) 591–596.
[32] T. An, W. Zhang, X. Xiao, G. Sheng, J. Fu, X. Zhu, Photoelectrocatalytic degradation
of quinoline with a novel three-dimensional electrode-packed bed photocatalytic
reactor, J. Photochem. Photobiol. A: Chem. 161 (2004) 233–242.
[33] J. Li, L. Zheng, L. Li, Y. Xian, L. Jin, Fabrication of TiO2/Ti electrode by laser assisted
anodic oxidation and its application on photoelectrocatalytic degradation of
methylene blue, J. Hazard. Mater. B139 (2007) 72–78.
[34] M.G. Neelavannan, M. Revathi, C. Ahmed Basha, Photocatalytic and electrochemical
combined treatment of textile wash water, J. Hazard. Mater. 149 (2007) 371–378.
[35] Z. Zainal, C. Yong Lee, M. Zobir Hussein, A. Kassim, N. Azah Yusof, Electrochemical-
assisted photodegradation of mixed dye and textile effluents using TiO2 thin films, J.
Hazard. Mater. 146 (2007) 73–80.
[36] H. Selcuk, M. Bekbolet, Photocatalytic and photoelectrocatalytic humic acid
removal and selectivity of TiO2 coated photoanode, Chemosphere 73 (2008)
854–858.
[37] S. Rengaraj, X.Z. Li, P.A. Tanner, Z.F. Pan, G.K.H. Pang, Photocatalytic degradation of
methylparathion—an endocrine disruptor by Bi3+-doped TiO2, J. Mol. Catal. A:
Chem. 247 (2005) 36–43.