Electro-Fenton degradation of synthetic dyes

Marco Panizza*, Giacomo Cerisola

Department of Chemical and Process Engineering, University of Genoa, P.le J.F. Kennedy 1, 16129 Genoa, Italy
a r t i c l e i n f o
Article history:
Received 31 July 2008
Received in revised form
14 October 2008
Accepted 15 October 2008
Published online 1 November 2008
Keywords:
Electro-Fenton
Gas-diffusion electrode
Alizarin red
Dyes removal
a b s t r a c t
The electrochemical removal of a synthetic solution containing 120 mg L
1
of alizarin red
has been studied by electro-Fenton process using a gas-diffusion cathode to produce in situ
hydrogen peroxide by oxygen reduction. The effect of operating conditions such as Fe
2
concentration, applied current, solution pH and temperature on the efcacy of the process
was investigated. It is shown that alizarin red and its products may be effectively degraded
by the OH

radicals produced by the reaction between the Fe

2
ions and the electro-
generated H
2
O
2
.
After 4 h of electrolysis COD removal was only 45% when no ferrous ions were added to the
solutions, while the presence of ferrous ion greatly improved COD removal up to more than
90%. In particular 1.0 mM was the optimal concentration of ferrous ions and the single step
or the stepwise addition of Fe
2
ions enables the same COD removal. The oxidation rate
increased with increasing of current density and temperature and with decreasing of pH.
The UVvis analysis indicated that the discoloration of the solution occurs simultaneous
with the destruction of aromatic rings and alizarin red is oxidised rstly to colourless
intermediates (mainly phthalic acid, small carbonyl species) and then to carbon dioxide.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
In recent decades the rapid growth of public awareness of
environmental problems has induced many governments to
introduce legislation that prescribes and limits the emission
of pollutants and consequently there was a notable increase
in research concerned with the treatment of industrial efu-
ents and, nowadays, many new technologies are available,
including biological, physical and chemical processes. Thanks
to the development of new electrode materials and more
compact reactors, electrochemical technologies have reached
a promising stage of development and can now also be
effectively used for the destruction of toxic or biorefractory
organics.
The electrochemical oxidation of organics for wastewater
treatment can be obtained by direct electrolysis, where the
pollutants are oxidised after adsorption on the anode surface
without the involvement of any substances other than the
electron, which is a clean reagent:
R
ads
ze

/P
ads
(1)
Direct electro-oxidation is theoretically possible at low
potentials, before oxygen evolution, but the reaction rate
usually has slow kinetics and above all during the process
there is a decrease in the catalytic activity, commonly called
the poisoning effect, due to the formation of a polymer layer
on the anode surface (Gherardini et al., 2001; Panizza et al.,
2001; Rodrigo et al., 2001; Canizares et al., 2004b). This elec-
trode deactivation can be avoided by performing the oxidation
at high potentials, in the region of water discharge, due to the
participation of intermediates of oxygen evolution (Johnson
et al., 1999; Canizares et al., 2004a; Panizza and Cerisola,
2004a,b; Boye et al., 2006; Faouzi et al., 2007):
H
2
O/OH

(2)
* Corresponding author. Tel.: 39 010 3536032; fax: 39 010 3536028.
E-mail addresses: marco.panizza@unige.it (M. Panizza), giacomo.cerisola@unige.it (G. Cerisola).
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ wat r es
0043-1354/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2008.10.028
wa t e r r e s e a r c h 4 3 ( 2 0 0 9 ) 3 3 9 3 4 4
However, working at high anodic potentials, the current
efciency is diminished by the secondary reaction of oxygen
evolution occurring during the oxidation.
H
2
O/1=2O
2
2H

2e

(3)
Another approach to the electrochemical treatment of
organic pollutants is the indirect electrolysis generating in situ
chemical oxidizing agents to react with the pollutants, such as
chlorine and/or hypochlorite and hydrogen peroxide.
Electrogenerated chlorine and/or hypochlorite, whose use
is well established in the disinfection of potable and swim-
ming pool waters and paper and pulp bleaching, have also
found wide applications as electro-oxidation mediators for
wastewater treatment, however, their use has the main
drawback of possible formation of organochlorinated
compounds (Bonfatti et al., 2000; Panizza et al., 2000; Iniesta
et al., 2001; Panizza and Cerisola, 2003; Panizza et al., 2005).
In contrast, hydrogen peroxide is an environmentally
friendly chemical that leaves no hazardous residuals since it
decomposes only to water and oxygen.
Hydrogen peroxide is electrogenerated in acidic solutions
by two-electron reduction of oxygen on the cathode surface:
O
2
2H

2e

/H
2
O
2
(4)
or in an alkaline solution by the reaction:
O
2
H
2
O 2e

/HO

2
OH

(5)
These reactions occur with high yield and satisfactory rate
only at three-dimensional carbon-based cathodes (Alvarez-
Gallegos and Pletcher, 1998; Sudoh et al., 2001; Yamada et al.,
2001; Qiang et al., 2002; Da Pozzo et al., 2005a), due to the low
solubility of oxygen in aqueous solutions. More recently, gas-
diffusion cathodes (GDE) have demonstrated to be promising
electrode materials for the electrogeneration of H
2
O
2
from
oxygen reduction (Harrington and Pletcher, 1999; Alcaide
et al., 2002, 2003; Da Pozzo et al., 2005b; Agladze et al., 2007b).
Many studies have reported the application of H
2
O
2
elec-
trogenerated on GDE, fed with pure oxygen, for the treatment
of wastewater containing organic pollutants, especially in the
presence of Fe
2
ions (electro-Fenton process) (Oturan et al.,
2000; Brillas and Casado, 2002; Boye et al., 2003; Guivarchet al.,
2003; Brillas et al., 2004; Hanna et al., 2005; Oturan and Oturan,
2005; Agladze et al., 2007a; Brillas et al., 2007; Liu et al., 2007a,b;
Sires et al., 2007) or with Fe
2
and UVA irradiation (photo-
electron-Fenton process) (Flox et al., 2006; Brillas et al., 2007;
Flox et al., 2007a,b).
In both processes, strong oxidizing OH

radicals are
generated in the solution by the well-known Fentons reaction
between Fe
2
and electrogenerated H
2
O
2
:
Fe
2
H
2
O
2
/Fe
3
OH

OH

(6)
Due to the high price of pure oxygen, to increase the
competitiveness of the electrochemical wastewater
treatment, it is interesting to evaluate GDE performance
when fed with air. In a previous paper (Panizza and
Cerisola, 2008) a preliminary study of hydrogen peroxide
electrogeneration at a gas-diffusion cathode fed with air
was carried out in low ionic strength solution under
different conditions of pH, current density, and temper-
ature and experimental results have indicated that gas-
diffusion cathodes enable a considerable production and
a good current efciency, even when pure oxygen feed is
replaced by air feed. Therefore, in the present paper we
report the results about the treatment of model waste-
water containing synthetic dye using hydrogen peroxide
electrogenerated at a gas diffusion cathode fed with air.
Alizarin red, an anthraquinone dye, was chosen as
a model compound because it is used in textile dyeing since
early antiquity, and it contains aromatic rings that make it
difcult to treat with traditional processes. The inuence of
the main operating parameters, such as current density,
ferrous ions concentration, solution pH and temperature
affecting COD and colour removal was investigated.
2. Experimental
2.1. Chemicals and analytical procedures
The dyestuff solution was prepared dissolving 120 mg L
1
of
alizarin red (Carlo Erba Reagents) used without further puri-
cation in bi-distilled water, using 0.05 M Na
2
SO
4
(Carlo Erba
Reagents) as supporting electrolyte. The physicochemical
properties of alizarin red are reported in Table 1. Heptahy-
drated ferrous sulphate was of analytical grade supplied by
Carlo Erba Reagents. Solution pH was adjusted to the desired
value by addition of H
2
SO
4
or NaOH. pH was measured using
a Schott Gerate CG822 pH-meter.
Colour removal was monitored by measuring absorbance
decrease, using a spectrophotometer (PerkinElmer Lambda
2). Solution COD was measured during electrolysis using a Dr.
Lange LASA50 system.
Current Efciency (CE) for anodic oxidation of alizarin red
was calculated from COD values, using the following rela-
tionship:
C:E: %
COD
0
COD
t

8 I t
F V 100 (7)
where COD
0
and COD
t
are chemical oxygen demands at times
t 0 (initial) and t (in g
O2
dm
3
) respectively, I is the current
(A), F is the Faraday constant (96487 Cmol
1
), V is the elec-
trolyte volume (dm
3
), and 8 is the oxygen equivalent mass
(g eq
1
).
Table 1 Physicochemical properties of alizarin red.
Chemical name 1,2-Dihydroxyanthraquinone
Chemical formula C
14
H
8
O
4
Chemical structure
O
O
OH
OH
Molecular Weight 240.2 g/mol
Class Anthraquinone
Colour index 58055
wa t e r r e s e a r c h 4 3 ( 2 0 0 9 ) 3 3 9 3 4 4 340
2.2. Electrochemical reactors and electrodes
The experiments were performed using an undivided cell with
a volume of 250 mL, supplied with a heat exchanger and
a magnetic stirrer under galvanostatic conditions using an
AMEL 2055 potentiostat/galvanostat. The GDE was used as
cathode electrode, a Pt grid with an area of about 5 cm
2
as
anode.
The uncatalyzed gas-diffusion cathode was a commercial
electrode supplied by Gaskatel, and consisting of a carbon
PTFE layer in contact with a nickel meshas current collector. It
was placed at the bottomof a cylindrical polypropylene holder
with 6.15 cm
2
apparent area of the outer electrode face in
contact with the solution. The electrical contact was made by
a copper wire introduced inside the holder and pressed on the
current collector.
The electrode was fed with air at a ow rate of 20 mL s
1
.
The gas owpassed over the inner face of the cathode through
a tube inside the holder, the top of which was connected to
a drechsel to maintain the right pressure in the Plexiglas
holder. No bubbles were observed on the cathode surface thus
excluding any passage of gas into the solution. The detailed
experimental setup has been given elsewhere (Panizza and
Cerisola, 2008).
3. Results and discussion
3.1. Inuence of Fe
2
concentration
The electrochemical oxidation of alizarin red by electro-Fen-
ton process was studied under different experimental condi-
tions in order to investigate the inuence of operative
parameters on COD and colour removal.
Fig. 1 shows the inuence of Fe
2
ions on the evolution of
COD during the treatment of 120 mg L
1
of alizarin red solu-
tion at 200 mA and pH 3.
In the absence of ferrous ions, only 45% of COD depletion
was obtained after 4 h of electrolysis because the main
oxidant was the electrogenerated H
2
O
2
that has limited
oxidation power.
In contrast, in the solution containing Fe
2
ions, alizarin
red oxidation was accelerated because of the formation of OH

radicals, according to Fentons reaction (Eq. (6)).

A gradual increase in COD abatement can be observed
when Fe
2
content increases, leading to a nal mineralization
of 67%, 89%and 93%for 0.25, 0.5 and 1.0 mMFe
2
, respectively
(Fig. 1, inset).
However, further increase in the concentration of ferrous
ions to 2.0 mMdid not bring about further improvement in dye
removal. It has been reported that an excess of ferrous ions
would consume hydroxyl radicals by the following non-
oxidizing reaction (Sun and Pignatello, 1993; Panizza and
Cerisola, 2001; Brillas et al., 2007; Zhou et al., 2008):
Fe
2
OH

/Fe
3
OH

(8)
Consequently 1.0 mM of ferrous ions has been used for the
further experiments.
The Fe
2
feeding type was also investigated in this study,
i.e., the Fe
2
ions were added in a single step (1.0 mMat 0 min)
or in two steps (0.5 mM at 0 min 0.5 mM at 2 h). The results
showed that, conversely from the chemical Fentons reagent,
in the electro-Fenton process the single step or the stepwise
addition of Fe
2
ions enable almost the same COD removal
(Fig. 2). In fact in the electro-Fenton, the propagation of Fen-
tons reaction can be enhanced by electrochemical regenera-
tion of Fe
2
ions on cathode surface (Brillas et al., 1996):
Fe
3
e

/Fe
2
(9)
3.2. Inuence of applied current
The inuence of current density on dye oxidation has been
investigated in the range 100200 mA and the results are
reported in Fig. 3.
These data show a gradual increase in COD removal rate
with raising current. This enhancement of the oxidation
0
50
100
150
200
250
0 1 2 3 4
Time (h)
C
O
D

(
m
g

L
-
1
)
0
25
50
75
100
0 0.5 1 1.5 2
Concentration of Fe
2+
(mM)
C
O
D

r
e
m
o
v
a
l

(
)
Fig. 1 Inuence of the Fe
2D
concentration on COD
evolution during the electrolysis of alizarin red.
Conditions: Na
2
SO
4
0.05 M, pH[3; T [25 8C; I [200 mA;
Fe
2D
concentration: (,) 0 mM; (O) 0.25 mM; (B) 0.5 mM;
(>) 1.0 mM; (3) 2.0 mM. The inset shows the evolution of
COD removal after 4 h of treatment as a function of Fe
2D
concentration.
0
50
100
150
200
250
0 1 2 3 4
Time (h)
C
O
D

(
m
g

L
-
1
)
Addition
Fig. 2 Effect of Fe
2D
feeding on COD evolution during the
electrolysis of alizarin red. Conditions: Na
2
SO
4
0.05 M,
pH[3; T [25 8C; I [200 mA; Fe
2D
feeding: (,) 1.0 mM at
t [0 h; (O) 0.5 mM at t [0 h; (B) 0.5 mM at
t [0 hD0.5 mM at t [2 h.
wa t e r r e s e a r c h 4 3 ( 2 0 0 9 ) 3 3 9 3 4 4 341
power can only be associated with a greater production of
H
2
O
2
from reaction (4) leading to the generation of higher
amount of hydroxyl radicals fromFentons reaction (Eq. (6)). In
fact the current efciency (Fig. 3, inset) was almost indepen-
dent on applied current and depends only on the specic
charge passed. Fig. 3 (inset) also shows that during the elec-
trolysis the efciency always undergoes a dramatic fall due to
the gradual formation of intermediates that are destroyed
with more difculty, as complexes of Fe
3
with carboxylic
acids (Flox et al., 2006).
3.3. Inuence of pH
To clarify the effect of pH, dye solutions with initial pH of 3.0,
4.0, 5.0 and 6.0 were electrolysed at 200 mA and the results are
illustrated in Fig. 4.
A notable pH effect was found for the electro-Fenton
process, reaching its faster degradation at pH 3.0 with
a maximum COD removal of 93% at 4 h. This result is entirely
consistent with the one reported by other authors (Brillas
et al., 2003; Zhou et al., 2007, 2008) for the degradation of
organic pollutants by electro-Fenton methods and it is also
very close to the optimum pH of 2.8 for Fentons reaction (Sun
and Pignatello, 1993).
At pH above 3.0 the decomposition rate decreased because
the oxidation potential of OH

and also the dissolved fraction

of iron species decrease with increasing pH. While at very
acidic pH, below pH 3.0, the electrogenerated hydrogen
peroxide solvates a proton to forman oxoniumion (H
3
O
2

) that
enhances its stability and reduce the reactivity with ferrous
ions and consequently less hydroxyl radicals are produced by
reaction (6) (Kwon et al., 1999).
3.4. Inuence of temperature
The decay of COD during the treatment of alizarin red at
200 mAand pH3 at different temperatures is depicted in Fig. 5.
An increase in degradation rate of dye is observed when
the temperature increases from 25 to 35

C which can be
associated with an increase in the reaction rate of organics
with hydroxyl radicals. However, similar COD decays are
obtained at 35 and 45

C probably because at high temperature
hydrogen peroxide produced at the cathode undergoes self-
decomposition (Eq. (10)).
H
2
O
2
/H
2
O 1=2O
2
(10)
Therefore, 35

C is the optimal temperature to perform
electrolysis under our working conditions.
3.5. Oxidation mechanism
To obtain additional qualitative information about the
oxidation pathways involved in the electro-oxidation process
of alizarin red, the samples obtained were analysed by UVvis
techniques. The UV spectra of alizarin red, reported in Fig. 6,
present one main band in the visible region with a peak at
420 nm and a strong sharp peak in the ultraviolet region at
280 nm that decreased until disappearing, during the elec-
trolysis. Furthermore, the intensity of both bands decreases
0
50
100
150
200
250
0 2 4 6 8
Time (h)
C
O
D

(
m
g

L
-
1
)
0
20
40
60
0 1 2 3 4
Q (Ah L
-1
)
C
.
E
.

(
)
Fig. 3 Inuence of applied current on COD and current
efciency (inset) evolution during the electrolysis of
alizarin red. Conditions: Na
2
SO
4
0.05 M, pH[3; T [25 8C;
Fe
2D
[1.0 mM; applied current: (,) 100 mA; (O) 150 mA;
(B) 200 mA.
0
20
40
60
80
100
0 1 2 3 4 5 6 7
pH (-)
C
O
D

r
e
m
o
v
a
l

(
)
Fig. 4 Effect of pH on the COD removal during the
electrolysis of alizarin red. Conditions: Na
2
SO
4
0.05 M;
T [25 8C; Fe
2D
[1.0 mM; applied current: 200 mA.
0
50
100
150
200
250
0 1 2 3 4
Time (h)
C
O
D

(
m
g

L
-
1
)
Fig. 5 Inuence of temperature on the COD removal
during the electrolysis of alizarin red. Conditions: Na
2
SO
4
0.05 M, pH[3; Fe
2D
[1.0 mM; I [200 mA; Temperature:
(B) 25 8C; (O) 35 8C; (,) 45 8C.
wa t e r r e s e a r c h 4 3 ( 2 0 0 9 ) 3 3 9 3 4 4 342
with the same ratios during the treatment and faster than the
COD (Fig. 6, inset). This fact indicates that, in agreement with
the mechanism proposed by Liu et al. (Liu et al., 1999), the rst
step in the oxidation of alizarin red is the cleavage of the
aromatic ring in the CC bond near the C]O group to form
colourless intermediates (mainly phthalic acid, small
carbonyl species) and nally these intermediates are miner-
alised to carbon dioxide.
4. Conclusions
It has been demonstrated that a synthetic solution containing
120 mg L
1
of alizarin red can be effectively depolluted by the
electro-Fenton process using a gas-diffusion cathode fed with
air to electrogenerate hydrogen peroxide. The results of the
bulk electrolysis under different experimental conditions
showed that the mineralization of alizarin red was primarily
affected by the concentration of ferrous ions, because elec-
trogenerated H
2
O
2
alone has limited oxidation power but
complete COD and colour removal can be obtained with
addition of ferrous ions that promoted the Fentons reaction.
In the presence of 1.0 mM of Fe
2
, the oxidation rate was also
inuenced by the current density, the solution pH and
temperature, but was almost unaffected by the type of ferrous
ions feed, i.e., single step or stepwise addition. The UVvis
analysis indicated that alizarin red is oxidised rstly to col-
ourless intermediates (mainly aliphatic acids) and then to
carbon dioxide.
Acknowledgements
The authors gratefully acknowledge Dr. Paolo Granone for his
helpful discussion.
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Wavelenght (nm)
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normalised COD (,).
wa t e r r e s e a r c h 4 3 ( 2 0 0 9 ) 3 3 9 3 4 4 343
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