Journal of Membrane Science 446 (2013) 4249

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Journal of Membrane Science

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

Elaboration and characterization of new conductive porous graphite

membranes for electrochemical advanced oxidation processes
Saloua Ayadi a, Ilyes Jedidi a, Matthieu Rivallin b, Frdric Gillot b, Stella Lacour b,
Sophie Cerneaux b, Marc Cretin b,n, Raja Ben Amar a
a

Laboratoire Sciences des Matriaux Environnement, Facult des Sciences de Sfax, Rte. de Soukra Km 4, 3000 Sfax, Tunisie
IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universit de Montpellier 2, Place E. Bataillon, F-34095 Montpellier, cedex 5,
France

art ic l e i nf o

a b s t r a c t

Article history:
Received 29 March 2013
Received in revised form
30 May 2013
Accepted 8 June 2013
Available online 24 June 2013

Three different graphite powders with different particles sizes were tested to synthesize tubular
monochannel carbon supports for micro and ultraltration membranes using a new process. Carbon
graphite powders and organic additives were mixed with an ethanolic solution of Resols type phenolic
resin. The extruded tubes were rstly consolidated by curing the resin at 150 1C then carbonized under
nitrogen stream (1 mL min1) for graphitization and pores opening.
Supports with optimal properties were obtained using a mixture of Resols resin and a 44 mm particle
size graphite powder, carbonized at 1000 1C. They showed a porosity value of 37%, an average pore size
diameter of 3 mm, high mechanical and chemical resistances and an average conductivity of
190 1 cm1.
The Raman spectroscopy results show that graphitization degree of the material is closely related to
the carbonization temperature, which explains the increase of conductivity with temperature.
Acid Orange 7 (AO7), a common dye, was nally used as a model molecule to demonstrate the ability
of the graphitic membranes to mineralize organic pollutants by electro-Fenton process. Spectrophotometric measurements were conducted on the treated solutions as a function of chemical and
electrochemical conditions to determine the degradation kinetic of AO7. Decolorization rate was also
measured as a function of time.
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Graphite powder
Phenolic resin
Extrusion
Tubular porous support
Electro-Fenton process

1. Introduction
One of the most pervasive problems aficting people throughout the world is the inadequate access to clean water. The industry
of textile is a major consumer of water and wastewater from
textile processing plants are highly loaded in organic pollutants,
mainly synthetic colorants. Azo-dyes form the largest group
among these synthetic colorants (6070%) [1]. The chromophoric
system consists of azo groups (NQN) in association with
aromatic systems and oxochromes (OH, NH2, etc.). Since
azo-dyes are intentionally designed to resist degradation, it is very
difcult to degrade them by conventional wastewater treatment
methods. In addition, the toxicity, mutagenicity and carcinogenicity of azo-dye degradation by-products are of great environmental concern [2].

Corresponding author. Tel.: 33467149194.

E-mail addresses: marc.cretin@univ-montp2.fr,
marc.cretin@iemm.univ-montp2.fr (M. Cretin).
0376-7388/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2013.06.005

To solve this problem, some research groups have reported that

electro-Fenton oxidation offers signicant advantages, without
requirement for special equipment, and high efciency in organic
pollutants removal [3,4]. Electro-Fenton process is a promising
technology that combines electrochemical reactions and Fenton
process. In this hybrid process, the electrical current induces the
reduction of oxygen to form hydrogen peroxide on graphite based
electrodes, which are needed for the Fenton reaction (i.e. the
reaction between H2O2 and Fe2+ to form highly oxidative OH
radicals).
Thus, H2O2 is generated in situ by the electrical current
externally applied to the carbon electrode, avoiding its transport
and continuous addition throughout the process due to its
decomposition in the medium [5]. Therefore, in the electroFenton process, the continuous electro-generation of H2O2 is
achieved by the reduction of dissolved O2 in the presence of Fe2+.
The propagation of the Fenton's reaction is obtained via a
catalytic cycle involving the reverse conversion of Fe3+ formed
by the Fenton reaction to Fe2+ by direct reduction at the cathode
or other reduction processes, involving H2O2 or organic intermediate radicals [6].

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

To get efcient degradation of organic molecules, high oxygen

reduction rates have to be reached. For this purpose, conductive
porous materials such as carbon mates [715] are good candidates.
The main drawback of carbon mates or polymeric porous lm is
their necessity to be supported for ltration applications.
Carbon membranes offer a better alternative for applications
under ux because of their high mechanical [16], chemical [17]
and thermal stabilities [18], along with their good permeability
and selectivity. They are largely used for the separation of
pesticides [19] and gas mixtures [20,21] because they provide a
better control of pore dimensions in the vicinity of the molecular
size ranges of interest. This has become possible due to the
availability of a variety of pore-forming organic precursors and
lm-making processes.
Nowadays, a lot of researchers have used different polymeric
precursors to prepare carbon membrane. The polymeric precursor
needs to have thermosetting property in order to avoid melting
when heated and thus retain its structural shape during heating
and pyrolysis.
Carbon membranes are produced through the pyrolysis of
carbon containing precursors (carbonization) either natural, such
as wood, coal, lignite, seeds and peat [22] or chemically synthesized such as polyimide [2326], polyacrylonitrile [27], phenolic
resins [2830], polyfurfuryl alcohol (PFA) [3133] or poly-vinylpyrrolidone (PVP) [34].
Phenolic resin, which can be obtained from various combinations of phenols and aldehydes by using either a base or acid as
catalyst, is one of the well-used synthetic precursors, due to their
low cost and high carbon yield, for the production of carbon bers
[31], porous carbons [32,33], carbon nanotubes (CNTs) [34] and
carbon membranes [3539]. Their use is made easier by the large
variety of presentation (in solution or powdered) and of types,
Novolacs and Resols, thermosetting respectively in the presence
or absence of a crosslinking agent.
During the last decade, tubular carbon supports have been
produced by extrusion using a Novolacs type phenolic resin [40
42]. The resin was semi-cured then ground in ne powder, which
was mixed (or not) with different additives. Sometimes another
source of carbon was added to better control the porosity
characteristics of the nal material. Water was the solvent
used to prepare the paste to be extruded and a curing step of
the obtained extrudate was done to consolidate the shape. A
carbonization step under nitrogen atmosphere enabled the pores
opening to generate the membrane porosity. In this process,
phenolic resin served as carbon source and as binder due to
the non-cured part in the powder. Nevertheless, it can be considered complicated since a semi-curing step followed by a
grinding step is needed with all the associated controls. One of
our objectives is therefore to propose an alternative to avoid
such steps.
Chengwen Song et al. used mineral coal as a major carbon
source, instead of the semi-cured phenolic resin, to prepare
symmetric tubular microltration membranes [43]. In this case,
the support was used directly as the ltrating medium. The binder
used to consolidate the extruded tubular forms was not specied
by the author. Results showed the effect of coal particle size on the
porosity of the nal product (pore size and pore volume %).
The present work proposes the development of a new process
to prepare conductive macroporous tubular carbon supports using
Resols type phenolic resin. This resin was dissolved in ethanol as a
solvent and mixed with binder, carbon source, porogen agent
and graphite powders, which are used to procure electronic
conductive properties to the material. These supports have been
tested as cathode for the degradation and the mineralization of the
AO7 dye using the electro-Fenton (EF) process under standard
conditions.

43

2. Experimental
2.1. Raw materials
Three different graphite powders from TIMCAL Group (Switzerland) were used as the main carbon source in the elaboration of
supports. They are identied in the text as KS25s, KS44s, KS150s
and their particles sizes are 25 mm, 44 mm and 150 mm, respectively. The wide range of particle sizes tested in the paste
formulation aimed to evidence the inuence of particle size on
the porosity, the pores distribution and the mechanical and
electrical properties of the nal material.
Resols type phenolic resin used in the elaboration of carbon
membranes was kindly supplied by Sumitomo Bakelite Europe
(Barcelona). The resin was used as carbon precursor, binder and
porosity agent. The resin curing temperature was recommended
by the manufacturer to be 150 1C.
Organic additives were dry mixed with the graphite powder.
Some of them, such as the corn starch powder (RG 03408, Cerestar,
France), were used to enhance the total porosity of the nal
material (since it totally degrades during carbonization), while
others, such as ethylene glycol, amijels (Cplus 12072, Cerestar,
France) and methyl cellulose (Dow Chemical Company) were used
as lubricants and plasticizers, respectively, in the paste formation.

2.2. Characterization techniques

Thermogravimetric (TGA) analyses were performed using a
SETARAM TG-DTA 92 apparatus. The temperature ramp was
10 1C min1 from room temperature to 1000 1C under nitrogen
stream.
The presence of possible defects in the carbonized supports as
well as their surface morphology was evidenced by Scanning
Electron Microscopy (SEM, HITACHI S-4800).
The porosity and pores size of the nal carbonized material
were measured by mercury intrusion analysis (Micromeritics,
AutoPore IV 9500).
Electrical conductivity measurements were carried out on at
supports using the four points method. The equipment used was
the HL 5500 Hall system from Nanometrics Company. Results
corresponded to an average of ve measurements performed in
various areas of the material surface.
Raman spectroscopy measurements were carried out at room
temperature at ambient atmosphere using an argon-ion laser
(Perx 1877 triple meet Spectrometer, USA) tuned to 514.5 nm.
The resolution of this instrument is approximately 1.7 cm1.
The mechanical resistance of the carbonized supports with
different graphite powder sizes was measured by the three-point
bending method (universal LLOYD Instruments, LRX apparatus).
All experiments were carried out on series of at least 5 membranes
to report an average strength for each series, following International Standard (IS) specications. To estimate the chemical
resistance of the carbonized supports, they were kept at 80 1C
for 7 days in both acidic and basic media at a pH of 1 and 12,
respectively.

2.3. Membrane support elaboration

As described in Fig. 1, the elaboration of the membrane
supports involved three steps: (i) the paste preparation, (ii) the
supports shaping by extrusion and (iii) the thermal treatment of
the tubes for solidication and carbonization.

44

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

In a rst step, tubes were placed at 150 1C for 2 h in the presence

of air in order to totally cure and thus harden part of the phenolic
resin. Then solidied tubes were carbonized under a nitrogen ow
of 1 mL min1 according to the temperature schedule described in
Fig. 2 to yield the porous carbon tubes with dimensions of 6 mm
Inner Diameter (ID)/10 mm Outer Diameter (OD).
2.4. Electrochemical cell and equipment

Fig. 1. Main steps of the processing route for supports elaboration.

Table 1
Paste formulation.
Raw materials

Weight percent (wt%)

Graphite carbon
Ethylene glycol
Corn starch
Amijel
Methocel
Phenolic Resin/Ethanol (50/50 wt%).

46
7
7
2
2
36

2.3.1. Paste preparation and extrusion

Plasticizer and binder were required to prepare a paste with
adequate rheological properties allowing the shaping by extrusion.
Their nature and proportion were chosen based on previous works
done in our laboratory concerning clay supports preparation [44].
The plastic paste was prepared from the graphite powder mixed
with organic additives and aliquots of phenolic resin solution
(obtained after dissolution in ethanol of the resin powder) to form
a soft mud after blending (Table 1).
The obtained plastic paste was then extruded into tubular
shape support under a pressure of 3040 bar, using a homemade
apparatus. The extruded tubes were immediately placed in an
oven under air at 70 1C for 1 h.

2.3.2. Carbonization and solidication

After extrusion and drying, tubes obtained were subjected to a
thermal treatment in a tubular electrical furnace (VTF7 VECSTAR).

Electrochemical experiments (i.e. AO7 degradation by the

electro-Fenton process) were carried out under galvanostatic and
potentiostatic modes using an EG&G Princeton Applied Research
273A potentiostat/galvanostat. They were performed in an undivided cylindrical glass cell of 7 cm inner diameter, equipped with
three electrodes. The counter electrode was a titanium/platinum
grid of 19 cm  5 cm placed on the inner wall of the cell. The
working electrode (cathode) was a 3 cm-long carbon graphite
membrane of the 0.6 cm inner diameter and 2 mm thick. The
reference electrode was a saturated calomel electrode (SCE). The
cathode and the reference electrode were installed in parallel in
the center of the electrolytic cell at a distance of 2 cm. The
treatment was performed using 170 mL of an aqueous solution,
which was thermostated at 15 71 1C. The Acid Orange 7 used as
the model molecule for wastewater was prepared at 0.1 mM
concentration. Na2SO4 (50 mM) used as supporting electrolyte
and a catalytic quantity of FeSO4  7H2O were introduced to the
initial solutions. The obtained solution was acidied at pH 3 with
sulfuric acid. In all experiments, solutions were magnetically
stirred at a constant speed of 900 rpm. To increase the competitiveness of the electro-Fenton process, the cathode was fed with
compressed air at a ow rate of 40 L h1 during the experiments.
Prior oxygen reduction, air was bubbled for 10 min to saturate the
aqueous solution, then the electric power was turned on and the
electro-Fenton reactions started simultaneously.
The linear scanning voltammetry (LSV) was employed to
observe the cathodic behavior of the carbon tube. LSV were
recorded on the EG&G Model 273A electrochemical workstation
at a scan rate of 5 mV s1 using the three-electrode system.

3. Results and discussion

3.1. Thermal behavior of the phenolic resin
In our case, the resin plays the role of binder, source of carbon
and porogen agent after carbonization. Indeed, a part of the
porosity of the nal material results from the loss of mass, which
undergoes the resin during the carbonization.
Phenolic resin weight loss as a function of temperature is given
in Fig. 3. Carbonization results in a char yield of 55.2% at 1000 1C.

Fig. 2. Temperature schedule applied for the carbonization of supports.

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

charge. The total porosity (Fig. 5) is thus the result of the mass loss
of the resin matrix besides the burning out of organic additives
(amijel, methocel, ethylene glycol and corn starch).
Average pores' size increases with particles size as shown in
Fig. 6. Average pore diameters were 1.7 mm, 3.0 mm and 4.6 mm for
materials prepared from graphite powders having particles size of
25 mm (KS25), 44 mm (KS44) and 150 mm (KS150), respectively,
after carbonization at a temperature of 1000 1C. Similar results
were obtained by Song et al. when using coal particles in place of
graphite [43,49]. It is then possible, from the same preparation, to
adjust the porosity and the average diameter of pores by modifying the temperature of carbonization.

100
1.762%
(0.2191mg)

Weignt (%)

90

10.03%
(1.247mg)

80

32.98%
(4.100mg)

70
D

60

50
0

200

400

600

800

45

1000

Temperature (C)
Fig. 3. Thermogravimetric analysis of phenolic resin under N2 atmosphere with
heating rate of 10 1C min1.

These results are consistent with the literature that suggests char
yields for phenol formaldehyde resins between 30% and 60%,
although higher yields are generally associated with more massive
samples, where loss of volatiles is more restricted [45,46].
The weight loss during carbonization takes place predominantly in the temperature range from 300 to 700 1C and occurs in
four zones. The weight losses (zones A and B) are due to
evaporation of retained water from the production process whilst
the majority of chemicals decomposition takes place in zones C
and D. From 700 1C, the phenolic resin is stable under nitrogen,
which is consistent with the use of this precursor as binder to get
sintered conductive membrane at high temperature.
3.2. Membrane support characterizations
For the development of high-quality supports, the following
properties are of major importance: pore size distribution, porosity, surface texture, mechanical properties and chemical stability.
3.2.1. Morphology of membrane support
3.2.1.1. Effect of the particle size of the graphite powder. Carbon
supports have homogenous and smooth surface structure and do
not present any macrodefects (cracks, etc.). Fig. 4 shows SEM
micrographs of membrane supports elaborated from KS25 (Fig. 4a
and b), KS44 (Fig. 4c and d) and KS150 (Fig. 4e and f) carbonized at
1000 1C. Dense areas resembling vitreous carbon material were
observed especially for the membrane synthesized from the KS25
graphite powder. Jedidi et al. concluded that these areas are
attributed to an accumulation of resin from the paste
preparation steps, which gave rise to a vitreous carbon domain
when carbonized [44]. These kinds of defects may be due to the
heterogeneity of the KS25 prepared paste. Moreover, the
macrostructure of the material elaborated from the graphite
powder KS25 presented defects in the form of cracks mainly in
the extrusion direction contrary to the material elaborated from
KS44 graphite powder that presented the best morphological
properties.
3.2.2. Pores characterization
The porous texture of the obtained tubular support is not the
result of a sintering phenomenon as observed during the formation of conventional ceramic porous materials. The material is not
consolidated due to a grain boundary or any other phenomenon
related to the sintering of inorganic materials such as clay, apatite
or metallic oxides [44,36,47,48]. In fact, the elaborated paste may
be assimilated to a composite polymer in which the resin represents the polymer matrix and the carbon particle the mineral

3.2.3. Electronic conductivity

Fig. 7 represents the evolution of the conductivity according to
the temperature treatment of the material. We can note a
remarkable evolution of the conductivity as a function of both
carbonization temperature increase and particles size of the
graphite powders used in the paste formulation. For small particle
sizes (44 and 25 m), the conductivity is the higher. This is mainly
due to a higher degree of percolation of smaller particles compared to bigger ones. At the same time, applying a higher
temperature yielded to a more important amount of graphitized
resin, which lead thus to a better conductivity of the nal material.
This was conrmed by the structural analysis of the carbon
membranes.
3.2.4. Structural morphology of supports characterized by Raman
spectroscopy
Fig. 8 shows the Raman spectra of pure KS44 graphite powder
and carbon porous support materials prepared from KS44 graphite
powder and carbonized at different temperatures. The study has
been conducted on the membrane prepared from KS44 powder
because of the good extrusion properties of the paste and the
adequate porous and electrical properties.
Two main strong peaks are observed in the region comprised
between 1200 cm1 and 1700 cm1. The rst band located at
1563 cml is due to the G mode of the graphite structure,
assigned to in plane displacement of the carbon strongly coupled
in hexagonal sheets [50,51]. The second band located at 1320 cm1
is due to a disordered structure in the carbon named D mode.
This mode is usually called the disorder-induced mode. The D
band, which has a low intensity in graphite and well-organized
materials, becomes equivalent or even more intense than the G
band for more disordered solids [52].
At 150 1C, no signicant difference was found between the
composite materials and the pure graphite powder spectra since
the resin was not yet fully carbonized at this temperature. Only the
graphite contained in the resin/graphite composite is responsible
of the observed D and G bands at 1320 cm1 and 1563 cm1,
respectively.
The TGA analysis of the material has shown that the resin starts
to carbonize at 400 1C. In fact, for samples carbonized at a
temperature higher than 400 1C (i.e. 500 1C), a band at
1600 cm1 appeared. This band was assigned to regions of
micro-crystalline order formed when the resin is carbonized
[54,55]. The G mode band, located at 1563 cm1 on the spectra
of the pure graphite and samples treated at 150 1C, shifts to higher
frequencies with an increasing carbonization temperature. This
shift of the G band position is due to the increase of order in
carbon directly related to the temperature increase [56]. The D
band intensity does not change for temperatures lower than
500 1C but increases from this temperature because of the resin
carbonization and the creation of a glassy carbon phase. At 700 1C,
the resin is totally transformed to random and disordered glassy

46

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

100 m

100 m

100 m

857 m

857 m

857 m

KS25

KS44

KS150

Fig. 4. SEM micrographs of the membrane supports elaborated with KS25 (a and b), KS44 (c and d), and KS150 (e and f) graphite powders after carbonization at 1000 1C.
Images a, c and e reect the surface morphology whereas images b, d and f are cross-section views.

250
KS25
KS44
KS150

45

Conductivity (-1cm-1)

Porous volume (%)

60

30

15

200
150
100
KS25
KS44
KS150

50
0

0
0

400

800

1200

600

1600

800

1000

1200

1400

1600

Temperature treatment (C)

Temperature treatment (C)

Fig. 5. Evolution of the porous volume according to the temperature treatment of
materials.

Fig. 7. Evolution of the conductivity according to the temperature treatment of

materials.

KS25
KS44
KS150

Pure graphite powder

150C

Arbitrary unit

Average pore size (m)

500C
700C
1000C
1500C

1800

0
0

400

800

1200

1600

Temperature treatment (C)

Fig. 6. Evolution of the average pore size diameter according to the temperature
treatment of materials.

carbon structures, as depicted by the increase of the D band

intensity [53]. For temperature higher than 1000 1C the intensity
of the band D decreases due to the graphitization of the carbonized resin domains that is attributed to the growth of the microcrystalline regions.

1700

1600

1500

1400

1300

1200

1100

Wavenumber (cm-1)
Fig. 8. Raman spectra of membrane supports elaborated from KS44 graphite
powder and carbonized at different temperatures.

The relationship between the D band and the G band intensities should be proportional to the degree of structural order with
respect to the graphite structure. The intensity ratio between the D
and G bands (ID/IG) (Fig. 9) denotes the degree of graphitization of
carbon graphite. A lower value of (ID/IG) means that a higher
degree of carbon graphitization is achieved. Even though this ratio
increases with the temperature, it appears that above 1000 1C, a

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

47

concentration of electrolyte and oxygen ow rate were determined to be: pH 3, Na2SO4 at 50 mM as electrolyte and a ow of O2
of 40 L h1, respectively [8]. In this study, those conditions were
further rened by optimizing the potential applied under potentiostatic mode and the catalyst concentration.

2
1.6

ID/IG

1.2
0.8
0.4
0
400

600

800

1000

1200

1400

1600

Carbonization temperature (C)

Fig. 9. Relationship between the ratio (ID/IG) and carbonization temperature for
KS44 membrane supports.

decrease is observed. This indicates that samples carbonized

below 1000 1C have a higher degree of amorphous phase than
the ones carbonized above that temperature according to Tse-Hao
Ko et al. [53].
3.2.5. Mechanical strength
KS25 and KS44 membrane supports treated at 1000 1C possess
a very good mechanical strength. Indeed, ten at samples resisted
to a mean maximum force of 46.0 N before breaking when tested
by three-points bending test. Note that this average force at break
was 69.0 N for cured/not carbonized samples. This decrease of the
material's strength is due to the porosity creation. On the other
hand, KS150 membrane supports did not show a sufcient
mechanical resistance to be used as supports.
3.2.6. Chemical resistance
The elaborated supports, carbonized at 1000 1C, present a
chemical resistance towards the acid and basic solutions. Actually,
the weight loss is negligible when a sample is exposed during
120 h into a soda aqueous solution at 80 1C at a pH 12 and does not
exceed 2 wt% when exposed to a nitric acid aqueous solution at a
pH of 1 under the same conditions in terms of time and
temperature.
3.3. Application to the degradation of AO7 organic dye by electroFenton process
Carbon membranes were investigated for treating articial
wastewater containing the Acid Orange 7 (AO7) dye by the
electrochemical advanced oxidation process, electro-Fenton. Main
signicant parameters affecting the dye degradation kinetics were
identied [8]: temperature, catalyst concentration (i.e. Fe2+ concentration), applied current or potential, O2 ow rate, pH and type
of supporting electrolyte. These parameters affect the dye degradation kinetics mainly through the hydrogen peroxide production
efciency related to Eq. (1).
O2+2H++2e-H2O2

3.3.1. Potential choice

Fig. 10 presents the electrochemical behavior of the KS44
membrane used as a cathode under oxygen bubbling (40 L h1)
in a solution of Na2SO4 (50 mM) at pH 3. The rst wave on the
voltamogram is due to oxygen reduction following reaction (1). At
lower potential, hydrogen peroxide is reduced to water by a 2e
reaction leading to hydrogen peroxide consumption. It is therefore
important to work at a potential between 0.8V/SCE and 1.2V/
SCE to get a high concentration of hydrogen peroxide available for
the Fenton reaction (Eq. (2)). In the following part, the carbon
membrane has then been polarized at 1V/SCE.
3.3.2. Effect of catalyst concentration
Fig. 11 shows changes in the absorption spectra of AO7
solutions during the electro-Fenton process runs at different times
for a catalyst concentration of 2  105 M conducted on the KS44
membrane. The potential has been xed at 1V/SCE. For AO7 dye,
the initial absorption spectrum consists of four bands at lambda
max of 228, 254, 310 and 485 nm. Bands correspond to absorption
of benzene rings, aromatic amines, naphthalene groups and azo
bonds, respectively, which is in accordance with the chemical
structure of the dye (Fig. 12).
As evidenced in Fig. 11, the solution decolorization is linked to
the decrease of the band at 485 nm. The evolution of the band at
254 nm (that increases during 40 min then decreases) clearly
shows that intermediate products are formed due to the cleavage
of the azo bonds that are further transformed throughout the
process. The intermediate compounds could be sulfanilic acid that
might be oxidized into various sub-products before complete
mineralization. This is in good agreement with results obtained
by Hammami et al. [57] who proposed a complete mineralization
pathway of the AO7 degradation by electro-Fenton. This phenomenon is also observed when the AO7 degradation kinetics is
plotted as the function of time for three different concentrations
of Fe2+ (Fig. 13).
The decolorization of AO7 solution is assumed to be efcient
after 60 min of electro-Fenton reaction as shown by both the
disappearance of the 485 nm band (azo group) and the kinetics of
discoloration in Fig. 13. In addition, best decolorization conditions
were obtained for a catalyst concentration of 2  104 M. Indeed, at
higher Fe2+ concentration (i.e. 2  103 M), the decolorization is

(1)

To get high degradation rate of pollutants, Eq. (2) (Fenton

reaction) clearly shows the interest to produce high concentration
of hydrogen peroxide in solution leading to high levels of hydroxyl
radicals and then mineralization of pollutants under optimal
conditions.
2H2O2+Fe2++H+-Fe3++OH+H2O

(2)

The optimized operating conditions for the degradation of azo

dyes by the electro-Fenton reaction, in terms of pH, nature and

Fig. 10. Potential choice for the degradation of AO7 organic dye by electro-Fenton
process with the KS44 membrane support.

48

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

3
t=0 min

Absorbance

2.5

t=5 min
t=10 min

t=15 min
1.5

t=20 min
t=30 min

t=40 min
t=60 min

0.5

t=120 min
0
200

300

400

500

600

Wavelength (nm)
Fig. 11. Extinction spectra of AO7 during electro-Fenton process conducted on the
KS44 membrane at different times under potentiostatic mode ([Fe2+] 2  105 M
and E 1V/SCE).

without affecting both the mechanical and chemical resistances.

The impact of the phenolic resin presence when using KS44
powder has been evidenced by Raman spectroscopy: after curing
at 150 1C and carbonization under nitrogen stream at 1000 1C, the
corresponding carbon supports showed the highest conductivity
and therefore the most important degree of carbon graphitization.
The KS44 membrane support was characterized by a total porosity
of 37%, an average pore diameter of 3 mm and a conductivity of
190 1 cm1. The ability of this carbon graphite membrane to be
used as working electrode in advanced oxidation processes was
demonstrated by studying the dye AO7 decolorization and degradation. The optimal conditions of the electro-Fenton process were
dened according to the KS44 support behavior in solution
regarding the hydrogen peroxide generation. Therefore, working
under a potentiostatic mode at a xed applied current of 1V/SCE
and O2 ow rate of 40 L h1, in a medium at pH 3 containing
Na2SO4 (50 mM) as electrolyte and Fe2+ at 2  104 M as catalyst,
lead to a rapid and efcient degradation kinetics with a high
degree of organic dye decolorization. These preliminary results
concerning carbon porous membrane supports elaboration and
their innovative role in the electro-Fenton reaction are very
promising for applications in wastewater treatment.

Acknowledgments
Authors thank CNRS (France), DGRS (Tunisia), Institut CARNOT
(France) and ENSCM (MontpellierFrance) for their nancial
support. Authors are also grateful to TIMCAL group for the gift of
graphite powders.

Fig. 12. Molecular structure of Acid Orange 7.

100

[Fe2+] = 2 10-5 M
[Fe2+] = 2 10-4 M
[Fe2+] = 2 10-3 M

A/A0 (%)

80

References

60

40

20

0
0

40

80

120

Time (min)
Fig. 13. Decolorization kinetics of AO7 under potentiostatic mode (E 1V/SCE)
obtained for the KS44 membrane using different concentrations of catalyst.

less effective because of an excess of ferrous ions that could

consume the hydroxyl radicals according to reaction (3) [13]:
Fe2++OH-Fe3++OH

(3)
5

On the other hand, a lower concentration (i.e. 2  10 M) leads

to a slightly slower decolorization kinetics because of the formation of complexes between Fe3+ and intermediates formed during
dye degradation, which does not allow catalyst regeneration [58].

4. Conclusion
Conductive porous membrane supports were elaborated
following a new route. Carbon graphite powders of various particle
sizes along with organic additives and an ethanolic solution of
Resols type phenolic resin were used in the paste formulation of
carbon membranes. The main objective was to dene the optimal
processing conditions leading to a porous and conductive material

[1] I.G. Laing, The impact of efuent regulations on the dyeing industry, Rev. Prog.
Color. 21 (1991) 5671.
[2] S.W. Oh, M.N. Kang, C.W. Cho, M.W. Lee, Detection of carcinogenic amines
from dye stuffs or dyed substrates, Dyes Pigm. 33 (1997) 119135.
[3] M. Faouzi, P. Canizares, A. Gadri, J. Lobato, B. Nasr, R. Paz, M.A. Rodrigo, C. Saez,
Advanced oxidation processes for the treatment of wastes polluted with azoic
dyes, Electrochim. Acta 52 (2006) 325331.
[4] M.S. Lucas, J.A. Peres, Decolorization of the azo dye Reactive Black 5 by Fenton
and photo-Fenton oxidation, Dyes Pigm. 71 (2006) 236244.
[5] E. Rosales, M. Pazos, M.A. Longo, M.A. Sanromn, Electro-Fenton decoloration
of dyes in a continuous reactor: a promising technology in colored wastewater
treatment, Chem. Eng. J. 155 (2009) 6267.
[6] Y. Fan, Z. Ai, L. Zhang, Design of an electro-Fenton system with a novel
sandwich lm cathode for wastewater treatment, J. Hazard. Mater. 176 (2010)
678684.
[7] A. Da Pozza, P. Ferrantelli, C. Merli, E. Petrucci, Oxidation efciency in the
electro-Fenton process, J. Appl. Electrochem. 35 (2005) 391398.
[8] S. Hammami, N. Oturan, N. Bellakhal, M. Dachraoui, M.A. Oturan, Oxidative
degradation of direct orange 61 by electro-Fenton process using a carbon felt
electrode: application of the experimental design methodology, J. Electroanal.
Chem 610 (2007) 7584.
[9] C. Flox, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodrguez, C. Arias, E. Brillas,
Electrochemical combustion of herbicide mecoprop in aqueous medium using
a ow reactor with a boron-doped diamond anode, Chemosphere 64 (2006)
892902.
[10] I. Sires, N. Oturan, M.A. Oturan, R.M. Rodriguez, J.A. Garrido, E. Brillas, Electro-.
Fenton degradation of antimicrobials triclosan and triclocarban, Electrochim.
Acta 52 (2007) 54935503.
[11] A. Ozcan, Y. Sahin, A.S. Koparal, M.A. Oturan, Degradation of picloram by the
electro-Fenton process, J. Hazard. Mater. 153 (2008) 718727.
[12] N. Oturan, M.A. Oturan, Degradation of three pesticides used in viticulture by
electrogenerated Fenton's reagent, Agron. Sustainable Dev. 25 (2005) 267270.
[13] M. Panizza, G. Cerisola, Electro-Fenton degradation of synthetics dyes, Water
Res. 43 (2009) 339344.
[14] I. Sires, E. Guivarch, N. Oturan, M.A. Oturan, Efcient removal of triphenylmethane dyes from aqueous medium by in situ electrogenerated Fenton's
reagent at carbon-felt cathode, Chemosphere 72 (2008) 592600.
[15] M. Panizza, G. Cerisola, Removal of organic pollutants from industrial
wastewater by electrogenerated Fenton's reagent, Water Res. 35 (2001) 3987.
[16] J.E. Koresh, A. Soffer, The carbon molecular-sieve membranesgeneral properties and the permeability of CH4/H2 mixture, Sep. Sci. Technol 22 (1987)
973978.

S. Ayadi et al. / Journal of Membrane Science 446 (2013) 4249

[17] CH. Liang, GY. Sha, SC. Guo, Carbon membrane for gas separation derived from
coal tar pitch, Carbon 37 (1999) 13911397.
[18] J. Petersen, M. Matsuda, K. Haraya, Capillary carbon molecular sieve membranes derived from kapton for high temperature gas separation, J. Membr.
Sci. 131 (1997) 8594.
[19] LE. Sojo, A. Brocke, J. Fillion, SM. Price, Application of activated carbon
membranes for on-line cleanup of vegetable and fruit extracts in the
determination of pesticide multi residues by gas chromatography with mass
selective detection, J. Chromatogr. 788 (1997) 141154.
[20] W. Wei, H. Hu, L. You, G. Chen, Preparation of carbon molecular-sieve
membrane from phenolformaldehyde Novolac resin, Carbon 40 (2002)
445467.
[21] TA. Centeno, AB. Fuertes, Supported carbon molecular-sieve membranes based
on a phenolic resin, J. Membr. Sci. 160 (1999) 201211.
[22] A. Soffer, J. Koresh, S. Saguee, Separation device, US Patent 4 (1987) 685940.
[23] A. Soffer, M. Azariah, A. Amar, H. Cohen, D. Golub, S. Saguee, H. Tobias, Method
of improving the selectivity of carbon membranes by chemical vapor deposition, US Patent 5 (1997) 695818.
[24] J. Hayashi, Y. Yamamoto, K. Kusakabe, S. Morooka, Simultaneous improvement
of permeance and permselectivity of BPDA-ODA polyimide membrane by
carbonization, Ind. Eng. Chem. Res. 34 (1995) 4364.
[25] J. Hayashi, H. Mizuta, Y. Yamamoto, K. Kusakabe, S. Morooka, Pore size control
of carbonized BPDA-ODA polyimide membrane by chemical vapor deposition
of carbon, J. Membr. Sci. 124 (1997) 243251.
[26] H. Suda, K. Haraya, Gas permeation through micropores of carbon molecular
sieve membranes derived from Kapton polyimide, J. Phys. Chem. B 101 (1997)
39883994.
[27] C.W. Jones, W.J. Koros, Carbon molecular sieve gas separation membranes. I.
Preparation and characterization based on polyimide precursors, Carbon 32
(1994) 14191425.
[28] Y. Kusuki, H. Shimazaki, N. Tanihara, S. Nakanishi, T. Yoshinaga, Gas permeation properties and characterization of asymmetric carbon membranes prepared by pyrolyzing asymmetric polyimide hollow ber membrane, J. Membr.
Sci. 134 (1997) 245253.
[29] A.S. Damle, S.K. Gangwal, V.K. Venkataraman, Carbon membrane for gas
separation: developmental studies, Gas Sep. Purif. 8 (1994) 137147.
[30] K. Fukuyama, T. Nishizawa, K. Nishikawa, Effect of hot isostatic pressing on
nanopore in glass-like carbon prepared from phenolformaldehyde resin,
Carbon 39 (2001) 18631867.
[31] N. Kasahara, S. Shiraishi, A. Oya, Heterogeneous graphitization of thin carbon
ber derived from phenolformaldehyde resin, Carbon 41 (2002) 16451687.
[32] J. Grka, A. Zawislak, J. Choma, M. Jaroniec, KOH activation of mesoporous
carbons obtained by soft-templating, Carbon 46 (2009) 11592274.
[33] M. Kubota, A. Hata, H. Matsuda, Preparation of activated carbon from phenolic
resin by KOH chemical activation under microwave heating, Carbon 47 (2009)
28052811.
[34] I. Stamatin, A. Morozan, A. Dumitru, V. Ciupina, G. Prodan, J. Niewolski,
H. Figiel, The synthesis of multi-walled carbon nanotubes (MWNTs) by
catalytic pyrolysis of the phenolformaldehyde resins, Physica E 37 (2007)
4448.
[35] M.B. Rao, S. Sircar, C. Golden, Adsorbent membranes for gas separation, US
Patent 5 (1992) 104425.
[36] I. Jedidi, Elaboration de membranes inorganiques de ltration: application la
purication de solutions chimiques (Ph.D. thesis), University of Sfax, Tunisia,
2005.
[37] I. Jedidi, R. Ben Amar, A. Larbot, S. Khemakhem, A. Ben Salah, A. Char, C.
Chtara, A. Fourati, N. Elloumi-Ammar et N. Abbes, Procd dlaboration de
membranes de ltration en carbone, Brevet No: SN08394, Tunisia, 2009.

49

[38] N. Kishore, S. Sachan, K.N. Rai, A. Kumar, Synthesis and characterization of a

nanoltration carbon membrane derived from phenolformaldehyde resin,
Carbon 41 (2003) 29612972.
[39] W. Wei, G. Qin, H. Hu, L. You, G. Chen, Preparation of supported carbon
molecular sieve membrane from Novolac phenolformaldehyde resin, J.
Membr. Sci. 303 (2007) 8085.
[40] J.H. Clint, A.M. Lear, L.F. Oliver, S.R. Tennison, Membranes, Eur. Patent no. 0 474
424 (1991).
[41] F.K. Katsaros, T.A. Steriotis, A.K. Stubos, A. Mitropoulos, N.K. Kanellopoulos, S.
R. Tennison, High pressure gas permeability of microporous carbon membranes, Microporous Mater. 8 (1997) 171176.
[42] F.K. Katsaros, Th.A. Steriotis, G.E. Romanos, M. Konstantakou, Preparation and
characterization of gas selective microporous carbon membranes, Microporous and Mesoporous Mater. 99 (2007) 181189.
[43] C. Song, T. Wang, Y. Pan, J. Qiu, Preparation of coal-based microltration
carbon membrane and application in oily wastewater treatment, Sep. Purif.
Technol. 51 (2006) 8084.
[44] I. Jedidi, S. Khemakhem, A. Larbot, R. Amar, Elaboration and characterization
of y ash based mineral supports for microltration and ultraltration
membranes, Ceram. Int. 35 (2009) 27472753.
[45] H.A. Mackay, The inuence of polymer structure on the conversion of
synthetic resins to carbon-coke, Carbon 8 (1970) 517526.
[46] E. Fitzer, W. Schafer, The effect of crosslinking on the formation of glasslike
carbons from thermosetting, Carbon 8 (1970) 353364.
[47] S. Masmoudi, A. Larbot, H. El Feki, R. Ben Amar, Elaboration and properties of
new ceramic microltration membranes from natural and synthesized apatite,
Desalination 190 (2006) 89103.
[48] A. Larbot, S. Alami-Younssi, M. Persin, J. Sarrazin, L. Cot, Preparation of a alumina nanoltration membrane, J. Membr. Sci. 97 (1994) 167173.
[49] Y. Pan, W. Wang, T. Wang, P. Yao, Fabrication of carbon membrane and
microltration of oil-in-water emulsion: an investigation on fouling mechanisms, Sep. Purif. Technol. 57 (2007) 388393.
[50] F. Tuinstra, J.L. Koening, Raman spectrum of graphite, J. Chem. Phys. 53 (1970)
11261131.
[51] S. Reich, C. Thomsen, Raman spectroscopy of graphite, Philos. Trans. R. Soc.
London A 362 (2004) 22712288.
[52] Y. Wang, D.C. Alsmeyer, R.L. Mc Creery, Raman spectroscopy of carbon
materials: structural basis of observed spectra, Chem. Mater. 2 (1990)
557563.
[53] T.H. Ko, W.S. Kuo, Y.H. Chang, Raman study of the microstructure changes of
phenolic resin during pyrolysis, Polym. Compos. 21 (2000) 745750.
[54] D. Cottinet, P. Couderc, J.L Saint-Romain, P. Dhamelincourt, Raman microprobe
study of heat-treated pitches, Carbon 26 (1988) 339344.
[55] P.D. Green, C.A. Johnson, K.M. Thomas, Application of laser Raman microprobe
spectroscopy to the characterization of coals and cokes, Fuel 62 (1983)
10131023.
[56] P. Lespade, A. Marchand, M. Couze, F. Gruege, Caractrisation de matriaux
carbons par microspectromtrie Raman, Carbon 22 (1984) 375385.
[57] S. Hammami, N. Bellakhal, N. Oturan, M.A. Oturan, M. Dachraoui, Degradation
of Acid Orange 7 by electrochemically generated 1OH radicals in acidic
aqueous medium using boron-doped diamond or platinum anode: a mechanistic study, Chemosphere 73 (2008) 678684.
[58] C. Flox, S. Ammar, C. Arias, E Brillas, A.V Vargas-Zavala, R. Abdelhedi, ElectroFenton and photoelectro-Fenton degradation of indigo carmine in acidic
aqueous medium, Appl. Catal. B Environ. 67 (2006) 93104.