Chemosphere 224 (2019) 698e706

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Towards understanding of heterogeneous Fenton reaction using

carbon-Fe catalysts coupled to in-situ H2O2 electro-generation as
clean technology for wastewater treatment

rate-Guzma
Ana I. Za
n a, Linda V. Gonza
rrez a, *, Luis A. Godínez a,

lez-Gutie
Alejandro Medel-Reyes , Francisco Carrasco-Marín b, Luis A. Romero-Cano a, b, 1
a

a
n y Desarrollo Tecnolo
Centro de Investigacio
gico en Electroquímica (CIDETEQ), Parque Tecnolo

gico Sanfandila, Pedro Escobedo, Quer
etaro, 76703, Mexico
b
Grupo de Investigacio
n en Materiales de Carbo
n, Facultad de Ciencias, Universidad de Granada, Av. Fuente Nueva, s/n., Granada, 18010, Spain

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Carbon catalyst was obtained with a

Fe2þ/Fe3þ rate of 1.29.

Heterogeneous Fenton reaction was
proved by surface-Fe and
OH radi-
cals analysis.

No iron enriched sludge or by prod-
ucts are generated.

In-situ H2O2 was produced at high
concentrations up to 30 mg L1 h1.

The complete mineralization of
Phenol as a model contaminant was
achieved.

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

Article history: Iron-supported catalyst on granular activated carbon was prepared for its use in heterogeneous Fenton
Received 29 November 2018 reaction coupled to an in situ H2O2 electro-generation. For this process, an electrolysis cell was employed,
Received in revised form using carbon felt as cathode and graphite as anode. A solution of H2O2 (electrogenerated at a rate of
14 February 2019
30 mg L1 h1) was obtained using a current intensity of 12 mA. In order to promote the decomposition
Accepted 15 February 2019
Available online 23 February 2019
of H2O2 to
OH, a Carbon-Fe catalyst was used. This catalyst was prepared by incipient wet impregnation
using FeSO4 as precursor salt to obtain samples with 9% wt of iron. Samples were characterized by EDX,
Handling Editor: E. Brillas FTIR and XPS spectroscopy before and after wastewater treatment using phenol as model molecule. Two
iron oxidation states on the samples were found, Fe2þ and Fe3þ. The ratio between Fe2þ/Fe3þ was 1.29
Keywords: which was later reduced to 0.92 after Fenton process; this might be associated with the metal oxidation
Hydroxyl radical
OH (Fe2þ to Feþ3) occurring during Fenton-reaction, thus indicating that H2O2 decomposition was carried out
Heterogeneous fenton by Fe2þ on carbon surface. Detection and quantification of hydroxyl radical were carried out by fluo-
Iron e activated carbon catalyst rescence spectroscopy, obtaining a radical concentration of 3.5 mM in solution. Iron in solution were
H2O2 electrogeneration
determined, showing a concentration of 0.1 mg L1, making evident that the supported metal is stable
and the reaction is carried out in a heterogeneous phase. Results showed an environmentally friendly
process that can generate reagents in situ, with high efficiencies in the degradation of pollutants and
minimizing the formation of toxic byproducts, which are common in conventional treatments.
© 2019 Published by Elsevier Ltd.

* Corresponding author.
E-mail addresses: lgonzalez@cideteq.mx (L.V. Gonza
lez-Gutie

rrez), luis.cano@
1. Introduction
edu.uag.mx (L.A. Romero-Cano).
1
Present address: Facultad de Ciencias Químicas. Universidad Auto
noma de
Guadalajara. Av. Patria 1201, Zapopan, Jalisco, 45129, Mexico. One of the advanced oxidation processes that recently has

https://doi.org/10.1016/j.chemosphere.2019.02.101
0045-6535/© 2019 Published by Elsevier Ltd.

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gained attention is the one that involves Fenton reaction in het-
erogeneous phase, mainly because this process has proven to be
effective in degradation processes of recalcitrant organic com-
pounds in water, and it also bears great advantages when compared
to conventional or homogeneous Fenton diminishment of unde-
sired byproducts (residual sludge) and the use of a catalyst during
repeated degradation cycles (Rahim Pouran et al., 2014; Yamaguchi
et al., 2018). In heterogeneous Fenton process, the
OH generation
takes place from the catalytic decomposition of H2O2 mainly in
acidic medium (pH 3), using as catalyst iron supported on a porous
material (He et al., 2016) this reaction usually takes place in wide
range of pH, how. In this sense, different materials have been re-
ported as catalyst supports, such as silicates (clay and zeolites)
(Chou and Huang, 1999; Cheng et al., 2006; Gokulakrishnan et al.,
2009; Luo et al., 2009) ionic exchange resins (Zeng and Lemley,
2009; Herney-Ramirez et al., 2011) and, carbon-based materials
(Duarte et al., 2009, 2012). From the supports above mentioned,
activated carbon is the most interesting one due to its multiple
advantages, such as: low cost, great surface area, textural, chemical
and morphological controllable properties (Mesquita et al., 2012).
Until now, there is little information available in the literature that
addresses the study of the mechanisms (kinetic and reaction
mechanisms) involved in the heterogeneous Fenton reaction (Lin
and Gurol, 1998; Andreozzi et al., 2002). However, the mecha-
nisms present in the heterogeneous Fenton reaction using iron
supported catalyst are still under discussion because there is few
information regarding how the process is taking place. Published
research have focused on the preparation and evaluation of the
catalyst performance during the degradation of different pollutants
(Ramírez et al., 2010; Mesquita et al., 2012; Banuelos et al., 2015);
this can be seen in Table SM-1, which presents a compilation and
comparison of the use of carbon-Fe catalysts for the Fenton reaction
in heterogeneous phase, according to this information, the papers
presented so far, report the catalytic activity of the Carbon-Fe cat-
alysts indirectly, through the degradation of a model compound,
being therefore necessary to provide fundamental information
about the process by studying the generation of
OH radicals by a
direct method (Duarte et al., 2009, 2012; Liao et al., 2009; Hu et al.,
2011; Chun et al., 2012; Duan et al., 2014). By having a global un-
derstanding of the mechanisms that take place during this process,
specific catalyst could be designed in order to promote the desired
reaction; also, clean technology could be optimized for its use in
wastewater treatment processes at industrial level.
In this work, a heterogeneous Fenton reaction promoted by the
use of Carbon-Fe catalyst is studied; also, H2O2 in situ electro-
generation was evaluated. With the aim of contributing with in-
formation that will help in the elucidation of the heterogeneous
Fenton reaction,
OH radicals were identified and quantified. These
latter were employed in the degradation of a model molecule
(phenol) during repeated cycles of reuse. Finally, characterization
studies on the catalyst, prior and after degradation processes, were
carried out by employing conventional spectroscopic techniques
(FTIR, EDX, XPS). Obtained information related to the degradation
efficiencies of the model molecules. The information obtained was
related to the degradation efficiencies of the model molecule and
allowed to elucidate the role of iron during the heterogeneous
Fenton reaction.
2. Experimental
2.1. Activated carbon modification as support for the iron catalyst
Clarimex PR-200 commercial granular activated carbon provided
by Clarimex S.A. de C.V. (sample C), was used as a support material of
iron and as a catalyst in Fenton process. With this purpose, as a first
699
step, material was functionalized with oxygen groups, which
function as metal binding sites. This functionalization was per-
formed by means of an acidic treatment that consists in rinsing the
material with 0.1 M HCl solution, in order to remove impurities
from the material. Then, a treatment using a 68% HNO3 solution was
carried out, in a 1:10 relation (g of carbon: mL of HNO3) and a
constant stirring at 180 rpm at room temperature for 15 h (Shi et al.,
2011). Finally, the sample was filtered and thoroughly rinsed with
distilled water until rinsed water reached a constant pH value (~pH
6). The obtained material was then dried at 105  C for 24 h (C-AC
sample). The iron catalyst was prepared by the incipient wet
impregnation method employing sample C-AC as support; for
which, 1.74 g of FeSO4$7H2O was dissolved in a small amount of
water (which corresponds to a modification for obtaining 9% wt of
iron in the carbon). This solution was slowly added until 5 g of C-AC
was moistened homogenously. This sample was kept wet for 12 h
with the aim of enhancing diffusion of salt along carbon texture.
Then, solvent was eliminated by means of evaporation in a con-
ventional oven at 105  C. Finally, dried sample was placed in a
tubular oven at 400  C in inert atmosphere; for this procedure, a
heating ramp of 10  C min1 was employed and the desired tem-
perature was kept for 2 h, this sample was denominated as C-AC-Fe
(Mesquita et al., 2012).
2.2. Characterization of the materials prepared
The textural properties of the carbon materials were studied
from the physisorption of N2 at 196  C, for which a QUADRASORB
SI (Quantachrome Inc.) equipment was used. From the obtained
isotherms, the specific surface areas and the size distribution of
meso-microporosity were calculated using the BET equation and
the DFT model.
Morphology of the materials was studied by electronic scan
microscopy coupled with energy-dispersive X-ray microscopy
(SEM-EDX), using a JSM-6510LVEDS instrument, where the presence
and homogeneity of the supported catalyst was evaluated. In
addition, with the aim of obtaining information on the crystallo-
graphic phases of iron that are present on the carbon surface, X-ray
diffraction (XRD) experiments were carried out. These experiments
were performed at room temperature with an XRD Bruker D8
advance diffractometer at 0.17 min1, from 10 to 70 (2q).
Surface chemistry of the materials was studied by infrared
spectroscopy with Fourier -transform infrared spectroscopy (FTIR)
from 4000 to 400 cm1 with a Shimadzu Iraffinity-1S spectropho-
tometer. In order to characterize the composition at the materials
surface, X-ray photoelectron spectroscopy (XPS) was employed.
This analysis was carried out with an Intercovamex XPS 110 device;
XP spectra were obtained with a monochromatic source of Al Ka X
ray (1486.71 eV) at a pressure of 6  1010 Torr in the analytic
chamber. For wide-scan spectra, an energy interval from 0 to
1100 eV, energy step of 80 eV and a step size of 1 eV were employed.
Once the signals were all examined, C1s, O1s and Fe2p regions were
explored at high resolutions at an energy step of 40 eV and step size
of 0.05 eV. Each region of interest was scanned several times in
order to obtain reasonable signal-noise ratio. With the aim of
obtaining the exact number of components, peak positions and
their respective areas, resulting spectra from background signal
correction were then adjusted to Lorentz and Gauss functions
(Voigt profile).
2.3. Electro-generation of H2O2
With the aim of proposing an ecological water treatment tech-
nology, in situ electro-generation of H2O2 was studied in an undi-
vided electrolysis cell (40 mL), using a 0.1 M Na2SO4 solution as
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supporting electrolyte at pH 3. Carbon felt (Alfa Aesar 14,630, metal
basis) and graphite (Alfa Aesar 10,132) were used as cathode and
anode, respectively; both with a geometric area of 3.6 cm2 and a
separation of 2.5 cm between them, since they have been suc-
cessfully applied in oxygen reduction to H2O2 (Pimentel et al., 2008;
€
Martínez-Huitle and Brillas, 2009; Ozcan et al., 2009). Studies were
carried out by applying different values of current: 0.9 mA, 5 mA,
9 mA and 20 mA. In each experiment, solution was saturated with
air prior to the beginning of electrolysis using an air flow of
0.15 L min1, this was maintained during all the process. H2O2
concentration was determined by UVeVis spectroscopy using the
TiOSO4 method (Ribeiro et al., 2009), with a Shimadzu UV 2600
spectrophotometer.
2.4. Identification and quantification OH radicals
Identification and quantification of radicals was achieved by
means of fluorescence spectroscopy, using coumarin as probe
molecule. The reaction that takes place when a coumarin molecule
reacts with an
OH radical (Rxn 1) is the formation of 7-
hydroxycoumarin, which is a stable compound with a well-
known fluorescence spectrum (lexcitation 345 nm and lemission
455 nm) (Ishibashi et al., 2000).
Fluorescence Spectra were obtained with an AGILENT Cary
Eclipse spectrophotometer; both excitation and emission slit values
were fixed to 10.0 nm for all measurements.
(1)
This method is effective for the determination of
OH radicals
due to its high sensitivity (detection limit of 3  1018 M) and
selectivity (Ishibashi et al., 2000; Louit et al., 2005).
2.5. Degradation of phenol as a probe molecule and reuse cycles
In order to evaluate heterogeneous Fenton reaction, phenol was
employed as model molecule. As a first step, adsorption studies
were carried out to saturate the sample; in this way, it becomes
possible to despise the effect of phenol removal due to adsorption
phenomena. This procedure was performed with 5 g of sample and
a 1000 mg L1 phenol solution, at a constant stirring of 180 rpm and
room temperature (~25  C) for 4 d. Once the material was satu-
rated, it was dried at 105 for 12 h.
As a second step, degradation of a 50 mg L1 phenol solution
was studied, using the electro-generated H2O2 and the saturated
catalyst (C-AC-Fe). For this purpose, a batch-type oxidation reactor
of 40 mL of capacity that contained 0.1 g of C-AC-Fe was used; the
reactor was fed with a H2O2 generated solution in the electro-
chemical reactor in a 4.6 M ratio H2O2/phenol, so as to achieve
complete mineralization of phenol and its byproducts (Espinosa
et al., 2015). The whole degradation process was monitored for
different periods of time by means of UVeVis spectroscopy at a
wavelength of 270 nm. Once this cycle was concluded, C-AC-Fe was
recovered, saturated again with phenol and then dried at 105  C in
order to study its performance in repeated cycles of reuse. Finally,
with the aim of study the degree of mineralization of phenol
molecule, total organic carbon (TOC) was determinate using a
Shimadzu TOC-L series analyzer. In order to obtain the minerali-
zation percentage of phenol to CO2, TOC data were processed ac-
cording with Moctezuma et al. (2016).
3. Results and discussion
3.1. Characterization of the prepared materials
N2 adsorption/desorption isotherms as well as, pore size dis-
tribution studies of the materials are showed in Table SM-2 and
Fig. SM-1. As observed, SBET areas of 769 and 575 m2 g-1 for C-AC and
C-AC-Fe respectively was obtained, this implies a decrease in the
SBET surface area as well as in the pore volume, this is associated
with the entry of iron into the porous structure blocking the
porosity and therefore decreasing the adsorption capacity of the N2
(Duarte et al., 2009). Functional groups that were introduced to the
carbon after different treatments were further studied by infrared
spectroscopy. Fig. 1a shows FT-IR spectra that corresponds to
samples C, C-AC and C-AC-Fe, in which five bands were identified.
The first at 3410 cm1 is associated with stretching vibrations of
OeH bonds due to phenolic, hydroxyl and carboxylic groups
(Khelifi et al., 2010; Rodríguez Estupin ~ an et al., 2011). The second
band at 2900 cm1 is due to symmetric and asymmetric stretching
vibrations of the CeH groups from aliphatic structures (Khelifi
et al., 2010). The third band of interest is found at 1640 cm1 and
is attributed to C¼O vibrations, both in carboxylic and carbonyl
groups that are highly conjugated (Khelifi et al., 2010; Gokce and
Aktas, 2014). The fourth signal, only present in the C-AC sample,
is found in the fingerprint region (approx. at 1100 cm1) and is
associated to an oxidation process of carbon, and to the increase
number of hydroxyl and ethers group in the sample (Swiatkowski
et al., 2004); this is due to the strong oxidant character of nitric
acid, which is capable of oxidizing carbon atoms and thus, it causes
that the material surface loses electrons; as a result, carbon surface
acquires a positive charge, promoting adsorption of oxygenated
anions in solution and hence, the number of oxygenated functional
groups considerably increases (Khelifi et al., 2010). Finally, the fifth
signal of interest, close to 570 cm1, is only appreciated in sample C-
AC-Fe and is related to FeeO bonds [3].
X-ray diffraction studies showed amorphous structures for
every case; however, for C-AC-Fe sample (Fig. 1b), two crystallo-
graphic phases were identified, being hematite the main one
(gFe2O3), with a diffraction angle of 29 . The second signal at 35
might be associated to similar structures to magnetite (Fe3O4)
(Mesquita et al., 2012). Then, it is expected that both Fe2þ and Fe3þ
species are present in the carbon structure.
The morphology of C-AC-Fe was studied by scanning electron
microscopy, the SEM images obtained are shown in Fig. SM-2a, in
which the metal particles supported in the carbon are observed,
with the aim of identifying metal distribution along carbon surface,
SEM-EDX micrographs were obtained. Fig. 1c shows a SEM-EDX
micrograph that corresponds to iron mapping of sample C, where
the absence of iron is evident whereas in Fig. 1d, which is obtained
from sample C-AC-Fe, the presence of iron is clearly appreciated
(highlighted in red) in the carbon surface. Quantification of iron
was performed by EDX spectra within different sample zones; from
the obtained measurements it can be concluded that metal
impregnation occurred in average in a 9% weight surface
proportion.
Quantitative chemical analysis performed by XP spectroscopy is
presented in Table SM-3; the following sensitivity factors were
used: 0.205 for C1s, 0.66 for O1s y 3.8 for Fe2p.
Oxygen content increases after functionalization with HNO3
from 10.6% to 16.4%; then it finally diminishes to 13.8% at the
moment when iron binds to these active sites. Moreover, it can be
observed that sample impregnated with FeSO4 presents a superfi-
cial iron content of 8.1%; therefore, most of the catalyst locates
available in the most exposed superficial part of the material, since

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Fig. 1. Characterization of the catalyst supported on activated carbon: a) FTIR spectra
g Fe2O3 and Fe3O4), SEM-EDX mapping of samples c) C-AC and d) C-AC-Fe.
XP spectroscopy is an analysis performed on the outermost layer,
3e5 nm. Fig. 2 show XP high resolution spectra of the Fe2p and C1s,
O1s, regions, respectively. C1s region (Fig. 2a) is deconvoluted into
6 peaks in all materials, in a similar way to other activated carbons
from the same origin (Rey et al., 2016). A signal whose binding
energy is close to 284.7 eV is attributed to CeC bonds located in the
graphitic layer; 286.0 eV signal is due to CeH bonds, whereas the
peak at 287.2 eV is related to CeOH bonds in phenolic functional
groups. Signals at 288.9 and 290.6 eV are associated with C¼O and
-COOH, respectively, which are carbonyl, carboxyl and ether func-
tional groups. Finally, the signal at 292.2 eV can be associated to
pp transitions between aromatic rings at the graphitic layers. As
expected, the presence of the functional groups described above
are confirmed, when the spectra near region O1s are decomposed;
their main feature are broad peaks that indicate the presence of
oxygen in its different chemical states, such as organic oxygen
(carboxyl, carbonyl and ether functional groups) and inorganic
oxygen (oxygen as iron oxides). The broad form of the spectra in the
O1s region (Fig. 2b) indicates the presence of oxygen in different
chemical states, for this reason the spectra were deconvoluted into
2 peaks centered at 531.6 and 533.0 eV; for the C and C-AC samples
can be attributed to species C¼O and CeO (Alvarez-Merino et al.,
2000; Fontecha-Ca
mara et al., 2011), due to functional groups
carboxyl, carbonyl and ester, which have been identified by FTIR
spectroscopy evidencing the functionalization of the material. The
fact that the spectrum of the C-AC-Fe sample was inclined at lower
binding energies is attributable to the incorporation of the metal in
the oxygenated functional groups, since signals centered at
531.5 ± 0.5 eV correspond to species FeO(OH) with different stoi-
chiometry and signal at 529.8 eV correspond to species Fe2O3 and
FeO (Grosvenor et al., 2004), corroborating the identification made
by XRD.
To complete the analysis, the XP spectrum in high resolution for
the Fe2p region was obtained, which is only perceptible for the C-

n et al. / Chemosphere 224 (2019) 698e706 701
C, C-AC, C-AC-Fe and C-AC-Fe spent b) Diffractograms of samples C-AC-Fe (
AC-Fe sample. The deconvolution of the obtained spectrum is
shown in Fig. 2c, in which a first peak is observed at a binding
energy close to 707.8 eV, which can be attributed to binding en-
ergies of FeeS compounds (Nesbitt, 1998; Mullet et al., 2002),
corresponding to ferrous sulphate used as a precursor salt for the
introduction of iron to the carbon porous structure. At higher
binding energies, the characteristic doublet of iron is shown,
showing two predominant peaks centered at 711.6 and 725.4 eV,
corresponding to the 2p3/2 and 2p1/2 orbitals, respectively (Borda
et al., 2003). The position and separation of energy are very
similar to those observed for FeO(OH) structures (Allen et al., 1974),
so it is possible to conclude that iron is incorporated into the
carbonaceous matrix through the oxygenated groups introduced
during functionalization with HNO3. At 720 eV a signal is also
observed, which is attributed to a satellite peak characteristic of

nya et al., 2001). The presence
Fe3þ species in the Fe2p3/2 region (Ko
of these components indicates the presence of iron with different
oxidation states (Ramirez et al., 2007), in such a way, the decom-
position of the spectrum was carried out in two peaks, the first of
them centered at 711.4 eV, associated with Fe2þ and the second
centered at 713.2 eV correspond to the Fe3þ species (Sobti et al.,
2014; Idczak et al., 2016). These results show that the iron sup-
ported in the carbon is present in the oxidation states II and III. A
parameter that can be used to identify the distribution of these
species in the sample is the ratio of peak areas of both species, for
the case of the sample C-AC-Fe a ratio of Fe2þ/Fe3þ ¼ 1.29 is
observed.
3.2. Electrogeneration of H2O2
With the aim of evaluating the use of an eco-friendly technol-
ogy, in situ H2O2 electro-generation was evaluated. Fig. 3a shows
the kinetics of H2O2 electro-generation using four current intensity
values for a period of 250 min; from this plot, an exponential
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Fig. 2. XP high resolution spectra for the regions: a) C1s, b) O1s and c) Fe2p of the activated carbon and Carbon-Fe catalysts.
Fig. 3. a) Electro-generation of H2O2 at different current intensity:
Response surface plot of H2O2 production for the DOE proposal.
behavior during the first 150 min is observed, where the H2O2 start
to gradually diminish until reaching a constant value at 200 min.
From experimental data, a response surface plot was built (Fig. 3b),
where the variation of H2O2 production in a range of concentrations
from 0 to 20 mA is presented. It can be observed that for current
intensity values under 6 mA, H2O2 production is inefficient due to
the energy supplied to the system is lower than the required for
promoting the desired reaction. From 6 mA, concentration starts to
increase considerably, reaching a maximum production at 12 mA;
hence, according with the experimental design proposed, 12 mA is
the optimal current requires to produce H2O2 in acidic medium
(Rxn 2)
O2 þ 2Hþ þ 2e / H2 O2
At this condition, the maximum concentration of H2O2 is

n et al. / Chemosphere 224 (2019) 698e706
i1 ¼ 0.9 mA, i2 ¼ 5 mA, : i3 ¼ 9 mA, i4 ¼ 20 mA, using carbon felt as cathode and graphite as anode. b)
100 mg L1 (30 mg L1 h1). This high rate of generation is higher
than the one obtained for other materials, such as graphite
(2.45 mg L1 h1) (Huang et al., 2013), and is due to the great
specific area of carbon felt (which is generally higher than
1000 m2 g1) and nitrogen functions that are present (Xia et al.,
2015). It should be noted that although the production rate pre-
sented in this research is high, other research groups such as Perez
et al. (2017) have reported higher production rates, which have
been attributed to changes in operating parameters, such as the air
pressure supplied to the system. At current intensity values higher
than 12 mA, H2O2 production starts to diminish drastically because
the cell potential is higher; this effect promotes undesired cathodic
reactions, such as hydrogen evolution (Rxn 3), oxygen reaction via
4e (Rxn 4), and the reduction of H2O2 to H2O (Rxn 5), (Brillas and
(2) Casado, 2002; Luo et al., 2015). Another factor that can affect H2O2
generation at these current intensity values is that generated H2O2

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decomposes immediately at the anode, generating hydroxyperoxyl
radical (Rxn 6) and (Rxn 7) (Martínez-Huitle and Brillas, 2009;
Babuponnusami and Muthukumar, 2012), or its direct decomposi-
tion in medium Rxn 8 (Qiang et al., 2002).
2Hþ þ 2e / H2
O2 þ 4Hþ þ 4e /2H2 O
H2 O2 þ 2Hþ þ 2e /2H2 O
1 of 7-hydroxycoumarin formation, that is proportional to
OH radi-
H2 O2 /H2 O þ O2
2
Once H2O2 is electro-generated, it is recovered and used for the


OH radical generation using C-AC-Fe sample, with the aim of
studying Fenton reaction in a heterogeneous Fenton process.
3.3. Identification and quantification of
OH radicals in phenol
degradation process
One of the critical factors to define if an advanced oxidation
process is taking place is the presence of highly oxidant species in
the system. Until today, there is little information in the literature
regarding Fenton process in heterogeneous phase. Studies indi-
rectly show how this process occurs, because they relate a dimin-
ishment in the concentration of a model compound with the
efficiency of an advanced oxidation process (Ramírez et al., 2010;
Banuelos et al., 2015); these reports do not provide enough infor-
mation for a clear elucidation of the reaction mechanism in het-
erogeneous phase.
With the purpose of obtaining information about this process,
the experimental system described in the section of materials and
methods. If the Fenton reaction takes place,
OH radicals must be
generated; these latter are able to react with coumarin molecule,
generating a fluorescent compound (7-hydroxycoumarin) whose
identification and quantification is proportional to the
OH radical
formation, according to Eq. (9) (Tokumura et al., 2011).
 
2 philic attack on the phenol molecule, leading to a hydroxylation of
½COH  ¼ * ½C7HC 
0:29
From Eq. (9), it would be necessary to know the concentration of
7-hydroxycoumarin in order to estimate the desired value. From
standard solutions of this compound at different concentrations,
fluorescence spectra were obtained (Fig. SM-3a), and a calibration
plot was built for its determination. Maximum fluorescence in-
tensity occurs at 455 nm, which corresponds to the wavelength of
the emission spectra of this molecule. Values of fluorescence in-
tensity versus 7-hydroxycoumarin concentrations were plotted;
from the calibration plot presented in Fig. SM-3b, a lineal behavior
is observed, along with a reasonable correlation coefficient
(R2 ¼ 0.9937). Lineal regression of the experimental data allows the
determination of an equation for 7-hydroxycoumarin quantifica-
tion (Eq. (10)):
½C7HC  ¼ 0:0006*ðF:I:455nm Þ þ 0:0104 (10)
From the combination of Eqs. (9) and (10), a mathematical
function for the quantification of
OH radicals by means of fluo-
rescence spectroscopy is obtained (Eq. (11)):
703
 
2
½COH  ¼ * ½0:0006*ðF:I:455nm Þ þ 0:0104 (11)
0:29
The first experiment consisted of placing C-AC sample in a cell
(3) containing electro-generated H2O2 and coumarin as probe mole-
cule. The process was monitored for 360 min and the characteristic
(4) signal of 7-hydroxycoumarin observed was insignificant, since
there is no catalyst that promotes the formation of
OH radicals as
shown Fig. SM-4a and SM-4b. However, with C-AC-Fe sample, the
(5)
result is different, as shown in Fig. SM 4c; after 1 min, the charac-
teristic signal of 7-hydroxycoumarin is observed, thus indicating
(6) the presence of
OH radicals in this experimental system. This
concentration starts to increase lineally with time for the first
(7) 150 min. From that moment, an asymptotic behavior is observed,
reaching a constant value of 3.5 mM (Fig. 4a, black plot). The kinetic
(8) cals, can be described into two stages: first,
OH radicals are
generated following a zero-order kinetics [C
OH] ¼ kt during
150 min, due that coumarin molecule exists in an adequate pro-
portion for promoting the conversion reaction to 7-
hydroxycoumarin; once that coumarin becomes the limiting re-
agent, the generation of the radical starts to seem constant and
then it gradually diminishes because of the lack of the necessary
species to form the fluorescent product. From experimental data, it
is concluded that during the first 150 min it is possible to obtain the
kinetics constant of the radical formation (Fig. SM-4d), which is
equal to 0.0197 min1. Finally, with the purpose of corroborating
that the Fenton reaction is taking place heterogeneously between
iron supported on carbon and H2O2 in solution, the concentration
of iron due to its possible lixiviation was monitored (Table 1). At the
end of the experiment, Fe2þ concentration was 0.1 mg L1; hence,
the supported catalyst remained stable in the carbon surface and
that reaction is occurring in the heterogeneous phase.
The results obtained in the quantification of the
OH radicals
were contrasted with those obtained in the degradation of phenol
to corroborate that the process of degradation of the contaminant is
due to the Fenton process in heterogeneous phase. The degradation
of phenol was monitored in the same time interval as the kinetics of
radical formation (Fig. 4a, blue graph); the kinetic degradation of
the model molecule is inversely proportional to the kinetics of the

OH radical formation, thus proving that its degradation is due to
oxidation with the radicals generated during the Fenton reaction in
heterogeneous phase. Therefore,
OH radicals initiate an electro-
(9)
the aromatic ring (Diaz-uribe et al., 2015), and therefore the
mineralization of the molecule through their respective reaction
intermediates, such as catechol, hydroquinone, benzoquinone and
carboxylic acids (Ramos et al., 2009; Espinosa et al., 2015; Jarrah
and Mu'azu, 2016; Mousset et al., 2016; Amado-Pin ~ a et al., 2017).
In order to evaluate the capacity of reuse of the catalyst, several
cycles of reuse for the degradation of phenol were carried out. In
each of them, the kinetics of phenol degradation (Fig. 5a) and
OH
radical formation were determined (Fig. 5b). According to the
experimental data obtained, it is concluded that the degradation
efficiency decreases in relation to the cycles of reuse (Table 1). It is
appreciated that during the first cycle of use of the catalyst there is
a high percentage of mineralization (99.1%) compared to a con-
ventional Fenton process, this effect is attributed to the low amount
of iron present in solution, this being one of the main advantages of
the Fenton process in heterogeneous phase. It is also important to
mention that after the fourth cycle a percentage of mineralization
of 88.6% was obtained showing the efficiency of the process. These
results can be related to the kinetics of formation of
OH radicals
determined for each cycle of reuse of the catalyst, observing that
704
rate-Guzma
A.I. Za
n et al. / Chemosphere 224 (2019) 698e706

Fig. 4. a) - Kinetics of
OH radicals production using 0.1 g of C-AC-Fe and phenol degradation, b) Graph of the depletion process of sample C-AC-Fe: , Formation of
OH radical
(%), B Phenol degradation (%).

Table 1
Monitoring of the process in repeated cycles of use of the catalyst for the degradation of phenol.

Cycle Phenol degradation efficiency (%) Mineralization of phenol to CO2a (%)

OH radical formation efficiency (%) Fe2þ leached mg L1 Fe2þ/Fe 3þ
Ratio

1 100.0 99.1 100.0 0.1 1.29

2 87.8 97.9 90.0 0.3 e
3 83.1 92.3 86.1 0.7 e
4 79.8 88.6 80.2 1.0 0.92
a
Obtained from TOC data of each cycle.

Fig. 5. Reuse cycle of C-AC-Fe as catalyst in Fenton reaction. a) Kinetics of phenol degradation A cycle I, cycle II, cycle III, and cycle IV b) Kinetics of
OH radicals production: ◊
cycle I, cycle II, cycle III and cycle IV.

the loss in efficiency is due to the fact that the catalyst begins to
deplete as the generation of
OH radicals begins to decrease.
With the aim of obtaining information on the catalyst spent
process in the Fenton reaction in heterogeneous phase, C-AC-Fe-
spent were characterized. The SEM images of the material are
shown in Fig. SM-2b, in which the metallic particles adhered to the
support can be seen; it is observed that the texture of the carbon
undergoes a slight chemical attack due to its exposure to the
oxidation process, however these changes are barely perceptible to
the 4th cycle of use. The FTIR spectroscopy studies are shown in
Fig. 1a (Green), in which it is observed that there is no change in the
functional groups of the material, thus, the possible adsorption of
by-products due to the oxidation of phenol can be discarded since
no new absorption bands are appreciated. The XP spectroscopy
studies are presented in Fig. 2; the spectrum shows significant
differences with respect to the material prior to its use in the
advanced oxidation process, once the supported catalyst begins to
be consumed, its XP spectrum its similar to the spectrum of Fe3O4
(Mullet et al., 2002), which can be considered as a ferric oxide
molecule bonded to a ferrous oxide molecule, that is, a molecule in
which there are two atoms of Fe (III) and one atom of Fe(II),
showing the change in the proportion of these species in compar-
ison with the original material. An increase in the signal attributed
to the characteristic satellite peak of Fe3þ species (720 eV) is
observed. The mathematical analysis after the deconvolution of the
spectra corresponding to spent sample presents a percentage of
oxygen higher than the original sample (23.6% vs. 13.8%), which is
due to the fact that during the process the generated
OH radical
does not carry out the selective oxidation of the phenol, since it also
attacks the activated carbon used as catalyst support. This chemical
attack on the surface of the carbon brings about changes in its
textural properties because the walls of the pores are easily
destroyed by the oxidizing agent (Mesquita et al., 2012). The
quantitative analysis performed for the spent catalyst showed a
surface iron amount of 7.8% vs. 8.1% for the initial sample, such a
low metal loss after 4 cycles of use, shows the stability of the
catalyst supported in the carbon structure.
After the deconvolution of the spectrum, the data obtained
showed that after 4 cycles of use, the Fe2þ/Fe3þ ratio is 0.92, that is,
28% less than that found for the C-AC-Fe sample. From the

rate-Guzma
A.I. Za
n et al. / Chemosphere 224 (2019) 698e706
information obtained, the graph presented in Fig. 4b was con-
structed, in which the process of catalyst depletion is clearly seen.
After four cycles of use of the supported catalyst, the efficiency in
the degradation of phenol decreases (Fig. 5a), which is attributed to
the decrease in the production of
OH radicals (Fig. 5b), this
decrease was of 20%. This phenomenon can be attributed to the
change of the iron species present in the material, as was observed
in the XP spectra, so that during the advanced oxidation process the
Fe2þsupported in the carbon catalyzes the decomposition of H2O2
to
OH, having as consequence its change of oxidation state to Fe3þ,
in a similar way as it happens in the reaction of oxidation in ho-
mogeneous phase. In such a way that the catalyst will be
completely depleted when all the Fe2þ species change their
oxidation state due to the reaction.
It is important to note that when using a heterogeneous catalyst
during the Fenton reaction, formation of undesirable precipitates is
avoided (sludge due to the presence of iron in the effluent, See
Fig. SM-5); therefore, leached iron was determined in the treated
solution. It is observed that after the first cycle of use of the catalyst,
the amount of total iron in the effluent is 0.8 mg L1 (0.1 mg L1 of
Fe2þ), which slowly increases for the subsequent cycles, reaching a
maximum of 1.2 mg L1 (1.0 mg L1 of Fe2þ) after the fourth cycle.
Finally, when comparing the amounts of iron leached in the process
against similar studies previously reported by Bayat et al. (2012),
6 mg L1, Ramirez et al. (2007), 2 mg L1, it can be concluded that
such a low degree of release makes the stability of the catalyst in
the carbon structure evident. Also, the concentration of the metal is
below the maximum permissible limits for treated water effluents
(2 mg L1 according to current European legislation) (Mesquita
et al., 2012).
So far, there are no studies reported in the literature on what is
the contribution of this iron leached in the overall efficiency of the
process, since the metal in solution would carry out the Fenton
reaction in homogeneous phase. Therefore, in order to determine
the contribution of leached Fe2þ, quantification of
OH radicals
generated by the homogenous Fenton process was performed
(Fig. 6). From this plot, concentration of OH radicals for the process
was estimated as 0.29 mM, whereas for the heterogeneous Fenton
process a concentration of 3.25 mM was obtained at the same
experimental conditions. This would represent that 92% of the
generation of
OH radicals is carried out by Fenton reaction in
heterogeneous phase, while 8% of the generation of those
OH
Fig. 6. Kinetics of generation of
OH radicals for heterogeneous Fenton, homoge-
neous Fenton and - global reaction (Homogeneous Fenton þ Heterogeneous Fenton).
705
radicals is carried out by the reaction in homogeneous phase.
Finally, TOC data obtained were converted to phenol mineralized to
CO2. Table 1, shows the conversion percentage of phenol to CO2 for
each reuse cycle. For the first cycle a mineralization of 99.1% was
obtained, thus indicating that almost all of by-products have been
converted to CO2. This mineralization percentage decreased with
each reuse cycle, and was congruent with
OH radicals generation
decrease obtained for each cycle too.
4. Conclusions
Fenton heterogeneous reaction is carried out on the surface of
the carbon impregnated with iron, where the supported metal
performs the catalytic decomposition of H2O2 obtaining a produc-
tion of
OH radicals of 3.5 mM using a mass of 0.1 g C-AC- Fe. Studies
of leached iron in solution showed a concentration of 0.1 mg L1,
thus evidencing that the supported metal is stable, and the reaction
is carried out in a heterogeneous phase. The depletion of the
catalyst is due to the fact that during the oxidation process, the iron
present in the surface changes its oxidation state from Fe2þ to Fe3þ,
directly affecting the degradation efficiency of the pollutant,
decreasing by 20% in the fourth cycle of use with respect to the first.
In-situ H2O2 production was obtained at high concentrations
(30 mg L1 h1). By coupling this experimental design with the use
of catalyst (previously described) the degradation of the model
pollutant was achieved in repeated cycles, showing that the pro-
posed process is a clean technology for the treatment of waste-
water, with a minimum generation of by-products, avoiding the
generation of sewage sludge and does not require the handling and
storage of reagents.
Acknowledgments
The authors thank the National Council of science and tech-
nology (CONACYT, Me
xico), for the project No. 256943 “Fondo de

n científica b

investigacio asica 2015”. A.I. Zarate-Guzma
n thanks
CONACyT for the support received with the scholarship number
265212, and also thanks to Dr. Gerardo Torres Delgado for his
valuable contributions to this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2019.02.101.
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