Effect of Ultrasound on the Structural and Textural Properties

of AlFe Pillared Clays in a Concentrated Medium

Nancy R. Sanabria Rafael Molina
Sonia Moreno
Received: 3 March 2009 / Accepted: 24 March 2009 / Published online: 7 April 2009
Springer Science+Business Media, LLC 2009
Abstract A modication of bentonite with the AlFe
mixed system in a concentrated medium was performed,
assisting the intercalation with ultrasound. The solid pil-
laring agent and clay powder were placed in a dialysis
membrane in contact with a minimum amount of water,
and ultrasound was used to promote species exchange.
AlFe pillared clays (2, 5 and 10 mol% Fe) were charac-
terized by XRF, CEC, XRD, H
2
-TPR and N
2
adsorption at
77 K, revealing changes in the structural and textural
properties of the modied clays in the presence of ultra-
sound during the intercalation. The catalytic properties of
pillared clays were evaluated by using the catalytic wet
peroxide oxidation of phenol in a diluted aqueous medium,
showing an activity comparable to that of a solid modied
through the conventional method.
Keywords PILC Concentrated medium
Multimetal polyhydroxy cation Ultrasound CWPO
1 Introduction
Barrer and MacLeod rst introduced the concept of trans-
forming a lamellar solid into a porous structure by inserting
laterally spaced molecular props between the layers of a
smectite clay mineral [1]. A pillaring agent is any com-
pound, which can be intercalated between adjacent layers
of a layered compound, which maintains the spacing
between adjacent layers upon removal of the solvent, and
which induces an experimentally observable pore structure
between the layers [2]. One of the pillaring cations is
usually Al, to which the second inorganic cation is added to
improve the thermal, adsorptive, and catalytic properties of
the pillared clays [3].
The classic method of pillaring involves two steps: rst,
the addition of the precursor polymer solution into the
dispersion of clay mineral (intercalation) followed by the
thermal treatment of the intercalated clay mineral. Variants
of the traditional method have been researched in order to
decrease the water volume and timing of the synthesis.
Thus, it has become possible to decrease the volume of
water by the use of concentrated suspensions, both clay
(10, 15, 20, 40, 50 and 100 wt%) and a pillaring agent
(chlorhydrol concentrate) [49]. Also, the time of interca-
lation of calcium montmorillonite with chlorhydrol
(commercial format of basic aluminum chloride solution)
has been reduced through the use ultrasound for a period of
a few minutes, having obtained Al-PILC with a high
thermal stability and textural properties superior to those of
clay modied with an exchange time of 24 h. In general,
during the intercalation, treatment with ultrasound [1012]
and microwaves [4, 1315] has proved an adequate method
for reducing the contact time between the clay and the
pillaring agent.
Although in the past 30 years several studies high-
lighting some applications of industrial pillared clays have
been published, such materials have not been used as
commercial catalysts primarily due to the difculty of
extending the laboratory synthesis to an industrial scale.
Aouad et al. recently developed a procedure for pillaring
clays with aluminum, which minimizes the processing time
and the amount of water used, allowing its extension to an
industrial level. To simplify the synthesis of Al-PILC, non
puried natural clay and the pillaring agent in a solid state
N. R. Sanabria R. Molina S. Moreno (&)
Estado Solido y Catalisis Ambiental (ESCA), Departamento de
Qu mica, Universidad Nacional de Colombia,
Carrera 30 No. 45-03, Bogota, Colombia
e-mail: smorenog@unal.edu.co
1 3
Catal Lett (2009) 130:664671
DOI 10.1007/s10562-009-9956-4
are used, so that clay powder and solid Al
13
nitrate are
placed together in a dialysis membrane [16].
Intercalation with Al and Fe solutions has been reported
in detail by several authors [1722]. Palinko et al. analyzed
the nature of the AlFe mixed species generated in pillared
clays, by FTIR and Mossbauer spectroscopy, as well as the
pillaring agent, and concluded that there is no tetrahedral or
octahedral isomorphous substitution of Fe in the Keggin
structure of Al
13
. They also suggest that the expansion of
montmorillonite is due to the presence of a mixture of Al
Keggin ions and hydrated iron oxides, admitting the
occurrence of co-hydrolysis and co-pillaring during the
modication [23, 24].
The mixed AlFe pillaring agent has traditionally been
used in solution [25, 26], although it has also been syn-
thesized following a procedure similar to that described by
Furrer et al. for the basic aluminum nitrate [27, 28].
Al
13
? Fe nitrates have been successfully characterized
and employed as pillaring agents in bentonite modication
in a concentrated medium, generating microporous and
mesoporous structures similar to those obtained through
traditional methods of synthesis that use the pillaring agent
in solution [29].
The synthesis of bentonite pillared by the mixed AlFe
system in a concentrated medium was conducted in this
study, having favored the exchange of species through the
use of ultrasound. The structural, textural and catalytic
properties of the solids modied by the AlFe mixed sys-
tem during intercalation with and without ultrasound were
evaluated.
2 Experimental
2.1 Synthesis of the Pillaring Agent
The polymeric precursor in an aqueous solution was syn-
thesized following the methodology of Furrer et al. for the
synthesis of basic aluminum chloride [27], but with the
addition of iron as a second metal. Four pillaring solutions
were synthesized from AlCl
3
6H
2
O, FeCl
3
6H
2
O and
NaOH: Al and AlFe with 2, 5 and 10%mol of Fe. The
OH/metal hydrolysis molar ratio was 2.46. Once the
hydrolysis was completed, the solutions were aged for 4 h
at 60 C.
Aqueous solutions of Al
13
and Al
13
? Fe chlorides were
added to 0.1 M Na
2
SO
4
in a metal/SO
4
molar ratio of 1.0,
agitated for 2 h, and then allowed to stand for 36 h. After
this time, the suspension was separated by centrifugation
and successive washings with a buffer solution of citric
acid/sodium citrate were made in order to dissolve the iron
that independently hydrolyzed.
Al
13
and Al
13
? Fe sulfate were dried at 60 C, dis-
solved in a Ba(NO
3
)
2
solution, and subjected to ultrasound
for 4.5 h. Finally, the solution was separated from the solid
(BaSO
4
) by centrifugation and evaporated at 60 C in the
oven until Al
13
and Al
13
? Fe nitrate crystals were
obtained. These nitrates were ground and sifted in a 100
mesh to then be used as pillaring agents in the modication
of clays.
The Al and AlFe nitrates used were the following:
Al
13
-NO
3
, Al
13
-NO
3
? Fe(2), Al
13
-NO
3
? Fe(5) and
Al
13
-NO
3
? Fe(10). The value in parentheses corresponds
to the nominal amount of Fe used in the synthesis,
expressed as a molar percentage.
Al and AlFe nitrates were characterized by X-ray
uorescence (XRF) and X-ray diffraction (XRD). The
complementary characterization of the Al
13
-NO
3
? Fe
pillaring agent and the Al
13
SO
4
? Fe precursor using
XRD, SEM and
27
Al-NMR has been described in a pre-
vious article [29].
2.2 Synthesis and Characterization of Pillared Clays
The starting clay was a natural bentonite from Valle del
CaucaColombia, segregated by particle size (fraction
\2lm). A fraction of the clay was homoionized with
0.5 M CaCl
2
, washed with distilled water until reaching a
conductivity of \20 ls/cm, dried at 60 C and nally
ground and sifted in a 100 mesh.
For the modication, clay powder and the solid pillaring
agent were dry mixed (ratio of 20 meq metal/g clay) and
were placed into a dialysis membrane (Spectra/Por 4),
which was covered with distilled water and agitated for
3 h, then, subjected to an ultrasound bath (50 kHz) for
30 min. Unassisted ultrasound intercalation was conducted
in the dialysis membrane for 36 h with constant agitation.
The modied material was removed from the membrane,
centrifugally washed until reaching a conductivity near that
of distilled water, dried at 60 C, ground and sifted in a 80
mesh and calcined for 2 h at 400 C (2 C/min).
Both the starting clay and those modied with and
without ultrasound were characterized by X-ray uores-
cence (XRF), cation exchange capacity (CEC), X-ray
diffraction (XRD), temperature programmed reduction
(H
2
-TPR) and adsorption of N
2
to 77 K.
Chemical analysis of the pillaring agent and clays
(natural and modied) was accomplished by X-ray uo-
rescence using a Magix Pro Philips PW2440 instrument.
The amount of leached metal was determined by atomic
absorption spectrometry using a PerkinElmer 400
spectrophotometer.
The cation exchange capacity (CEC) was determined by
micro-Kjeldahl analyses. Clay samples were saturated with
ammonium acetate. The exchanged ammonium was
Effect of Ultrasound on the Structural and Textural Properties of AlFe Pillared Clays 665
1 3
collected in a solution of boric acid and potentiometrically
titrated with HCl. The residual CEC provided an evaluation
of the layer charge, which was not compensated by the
positively charged pillaring species.
X-ray diffraction (XRD) patterns were determined in a
LabX Shimadzu XRD-6000 diffractometer using Cu Ka
radiation (steps of 0.01 2h and 2 s/step).
Temperature programmed reduction (H
2
-TPR) was
measured using a Chembet 300 (Quantachrome) with a
thermal conductivity detector (TCD). The samples were
taken inside a quartz U tube and degassed at 400 C for
1 h with an argon ow and kept constant at this tempera-
ture for 30 min. The samples were then cooled to room
temperature and stabilized under an argon/hydrogen ow
(99.998% purity, 90/10 volumetric ratio). The temperature
and thermal conductivity detector signals were continu-
ously recorded during heating at 10 C/min to 900 C in
order to obtain the prole.
Nitrogen adsorption-desorption isotherms were deter-
mined in a Micromeritics ASAP 2020 instrument at 77 K
after outgassing the samples for 1 h at 90 C and 3 h at
300 C in a vacuum.
2.3 Catalytic Activity
The catalytic activity of the solids was evaluated in the
oxidation reaction of phenol in a dilute aqueous medium by
the procedure reported in previous works [3032]. For each
test, the reactor was loaded with 100 mL of a 5 9 10
-4
M
phenol solution, 0.5 g of the catalyst, and a 0.1 M hydro-
gen peroxide solution, and brought to a pH of 3.7.
Monitoring of the phenol conversion over time and the
production of subproducts in the oxidation reaction were
carried out by high performance liquid chromatography
(HPLC) using a Hitachi D-7000 (LaChrom) instrument
equipped with a Lichrosphere 60 Select B column. The
assessment of total organic carbon (TOC) was carried out
by means of an AnaTOC instrument.
3 Results and Discussion
3.1 Characterization of the Pillaring Agent
Table 1 summarizes the results of the chemical analysis for
Al
13
and Al
13
? Fe nitrates. The amount of Fe incorpo-
rated into Al
13
Fe nitrate is very low compared with the
nominal amount used in the synthesis since only an
incorporation of 1.79, 5.04 and 2.81% Fe for the Al
13
-
NO
3
? Fe(2), Al
13
-NO
3
? Fe(5) and Al
13
-NO
3
? Fe(10),
respectively, is achieved. A limited incorporation of Fe in
the polymers becomes evident.
As the nominal amount of Fe in the synthesis of the
pillaring agent increases, the amount of product obtained
(Al
13
-NO
3
? Fe) is considerably reduced, especially
regarding the molar ratio of 10% Fe. The use of Fe in a 5%
molar ratio makes the separation of the precipitate formed
by the addition of Na
2
SO
4
difcult and lowers the synthesis
yields.
However, the synthesis of Al
13
-NO
3
? Fe and its use as
a solid pillaring agent has advantages over the use of the
conventional pillaring solution (diluted solution), given
that precipitation with Na
2
SO
4
allows the selective sepa-
ration of the polymeric species of Al [33] and the
elimination of iron that has independently hydrolyzed. In
addition, the solid pillaring agent is stable (it does not
decompose, it is not hygroscopic), can be stored for long
periods of time and is easily transported.
The patterns of X-ray diffraction of Al and AlFe
nitrates (Fig. 1) show a low crystallinity and a wide peak
similar to what has been reported in the literature for Al
13
associated with the nitrate anion [34]. For Al
13
-NO
3
,
the signal shows a spacing of 11.8 A

, while in
Al
13
-NO
3
? Fe(2), Al
13
-NO
3
? Fe(5) and Al
13
-NO
3
?
Fe(10) the signal is centered at 12.8 A

. The X-ray dif-

fraction pattern of Al
13
-NO
3
? Fe(10) showed impurities
of Ba(NO
3
)
2
(JCPDS 76-0920), which probably correlate
Table 1 Chemical analysis of Al
13
and Al
13
? Fe nitrates
Sample Al (%) Fe (%) Na (%) S (%)
Al
13
-NO
3
31.52 0.00 2.30 0.25
Al
13
-NO
3
? Fe(2) 31.51 0.02 2.54 0.35
Al
13
-NO
3
? Fe(5) 31.62 0.17 2.39 0.11
Al
13
-NO
3
? Fe(10) 32.54 0.11 2.26 0.15
10 20 30 40 50 60 70
* Ba(NO
3
)
2
Al
13
-NO
3
+Fe(10)
Al
13
-NO
3
+Fe(5)
Al
13
-NO
3
+Fe(2)
*
*
*
* *
*
*
*
*
*
*
2 theta
I
n
t
e
n
s
i
t
y

(
a
.
u
)
11.8-12-8
*
Al
13
-NO
3
Fig. 1 XRD of Al and AlFe nitrates
666 N. R. Sanabria et al.
1 3
with an incomplete interchange of pillaring sulfate to
nitrate species.
3.2 Synthesis and Characterization of Pillared Clays
Table 2 shows the chemical analysis of natural and ben-
tonite clays modied with Al and AlFe. In general, all the
clays show an increase in the content of aluminum and thus
a decrease in the Si/Al ratio with respect to the starting
clay. Likewise, it is evident that the introduction of alu-
minum is higher in intercalated clay in the presence of
ultrasound. The Si/Fe ratio remained fairly constant in all
the modied samples since the contents of Fe in the pil-
laring agents is very low.
The cation exchange capacity (CEC) of the modied clays
(Table 2) shows a signicant decrease regarding the starting
material, which conrms the successful ion exchange in
bentonite. It is important to note that in all modied solids,
the fraction of balanced load remains between 7 and 14%
higher when the intercalation is assisted by ultrasound.
The higher addition of Al and/or Fe to clays where
intercalation was assisted by ultrasound is directly related to
a larger fraction of balanced load, which meanwhile dem-
onstrates the positive effect of ultrasound towards a greater
introduction of the pillaring agent in the clay structure.
In the X-ray diffraction patterns of natural and modied
clays (Fig. 2), the effective introduction of metal polyhy-
droxy cations and the subsequent formation of pillars in the
interlamellar spacing become evident. The shift of the d
001
reection of the basal spacing of 13.8 A

for the starting

clay (not calcined B-nat) at higher values, conrms the
successful modication of all the solids by pillaring.
Clays modied with ultrasound show higher basal
spacing and narrower and more dened signals at the stage
of intercalation than those modied in the absence of
ultrasound. In general, it can be noted that, from a structural
point of view, the use of ultrasound during intercalation
favors the formation of larger, more homogeneous and
better-distributed pillars. The B-AlFe (5) with US solid
shows a higher increase in basal spacing (d
001
= 18.2 A

)
and lower width at average height (FWHM de 1.2 2h). The
broad signals that characterize the solids modied in the
absence of ultrasound (FWHM between 1.5 and 2.0 2h) are
probably associated with the heterogeneity in the distribu-
tion of pillars in the interlamellar space.
Indeed, the use of ultrasound in the intercalation stage
probably increases the matter transport (exchange of spe-
cies), and improves the dispersion and homogenization of
the suspended solids (by collision effect). These chemical
effects produced by ultrasound are derived from the phe-
nomenon called cavitation, which includes the creation,
expansion and destruction of small bubbles when the liquid
is irradiated with US, locally generating high temperatures
and pressures [10, 35].
As for the H
2
-TPR proles (Fig. 3), the reductibility of
the Fe species in natural clay (6.89% Fe) and modied
clays was analyzed. The calcined natural bentonite evi-
dences three reduction peaks at around 478, 567 and
691 C. The signal at 478 C corresponds to the reduction
of a-Fe
2
O
3
to the Fe
3
O
4
surface iron oxide; the signal at
567 C is associated with the reduction of Fe
3
O
4
to FeO,
and the signal at 691 C is related to the reduction of FeO
to Fe metal [36, 37].
Bentonite modied with Al and AlFe shows the same
three signs of reduction of calcined natural bentonite.
However, the reduction associated with the three events of
maximum hydrogen consumption is achieved at lower
temperatures (around 465, 545 and 673 C), on the grounds
that, as a result of pillaring, the access to the active species
of the material is increased, making it easier to reduce.
Given that the bentonite pillared with the AlFe mixed
system contains a very low amount of Fe (see Table 1), it is
not possible to see signicant changes in the proles of H
2
-
TPR, except for B-AlFe(10) without US where a slight
shoulder at the rst signal appears, probably corresponding
to the reduction of the surface iron oxides.
For the clays modied with AlFe and Al in the presence
of ultrasound, the three signs of reduction appear at slightly
Table 2 Chemical analysis, mass ratios of Si/Al and Si/Fe and cation exchange capacity (CEC) of natural bentonite and modied clays
Sample Si (%) Al (%) Fe (%) Si/Al Si/Fe CEC (meq/100 g) Compensated charge (%)
B-nat 24.91 11.02 6.89 2.26 3.62 46.4
B-Al without US 22.13 13.91 5.16 1.59 4.29 15.4 66.8
B-Al with US 20.47 15.22 5.08 1.35 4.03 10.4 77.6
B-AlFe(2) without US 22.39 14.24 5.71 1.57 3.92 15.4 66.8
B-AlFe(2) with US 22.30 15.00 5.50 1.49 4.05 12.9 72.2
B-AlFe(5) without US 22.08 13.38 5.62 1.65 3.93 17.6 62.1
B-AlFe(5) with US 21.57 13.45 5.39 1.60 4.00 13.9 70.0
B-AlFe(10) without US 22.58 13.87 5.64 1.63 4.00 16.9 63.6
B-AlFe(10) with US 22.38 14.04 5.56 1.59 4.03 13.4 71.1
Effect of Ultrasound on the Structural and Textural Properties of AlFe Pillared Clays 667
1 3
lower temperatures (between 3 and 8 C) than those
observed for clay modied without ultrasound. It is possible
that the use of ultrasound in the stage of intercalation makes
the iron species in the modied clays more accessible.
H
2
-TPR proles were mathematically processed by
Gaussian deconvolution (GRAMS/AI 7.02 Thermo
Galactic program) to semiquantitatively determine the rate
of species associated to each reduction event. The area
ratio for the rst and second reduction signals (A
2
/A
1
) is
practically equal in all of the solids evaluated.
However, when comparing this relationship and the
H
2
-TPR prole of the solids synthesized in this work with
an equivalent solid obtained by the conventional method
(2% clay suspension and a pillaring solution diluted with
10% Fe molar), denoted as B-AlFe(10) conven, it is clear
that there are differences. It is possible to suggest that in
the solids synthesized with and without the use of ultra-
sound, the iron introduced in the clay is preferentially
associated with the alumina pillar (signal 2) and not as iron
oxide (cluster) on the external surface (signal 1).
Since as the rst sign of reduction is associated with the
reduction of surface iron oxides, the B-AlFe(10) conven
solid shows the maximum consumption of hydrogen at a
lower temperature, because all the iron used in the syn-
thesis of the pillaring agent is in contact with the clay, and
iron oxides probably appear on the outer surface of the
solid (cluster) [31].
Adsorption isotherms of clays modied with Al and
AlFe, with and without ultrasound during the intercalation
(Fig. 4), show an increase in the capacity of adsorption
compared with natural bentonite. The isotherm of natural
bentonite is a type II [37, 38], and is an adsorption of a
nonporous or macro-porous solid with a heterogeneous
texture [39], while isotherms of clays modied with Al and
AlFe are type I, characteristic of microporous solids [38].
200 400 600 800 200 400 600 800
A
2
/A
1
=1.05
B-AlFe(10) without US
A
2
/A
1
=1.22
B-AlFe(10) with US
A
2
/A
1
=1.30
B-AlFe(5) without US
A
2
/A
1
=1.32
B-AlFe(5) with US
A
2
/A
1
=1.24
B-AlFe(2) without US
H
2

c
o
m
s
u
p
t
i
o
n

(
a
.
u
)
A
2
/A
1
=1.25
B-AlFe(2) with US
H
2

c
o
m
s
u
p
t
i
o
n

(
a
.
u
)
A
2
/A
1
=1.22
B-Al without US
A
2
/A
1
=1.24
B-Al with US
A
2
/A
1
=1.20
B-nat (calcined)
Temperature (C) Temperature (C)
A
2
/A
1
=0.55
B-AlFe(10) conven
Fig. 3 H
2
-TPR proles of
calcined natural bentonite and
modied clays
4 8 12 16
0
1250
2500
3750
5000
6250
B-AlFe(10) with US d
001
=18.2
B-AlFe(10) without US d
001
=15.2
B-AlFe(5) with US d
001
=18.2
B-AlFe(2) with US d
001
=17.3
B-AlFe(5) without US d
001
=15.7
B-AlFe(2) without US d
001
=15.6
B-Al with US d
001
=17.2
B-Al without US d
001
=16.1
B-nat d
001
=13.8
I
n
t
e
n
s
i
t
y

(
a
.
u
)
2 theta
Fig. 2 XRD of natural bentonite and modied clays
668 N. R. Sanabria et al.
1 3
The surface area was determined by the models of
Langmuir [38] and modied BET [40, 41], and the external
surface area and micropore volume through the t curves (t
statistical thickness between 3.5 and 5.0 A

) using the
HarkinsJura [42] equation (Table 3).
In general, the pillaring process with Al and AlFe leads
to changes in the texture of the solids regarding the starting
clay, greatly increasing the total surface area, microporous
area and micropore volume. The addition of iron in a low
nominal rate in the synthesis (2 and 5% molar) leads to
higher surface area values. B-AlFe(5) with and without US,
shows the highest values of total surface area and micro-
porous surface, with the latter accounting for 74 and 70%
of the total area. These results support the proposal
Marinkovic et al., stipulating that clays modied with the
mixed AlFe system have a higher thermal stability than
those pillared only with Al, generating more microporous
structures [43].
On the other hand, when the nominal iron content is
higher (10% molar), the textural properties of the pillared
clay are very similar to those of clay modied only with
aluminum, indicating that such nominal ratios do not favor
the formation and stability of the pillar.
It is important to emphasize that in all cases the values
of the microporous area and micropore volumes for clays
modied with AlFe and Al in the presence of ultrasound
are superior to those obtained when the intercalation is not
assisted by ultrasound. Such a result conrms the benets
of acoustic radiation during the intercalation stage, since it
promotes the exchange of species, dispersion of the mix-
ture and, therefore, the homogeneous distribution of the
pillars, allowing to obtain solids with excellent textural
characteristics.
The textural properties of bentonite pillared with Al and
AlFe through the conventional methodology (diluted
pillaring solution, clay suspension at 2% and longer syn-
thesis times) are lower [31] than those of the solids
modied in this work, demonstrating the viability of using
concentrated suspensions of clay-pillared agent, as well as
the benets of the use of ultrasound in the intercalation,
achieving a signicant decrease in the volume of water and
in the synthesis time to obtain successfully modied solids.
0
20
40
60
80
0.0 0.2 0.4 0.6 0.8 1.0
P/Po
0.0 0.2 0.4 0.6 0.8 1.0
P/Po
V
o
l
u
m
e

a
d
s
o
r
b
e
d

(
c
m
3
S
T
P
/
g
)
B-nat
B-Al without US
B-AlFe(2) without US
B-AlFe(5) without US
B-AlFe(10) without US
0
20
40
60
80
V
o
l
u
m
e

a
d
s
o
r
b
e
d

(
c
m
3
S
T
P
/
g
)
B-nat
B-Al with US
B-AlFe(2) with US
B-AlFe(5) with US
B-AlFe(10) with US
Fig. 4 Nitrogen adsorptiondesorption isotherms of natural bentonite and modied clays
Table 3 Textural characterization of natural bentonite and modied clays
Sample S
Langmuir
(m
2
/g) S
BET-Remy
(m
2
/g) S
External
(m
2
/g) S
micropore
(m
2
/g) V
micropore
(cm
3
/g)
B-nat 43.7 43.3 41.6 1.7 0.0006
B-Al without US 60.7 58.6 24.0 34.6 0.0123
B-Al with US 118.7 115.5 36.2 79.3 0.0285
B-AlFe(2) without US 81.1 81.2 28.6 52.6 0.0186
B-AlFe(2) with US 119.7 121.9 28.8 93.1 0.0330
B-AlFe(5) without US 129.6 128.1 38.2 90.0 0.0319
B-AlFe(5) with US 161.5 159.7 33.3 126.4 0.0447
B-AlFe(10) without US 75.7 74.9 27.8 47.1 0.0167
B-AlFe(10) with US 113.9 114.6 25.6 89.0 0.0315
Effect of Ultrasound on the Structural and Textural Properties of AlFe Pillared Clays 669
1 3
3.3 Catalytic Activity in the Oxidative Reaction
of Phenol in an Aqueous Medium
The results of the catalytic reaction of clays pillared with
AlFe show the benecial effect of the introduction of Fe
in the solids, both in the conversion of phenol (Fig. 5) and
in that of the total organic carbon, TOC (Fig. 6). These
solids reach a 100% phenol conversion after 2 h of reac-
tion, while the BAl solid reaches this point after 3 h. The
calcinated B-nat- only reaches 37.8% phenol conversion
after 4 h of reaction.
All pillared clays show conversion values of total
organic carbon much higher than those of natural bentonite.
The TOC conversion percentage for solids modied with
AlFe ranges between 37 and 48%, being higher for the
B-AlFe (5) solids with US and B-AlFe(2) with US.
Comparing the catalytic results of these solids (synthe-
sized in a concentrated medium) with those of the solids
synthesized using the conventional method (2% clay and a
diluted pillaring solution) [25, 3032] signicant differ-
ences in the conversion of phenol and TOC are not found,
especially since the solids in this work contain smaller
amounts of Fe. This last aspect has great advantages, since
the amount of Fe leachate into the reaction is much lower
(between 0.16 and 0.18 ppm of Fe).
In likewise manner, as evidenced in the results of dif-
ferent techniques used for characterization, the use of
ultrasound during the intercalation of clay is desirable, and
it leads to more active and selective materials being
obtained in the phenol oxidative reaction in a diluted
aqueous medium.
4 Conclusions
The synthesis of clays pillared through the mixed AlFe
system in a highly concentrated medium, assisting the
intercalation with ultrasound, allows a considerable
0
20
40
60
80
100
0 60 120 180 240
Time (min)
P
h
e
n
o
l

c
o
n
v
e
r
s
i
o
n

(
%
)

B-nat (calcined)
B-Al without US
B-Al with US
B-AlFe(2) without US
B-AlFe(2) with US
B-AlFe(5) without US
B-AlFe(5) with US
B-AlFe(10) without US
B-AlFe(10) with US
Fig. 5 Phenol conversion of
calcined natural bentonite and
modied clays at 25 C
0
5
10
15
20
25
30
35
40
45
50
0 60 120 180 240
Time (min)
T
O
C

c
o
n
v
e
r
s
i
o
n

(
%
)

B-nat (calcined)
B-Al without US
B-Al with US
B-AlFe(2) without US
B-AlFe(2) with US
B-AlFe(5) without US
B-AlFe(5) with US
B-AlFe(10) without US
B-AlFe(10) with US
Fig. 6 TOC conversion of
calcined natural bentonite and
modied clays at 25 C
670 N. R. Sanabria et al.
1 3
decrease in the volume of water and the synthesis times
compared with the conventional methodology.
The Fe introduced into the clays is preferentially asso-
ciated with the alumina pillars and not with surface Fe
oxides (cluster). This is related to the high stability of the
active phase in the reaction medium.
The addition of small quantities of Fe in the synthesis of
the pillaring agent (2 and 5% molar) favors the formation
of larger and better distributed pillars, which determines
the good catalytic performance of these solids in the oxi-
dative reaction of phenol in a diluted aqueous medium.
Sonication favors the formation of larger and better-
distributed pillars, generating very microporous structures
that are active and selective in the reaction of phenol
oxidation.
Acknowledgments The authors are grateful for the nancial sup-
port offered by projects DIB (code 202010012015, and
202010012019) of Universidad Nacional de Colombia Sede Bogota.
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