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Toluene total oxidation over Co supported catalysts synthesised using

‘‘memory effect” of Mg–Al hydrotalcite

Article  in  Catalysis Communications · January 2008

DOI: 10.1016/j.catcom.2008.01.015

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Catalysis Communications 9 (2008) 1639–1643

www.elsevier.com/locate/catcom

Toluene total oxidation over Co supported catalysts synthesised using

‘‘memory effect” of Mg–Al hydrotalcite
C. Gennequin, R. Cousin, J.-F. Lamonier 1, S. Siffert *, A. Aboukaı̈s
Laboratoire de Catalyse et Environnement, E.A. 2598, MREI, Université du Littoral – Côte d’Opale, 145 Avenue Schumann, 59140 Dunkerque, France

Received 24 October 2007; received in revised form 20 December 2007; accepted 14 January 2008
Available online 19 January 2008

Abstract

Cobalt supported on calcined hydrotalcite catalysts were prepared using the memory effect of Mg–Al hydrotalcite. Mg–Al was cal-
cined at different temperatures (500, 600 and 700 °C) and dipped in a Co nitrate aqueous solution. Mg–Al was regenerated and Co cat-
alysts were obtained after the calcination under air at 500 °C. The catalyst synthesised with hydrotalcite calcined at 700 °C (Co/Mg–
Al(700)500) showed high activity and selectivity for toluene oxidation. This interesting catalytic behaviour was correlated to the high
quantity of Co species reducible at low temperature.
Ó 2008 Elsevier B.V. All rights reserved.

Keywords: Cobalt; Hydrotalcite; XRD; TPR; Toluene oxidation; Memory effect

1. Introduction transition metal oxides catalysts with high activity [4,5].

The increasing environmental awareness in the last two
decades has prompted the emergence of stricter regulations
covering automobile and industrial activities. Among
these, the reduction of volatile organic compounds (VOCs)
is particularly important because VOCs represent a serious
environmental problem.
The deep catalytic oxidation of these pollutants to car-
bon dioxide and water has been identified as one of the
most efficient ways to destroy VOCs at low concentrations
and to meet the increasingly stringent environmental regu-
lations. In practice, the catalytic oxidation process requires
heating large amounts of gas containing low concentra-
tions of VOCs to the oxidation temperature. Therefore,
highly active catalysts which work at low temperatures
are required. Noble metal catalysts present higher activity
[1–3] than other metal catalysts, but their manufacturing
cost is relatively high. Therefore efforts are done to develop
*
Corresponding author. Tel.: +33 03 28 65 82 56.
E-mail address: Siffert@univ-littoral.fr (S. Siffert).
1
Present address: UCCS UMR CNRS 8181, Université des Sciences et
Technologies de Lille, 59655 Villeneuve d’Ascq, France.
Among it, cobalt oxides are known to be active for VOC
oxidation but it presents a low surface area and poor ther-
mal stability [5]. Supported cobalt catalysts are convention-
ally studied for hydrocarbon oxidation [6,7]. Wyrwalski
et al. [6] have shown that the zirconia modification by
yttrium and the use of ethylenediamine with the cobalt pre-
cursor result in an efficient catalyst. These two combined
effects generate a high quantity of cobalt species, reducible
at low temperature leading to a more active catalyst for tol-
uene total oxidation. The catalytic results have been
explained in terms of cobalt oxides dispersion which is
strongly improved when the support and/or the cobalt pre-
cursor are modified. Indeed, the nature of supports and the
dispersion of active phases are determinant in the prepara-
tion of a catalyst. Another way to obtain a good support
and a good dispersion of the active phases can be obtained
using hydrotalcite precursors. Their structure are made of
brucite-like layers (Mg(OH)2) with partial substitution of
divalent cations by trivalent cations resulting in a net posi-
tive charge balanced by interlayer anions associated with
variable amounts of water. These compounds have
received a great attention since the 1970’s due to their
potential technological applications. They can be used

1566-7367/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2008.01.015
1640 C. Gennequin et al. / Catalysis Communications 9 (2008) 1639–1643
directly as catalysts or as catalyst precursors [8,9]. Indeed,
it has been shown that the calcination of layered double
hydroxide (LDHs) at temperatures, depending on the par-
ticular cations in the layers and anions in the interlayers,
leads to mixed oxides. These oxides are characterised by
their structural homogeneity, the absence of chemical seg-
regation and their basic sites useful for catalysis [10–12].
LDHs can also be used as support for catalysts [13]. As
anions in the interlayer space are necessary to counterbal-
ance the positive charge of the brucite-like layers, LDHs
are widely used as ion exchangers [14–16] and for depollu-
tion [17–20].
One of the most interesting and useful property of
LDHs is their regeneration ability after moderate heating,
often called ‘‘memory effect’’ [9]. Indeed, a moderate heat-
ing of LDHs leads to the formation of mixed oxides often
amorphous, with high specific area, which are able to
recover the layered structure by water solution contact.
In this paper, new cobalt based catalysts using the mem-
ory effect of LDH were synthesised and their activity for
VOC oxidation were determined. Toluene was chosen as
a probe molecule for the catalytic oxidation, because it is
often found in industrial exhausts and presents high Photo-
chemical Ozone Creation Potentials (POCP) [21].
2. Experimental
Mg–Al (HT) support was prepared with an Mg/Al
atomic ratio of 3/1 as following: an aqueous solution
(100 mL) containing Mg(NO3)2 (FLUKA) and Al(NO3)3
(FLUKA) was added slowly into an aqueous solution of
sodium carbonate (LABOSI, 200 mL, 1M), the pH of the
solution being adjusted at 10 by adding an aqueous solu-
tion of sodium hydroxide (1M). The resulting slurry was
heated at 60 °C for 24 h. Then, the precipitate was filtered,
washed several times with hot deionized water (50 °C) and
dried at 60 °C for 48 h. The dried solid was calcined at var-
ious temperature in the range of 500–700 °C. These support
were denoted Mg–Al(T) with T = 500, 600, 700 °C.
Aqueous impregnation of cobalt nitrate (FLUKA,
5 wt% of Co, 100 mL) was performed on the support cal-
cined at various temperatures. The solution was main-
tained at ambient temperature with vigorous stirring
during 30 min. The solution was then evaporated under
vacuum at 60 °C. Solids obtained were denoted Co/Mg–
Al(T). Final products are obtained after activation at
500 °C and denoted Co/Mg–Al(T)500. For comparison,
we prepared a catalyst by alcohol impregnation of cobalt
nitrates (5 wt% of Co, 100 mL) on support calcined at
700 °C. The solid was called Co(EtOH)/Mg–Al(700)500.
BET surface areas of the solids were measured by nitro-
gen adsorption at 196 °C using thermo-electron Q surf
M1 apparatus. The samples were outgassed for 1 h at
120 °C.
The structure of solids was analyzed at room tempera-
ture by X-Ray diffraction (XRD) technique in a Brüker
D8 advance diffractometer equipped with a copper anode
(k = 1.5406 Å). The scattering intensities were measured
over an angular range of 4° < 2h < 80° for all the samples
with a step-size of D(2h) = 0.02° and a count time of 6 s
per step. The diffraction patterns were indexed by compar-
ison with the JCPDS files.
H2-temperature – programmed reduction (TPR) of the
calcined catalysts was carried out in an Altamira AMI
200 apparatus. Prior to the TPR experiments, samples
(30 mg) were activated under argon at 150 °C for 1 h.
The samples were then heated from ambient to 900 °C
under H2 flow (5 vol.% in argon 30 mL min1) at a heat-
ing rate of 5 °C min1.
The activity of the catalysts (100 mg per sample with
granule size catalysts between 0.3 nm and 0.8 nm) was mea-
sured in a continuous flow system with a fixed bed reactor
at atmospheric pressure. Before each test, the catalyst was
reactivated in flowing air (2 L h1) at 500 °C for 4 h. The
flow of the reactant gases (0.09 mL min1 of C7H8 balance
with air) was adjusted by a Calibrage CALPC-5 apparatus
constituted of a saturator and mass flow controllers. After
reaching a stable flow, reactants passed through the cata-
lyst bed and the temperature was increased from room tem-
perature to 500 °C (1 °C min1). The feed and the reactor
outflow gases were analyzed on line by a micro-gas chro-
matograph (VARIAN CP4900).
3. Results and discussion
The catalytic behaviour of the samples for toluene oxi-
dation is represented in Fig. 1. The catalytic performance
of the samples according to the T50 values, (the tempera-
ture of 50% toluene conversion), follows the order:
Co=Mg–Alð700Þ500 ðT 50 ¼ 320  CÞ > Co=MgAl–ð600Þ500
ðT 50 ¼ 342  CÞ > CoðEtOHÞ =Mg–Alð700Þ500
ðT 50 ¼ 350  CÞ > Co=Mg–Alð500Þ500
ðT 50 > 450  CÞ > Mg–Alð700ÞðT 50 > 450  CÞ
These results show that the catalysts are active for toluene
oxidation. CO2 and H2O are the only products detected at
100% of conversion. The conversion of the support cal-
100
Toluene conversion (%)
80
60
40
20
0
150 200 250 300 350 400
Temperature (°C)
Fig. 1. Toluene conversion versus temperature for the samples (-): Co/
Mg–Al(700)500; (}): Co/Mg–Al(600)500; (N): Co(EtOH)/Mg–Al(700)500;
(): Co/Mg–Al(500)500; (o): Mg–Al(700).
 C. Gennequin et al. / Catalysis Communications 9 (2008) 1639–1643 1641

cined at 700 °C is compared and presents a weak activity
with 10% of conversion at 400 °C. Thus, the use of cobalt
has a beneficial effect on the activity. Moreover, the activity
(Fig. 1) depends on calcination temperature of the support
and on the impregnation method. The best activity is ob-
tained with Co/Mg–Al(700)500 catalysts with a complete
conversion at 350 °C.
For a better understanding of these catalytic results, H2-
TPR was carried out. Indeed, a redox mechanism is often
advanced to describe the catalytic oxidation of VOC.
Fig. 2 shows the H2-TPR profiles of catalysts. A prelimin-
ary TPR study (not shown here) of the calcined supports at
700 °C indicates no hydrogen consumption till 900 °C. The
observed H2 consumption (Table 1) should be then
assigned only to the reduction of cobalt species on calcined
support. TPR analysis of the calcined solids reveals several
peaks which can be attributed to various cobalt species,
reduced at different temperatures. Table 1 shows the total
hydrogen consumption and hydrogen consumption at
low temperature (up to 400 °C) obtained for the various
solids. This latter consumption corresponds to the range
of temperature in which the catalytic test is carried out.
Moreover, for the catalysts Co/Mg–Al(600)500 and Co/
Mg–Al(700)500, the total amount of hydrogen consumed
during the reduction is higher comparing to the other sam-
ples. Above 400 °C, TPR profiles of these solids are similar
Co(EtOH)/Mg-Al(700)500
H2 consumption (a.u.)
and both hydrogen consumption peaks observed should
correspond to both reduction steps of the Co3O4 spinel into
metallic Co which is in agreement with the literature [21].
These two samples present the same hydrogen consump-
tions at around 300 °C and also similar catalytic behaviour
at this temperature. However, the catalyst Co/Mg–
Al(600)500 presents a decrease of activity when a tempera-
ture is higher than 300 °C. This result could be explained
by a possible instability of the solids related to the presence
of water during the catalytic test.
For the sample Co/Mg–Al(500)500, there are less cobalt
species reduced until 400 °C compared to the other solids.
This sample presents also the worst catalytic activity. Cal-
cination at 500 °C leads to the formation of cobalt alumi-
nate species which are reduced at higher temperature at
about 550 °C [22]. The differences between solids activities
are thus related to the nature of the cobalt species reduced
at low temperature [23]. The catalytic behaviour can be
then related to the reducibility of cobalt oxides species:
the higher is the reducibility the higher is the catalytic
activity.
The dispersion and the nature of the cobalt species are
related to the calcination temperature of the support and
to the impregnation method.
The XRD patterns of the dried hydrotalcite and the cal-
cined hydrotalcite as catalyst supports are reported in
Fig. 3. The patterns of the calcined supports clearly indi-
cate MgO ‘‘periclase” type phase identified in agreement
with JCPDS files n°450946. However a low shift towards

the highest values of 2h is observed and explained by the

Mg substitution by Al ions in the lattice of MgO oxide
Co/Mg-Al(700)500 [24]. This result can be confirmed by the calculations of lat-
tice parameters (Table 1). Indeed, pure MgO oxide crystal-
Co/Mg-Al(600)500
lizes in a face centered cubic structure with a cell parameter
Co/Mg-Al(500)500 of a = 4.21 Å. The lattice parameter ‘‘a” corresponding to
MgO structure obtained after calcination at 500 °C has a
100 300 500 700 900 value of 4.19 Å. The surface area of Mg–Al hydrotalcite
Temperature (°C) increases significantly after calcinations from 77 m2 g1
(dried hydrotalcite) (Table 1) which can be correlated to
Fig. 2. TPR profiles of cobalt supported on Co/Mg–Al(T)500 (T = 500,
600, 700 °C). the destruction of hydrotalcite lamellar structure.

Table 1
Specific area of the samples; ‘‘a” parameter and corresponding 2H angle of the supports and the TPR H2 consumptions of catalysts
Sample Specific surface 2H (°) a (Å) H2 total consumption H2 consumption up to
area (m2 g1) 100–900 °C (lmol H2/g) 400 °C (lmol H2/g)
Mg–Al(500) 214 43.40 4.16 – –
Mg–Al(600) 188 43.48 4.15 – –
Mg–Al(700) 132 43.08 4.19 – –
Co/Mg–Al(500) 3 – – – –
Co/Mg–Al(600) 4 – – – –
Co/Mg–Al(700) 6 – – – –
Co(EtOH)/Mg–Al(700) 45 – – – –
Co/Mg–Al(500)500 112 – – 922 261
Co/Mg–Al(600)500 126 – – 1344 470
Co/Mg–Al(700)500 94 – – 1283 461
Co(EtOH)/MgAl(700)500 98 – – 980 232
1642
O : MgO
: HT
Intensity (a.u.)
4 12 20 28
Fig. 3. XRD patterns of Mg–Al hydrotalcite calcined at 500, 600 and
700 °C.
Fig. 4 shows the patterns of the solids obtained after
aqueous and alcohol impregnations of cobalt nitrate on
the supports calcined at various temperatures. Three
distinct crystalline phases are observed for both samples
Co/Mg–Al(500) and Co/Mg–Al(600). The first phase
detected corresponds to MgO structure in agreement with
JCPDS files n°450946. This phase results from the calcina-
tion of the Mg–Al hydrotalcite as in the case of the calcined
supports. The hydrotalcite phase (HT) is also detected in
agreement with JCPDS files n°220700. The presence of this
phase is related to the regeneration capacity of hydrotal-
cite. The layered hydrotalcite structure is recovered with
hydratation and depends of the previous calcinations
temperature. The easier reconstruction of the support is
obtained when samples are calcined at low temperature;
the intensity of the XRD peak at 2H = 11.3° (Fig. 4)
proves the regeneration of the hydrotalcite phase. For
CoEtOH/Mg–Al(700) sample, hydrotalcite phase is not
detected, no reconstruction of the structure occurred dur-
ing the impregnation. In the literature, the conversion of
the Mg(Al)O periclase-like solid solution into hydrotalcite
is referred to: regeneration, reconstruction, memory effect.
Indeed, the presence of water during the impregnation step
and the presence of CO2 dissolved in the aqueous solution
are enough to reform partially the lamellar structure [25–
28]. The third phase detected is a cobalt oxyhydroxide
O : MgO *
* *O
* : HT
# : CoOOH
Intensity (a.u.)
#
4 12 20 28 36
Fig. 4. XRD patterns of Co/Mg–Al(T) (T = 500, 600, 700 °C) dried
samples.
C. Gennequin et al. / Catalysis Communications 9 (2008) 1639–1643
CoOOH phase in agreement with JCPDS files n°731213.
This phase is present in a small quantity for the samples
o o
Co/Mg–Al(500) and Co/Mg–Al(600) and observed by a
shoulder towards 2H = 20.2°. However, for the sample
Mg-Al(HT) Co/Mg–Al(600), this peak located at 2H = 20.2° is more
Mg-Al(500) intense. The formation of this phase can be explained ini-
tially by the reaction of cobalt with hydroxides formed dur-
Mg-Al(600)
ing the step of reconstruction of the hydrotalcite structure
Mg-Al(700)
to form cobalt hydroxide. The formation of this cobalt
36 44 52 60 68 76 phase would be thus related to the basic character of the
2Θ (°) MgO oxides obtained after calcination of the hydrotalcite
precursor. The presence of this phase can be also explained
by the presence of ‘‘metahydrotalcite P amorphous peri-
clase” phase described by Staminirova et al. [28] which still
contains hydroxide ions. These ions can react with cobalt
in solution to form the cobalt oxyhydroxide phase. During
the aqueous impregnation by a cobalt solution on a
Mg(Al)O oxide resulting from the calcination of a hydro-
talcite, Staminirova et al. [29] showed that the reconstruc-
tion of the lamellar structure occurred by a mechanism of
dissolution and recrystallization. This mechanism involves
though a cation exchange between the ions Mg2+ and
Co2+. It is then probable that cobalt is partially present
as cobalt oxyhydroxide (CoOOH) and partially replacing
magnesium in the structure. Thus it is possible to find sev-
eral types of cobalt species dispersed on the support. The
step of the partial reconstruction on the surface of the
Mg(Al)O oxide influences the nature and the dispersion
of the cobalt species on the surface and explains the TPR
results. The reducibility difference of cobalt species is visi-
ble for samples synthesised by aqueous impregnation and
alcoholic preparation.
Table 1 shows the specific surface evolution of the solids
after impregnation. The results show a very significant
decrease of the specific surface for these samples
(Co/Mg–Al(500), Co/Mg–Al(600) and Co/Mg–Al(700))
compared with those obtained for the calcined supports
(Table 1). These results are explained by a structural
change of the Mg(Al)O oxides related to the phenomenon
of regeneration of the hydrotalcite structure. This specific
surface change was already explained in the literature [30]
by a formation of a dense layer of hydrotalcite type on
the surface. The value of specific area of CoEtOH/
O *O
MgAl(700) (Table 1) is in accordance with the absence of
Co(EtOH)/Mg-Al(700)
reconstruction of the structure (Fig. 4).
Fig. 5 displays XRD patterns for the catalysts Co/
MgAl(T)500. Two distinct crystalline phases are observed.
Co/Mg-Al(700)
The first corresponds to the MgO periclase phase (JCPDS
Co/Mg-Al(600)
files n°450946) with insertion of aluminium. This phase
comes from calcination at 500 °C of the solids impregnated
and was described in previous paragraphs. The second
Co/Mg-Al(500) phase is assigned to spinel structures Co3O4 and/or
CoAl2O4 and/or Co2AlO4. Nevertheless it is not possible
44 52 60 68 76 to identify surely the nature of the spinel phase. Indeed dif-
2Θ (°)
fraction peaks for Co3O4 (JCPDS n°421467), CoAl2O4
(JCPDS n°440160), Co2AlO4 (JCPDS n°380814) phases
are very similar comparing 2h values and intensities. The
 C. Gennequin et al. / Catalysis Communications 9 (2008) 1639–1643
O : MgO
S : spinel O O
S 500 °C and led to an active and stable catalyst for tolu-
Intensity (a.u.)
Co/Mg-Al(700)500
Co/Mg-Al(600)500
Co/Mg-Al(500)500
4 12 20 28 36 44
2Θ (°)
Fig. 5. XRD patterns of Co/Mg–Al(T) activated under air at 500 °C.
presence of the Co3O4 phase is probable since, for the
impregnated solids, cobalt oxyhydroxide phase was
detected and the calcination of this phase at 500 °C led to
the formation of Co3O4 spinel [31]. However, the forma-
tion of the other spinel phases are possible since during
the impregnation, cobalt is exchanged with magnesium in
the brucite layers and thus after calcination at 500 °C some
cobalt aluminate CoxAlyO4 could be formed. In fact, the
polarization of CoAO bonds by Al3+ ions in CoxAlyO4
compounds could induce an increase in the reduction
temperature of Co2+ species and then explain the presence
of the second TPR peak above 500 °C. In accordance
with the XRD patterns, for the Co/Mg–Al(500) and
Co/Mg–Al(600) solids, the reconstruction phase is more
important than that of Co/Mg–Al(700). Advanced Mg
substitution by Co leads to large quantity of cobalt alumi-
nate CoxAlyO4 after calcination at 500 °C. This phenome-
non could explain the lower performance of Co/Mg–
Al(500)500,Co/Mg–Al(600)500 and the better performance
of Co/Mg–Al(700)500 than CoEtOH/MgAl(700)500 cata-
lyst, for which the regeneration does not occur.
Despite the same specific area, the difference between
Co/Mg–Al(700)500 and CoEtOH/MgAl(700)500 samples
activities could be explained by a higher reducible amount
of cobalt species at low temperature for Co/Mg–Al
(700)500 catalyst.
Therefore, the step of the reconstruction is very impor-
tant and the degree of Mg and Co exchange influences
the nature and the dispersion of the cobalt species on the
support and allows to explain TPR and catalytic results.
4. Conclusion
In this work, new catalysts synthesized by using mem-
ory effect of hydrotalcite were described. These new cat-
alysts presented an interesting activity for toluene
oxidation with a high selectivity to CO2 and H2O forma-
tion. The high activity can be explained by a high quan-
tity of Cobalt species reducible at low temperatures.
These Cobalt species were obtained after calcination of
Mg–Al hydrotalcite which was dipped in an aqueous
solution of Co2+ nitrate. Reconstruction of Mg–Al took
place by regeneration of the layered structure on the sur-
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1643
face of mixed oxides. The solid obtained by reconstruc-
tion after a calcination at 700 °C was activated at
ene deep oxidation. Thus, the reconstruction of the sup-
port can generate high quantity of active cobalt species
reducible at low temperature.
Acknowledgements
This work is supported by the ‘‘Région Nord Pas de
52 60 68 76
Calais”, Interreg III A and the European Community
(European Regional Development Fund).
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