CRYSTAL

GROWTH
& DESIGN

Uniform Fast Growth of Hydrotalcite-like Compounds

2006
VOL. 6, NO. 8
1961-1966

Patricia Benito, Francisco M. Labajos, and Vicente Rives*

Departamento de Qumica Inorga nica, UniVersidad de Salamanca, 37008-Salamanca, Spain
ReceiVed NoVember 23, 2005; ReVised Manuscript ReceiVed June 7, 2006

ABSTRACT: Small size, monodispersed hexagonal particles of Mg,Al-CO3 hydrotalcite-like compounds have been synthesized in
short periods of time by the microwave-hydrothermal method. An in-depth study of the influence of the irradiation time and the
process temperature has been carried out. Well-crystalized materials with relatively high specific surface area values have been
prepared in 30 min at 150 C.
Introduction
Much research has been carried out in recent years on the
synthesis of materials by methods that permit control of both
their chemical and their physical properties; additionally, it
would be even better if the method employed saves time and
money and it is environmentally friendly.
Hydrotalcite-like (HT-l) compounds are materials not very
commonly found in nature, but they are easily synthesized. They
consist of stacked layers with a brucite structure, positively
charged as a consequence of a partial substitution of divalent
cations by trivalent ones, anionic species being located in the
interlamellar region to balance the net charge; water molecules
occupy part of the free interlayer room. They are also known
as layered double hydroxides (LDHs) or anionic clays. A large
amount of hydrotalcite compounds have been prepared by
modifying both the layer composition1 and the anionic interlayer
species, so it is possible to control the chemical composition
(and properties) of the material and to prepare tailored materials
for specific applications. These materials have been synthesized
by a variety of methods,2,3 but most of them do not provide
fine control of the physical properties of the final solids.
Urea is an agent used for homogeneous precipitation from a
solution that allows morphological control of crystallite size, a
factor that plays a critical role in industrial applications. On
heating of the sample, decomposition of urea releases ammonia
and carbonate ions into the solution in a very uniform fashion,
resulting in a gradual and uniform increase in the pH of the
solution.4 A pH about 7-9, depending on the temperature, is
suitable for precipitating solids with the hydrotalcite phase;
therefore, urea hydrolysis has been applied successfully as a
new synthetic route to the preparation of well-crystallized
LDHs.5-18 By controlling the urea concentration and the
temperature, hydrolysis proceeds very slowly, leading to a low
degree of supersaturation during precipitation and resulting in
a decrease in the nucleation rate. As a result, the materials
develop a better degree of crystallinity, forming larger particle
than those of hydrothermally treated samples but with a narrower
particle size distribution,13 thus permitting control of particle
size. On the contrary, in the commonly applied coprecipitation
method, precipitation of the hydroxide crystallites starts immediately once the first drops of the basic solution are added
to the mixed solution of the cations (or vice versa), and thus
nucleation and particle growth overlap, resulting in particles
with a broad distribution of particle size.16 The crystallinity of
the HT-l compounds thus obtained depends on the total metal
* To whom correspondence should be addressed. Tel. +34923294400.
Fax +34923294574. E-mail: vrives@usal.es.

cation concentration, the M3+/(M2+ + M3+) molar fraction, the

urea concentration, the precipitation temperature, and aging
time,9,12,13 but this method presents a drawback, as the time
required for carrying out the precipitation is quite large, ranging
from 1 month5,6 to 6 h for Mg,Al-LDHs.13 However, the
combination of hydrothermal conditions with urea decomposition has been very recently reported, allowing a shortening of
the reaction time to 3 h.18
Since the discovery of the heating ability of microwaves in
1946, microwave ovens have been used as an alternative source
of heating versus conventional ovens, first in domestic applications and later in organic synthesis,19 analytical chemistry,20
ceramics processing,21 catalysis,22 and inorganic synthesis both
in the solid state and in liquid media.23 All these applications
have a very important common aspect, that is, the reduction of
the process time, which implies a savings in energy as well.
On the other hand, it must be taken into account that dielectric
heating, due to the interaction of microwaves with dipoles, and
ionic conduction (if charged species able to be driven under
the microwave field exist) produce uniform heating, without
thermal gradients, known as volumetric heating.
Previous works reported the use of microwave radiation in
the synthesis of hydrotalcite-like compounds during the aging
treatment coupled to the coprecipitation process.24-26 However,
in the present work, for the first time, the precipitation of
Mg,Al-CO3 hydrotalcite-like compounds has been carried out
using urea as precipitation agent and simultaneously heating
the solutions under the influence of a microwave field at
autogenous pressure, the so-called microwave-hydrothermal
treatment (MW-HT).27 The advantages of using both methods
simultaneously are reported.
Experimental Section
Synthesis Procedure. A method similar to that proposed by
Costantino et al. has been followed.11 All chemicals were from Fluka
(Switzerland), and the gases were from LAir Liquide (Spain); all were
used without any further purification. The mixture solution (containing
0.5 M in MgCl26H2O and AlCl39H2O, with a Mg2+/Al3+ molar ratio
equal to 2, and urea, added to reach a urea/metal ions molar ratio of
3.3) was placed in a reaction vessel of a microwave oven (Milestone
Ethos Plus). The microwave oven applies the power necessary to reach
the programmed temperature in each moment. An initial ramp program
from ambient temperature to 100, 125, or 150 C was established for
all samples, and then the solutions were maintained at the selected
temperature for 5, 10, 20, 30, 60, and 120 min. After the sample was
cooled at room temperature, the precipitate was centrifuged and washed
with distilled water until the washings were completely free of chloride
anions and products formed during urea decomposition. Finally, the
solids were dried in an oven at 40 C in air. The solids prepared are

10.1021/cg0506222 CCC: $33.50 2006 American Chemical Society

Published on Web 07/08/2006

1962 Crystal Growth & Design, Vol. 6, No. 8, 2006

Benito et al.

Table 1. Mg2+/Al3+ Molar Ratios, Lattice Parameters (c and a),

Crystallite Size (D), and Specific Surface Areas (SBET) for Samples
Irradiated at 150 C, MAUt
sample

Mg2+/
Al3+

c/

a/

D(003)

D(006)

SBET
m2 g-1

MAU5-2
MAU10-2
MAU20-2
MAU30-2
MAU60-2
MAU120-2

0.657
0.763
1.109
2.125
2.33
2.33

22.57
22.53
22.56
22.44
22.65
22.62

3.034
3.032
3.036
3.036
3.038
3.039

224
203
219
215
256
268

232
215
239
233
256
263

117
106
73
40
24
21

Table 2. Mg2+/Al3+ Molar Ratios, Lattice Parameters (c and a),

Crystallite Size (D), and Specific Surface Areas (SBET) for Samples
Prepared by the Conventional Method at 150 C
sample

Mg2+/
Al3+

c/

a/

D(003)

D(006)

SBET
m2 g-1

MAUHT3
MAUHT5
MAUHT12
MAUHT24

0.977
1.710
1.860
1.864

22.39
22.64
22.58
22.65

3.030
3.039
3.041
3.042

423
346
346
616

416
313
385
696

15
8

named MAUt-a, where t stands for the heating time in minutes and a
) 1 when the reaction is carried out at 125 C and a ) 2 when it is
performed at 150 C; the samples treated under conventional hydrothermal conditions are named MAUHTt, where t represents the time
in hours.
Techniques. Element chemical analysis for Mg and Al was carried
out by atomic absoprtion in a Mark 2 ELL-240 apparatus, in Servicio
General de Analisis Qumico Aplicado (University of Salamanca,
Spain). The phase composition of the samples was determined by
powder X-ray diffraction (PXRD); the patterns were recorded in a
Siemens D-500 instrument using Cu-KR radiation ( ) 1.54050 )
equipped with Diffrac AT software. Identification of the crystalline
phases was made by comparison with the JCPDS files.28 The FT-IR
spectra were recorded in a Perkin-Elmer FT1730 instrument, using KBr
pellets; 100 spectra (recorded with a nominal resolution of 4 cm-1)
were averaged to improve the signal-to-noise-ratio. Specific surface
area assessment was carried out in a Gemini instrument from Micromeritics. The sample (ca. 80-100 mg) was previously degassed in
flowing nitrogen at 150 C for 2 h in a FlowPrep 060 apparatus, also
from Micromeritics, to remove physisorbed water, and the data were
analyzed using published software.29 Thermal decomposition of the
solids to the calcined products was studied by thermogravimetric (TG)
and differential thermal analyses (DTA) carried out in TG-7 and DTA-7
instruments, respectively, from Perkin-Elmer, in flowing oxygen and/
or nitrogen (from LAir Liquide, Spain), at a heating rate of 10 C
min-1. Scanning electron microscopy (SEM) images were recorded by
a JEOL 6300 instrument at 25 kV.

Results and Discussion

Element Chemical Analysis. The amount of Mg2+ ions
incorporated in the solid depended on both the reaction
temperature and the irradiation time; remarkable differences
were found between the samples prepared by the MW-HT and
conventional hydrothermal treatments. Regarding the samples
microwave-irradiated at 100 C, the Mg/Al ratio was quite far
from the expected one (2.0), the amount of Mg in the solid
being negligible. When the reaction was carried out at 125 C,
a value of 0.782 for Mg2+/Al3+ was reached after 120 min.
However, this ratio reached a value very close to the expected
one in 30 min when the treatment was performed at 150 C,
and slightly deviations were observed if the irradiation treatment
was further prolonged (Table 1). On the other hand, the values
measured for the samples prepared by the conventional hydrothermal treatment were always lower than 2, (Table 2).
Powder X-ray Diffraction. The key role of the synthesis
temperature, and its great influence on the preparation of solids
with the HT-l structure, can be clearly concluded from the
evolution of the PXRD patterns. At 100 C (results not shown),

Figure 1. PXRD patterns of the samples prepared at 125 C for 30,

60, and 120 min under MW-HT conditions. Legend: MAUt-a, where
t stands for the heating time in minutes and a ) 1 when the reaction
is carried out at 125 C.

Figure 2. PXRD patterns of the samples prepared at 150 C for 5, 10,

20, and 30 min under MW-HT conditions. Legend: MAUt-a, where t
stands for the heating time in minutes and a ) 2 when the reaction is
carried out at 150 C.

even after 180 min treatment, no hydrotalcite phase was formed

and merely some broad peaks attributed to the pseudo-boehmite
structure were recorded in the PXRD pattern. At 125 C, Figure
1, it was necessary to extend the MW-HT treatment for at least
60 min to detect some traces of the hydrotalcite phase, which
coexist with broad peaks of pseudo-boehmite; even after
exposure to microwaves for 120 min, no single-hydrotalcite
diffraction lines were recorded. When the temperature was only
25 C higher, 150 C, Figure 2, the lamellar structure formed
in just 5 min, and a crystallographically single phase was
obtained in 30 min; an increase in the treatment time led to
well-crystallized solids. The patterns recorded show symmetric
and sharp reflections due to well-crystallized compounds without
appreciable turbostratic disorder. The results shown by the
PXRD patterns support the conclusions reached from the chemical analyses, i.e., the low Mg2+/Al3+ ratios obtained when the
reaction is carried out at 100-125 C for short periods of time
are due to the presence of a large content of an alumina phase.

Fast Growth of Hydrotalcite-like Compounds

Figure 3. pH variation during the microwave and conventional

hydrothermal treatments.

The cell parameters (c and a) were calculated from the (003)

and (006) diffraction lines according to c ) 3[0.5(d(003) +
2d(006))] and (110), a ) 2d(110).30 The rather low c values (in
comparison to those of HTlcs synthesized by a coprecipitation
method with a c value close to 22.8-22.9 ),30 Tables 1 and
2, suggest a strong interaction between the layers and the
interlayer species, probably as a consequence of a well-arranged
interlamellar region. The a parameter increases slightly with
the irradiation time, probably due to a steady release of Al3+
ions to diminish the distortions related to its presence in the
structure31 (parameter a is related to the average cation-cation
distance within the layers, and the ionic radius of Al3+ is smaller
than that of Mg2+ in an octahedral coordination).
The crystallite size (Table 1) was calculated by using the
Debye-Scherrer equation.32 The crystallinity increased as the
aging time was increased. However, the thickness of the
crystallites does not change once the HT-l phase is formed.16
As shown in Tables 1 and 2, the crystallite size was determined
from the broadening at half-height of the diffraction peaks due
to planes (003) and (006). Although the values calculated should
coincide, whichever diffraction peak is used to determine them,
it should be noted that for samples treated at low temperature
or for short irradiation times, the presence of an amorphous
phase responsible for the broad background of the diagram for
low diffraction angles might give rise to unreal broadening of
the peak due to diffraction by planes (003); so, in this case, the
values calculated from the peak due to planes (006) should be
more realistic than those determined from the peak due to planes
(003). This fact is more evident for samples prepared following
conventional heating methods (Table 2) than for those prepared
following the HT-MW method (Table 1).
pH Variation. From the above results, it is evident that the
reaction temperature is the key factor of the process. For each
of the conventional and microwave hydrothermal reactions, the
pH was measured at room temperature once the reaction had
finished. The variations in pH are shown in Figure 3. As it can
be expected, the pH evolution depends on the temperature at
which the sample is treated, but it should be remarked that it is
also dependent on the specific treatment to which the samples
are submitted, microwave or conventional hydrothermal. At 125
C under MW-HT conditions, the pH increased with the
irradiation time, and at 60 min, despite the low pH value reached
(6.5), the hydrotalcite phase was already formed, although it
coexisted with the aluminum hydroxide phase. Upon increasing

Crystal Growth & Design, Vol. 6, No. 8, 2006 1963

the temperature to 150 C, the same pH value was attained in

only 5 min; it remained almost constant for the first 30 min,
then increased until a final value close to 7.5 was reached. In
these two examples, the curves indicate that if the irradiation
time is further prolonged, the pH would increase as well. When
the synthesis was carried out at 150 C under conventional
hydrothermal conditions, urea was not decomposed up to 1 h
reaction time, so the pH of the solution was not modified; the
value reached was barely one-half of that obtained when the
solution was heated at the same temperature under MW-HT
conditions. After 60 min reaction, urea decomposition started
and the pH increased rather rapidly, reaching a value similar to
that reached at 150 C under MW-HT conditions in just 5 min.
However, PXRD results (not shown) above indicated that under
these conditions the HT-l structure was not even formed, and
the reaction should be prolonged 1 h further. After 180 min,
some traces of this secondary phase were still observed and
only after 300 min well-crystallized phases were obtained, but
the presence of pseudo-boehmite cannot be completely ruled
out. Prolonging the treatment to 12 or even 24 h led to the
crystallization of secondary phases, and a slight decrease in pH,
after reaching a maximum close to 9, was observed. Taking
into account these results, it can be concluded that the
microwave radiation plays a critical role on the synthesis
process, even more important than a single effect of temperature.
Thermal Analysis. The DTA curves of the samples synthesized at 150 C both in the microwave oven and in the
conventional furnace are displayed in Figure 4. The thermal
stability of the samples is also dependent on the crystallinity
degree, which itself depends on the irradiation time. In the DTA
curve of the sample aged under microwave radiation for 5 min,
two endothermic effects (I1 and I2) at low temperatures were
recorded, with two shoulders (I3 and I4) at higher temperatures.
Increasing the treatment time led to the progressive disappearance of the first peak, while the shoulders strengthen giving
rise to two well-resolved peaks in the MAU120-2 sample, where
the first endothermic effect is completely absent. From comparison of the positions of these effects with other studies where
analysis of evolved gases was carried out,33 the I1 and I2 peaks
should correspond to removal of physisorbed and interlamellar
water molecules, respectively, and layers collapse giving rise
to the high-temperature effects, I3 and I4. The symmetry and
sharpness of peak I2 points to the presence of interlayer water
molecules linked with similar strength to interlayer carbonates
and to the layers. The PXRD pattern for sample MAU30-2
strongly suggests a good crystallinity of the sample, but the
DTA curve indicates that the better interlamellar order is
achieved in samples MAU60-2 and MAU120-2 since in the
latter I3 and I4 are better resolved.
For the samples submitted to the conventional hydrothermal
treatment, Figure 4 right panel, the same behavior is observed,
but it should be remarked that for samples aged during 12 and
24 h the DTA curves show an additional effect centered at
around 650 C, which may be related to the secondary phase
registered in the PXRD patterns (not shown), due to the presence
of pseudo-boehmite together with the pursued hydrotalcite-like
phase, which is not detected for the samples prepared using
microwave radiation.
Fourier Transform-Infrared (FT-IR) Spectroscopy. FTIR spectroscopy was used to follow the changes undergone by
the samples synthesized by the MW-HT method at 125 C, as
the HT-l phase was already formed at the very first stages of
reaction when this was carried out at 150 C. As described
above, the solid formed after short reaction times is mainly

1964 Crystal Growth & Design, Vol. 6, No. 8, 2006

Benito et al.

Figure 4. DTA curves of the samples synthesized at 150 C by the microwave (left) and the conventional treatment (right). Legend: (left) MAUta, where t stands for the heating time in minutes and a ) 2 when the reaction is carried out at 150 C; (right) MAUHTt, where t represents the time
in hours.

Figure 5. FT-IR spectra of the samples synthesized at 125 C under

MW-HT conditions. Legend: MAUt, where t stands for the heating
time in minutes.

constituted by an aluminum hydroxide phase, and as the reaction

proceeds the HT-l phase was formed; we have followed these
changes from the FT-IR spectrum in the region corresponding
to mode 3 of carbonate. The spectrum recorded for sample
MAU20-1, Figure 5, is characteristic of aluminum hydroxide.
As the reaction time under MW-HT treatment at 125 C was
prolonged, formation of the HT-l phase, with intercalated
carbonate anions, proceeded, as shown by the development of
a band close to 1360 cm-1, due to the 3 mode of carbonate; in
addition, other characteristic bands of carbonate and M-O
vibrations34 are recorded in the low wavenumbers region. The
spectrum recorded after 2 h reaction is characteristic of a wellcrystallized hydrotalcite-like phase.35,36 The same behavior is
observed when the reaction was carried out at 150 C; however,
in this case the time necessary to form the HT-l structure was

much shorter, and after 10 min the characteristic carbonate band

is already recorded. This behavior confirms that formation of
the hydrotalcite phase is facilitated both by the temperature and
the microwave radiation, the latter one giving rise to a selective
redisolution of the alumina phase and formation of the LDH.
An increase in the reaction time leads to an enhancement in
the crystallinity of the solids, as shown by the evolution of the
shoulder close to 2900 cm-1 (not shown) due to the OH
stretching of hydroxyl groups and water molecules hydrogen
bonded to carbonate ions in the interlayer, a decrease in the
bandwidth, as well as from the better resolution of the bands in
the low wavenumber region.37
SEM Images. The SEM micrographs of the samples aged at
150 C are shown in Figure 6. Particles with randomly
distributed size and shape formed after 10 min reaction at this
temperature; platelets with rounded edges are observed after
20 min, with sizes in the range 1.5-2 m, although some
smaller particles are still seen. After 30 min reaction the particles
show a uniform size close to 1 m, and no significant changes
are observed for samples treated for 60 or 120 min.
Textural Properties. The nitrogen adsorption-desorption
isotherms recorded belong to type II of the IUPAC classification,
with narrow H3 hysteresis loops attributed to aggregates of
platelike particles leading to slit-shaped pores.38 The hysteresis
loop is rather narrow, suggesting the presence of small and
homogeneous interparticle pores. Specific surface areas data for
all samples are reported in Table 1. Sample MAU5-2 shows
the largest value, close to 120 m2 g-1, but it sharply decreases
to 40 m2 g-1 after 30 min irradiation, and then, while still
decreasing, it is rather smooth, reaching a value of 21 m2 g-1
for sample MAU60-2. The large specific surface area values
determined for the samples treated for a short period of time
are attributed to the presence of pseudo-boehmite, which might
be a mostly amorphous gel (it is not fully identified by PXRD),
displaying a large specific surface area. On the other hand, the
specific surface area of sample MAU30-2, wherein hydrotalcite

Fast Growth of Hydrotalcite-like Compounds

Crystal Growth & Design, Vol. 6, No. 8, 2006 1965

Figure 6. SEM images of the samples MAU10-2, MAU20-2, MAU30-2, and MAU60-2. Legend: MAUt-a, where t stands for the heating time
in minutes and a ) 2 when the reaction is carried out at 150 C.

is the only crystalline phase identified, is also larger than the

specific surface area of the samples obtained by the conventional
hydrothermal treatment and those previously reported for similar
compounds also prepared by the urea method.9 This behavior
may be a consequence of the rapid heating of the solution under
the microwave field; since the time has been shortened to 30
min, the main process that takes place is nucleation. Upon
increasing the treatment time to 60 and 120 min, the sinterization
process becomes more important, and a decrease in the specific
surface area is also detected. These data correlate fairly well
with the crystallite size data (Table 1).
Final Remarks. The result above confirms the formation
mechanism stated by Adachi-Pagano et al. for the precipitation
of layered double hydroxides using urea and also confirms the
mechanism previously proposed by Boclair et al.39 and recently
stated by Xu and co-workers.40 When the pH values are low,
the trivalent metal hydroxide precipitates and formation of the
LDH takes place at higher pH values. This mechanism also
explains the high aluminum content in the samples aged for
short periods of time, formation of the pseudo-boehmite phase
identified in the PXRD pattern, and the high specific surface
areas determined for these samples, mostly due to the presence
of this secondary phase forming an amorphous gel.
The rate enhancement, using microwave radiation as a heating
source, can be consider as a purely thermal/kinetic effect, that
is, a consequence of the high reaction temperatures that can be
rapidly attained when irradiating polar materials in a microwave
field; however, the existence of nonthermal effects is still a
matter of controversy.41 In this case, the introduction of
microwaves in the synthesis modifies the nucleation process.
Making use of urea as a precipitating agent provides slow release
of the base, leading to a slow nucleation process and favoring
the crystal growth. However, using microwave radiation must
lead to an increase in the rate of urea hydrolysis and consequently to rapid precipitation of hydrotalcite compounds;

furthermore, an uniform growth environment is attained, since

on microwave irradiation of the liquid sample, temperature and
concentration gradients can be avoided, providing an uniform
environment for nucleation. In conclusion, the microwave
radiation plays a key role in the process, as it favors a fast
nucleation, giving rise to a large number of nuclei, which
produces a big number of small crystals of uniform size (see
the SEM images); consequently, the specific surface area values
are larger than those previously reported for samples prepared
by the urea method9 and than one of MAUHT5 samples,
prepared by conventional hydrothermal heating. On the other
hand, we have previously reported42 that hydrotalcite-like
compounds can be considered as good microwave absorbers,
so that once the solid begins to be formed it could act as
microwave absorber, giving rise not only to a better layer
stacking but also to an ordered interlamellar region, which can
explain the splitting of the second endothermic effect in samples
MAU60-2 and MAU120-2.
Conclusions
Some Mg,Al-CO3 hydrotalcite-like compounds have been
synthesized by the urea method assisted by microwave radiation
at different temperatures and periods of time. The elemental
chemical analyses, PXRD patterns, FT-IR spectra, and SBET data
confirm the mechanism of formation of the LDH previously
proposed, with previous formation of an aluminum hydroxide
and the incorporation of magnesium to the structure as the pH
is increased. The use of the microwave radiation as heating
source allows a considerable reduction of the synthesis time to
yield pure hydrotalcite-phase and well-crystallized compounds,
in comparison to the conventional hydrothermal treatment. In
addition, the SEM micrographs show well-defined and very
uniformly sized hexagonal platelets that display considerably
large specific surface areas.

1966 Crystal Growth & Design, Vol. 6, No. 8, 2006

Preliminary results have demonstrated the ability to prepare

Ni,Al-LDHs by microwave-asssited homogeneous precipitation
by the urea method.43 Current studies are in progress to provide
insight into suitable synthesis conditions and to complete the
characterization of the solids obtained.
Acknowledgment. The authors thank to Dr. Cristobalina
Barriga for her assistance in obtaining some of the experimental
results. Finantial support from MCyT (Grant MAT2003-06605C02-01) and JCyL (Grant SA030/03) and a grant from JCyL
to P.B. are acknowledged.
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