ARTICLE
DOI: 10.1002/zaac.200801287
A Simple Mechanochemical Route to Layered Double Hydroxides: Synthesis of
Hydrotalcite-Like Mg-Al-NO3-LDH by Manual Grinding in a Mortar
Ahmet N. Ay,[a] Birgül Zümreoglu-Karan,*[a] and Luis Mafra[b]
Keywords: Mechanochemistry; Layered double hydroxides; Intercalations; NMR spectroscopy; Borates
Abstract. Hydrotalcite-like Mg-Al-NO3-layered double hydroxide
(LDH) was successfully prepared in a mortar by manually grinding
the hydrated magnesium and aluminum nitrate salts with sodium
hydroxide. Various techniques, including XRD, MAS NMR,
FTIR, SEM; thermogravimetric and differential thermal analyses
(TGA,DTA), surface area and zeta potential measurements were
used to establish a correlation between the LDH samples prepared
in the mortar and by co-precipitation. The LDH prepared in the
1. Introduction
Layered Double Hydroxides (LDHs) have been the focus
of considerable interest owing to their wide range of pos-
sible applications in catalytic, ion exchange and medical
processes [1, 2]. LDHs are a class of ionic lamellar solids
with positively charged layers and small, exchangeable
gallery ions. Hydrotalcite (HT)-like LDHs consist of
brucite-like layers, Mg(OH)2, in which some of the Mg2⫹
ions in octahedral positions are replaced by Al3⫹ ions. The
layers are separated by interlayers of water molecules and
anions such as Cl⫺, NO3⫺ or CO32⫺. A HT-like NO3-
intercalated LDH may be represented by the formula
[Mg2Al(OH)6]NO3.yH2O.
Many different chemical methods of synthesis have been
developed for LDHs. The most common synthesis method
is the co-precipitation of the metal salts from a mixed solu-
tion at constant pH and in the presence of anionic species
that is to be intercalated [3, 4]. The co-precipitation method
is time consuming and produces large amounts of wastes.
Various other techniques have been proposed including pre-
cipitation at variable pH [5, 6], sol-gel and hydrothermal
synthesis [7⫺10], structure reconstruction [3, 11] and hy-
drolysis [12]; each one has its own advantages and disad-
* Prof. Dr. B. Zümreoglu-Karan
Fax: ⫹90-312-299-21-63
E-Mail: bkaran@hacettepe@edu.tr
[a] Department of Chemistry,Faculty of Science
Hacettepe University
06800 Ankara, Turkey
[b] Department of Chemistry
University of Aveiro
CICECO
3810⫺193 Aveiro, Portugal
1470  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
mortar showed all the characteristics of a layered structure but with
a lower crystallinity. This product was tested for its anion exhange
property with tetraborate anions and 52 % of the theoretical ex-
change capacity was reached. The mortar route does not require
heating/refluxing treatment, CO2-free atmosphere and solvent as in
the conventional preparation methods and allows obtaining LDHs
in a short reaction time.
vantages. The search for new methods of synthesis that al-
lows the rapid preparation of intercalation compounds has
directed the attention to solid state reactions [13]. Among
these, mechanochemical activation looks as a promising
alternative method due to its simplicity and versatility.
Mechanochemical reactions have been known for a long
time where the transformation can be induced by milling
or manual grinding. Such reactions between solid reactants
without a solvent are important from both the environmen-
tal and topochemical viewpoints. Using mechanochemical
synthesis, one can avoid manipulations with large amounts
of solutions, the emission of noxious gases and the release
of wastewater. These solvent-free, less conventional
procedures are beginning to be used as viable routes for
the preparation of LDHs. The synthesis of a HT-like
LiAl2(OH)7.2H2O phase via salt imbibition technique,
grinding the solid lithium and aluminum hydroxides in a
mortar and then treating the mixture with water vapor in a
glass flow reactor, was first reported in 1987 by Poeppel-
meier and Hwu [14, 15]. Isupov et al. [16] later reported the
formation of Mg-Al-LDHs by mixing magnesium hydrox-
ide with aluminum chloride, nitrate and sulfate in high-
energy planetary-type activators. A similar process was
applied to obtain the hydroxycarbonate form of layered
magnesium aluminum hydroxides by mechanical activation
of a mixture of magnesium- and aluminum hydroxides and
sodium hydrogen carbonate in a planetary mill followed by
water washing [17]. Chitrakar et al. [18] have described a
solvent-free procedure for Zn-Al-LDHs by first grinding
and then autoclaving the solid precursors at 150 °C for 1
day while Tongamp et al. [19] have prepared a meixnerite
type LDH by milling anhydrous magnesium and aluminum
hydroxides for 1 h in a planetary ball mill and then milling
again for 2h in the presence of water. A recent study of
Z. Anorg. Allg. Chem. 2009, 635, 1470⫺1475
Synthesis of Mg-Al-NO3-LDH by Manual Grinding in a Mortar
Tongamp et al. [20] describes again a two-step process but
involving hydrated Mg nitrate in the second step. Two prob-
lems are generally associated with the conventional mech-
anochemical methods that CO2 incorporation is difficult to
avoid and the synthesis of hydrated compounds can make
the milling operation wet and thus difficult to be completed.
We report here a more convenient route for the synthesis of
LDHs. In this process, HT-like Mg-Al-NO3-LDH can be
synthesized much more easily and rapidly in a mortar by
manually grinding the hydrated metal salts with sodium
hydroxide. The as-obtained product was characterized in
comparison with an analogous LDH prepared by the con-
ventional co-precipitation method and its performance in
ion-exchange reactions was examined by probing the reac-
tion with borate ions.
2. Experimental Section
2.1. Chemicals
The reagents Mg(NO3)2 · 6H2O (Sigma), Al(NO3)3 · 9H2O (Carlo⫺
Erba) and NaOH (Merck), were used as received.
2.2. Synthesis of Mg-Al-NO3-LDH in a Mortar
NaOH pellets (1.940 g, 50.0 mmol) were added to a powder mix-
ture of magnesium- (4.00 g, 15.6 mmol) and aluminum nitrates
(2.93 g, 7.80 mmol) and manually ground to a paste. The paste was
washed four times with deionized water (20 mL), dried under vac-
uum at 40 °C, powdered and analyzed. 1.65 g product (1) was ob-
tained.
2.3. Synthesis of Mg-Al-NO3-LDH by Co-precipitation
NaOH solution (300 mL, 0.74 ) was added dropwise from a sep-
aration funnel to a solution (200 mL) containing Mg(NO3)2 · 6H2O
(22.0 g, 86.0 mmol) and Al(NO3)2 · 9H2O (16.1 g, 43.0 mmol),
where Mg/Al ⫽ 2, at room temperature. After adding the base solu-
tion, the system was stirred under nitrogen atmosphere at 90 °C for
four hours. The slurry was aged for 3 weeks before filtration. The
product was washed several times with deionized water and dried
in a vacuum oven at 40 °C. 8.82 g product (2) was obtained.
2.4. Incorporation of Boron in the LDH Structure
Compound 1 (or 2) (0.5 g) was added to a borate solution (100 mL)
containing (NH4)2B4O7 · 4H2O (3.0 g). The system was refluxed at
90 °C under nitrogen atmosphere for 6 hours and then continu-
ously stirred for 80 hours. The boron-intercalated precipitate 1B
(or 2B) was washed several times with deionized water and dried
under vacuum at 40 °C.
2.5. Characterization
C, H, N contents were determined with a LECO CHNS-932
elemental analyzer. Magnesium and aluminum contents were
determined with a Horiba Jovin Yvon Ultima-2 ICP-OES Atomic
Emission Spectrometer after dissolving the samples in acid solution
(100 mL, 60 % HNO3).
Z. Anorg. Allg. Chem. 2009, 1470⫺1475  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
The powder X-ray diffraction (PXRD) patterns were obtained by
reflection from the powder samples packed in a sample holder with
a Philips PW 1140 diffractometer using Cu-Kα radiation (λ ⫽
1.5418 Å). The diagrams were recorded in the 3⫺70° (2theta) range
at a scan speed of 2° · min⫺1 and a time constant of 1 s.
FTIR spectroscopic data were obtained in the range
400⫺4000 cm⫺1, by using the KBr pellet technique with a Mattson
1000 instrument.
27
Al and 11B MAS NMR spectra were recorded at 104.3 MHz and
128.4 MHz (9.4T), respectively, with a Bruker Avance 400 spec-
trometer using short, 0.6 µs (equivalent to 10° and 15° flip angles
for 27Al and 11B, respectively) radio-frequency (rf) excitation pulse,
1⫺2 s recycle delay, and 14 kHz spinning rate. Chemical shifts are
quoted in ppm from Al(NO3)3 and BF3.O(C2H5)2 for 27Al and 11B,
respectively. The 11B MAS NMR powder patterns were simulated
employing a home-built program. The integration of the boron
species was made using a second-order quadrupole powder func-
tion for the tri-coordinated 11B resonance using a quadrupole
coupling constant of ca. CQ ⫽ 2.5 MHz, and an asymmetry param-
eter of ca. ηQ ⫽ 0.88. The tetra-coordinated 11B resonance was
simulated employing a gaussian function.
Thermogravimetric analysis (TGA) and differential thermal analy-
sis (DTA) were performed with the Shimadzu DTG-60H system,
in dynamic nitrogen atmosphere (30 mL · min⫺1) at a heating rate
of 10 °C · min⫺1.
SEM images were recorded with Cameca SU-30 Semprobe and
Zeiss Evo 50 EP SEM with 12 kV accelerating voltage and
130⫺150 pA beam current.
The specific surface areas were determined with Monosorp Model/
Quantochrome instruments according to the Brauner-Emmett-
Teller (BET) method [21]. Zeta potential measurements were car-
ried out using a Malvern Nano ZS90.
3. Results and Discussion
Chemical compositions of the LDH samples prepared in
the mortar (1) and by co-precipitation (2), are given in
Table 1. The charge balance in the formulas was established
by assuming the complete neutralization of aluminum
atoms by the interlayer nitrate ions. The Mg/Al molar ratios
of the LDH samples in the bulk compositions were deter-
mined to be smaller than the ratios that charged in the
preparation processes The Mg/Al ratio for the sample pre-
pared by co-precipitation, was particularly lower. A con-
siderable amount of Mg2⫹ might have been removed from
the layers to the solution phase throughout the long co-
precipitation process and lost during washing. Mg(OH)2 is
fairly soluble at pH 8 and below. Even at high pH values,
some Mg2⫹ can be lost due to the changes in the local pH
of the layers [22]. Nevertheless, a convenient Mg/Al ratio
appears to have been established in the layers to allow the
proper construction of the structure since the PXRD pat-
terns of 1 and 2 both exhibited the characteristics of a
layered structure as discussed in the following paragraph.
Figure 1 displays the PXRD patterns of the compounds
prepared mechanochemically and by co-precipitation. The
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ARTICLE A. N. Ay, B. Zümreoglu-Karan, L. Mafra

Table 1. Bulk chemical compositions and some properties of LDH samples.

LDH Formula Mg/Al d003 /Å SBET /m2 · g⫺1 ζ pot. /mV
1 [Mg0.64Al0.36(OH)2](NO3)0.36 · 0.6H2O 1.8 8.59 5.90 ⫹9.86
2 [Mg0.58Al0.42(OH)2](NO3)0.42 · 0.6H2O 1.4 8.63 22.6 ⫹0.85
1B [Mg0.62Al0.38(OH)2](NO3)0.18[B4O5(OH)2]0.10 · 0.6H2O 1.6 10.9 25.3 ⫺
2B [Mg0.53Al0.47(OH)2](NO3)0.08[B4O5(OH)2]0.19 · 0.6H2O 1.1 11.0 83.3 ⫺

close structural similarity between the two compounds is brations of interlayer and/or adsorbed water are seen at
obvious from the nearly identical diffraction data. Even 1635 cm⫺1. The ν3 and ν2 modes of nitrate anions appear
though the crystallinity of 1 is not so high, all the character- at 1377 cm⫺1 and 827 cm⫺1, respectively. Finally, the bands
istic peaks of layered double hydroxides can be easily recog- at 655 cm⫺1 (1), 668 cm⫺1 (2) and 557 cm⫺1 (1), 550 cm⫺1
nized. The characteristic first (003, 2θ ⫽ 10.30°) and second (2) correspond to Mg⫺O and Al⫺O stretching modes,
(006, 2θ ⫽ 20.30°) sharp basal reflections were observed at respectively [21, 22, 26].
nearly the same positions for 1, 2 and for the unwashed
sample 1 U. As the major reflections characterizing the HT-
like LDH’s were observed in the diffractogram of 1 U, it
appears that the LDH structure already exists in the paste
before being wetted with water. Other smaller intensity
characteristic reflections were overlapped with impurity
reflections, mainly with those of NaNO3. The eight strong
peaks located at 29.32°(012), 29.44°(104), 32.02°(006),
35.48°(110), 39.04°(113), 42.62°(202), 48.00°(018) and
48.44°(116) can be assigned to the NaNO3 impurity phase
(JCPDS 7⫺271). Combination of the non-intercalated
nitrate ions with the sodium ions present in the paste results
in the formation of a NaNO3 phase which can be easily
removed through washing to obtain the LDH product.
The d spacings, 8.59 Å for 1 and 8.63 Å for 2, were calcu- Figure 2. FTIR spectra of 1 and 2.
lated from the first sharp basal reflections (d003; 2θ ⫽ 10.30°
for 1, 2θ ⫽ 10.25° for 2) by using the Bragg equation. The
interlayer distances were calculated by subtracting the sheet
thickness (4.8 Å) from the d values. The gallery heights thus
obtained, 3.79 Å(1) and 3.83 Å(2), allow the accommo-
dation of NO3⫺ anions between the layers in tilted posi-
tion [23].

Figure 3. 27Al MAS NMR spectra of the as-prepared LDHs 1 (a),

Figure 1. PXRD patterns of 1, 2 and 1 U.
FTIR spectra also displayed similar features for the LDH
samples (Figure 2). Like in every hydroxide compound, the
layer O⫺H vibrations can be identified around
3400⫺3600 cm⫺1 (stretching) and 950⫺1000 cm⫺1 (bend-
ing) [24]. The bands at 3467 cm⫺1 (1) and 3525 cm⫺1 (2)
are due to Mg,Al⫺OH stretching modes [25]. Bending vi-
2 (b) and their boron intercalated derivatives 1B (c), 2B (d).
Substitution of some of the Mg⫹2 ions with Al⫹3 ions
creates a net positive charge on the layers. To minimize the
repulsion, Al⫹3 ions locate themselves as far apart as pos-
sible, in the octahedral sites of the layers. For better charac-
terization of the aluminum sites, 27Al MAS NMR analyses
were employed. As shown in Figure 3a⫺b, both samples
displayed a single, sharp resonance centered at 9⫺10 ppm

1472 www.zaac.wiley-vch.de  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2009, 1470⫺1475
Synthesis of Mg-Al-NO3-LDH by Manual Grinding in a Mortar
(ca. 10.4 ppm for 1 and ca. 9.76 ppm for 2) with similar
Full Width at the Half-Height (FWHH) indicating the pres-
ence of the hexacoordinate aluminium atoms with equal
chemical surroundings rather than perturbed aluminum
atoms [23]. The tailing observed in the low frequency region
can be attributed to electric field gradient distributions aris-
ing from the disorder in the 27Al environments [27].
Thermal decomposition behavior of 1 and 2 are also
similar as shown in Figure 4. Surface (free) water evapor-
ates below 140 °C. In the following stage, interlayer water
molecules are lost up to 375 °C. Dehydroxylation, removal
of the hydroxyl groups from the layers as water vapour, and
decomposition of the interlayer anions occur at higher
temperatures up to 600 °C.
Figure 4. TGA curves of 1 and 2.
The surface characteristics of the two samples were
examined. The zeta potential value of 2 at neutral pH is
nearly zero which means that the surface possesses no re-
sidual positive charge and the layer charge is completely
balanced. BET surface area of 2 is correlated with the pres-
ence of intercrystalline pores related with the better crystal-
linity of the sample [28]. On the other hand, due to the
rapid nucleation in the mechanochemical process, some
Al3⫹ ions might have become crowded on the surface sites
Figure 5. SEM images of 1 (a) and 2 (b).
Z. Anorg. Allg. Chem. 2009, 1470⫺1475  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
in 1, resulting in a higher surface charge and hence giving
a positive ζ value. The correlation of surface charge density
and the Mg:Al ratio with the microporous structure of
LDHs has been analyzed by Weir and Kydd [29]. It is likely
that the materials with high surface charge density contain
smaller pores and slight changes in the layer composition
may yield different BET surface areas. The products have
similar morphologies as shown in Figure 5. The layers can
be visualized from the SEM images.
The use of mechanochemically prepared LDHs in practi-
cal applications would be more profitable due to the ease
in their synthesis. One possible application might be their
use in waste treatment processes to remove anionic pol-
lutants [30] and further using the subsequent materials for
miscellaneous purposes, e.g. calcination to prepare tailored
mixed oxides for catalytic applications [31]. Product 1 was
tested for its anion exchange property with tetraborate ions
(B42⫺ species) and the obtained boron intercalated deriva-
tive (1B) was structurally analyzed in comparison with the
analogous 2B.
The charge balance in the formulas of boron intercalated
samples, 1B and 2B, was established by assuming the neu-
tralization of aluminum atoms by the entering B42⫺ ions
and the nitrate ions remaining in the galleries (Table 1).
Based on the NO3⫺ contents, the theoretical exchange capa-
cites of 1 and 2 are respectively 1.95 mmol B42⫺ g⫺1 and
2.20 mmol B42⫺ g⫺1. 1B and 2B were found to contain
1.03 mmol B42⫺ g⫺1 and 1.80 mmol B42⫺ g⫺1, respectively.
The values point out that about 52 % of the theoretical ex-
change capacity of 1 and 85 % of the theoretical exchange
capacity of 2 and have been reached under identical uptake
conditions. Thus, the removal of boron from aqueous
wastes by a LDH simply prepared as described here and
then using the boron-intercalated material as a flame-
retardant agent or acid catalyst [32⫺35] might be expected
to be beneficial through ecological and industrial aspects.
The following structural and spectroscopic data clearly
demonstrate the similarity between the boron-intercalated
materials prepared from precursors 1 and 2. Figure 6 shows
the PXRD diagram of 1B and 2B. The close proximity in
the d003 values of boron intercalated samples further em-
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ARTICLE A. N. Ay, B. Zümreoglu-Karan, L. Mafra

phasizes the structural relationship between the parent that boron incorporation into the structure does not cause
LDH samples prepared mechanochemically and by co-pre- any significant disturbance in the brucite-like layers, par-
cipitation. Intercalation of boron was confirmed by the ticularly in the local surroundings of the Al atoms.
expansion in the basal spacings. The accommodation of
borate anions gives rise to an increase in the interlayer dis-
tance. A monolayer of B42⫺ species with average dimensions
of ⬃6 Å [32] can be incorporated in the interlayer space for
which the height is 6.2 Å, either in perpendicular or flat
orientation. In parallel to the increase in the interlayer
pores due to exchanging the smaller nitrate anions with the
larger borate anions, the surface areas increased from
5.9 m2 · g⫺1 (1) to 25.3 m2 · g⫺1 (1B) and from 22.6 m2 · g⫺1
(2) to 83.3 m2 · g⫺1 (2B). The fourfold increase in the BET
values after borate intercalation is noteworthy. The mecha-
nism of borate uptake has been recently described by Ay et
al. [36] that LDH transforms into a pillared material with
high porosity by borate intercalation.

Figure 6. PXRD patterns of 1B and 2B.

The FTIR spectra of 1B and 2B displayed very similar

features. The ν3 BO3 stretching and B⫺OH in plane bend-
ing vibrations appeared around 1450 cm⫺1 and 1360 cm⫺1.
Other peaks observed at 1150 cm⫺1, 935 cm⫺1 and
800 cm⫺1 can be assigned to ν3 BO4 stretching vibrations
and to the ν1 and ν2 trigonal borate modes, respectively [32].
11
B MAS NMR spectra of 1B and 2B (Figure 7) exhib-
ited almost the same feature and the characteristic peaks
for tetrahedral (ca. 2 ppm) and trigonal (centred at ca.
10 ppm) 11B species, where the latter shows a typical
second-order quadrupolar powder pattern [37]. Decon-
volution of the experimental 11B spectra gives a triborate :
tetraborate ratio of 1:1 for both LDH samples, correspond-
ing to the intercalation of B42⫺ species (see the structure in
Figure 7) where two tri- and two tetra-coordinated boron
atoms are present. Moreover, the 27Al MAS NMR spectra
of the boron intercalated LDHs (Figure 3c-d) presented the
same shape and FWHH and thus further confirmed the
structural correlation between the two LDH samples. A re-
markable point is that the 27Al MAS NMR spectra of the
boron intercalated LDHs (Figure 3c-d) and of the non-in-
tercalated samples (Figure 3a-b) are also similar. It appears
Figure 7. Experimental and simulated 11B MAS NMR spectra of
1B and 2B. Structure of the B42⫺ ion is depicted in the Figure.
4. Conclusions
A simple and more productive method was developed to
prepare layered double hydroxides by grinding the hydrated
metal salts and sodium hydroxide manually in a mortar and
washing the paste several times. The method yielded a prod-
uct with similar characteristics to that obtained by co-pre-
cipitation. The reaction proceeds faster by activating the
reagents mechanically and only five to ten minutes manual
grinding is sufficient to obtain a LDH paste. The role of
hydrate water in the initial mixture is fundamental to the
reaction. It has been demonstrated before that the anal-
ogous reaction between LiOH monohydrate and Al(OH)3
does not occur if the reaction condition is kept dry [14]. The
fast reaction between hydrated magnesium- and aluminum
nitrates and sodium hydroxide results in the rapid intercal-
ation of nitrate ions between brucite-like layers and avoids

1474 www.zaac.wiley-vch.de  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2009, 1470⫺1475
Synthesis of Mg-Al-NO3-LDH by Manual Grinding in a Mortar
incorporation of atmospheric CO2. In addition, water from
atmosphere promotes the reaction which is also assisted by
the local heat generated during the grinding process. Many
of the LDHs with possible M2⫹ and M3⫹ compositions can
be prepared with this method using metal salts with high
water content as described herein. The process is sche-
matically depicted in Scheme 1.
Scheme 1. Mechanochemical and conventional synthesis of LDHs.
The mortar method reported herein is a straightforward
and environment-friendly technique that does not require
heating/refluxing treatment, CO2-free atmosphere or sol-
vent as in the conventional methods. Thus, prepared LDHs
may well be used in catalytic or ion-exchange processes
where a disorder in the structure does not present a serious
problem. Future work should now focus on exploring the
preparation of other types of materials with this highly re-
producible and productive way.
Acknowledgement
The authors gratefully acknowledge Prof. J. Rocha (Aveiro Univer-
sity) for providing the laboratory facilities and Prof. A. Temel
(Hacettepe University) and Prof. F. Ercan (Hacettepe University)
for recording the PXRD patterns. ANA thanks TUBITAK research
fellowship for young scientists.
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Received: September 7, 2008
Published Online: March 25, 2009
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