Microporous and Mesoporous Materials 171 (2013) 24–34

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Microporous and Mesoporous Materials

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Ultrasounds and microwave-assisted synthesis of mesoporous hectorites

Tatiana Sánchez, Pilar Salagre ⇑, Yolanda Cesteros
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcellí Domingo s/n, 43007 Tarragona, Spain

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

Article history: Stable mesoporous delaminated and silicate-bearing hectorites were synthesized at short times (1–2 h)
Received 12 April 2012 varying the pH of the hydrothermal treatment (7 and 10) and using microwaves and ultrasounds during
Received in revised form 20 December 2012 the synthesis. The use of microwaves, ultrasounds and aging pH of 10 improved hectorite crystallinity.
Accepted 2 January 2013
Additionally, longer times of ultrasounds involved a better incorporation of magnesium and lithium cat-
Available online 9 January 2013
ions in the octahedral sheet for the delaminated hectorites prepared a pH 7. Delaminated hectorites
showed higher BET areas (536–603 m2/g) than silicate-bearing hectorites, due to delamination and prob-
Keywords:
ably to the presence of magnesium vacancies in the octahedral sheet. The formation of vacancies was
Mesoporous hectorites
Delaminated hectorites
favored with the use of microwaves and at short times of ultrasounds. This agrees with the C.E.C. values
Silicate-bearing hectorites and the low amounts of lithium obtained for delaminated samples.
Microwaves Ó 2013 Elsevier Inc. All rights reserved.
Ultrasounds

1. Introduction associated with a pseudo-smectite structure of condensed silica

Smectite clays constitute a family of complex layered oxides
with 2:1 layer lattice structures. Aluminum, iron, magnesium and
sometimes lithium occupy the octahedral sites, whereas silicon
and, in part aluminum occupy tetrahedral sites. Various cations,
but specially Na+ and Ca2+, may occupy interlamellar positions [1].
Hectorite is an smectite clay with general formula Mx[LixMg6xSi8
O20(OH)4] (M@Na, Li, NH4) where all octahedral sites are occupied
with either Mg2+ or Li+.
Hectorites are interesting materials for industrial applications
such as ceramics, suspending agent in glazes, plasticizing agent
for non-plastic formulations, paints and cosmetic industries, oil
drilling fluid and catalysis due to their cation exchange capacity
(C.E.C.) and acid properties together with their ability to swell in
water and to form organic and inorganic interlayer complexes
[2]. Classical methods of hectorite synthesis usually involve the
use of high temperatures (>623 K) or long aging times (from sev-
eral days to several weeks) [3–5]. However, synthetic hectorites
have been also prepared at short times (2–3 h) by Iwasaki et al.
in autoclave at 423–573 K. At these lower temperatures, the incor-
poration of Li in the structure was lower and the layer charge of
hectorites was mainly related to the presence of octahedral vacan-
cies [6]. Additionally, the particle size of these samples was higher
than those obtained for hectorites prepared at higher temperature.
The presence of vacancies in the initial steps of the hectorite syn-
thesis has been previously described by other authors [4,7] being
⇑ Corresponding author. Tel.: +34 977559571; fax: +34 977559563.
E-mail addresses: pilar.salagre@urv.net, pilar.salagre@urv.cat (P. Salagre).
monomers onto previously formed brucite-like sheets.
To overcome the disadvantages of using long times and high
temperatures for the synthesis of hectorites, new technologies
can be applied. Thus, the use of microwaves for hydrothermal
treatments is a good alternative to reduce the synthesis time, as
reported in the literature for the synthesis of zeolites where the
significant reduction in the crystallization time has been related
to a faster and homogeneous heating with microwaves [8–11]. In
contrast, there are few studies about the application of microwaves
for clay synthesis. Vicente et al. reported a faster synthesis of a
higher crystalline hectorite by microwave–hydrothermal treat-
ment at 393 K for 16 h [12] compared to the 8 days needed by con-
ventional heating. The surface area and C.E.C. values were slightly
higher for the hectorite prepared with microwaves (170 m2/g,
67 meq/100 g) than for that prepared conventionally (165 m2/g,
53 meq/100 g). In the same way, the use of microwaves for the
synthesis of saponites reduced the preparation time from 72 h to
6 h [13]. Trujillano et al. prepared saponites under microwaves
with good ordering and properties [14]. Reduction of the reaction
time was also observed during the acid activation of bentonite
under microwaves [15].
Ultrasound is another interesting technique to improve the syn-
thesis of materials since it allows obtaining more homogeneous
materials. Singh et al. reported the better distribution of ZrO2 in
the interlamellar space of clay by using ultrasounds in the interca-
lation process [16]. Katdare et al. stated similar benefits in the
preparation of aluminium pillaring clays [17,18].
Another disadvantage characteristic of clays is the collapse of
their structure at relatively low temperatures. This could be solved

1387-1811/$ - see front matter Ó 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2013.01.001
 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34
with the introduction of pillars in the interlamellar space or by clay
delamination. Both procedures are usually accompanied by an in-
crease of surface area that can be of interest for their use in catalysis.
Torii and Iwasaki proposed a conventional hydrothermal method to
obtain in 2 h, lamellar structures with silicate pillars, called by the
authors as silicate-bearing hectorites, which were converted into
hectorites with higher porous size after treatment with an ammo-
nium quaternary salt and later calcination [19–21]. Later, Iwasaki
et al. reported the obtention of delaminated hectorites, which were
synthesized by conventional hydrothermal treatment of a mixture
containing Si, Mg and quaternary ammonium salts at pH 10–12
[22]. In delaminated hectorites, the mesopores correspond to the
interparticle space of lamellar-shaped crystallites, aggregated by
edge-to-face bonding. In a previous work, the high surface area
(353 m2/g) and low hydrophilic capacity, related to a low C.E.C. value
(44 meq/100 g sample), of one delaminated hectorite prepared by
conventional hydrothermal heating at pH 12 for 1 h, made this
material an excellent support of copper catalysts for the hydrogen-
olysis of glycerol [23]. Natural clays have been also used as raw
material for the preparation of mesoporous molecular sieves using
templates together with the addition of sodium silicate [24,25].
In this paper, we describe the synthesis of mesoporous hector-
ites (delaminated and silicate-bearing hectorites) by using micro-
waves during the hydrothermal treatment and ultrasounds for
the mixture of the starting reagents with the aim to reduce the
synthesis time and to obtain mesoporous materials with higher
crystallinity, through a more sustainable process. Additionally,
we will study the effect of the aging pH (7 and 10) used during
Scheme 1. Steps of Silicate Bearing-Hectorites synthesis.
25
the synthesis on the structure, composition and surface properties
of the synthesized delaminated hectorites.
2. Experimental
2.1. Synthesis of mesoporous hectorites
2.1.1. Silicate bearing-hectorites
Hectorites were prepared following the method reported by
Torii et al. [20] but modifying several parameters and using micro-
waves for the hydrothermal aging. The preparation steps, indicated
in Scheme 1, were the following: (1) 8.73 g of sodium silicate
solution (SiO2 27 wt.%, density 1.39 g/cm3, Sigma–Aldrich) was
acidified with 43 ml of HNO3 1 M and later mixed with MgCl2
(98 wt.% Sigma–Aldrich); (2) NaOH was added until pH 10 for pre-
cipitation, the precipitate was filtered, washed and dried; (3) the
solid was suspended in water to 10 wt.% and mixed with LiF
(99.9 wt.% Sigma–Aldrich), the molar ratio of reagents was
Si:Mg:Li = 8.0:5.4:0.6; (4) the hydrothermal treatment of the water
suspension was performed into a 85 ml Teflon reactor filled with
45 ml of the suspension by autoclaving in two ways: the first one
with microwaves in a Milestone Ethos Touch Control furnace
(2.45 GHz) with a power of 600 W at 453 K for 1 h under magnetic
stirring, and the other one by conventional heating at 453 K for 2 h;
(5) the products were washed, dried, suspended in hot water at
2 wt.%, mixed with a trimethyldodecylammonium chloride (AQ)
(98 wt.% Sigma–Aldrich) water solution at 2 wt.% in a molar ratio
Li:AQ = 1:1 and refluxed at 353 K for 1 h; (6) the products were
26 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34

Table 1 chloride (AQ) in a molar ratio Li:AQ = 1:1. The hydrothermal treat-
Preparation conditions of the samples. ment of the water suspension was performed into a 85 ml Teflon
Hectorite Ultrasounds Hydrothermal pH during hydrothermal reactor filled with 45 ml of the suspension by autoclaving in two
time (min) treatment treatment ways: the first with microwaves at 453 K for 1 h under magnetic
7HD20MW 20 Microwave 7 stirring and the second by conventional heating at 453 K for 2 h;
7HD40MW 40 Microwave 7 (5) the products were calcined at 893 K under airflow for 75 min.
7HD60MW 60 Microwave 7 Samples were named as 7HD20MW, 7HD40MW, 7HD60MW, 7HD20C,
7HD20C 20 Conventional 7
7HD40C 40 Conventional 7
7HD40C, 7HD60C, 10HD20MW and 10HD20C where the first number,
7HD60C 60 Conventional 7 which indicates the pH of the suspension during the hydrothermal
10HD20MW 20 Microwave 10 treatment, is followed by the letters HD, the number of minutes
10HD20C 20 Conventional 10 performed under ultrasounds and the letters MW or C depending
10HBMW – Microwave 10
on the hydrothermal treatment made (Table 1).
10HBC – Conventional 10

2.2. X-ray diffraction (XRD)

XRD measurements were made using a Siemens D5000 diffrac-

tometer (Bragg–Brentano parafocusing geometry and vertical h–h
goniometer) fitted with a curved graphite diffracted-beam mono-
chromator and diffracted-beam Soller slits, a 0.06° receiving slit,
and scintillation counter as a detector. The angular 2h diffraction
range was between 5 and 70°. Sample was dusted onto a low back-
ground Si (5 1 0) sample holder. The data were collected with an
angular step of 0.05° at 3 s per step and sample rotation. CuKa
radiation was obtained from a copper X-ray tube operated at
40 kV and 30 mA.
The X-ray pattern was analyzed implementing the program TO-
PAS 3.0 [26]. This approach calculates the contribution to the
reflection width produced by a specific instrument configuration.
The crystallite size was calculated from the net integral breadth
of the reflections, bi, [27] according to the following formula that
comes from the Scherrer expression: bi = k/ecosH where k is the
X-ray wavelength, e is the crystallite size and h is the Bragg angle.
(0 6 0) reflection was used to calculate the crystallite size of the
hectorites.

2.3. N2 physisorption

N2-adsorption–desorption isotherms were recorded at 77 K

using a Micromeritics ASAP 2000 surface analyzer. Prior to analysis
samples were outgassed at 393 K. Specific surface areas were cal-
Scheme 2. Steps of Delaminated Hectorites synthesis.
culated from the BET method. Isotherms were related to the shape
of layers aggregations.

calcined at 893 K under airflow for 75 min. The sample obtained
from the hydrothermal treatment with microwaves was desig-
nated as 10HBMW whereas that prepared from conventional hydro-
thermal treatment was named as 10HBC (Table 1).
2.1.2. Delaminated hectorites
This type of hectorites were prepared following the method re-
ported by Iwasaki et al. [22] but introducing ultrasounds for mixing
the starting reagents and microwave irradiation during the hydro-
thermal treatment. The reagents had the same purity and were pro-
vided by the same suppliers than those used for preparing silicate
bearing-hectorites. The steps of preparation were (Scheme 2): (1)
8.73 g of the sodium silicate solution was acidified with nitric acid
and mixed with MgCl2 and LiF; (2) LiOH (98% Sigma–Aldrich) was
added to get Si–Mg-hydroxide precipitates at pH 10. The molar ratio
of reagents was Si:Mg:Li = 8.0:5.2:0.8; (3) (a) the resulting suspen-
sion was maintained for 20, 40 and 60 min at room temperature
in a Selecta ultrasound water bath with a power of 150 W and a
frequency of 40 kHz, and later filtered and washed until pH 7; (b)
another sample was mixed under ultrasounds for 20 min was just
slightly washed to maintain pH 10; (4) precipitates were suspended
in water to 10 wt.% and mixed with trimethyldodecylammonium
2.4. Transmission electronic microscopy (TEM)
TEM images were collected using a JEOL 1011 Transmission
Electron Microscope operating at 80 kV and magnification values
of 200–250 k. Samples were dispersed in n-hexanol, and a drop
of the resultant suspensions was poured on carbon coated-copper
grids. This technique allowed us to monitor the different layers
aggregations of the samples.
2.5. Cation exchange capacity (C.E.C.)
The cation exchange capacity (C.E.C.) was determined following
the method reported by Bergaya and Vayer [28]. The measure of
C.E.C. was used to detect additional negative charge in the layers
and, in consequence, the presence of magnesium vacancies in sev-
eral samples.
2.6. Thermogravimetric analyses (TGA)
Thermogravimetric analyses (TGA) were carried out in a Perkin
Elmer TGA 7 microbalance equipped with a 273–1272 K program-
mable temperature furnace. The accuracy was ±1 lg. Each sample
(30 mg) was heated in an airflow (80 cm3) from room
 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34
temperature to 1223 at 10 K/min. Weight losses were related to
the different steps occurred during decomposition of the clays.
29
2.7. Si MAS-NMR
29
Si, MAS-NMR spectra were obtained at a frequency of
400 MHz by spinning at 5 kHz. The pulse duration was 2 ls and
the delay time was 5 s. The chemical shift reference for silicon
was silicon nitride Si3N4. The shift of the bands was associated to
the composition of the clays.
2.8. Icp-oes
The Li and Na contents of the catalysts were determined by ICP-
OES (Perkin Elmer Optimal 4300 D). Analyses were made by
triplicate.
2.9. X-ray fluorescence (XRF)
In order to determine the content of Si and Mg of hectorite
samples, X-ray fluorescence (XRF) were obtained with a Philips
PW-2400 sequential XRF analyser with Phillips Super Q software.
Analyses were made by triplicate.
3. Results and discussion
3.1. Characterization of hectorites
XRD patterns of all samples were typical of clays materials and
showed only one crystalline phase corresponding to hectorite
(Figs. 1–3). However, (0 0 1) reflection, related to layer stacking,
was not observed in any case. In order to confirm this fact, addi-
tional diffractograms were recorded at lower angles (2h = 0–10)
for all samples but any new reflection was observed. The low de-
gree of order stacking in mesoporous hectorites could be associ-
ated with delamination in HD hectorites and with a very limited
Fig. 1. X-ray diffraction patterns of samples 7HD40MW, 7HD40C.
27
ordering in the c-axis for the HB ones, due to a lack of long range
face-to-face stacking of the clay silicate layers, in agreement with
Occeli et al. [29]. Actually, for HB samples a shoulder appeared at
low 2H angles, more defined in the sample aged with microwaves
(Fig. 3). This shoulder can be related to reflexion (0 0 1). In contrast,
(0 6 0) reflection appeared enough well defined for all samples
(Figs. 1–3). For this reason, this reflection was used to determine
the crystallite size using the Scherrer equation.
Table 2 summarizes the characteristics of the synthesized hect-
orites. For the hectorites aged at pH 7 (7HD20MW, 7HD40MW,
7HD60MW, 7HD20C, 7HD40C, 7HD60C), using microwaves or conven-
tional heating, we observed a slight higher crystallite size by
increasing the time of ultrasounds (Table 2). Additionally, the hect-
orites aged with microwaves showed slight higher crystallite size
than those aged by conventional heating (Table 2).
The hectorites (delaminated and silicate-bearing) aged at pH 10
(10HD20MW, 10HD20C, 10HBMW and 10HBC) exhibited higher crys-
tallinity, with more defined (0 6 0) reflection, than the hectorites
aged at pH 7 (Table 2, Figs. 1–3). Again, the samples hydrotermally
treated with microwaves achieved higher crystallinity at shorter
time of hydrothermal treatment (1 h) than the hectorites prepared
by conventional heating (2 h). Thus, the crystallite size of
10HD20MW (7.1 nm) was higher than that of 10HD20C (6.3 nm)
whereas the crystallite size of 10HBMW (11.9 nm) was higher than
that of 10HBC (8.9 nm) (Table 2). It is important to remark the best
definition of the reflection (0 0 4) in the silicate-bearing hectorite
prepared by microwaves (10HBMW), which is in agreement with
the shoulder related to the reflection (0 0 1) observed in this sample
(Fig. 3).
TEM images of the hectorites showed their lamellar morphol-
ogy (Figs. 4–6). As we can observe, delaminated hectorites had
nano-sized disordered layers aggregated to make mesoporous
(Figs. 4 and 5). Interestingly, the delaminated hectorites prepared
with microwaves (Figs. 4 and 5a) exhibited higher delamination
of the sheets than those aged by conventional heating (Figs. 4
and 5b). For the microwaved delaminated samples, the model of
28 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34

Fig. 2. X-ray diffraction patterns of samples 10HD20MW, 10HD20C.

Fig. 3. X-ray diffraction patterns of samples 10HBMW, 10HBC.

edge-to-face connections appear to be the main mode of plate conventional heating, a combination of oriented and disordered
aggregation (Fig 7a), forming a stable structure with mesoporosity, layers was observed. This distribution can be related to a model
whereas in the case of the delaminated hectorites prepared by of network with face-to face and edge-to-face connections
 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34 29

Table 2
Characterization of mesoporous hectorites.

Hectorite Crystallite size (nm) Average pore size (Å) Dehydroxylation temperaturea (K) BET (m2/g) C.E.C. (meq/100 g)
7HD20MW 6.5 29 1066 603 75.7
7HD40MW 7.3 28 1076 601 75.9
7HD60MW 7.5 30 1073 572 63.7
7HD20C 6.0 24 1083 563 61.6
7HD40C 6.5 24 1070 561 53.0
7HD60C 6.8 25 1081 536 51.2
10HD20MW 7.1 29 1077 599 84.4
10HD20C 6.3 31 1075 590 73.1
10HBMW 11.9 29 1013 262 39.0
10HBC 8.7 28 1023 356 33.5
ª
Temperature of the minimum of the TG second band.

Fig. 4. TEM images of samples (a) 7HD20MW and (b) 7HD20C.

Fig. 5. TEM images of samples (a) 10HD20MW and (b) 10HD20C.

(Fig 7b). On the other hand, TEM images of silicate-bearing hector- The chemical composition of delaminated hectorites and sili-
ites mainly showed compact particles of parallel layers with strong cate bearing hectorites are given in Table 3. The high Mg/Alkaline
interaction between them (Fig 7c) [30]. ratio of the majority of delaminated hectorites and the low values
30 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34

Fig. 6. TEM images of samples (a) 10HBMW and (b) 10HBC.

Fig. 8. N2 adsorption/desorption isotherms for samples 7HD20MW, 7HD40MW and

Fig. 7. Models of layers aggregation (a) House of cards (edge–face interactions), (b)
edge–face and face–face interactions, and (c) compact particles with strong face–
face interactions.
of Li suggest a very low degree of lithium incorporation in the
hectorite layer. In the case of delaminated hectorites aged at pH
7 with microwaves, we observed Si/Mg ratios near to the expected
7HD60MW.
theoretical values (1.54). However, for the hectorites aged by
conventional heating, we observed a higher Si/Mg ratio, which
increased slightly by increasing the time of ultrasounds. Similar
behavior was observed for delaminated hectorites synthesized at
pH 10.

Table 3
Composition of mesoporous hectorites.

Hectorite Mg (mol/100 g) Si (mol/100 g) Li (mol/100 g)  103 Na (mol/100 g)  103 Si/Mga Mg/Alkb Mg Vacanciesmmol/100 g
7HD20MW 0.76 1.11 9.28 1.74 1.46 68.97 33.21
7HD40MW 0.60 0.91 17.20 0.40 1.52 34.08 29.35
7HD60MW 0.70 1.00 17.50 0.51 1.43 38.85 23.10
7HD20C 0.59 1.21 9.13 5.40 2.05 40.69 26.23
7HD40C 0.56 1.23 31.83 6.41 2.20 14.64 10.58
7HD60C 0.56 1.24 43.41 10.40 2.21 10.41 3.90
10HD20MW 0.59 1.10 14.80 0.69 1.86 38.07 34.80
10HD20C 0.50 1.10 8.84 0.03 2.20 56.38 32.13
10HBMW 0.70 1.00 47.60 50.30 1.43 7.15 –
10HBC 0.68 0.92 36.00 57.60 1.53 7.26 –
a
Theoretical value HD Si/Mg: 1.54, HB Si/Mg: 1.48.
b
Alk: Na + Li, theoretical value HD Mg/Li: 6.5, HB Mg/Li: 9.0.
 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34 31

of magnesium vacancies (mmol/100 g) in the octahedral sheet

was calculated from Eq. (1).

Fig. 9. N2 adsorption/desorption isotherms for samples 7HD20C, 7HD40C and
7HD60C.
Fig. 10. N2 adsorption/desorption isotherms for samples 10HD20MW, and 10HD20C.
C.E.C. values, calculated for all samples, are indicated in Table 2.
The higher C.E.C. values were obtained for delaminated hectorites
aged with microwaves after shorter times of ultrasounds
(10HD20MW, 7HD20MW and 7HD40MW). Having in mind the low
degree of lithium incorporation in these samples, it is difficult to
explain these C.E.C. values. We believe that these materials
presented octahedral vacancies [6], and, consequently higher layer
charge can be expected. The total negative charge of the layers is
generated by the substitution of Mg2+ by Li in the octahedral sheet
and by the presence of magnesium vacancies, and could be bal-
anced by interlayer magnesium and sodium ions. The estimation
Mg vacancies ðmmol=100gÞ
C:E:C: ðmeq=100 gÞ  Li ðmeq=100 gÞ
¼ ð1Þ
2
The calculated Mg vacancies values are shown in Table 3.
Higher amounts of vacancies were obtained for the hectorites
hydrothermally treated with microwaves after short times of ultra-
sounds. An increase of the ultrasounds time could justify a better
construction of the layers during the hydrothermal treatment since
the best and more homogeneous mixture of the reagents at longer
ultrasound times should favor the incorporation of Mg and lithium
in the octahedral sheet. The higher amount of magnesium vacan-
cies obtained for the samples prepared with microwaves could
be related to their higher crystallite size. Actually, the hectorites
obtained by conventional heating were more amorphous, as ob-
served by XRD, and probably the incorporation of magnesium into
smaller particles was easier. On the other hand, very high amounts
of alkaline, especially of sodium, were observed for silicate-bearing
hectorites. This could be related to the presence of sodium silicate
pillars in their interlamellar space.
The delamination observed by TEM and the presence of octahe-
dral vacancies in the hectorite structure could explain the high BET
area (around 600 m2/g, Table 2) observed for the delaminated hect-
orites with higher amounts of vacancies (10HD20MW, 7HD20MW and
7HD40MW). The increase of the ultrasounds time and the use of con-
ventional heating led to lower surface areas (Table 2). This can be
related to the presence of fewer vacancies. The silicate-bearing
hectorites presented the lowest BET areas. This can be explained
by the layers compactation and probably because the sheets of
the layers were well constructed.
With respect to porosity, it is important to remark that delami-
nated samples prepared with microwaves showed isotherms with
contribution of microporosity and mesoporosity (Type IV, accord-
ing to IUPAC classification) (Figs. 8 and 10). In contrast, the iso-
therms of the samples prepared by conventional heating (Fig. 9
and 10) could be better described with a higher contribution of
type I, which correspond to more microporous samples with lim-
ited adsorption to few layers. In the Figs. 8–10, we can observe that
all the nitrogen isotherms presented hysteresis with a plateau at
high P/P0 indicative of the complete filling of the mesoporous.
The hysteresis loop was a mix of type B and D, following Boer clas-
sification [31], associated with the presence of aggregates of plate-
like particles. Specifically, hysteresis type B and D are characteristic
of lamellar particles with and without orientation, respectively, as
observed by TEM.
Table 4 shows the most significant results about the effect of
microwaves and ultrasounds on the crystallinity, C.E.C. and surface

Table 4
Most significant results comparing the use of microwaves and ultrasounds for the synthesis of delaminated hectorites.

Hectorite Mw/conv Crystallite size (nm) C.E.C. (meq/100 g) BET (m2/g) Mg vacanciesmmol/100 g
Microwaves effect
7HD20 7HD20MWC 6.5 75.7 603 33.21
7HD20 6.0 61.6 563 26.23
10HD20 10HD20MW 7.1 84.4 599 34.80
10HD20C 6.3 73.1 590 32.13
Ultrasounds effect
7HD20 7HD20MW 6.5 75.7 603 33.21
7HD20C 6.0 61.6 563 26.23
7HD40 7HD40MW 7.3 75.9 601 29.35
7HD40C 6.5 53 561 10.58
7HD60 7HD60MW 7.5 63.7 572 23.10
7HD60C 6.8 51.2 536 3.90
32 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34

29
Fig. 11. Si NMR spectrum of samples (a) 7HD40MW and (b) 7HD40C.

area values of delaminated hectorites. The use of microwaves im-
proved the three properties while longer time of ultrasounds only
improved crystallinity. These effects can be related to the increase
of the crystallite growth rate and the increase of Mg vacancies due
to the action of microwaves whereas the crystallite size increased
but the amount of Mg vacancies decreased because of the ultra-
sounds action. From the results shown in Table 4, we also ob-
served: (1) the use of ultrasounds plus conventional heating
provides a better incorporation of magnesium and lithium in the
structure than the use of ultrasounds plus microwaves, obtaining
better constructed layers. This behavior is interesting to obtain
hectorites with defined structures; (2) the presence of higher
amounts of vacancies involves higher C.E.C. and surface area values
for the corresponding hectorites. These properties are very inter-
esting for some applications, as for example in catalysis.
In order to have more information, 29Si NMR and TGA of several
samples were recorded. The 29Si NMR spectra of samples showed
two peaks: one more intense at 101.23 ppm and other less
 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34 33

Fig. 12. Thermogravimetric weight loss curves of samples (a) 10HBMW and (b) 7HD40MW.

intense around 90 ppm (e.g. Fig. 11a and b). 29Si NMR spectra are
interpreted in terms of the number of SiO4 tetrahedron linked to
other tetrahedron via bridging oxygen atoms. The peak assigna-
tions in clays are referred as Q3 and Q2 silicon resonances, which
correspond to SiO4 group with common corners with three or
two SiO4 tetrahedron, respectively [32]. The 29Si NMR spectra of
silica, laponite and talc had significant differences since in the silica
sample the Q4 band around 110 ppm is the most intense peak,
while in the talc the Q3 peak appeared at 98 ppm and in the lap-
onite at 93.6 ppm [33,34]. The substitution of Mg2+ by Li+ in the
laponite, led to a deshielding of the silicon atoms in the tetrahedral
layer. It has been argued that the deshielding observed as a conse-
quence of the replacement of one Mg by Li can be attributed to
slightly more covalent Li–O than Mg–O bonds [31]. Comparing
the values of chemicals shifts (ppm) obtained for silica, laponite
and talc with those obtained for our samples (101 ppm and
34 T. Sánchez et al. / Microporous and Mesoporous Materials 171 (2013) 24–34
90 ppm), we could assign these peaks to Q3 silicon resonances,
with a limited incorporation of Mg in the octahedral layer for
101 ppm (P2) and with incorporation of Mg and alkaline for the
90 ppm (P1). The ratio intensities of the two peaks I(P1)/I(P2)
could be a measure of the lamellar construction in the clays, with
the expected distribution of Si in Td and Mg and alkaline in Oh
sites. This ratio was higher when longer times of ultrasounds and
conventional heating treatment were used. This confirms that the
efficiency in the mixing of reagents and the small crystallite size fa-
vor the incorporation of magnesium and alkaline in the structure.
The thermogravimetric analysis of all samples showed the
typical TGA curves and derivatives of hectorites [35,36], with the
presence of two bands (e.g. Fig. 12), one at lower temperature
(373–423 K), related to dehydratation and the other at higher
temperature, attributed to dehydroxylation. This second band
can be used for measuring hectorite thermal stability. Thus, good
thermal stability was found for both, silicate-bearing hectorites
and delaminated hectorites since the temperature of dehydroxyla-
tion (value measured in the minimum of the second band) was
higher than in a microporous hectorite, shifting from 893 K to
1013 and 1023 K for 10HBMW and 10HBC, respectively, and to
above 1063 K for delaminated hectorites (Table 2).
4. Conclusions
Delaminated hectorites have been synthesized by hydrothermal
treatment at pH 7 and 10, for 1 h with microwaves and for 2 h by
conventional heating, using different times of ultrasounds for mix-
ing the starting reagents. The layered structure, with a disordered
lamellar distribution, of these materials has been corroborated by
TEM and XRD. On the other hand, silicate-bearing hectorites pre-
sented oriented layers. TGA of all hectorites allowed us to conclude
that they were more resistant to dehydroxylation than micropo-
rous hectorites.
The hectorites (delaminated and silicate-bearing) obtained
using microwaves were more crystalline than those prepared by
conventional heating. For delaminated hectorites, when pH 10
was used during the hydrothermal treatment, the hectorite crystal-
linity was also improved. Another interesting characteristic of del-
aminated hectorites prepared with microwaves was their high
surface area (around 600 m2/g). On the other hand, the low amount
of lithium present in their composition was not in agreement with
their C.E.C. values. This can be explained by the presence of magne-
sium vacancies in a pseudo-smectite structure with negative
charged layers of silicates. Higher amounts of these vacancies
could also justify the high surface area values obtained. The use
of conventional heating for preparing delaminated hectorites and
the increase of the ultrasound time during the reagents mixture
of the delaminated hectorites prepared a pH 7 involved a better
incorporation of magnesium and lithium cations in the octahedral
sites, with a consequent decrease of vacancies. The increase of
ultrasounds time favored crystallization too, since higher crystal-
lite sizes were obtained.
Summarizing, the use of microwaves favors the synthesis of
hectorites with higher crystallinity, surface area and C.E.C., than
when using conventional heating, while the use of ultrasounds in-
volves an increase of crystallinity, but a decrease of surface area
and C.E.C. values, especially at longer ultrasounds times. Addition-
ally, the use of ultrasounds plus conventional heating provides a
better incorporation of magnesium and lithium in the hectorite
structure than the use of ultrasounds plus microwaves, obtaining
better constructed layers. The amount of magnesium vacancies
was estimated, explaining the surface areas, the C.E.C. values, and
the composition of the synthesized mesoporous hectorites.
Acknowledgments
The authors are grateful for the financial support of the Minis-
terio de Ciencia e Innovación of Spain and FEDER funds
(CTQ2008-04433/PPQ and CTQ2011-24610).
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