Microporous and Mesoporous Materials 138 (2011) 157–166

Contents lists available at ScienceDirect

Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Centimeter-sized zeolite bodies of intergrown crystals:

Preparation, characterization and study of binder evolution
Lama Itani a, Valentin Valtchev a, Joël Patarin a,⇑, Séverinne Rigolet a, Feifei Gao a, Gérard Baudin b
a
Equipe Matériaux à Porosité Contrôlée (MPC), Institut de Science des Matériaux de Mulhouse (IS2M), LRC-CNRS 7228, Université de Haute Alsace (UHA),
Ecole Nationale Supérieure de Chimie de Mulhouse (ENSCMu), 68093 Mulhouse, France
b
Commissariat aux Énergies Atomiques et Alternatives (CEA), Direction des Applications Militaires (DAM), Gramat, F46500 Gramat, France

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

Article history: The control of the inter-particle porosity in polycrystalline zeolite bodies remains a challenge. The pres-
Received 22 July 2010 ent study reports on the preparation of centimeter-sized zeolite bodies (32  2 mm pellets) with reduced
Received in revised form 15 September inter-particle porosity. The bodies were prepared by assembling zeolite colloidal nanocrystals with
2010
monomodal particle size distribution and sub-colloidal aluminum hydroxide binder. A secondary growth
Accepted 16 September 2010
Available online 21 September 2010
treatment under hydrothermal conditions was performed in order to fill up the inter-particle voids and
obtain polycrystalline zeolite materials with textural characteristics close to those of single zeolite
crystals. Initial material, intermediates and ultimate product were studied with a combination of comple-
Keywords:
Zeolite bodies
mentary methods revealing a substantial reduction even an elimination of the inter-particle porosity.
Inter-particle pores Particular attention was paid to the chemical evolution of the binder and the migration of aluminum
Secondary growth treatment species, employing X-ray powder diffraction, 27Al-MAS, 27Al-3QMAS NMR and X-ray fluorescence
spectroscopy analyses. Evidences for insertion of aluminum from the binder into the zeolite framework
during secondary growth step were found. Consequently the ultimate pellets comprised aluminum-
rich zeolite beta crystals and very low binder content.
Ó 2010 Elsevier Inc. All rights reserved.

1. Introduction binder is used [10]. Traditionally employed binders are alumina,

Zeolites are crystalline microporous materials with uniform
pore size ranging between 0.3 and 2 nm. Stereo selectivity com-
bined with surface activity make zeolites indispensable for numer-
ous chemical processes. Zeolite synthesis is usually performed in
alkaline media under hydrothermal conditions and leads typically
to powder of micrometer-sized crystals. These crystals are difficult
to handle and use in liquid and gas phase reactions. On the other
hand, the synthesis of larger zeolite crystals is difficult to be
achieved on a larger than a laboratory scale. The application of
such crystals is limited to fundamental studies of zeolite structure,
diffusion properties and growth process [1–4]. Large zeolite crys-
tals might also find applications as hosts for guest molecules
(alignments of dye molecules), ions, and clusters for optical, elec-
tric and magnetic microdevices [5–7]. Generally fairly exotic meth-
ods that is difficult to be used in an industrial scale are employed
[8,9]. In addition, such synthesis suffer from other limitations such
as long synthesis time laying usually between several days and
several weeks, the formation of co-crystalline phases, and low
yield. Thus most of the industrial applications require shaping
the zeolite powders in larger constructs where in most cases a
⇑ Corresponding author. Tel.: +33 3 89 33 68 80; fax: +33 3 89 33 68 85.
E-mail addresses: j.patarin@univ-mulhouse.fr, joel.patarin@uha.fr (J. Patarin).
silica and natural clays (kaolin, kaolinite, montmorillonite, benton-
ite, etc.) [11]. In general it is accepted that these binders are
chemically inert and do not contribute to the performance of
zeolite-binder composite. However, there are studies revealing
that the catalytic properties of the zeolite might be strongly influ-
enced by the binder. For instance, many studies show that the use
of aluminosilicate clays decreased strongly the number of strong
acid sites in the catalyst [11–14]. The influence of the binder on
the deactivation of the zeolite catalyst by coking was also observed
[15–17]. On the other hand, when using an alumina binder, Shihabi
et al. showed that the activity for acid catalyzed reactions of high-
silica ZSM-5 was enhanced [18]. They attributed this result to the
formation of new acid sites during the catalyst preparation.
Namely, the higher activity was attributed to incorporation of alu-
minum species released from the binder into zeolite framework.
Kubicek et al. has also reported enhancement of zeolite beta cata-
lytic properties after embedding in alumina and alumino-silicate
amorphous matrixes [19]. These studies confirmed the possible
aluminum incorporation into zeolite frameworks of species issued
from the binder. Another important feature of binder-containing
zeolite constructs is the presence of secondary porosity due to
the uncontrolled aggregation of zeolite crystals and the binder. In
some applications, particularly in catalysis, this porosity can have
a positive effect for the diffusion of the reactants and products.

1387-1811/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2010.09.011
158 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166
In contrary, such porosity can be undesirable and it is the case of
the present study which deals with the preparation of zeolite
bodies that contain only the intrinsic zeolite porosity. The aimed
objective is to determine the behavior of these materials under
shock-waves for modeling studies. To achieve this goal, assembling
zeolite nanocrystals with binder of sub-colloidal size was em-
ployed. In order to reduce inter-particle space, a secondary growth
treatment was carried out.
The preparation of zeolite bodies with reduced to minimum
inter-particle porosity and characteristics close to single crystals
is exemplified by the preparation of zeolite beta (*BEA-type)
pellets. Zeolite beta is one of most largely used high-silica zeolites
possessing a three dimensional interconnected channel system
with 12-membered ring openings and pore diameters of 0.53 
0.57 and 0.71  0.73 nm. Strong acidity combined with large pores
and high thermal and chemical stability make this zeolite attrac-
tive material for a number of applications [20–26]. A combination
of complementary methods was employed in order to fully charac-
terize the initial materials, the intermediates and the ultimate
bodies.
Since the preparation of zeolite bodies in this study required the
addition of a binder, particular attention was paid to the evolution
of the binder throughout different preparation steps and to its ef-
fect on the physicochemical properties of the composite.
2. Experimental section
2.1. Samples preparation
Zeolite beta nanocrystals used for the preparation of zeolite
beta–alumina binder pellets were synthesized according to
reference 27 from a clear solution having the following composi-
tion: 0.3Na2O:9TEAOH:0.25Al2O3:25SiO2:260H2O. Ludox HS-40
(40 wt% in water, Sigma–Aldrich), sodium aluminate (53 wt%
Evaporation at 70 °C
for 48 h
Mixture of nanozeolite beta suspension
and Al-binder
Mechanical pressing at 9 T for 15 min.
Nanozeolite beta-binder powder
PTFE (teflon)
support
Fig. 1. Illustration of the preparation method of zeolite beta–alumina binder pellets.
Al2O3, 42 wt% Na2O, Riedel-de-Haën) and tetraethylammonium
hydroxide (TEAOH, 35 wt% in water, Aldrich) were employed as
silica source, aluminum source and structure-directing agent,
respectively. The silicate and aluminate solutions (in TEAOH solu-
tion) were prepared separately under stirring at 50 °C for 2 h.
Afterwards, these solutions were vigorously mixed and aged at
50 °C for 1 h, where all components were expected to be relatively
homogeneously distributed. The solution was then transferred into
polypropylene bottles and heated in an oven at 100 °C for 7 days
under static conditions. Zeolite beta nanocrystals were recovered
and purified by three steps of high speed centrifugation at
25,000 rpm for 30 min and redispersion in distilled water in an
ultrasonic bath. The final pH of the suspension was adjusted to 9
by the addition of NH4OH (0.1 M).
Centimeter-sized zeolite beta pellets were prepared by mixing
zeolite beta nanocrystals suspension with an aluminum hydroxide
binder solution (Al(OH)3, 13 mg/L in water, Sigma) in a weight ra-
tio zeolite: binder = 60:40. The mixture was then heated at 70 °C in
order to evaporate water and obtain dried powder. Two grams of
the zeolite-binder powder mixture were further shaped into centi-
meter-sized (32  2 mm) pellets via mechanical pressure at 9 tons
for 15 min in a cylindrical holder with the inner diameter of
32 mm. In order to eliminate the inter-particle porosity, a second-
ary growth treatment was necessary. Pellets placed on a PTFE
(Teflon) support were immersed in a solution having similar com-
position to the one employed for the synthesis of primary zeolite
beta nanocrystals. The secondary growth treatment was carried
out in polypropylene bottles at 100 °C for 2 days. This treatment
was performed one (sample A) or two times (sample B). A
schematic presentation of the method used for the preparation of
zeolite beta–alumina binder pellets is shown in Fig. 1. Finally,
the pellets were washed several times with distilled water, dried
overnight at 60 °C then calcined at 500 °C for 4 h under nitrogen
flow and 2 h under air flow.
Grinding
Solid mixture of
nanozeolite beta-binder
Nanozeolite beta-binder pellet
calcined at 500 °C for 9 h
Calcination
Secondary growth treatment
one (sample A) or two times
(sample B)
 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166
2.2. Characterization
Powder X-ray diffraction (XRD) patterns were obtained from a
PANalytical X’pert Pro diffractometer with fixed slits using Cu/Ka
radiation (k = 1.5418 Å) with h–2h mounting. Before analysis sam-
ples were finely ground and pressed in a stainless steel sample
holder. The patterns were registered in 2h range of 5–50° with
scanning step of 0.1° s 1. Scanning electron microscopy (SEM)
micrographs were taken with a Philips XL30-FEG instrument.
The particle size distribution of the colloidal zeolite beta sus-
pension was determined by dynamic light scattering (DLS) using
a Malvern Zetasizer instrument.
Nitrogen adsorption/desorption measurements were performed
with a Micromeritics ASAP2420 surface area analyzer after outgas-
ing the calcined samples at 90 °C for 1 h and 300 °C for 15 h. Sur-
face areas were calculated using BET equation and micropore
volumes were obtained from the t-plot method. The total pore vol-
ume corresponds to the nitrogen adsorbed volume under S.T.P.
conditions at P/P0 of 0.99.
Large mesopores and macropores of the pellets before and after
the secondary growth treatment were estimated by mercury
porosimetry. Measurements were carried out on a Carlo Erba
porosimeter (Porosimeter 2000) operating at the maximum pres-
sure of 2000 bar with Hg surface tension of 480 N m 1 and a con-
tact angle of 141.3°. It is worth calling that nitrogen adsorption
and Hg porosimetry measurements were performed directly on
pieces of pellets of 0.1 and 0.2 g, respectively.
In order to estimate the organic material amounts remaining
after calcination (if present), thermal analyses were performed
using a Setaram TGA LABSYS thermal analyzer.
The elemental analyses of the solids were performed on an
X-ray fluorescence spectrometer MagiX (Philips). Prior to analyses
the powdery samples were pelletized via mechanical pressure.
Resultant pellets were analyzed under vacuum with a Rhodium
anticathode (2.4 kW).
27
Al (I = 5/2) nuclear magnetic resonance at magic angle spin-
ning (MAS-NMR) experiments were carried out on a Bruker avance
II 400 spectrometer operating at B0 = 9.4 T (Larmor frequency
m0 = 104.2 MHz). Quantitative 27Al-MAS NMR spectra were ac-
quired with p/12 pulse duration of 0.6 ls, a recycle delay of 1 s
and a frequency speed of 15 kHz. Such experimental parameters
were accepted elsewhere [27,28] to be suitable for quantitative
analyses. Spectra with high sensitivity and good signal/noise
ratio have been obtained after 800–1000 scans accumulation.
27
Al-3QMAS NMR spectra were recorded with a z-filter MQMAS
pulse sequence [29]. First and second pulse durations were
adjusted to 4.5 and 1.5 ls respectively so that the triple quantum
a b
Intensity (a.u.)
10 20 30 40
2 theta (°) / CuKα
Fig. 2. Characterization of the as-synthesized zeolite beta nanocrystals obtained at 100 °C after 7 days of hydrothermal treatment: (a) powder XRD pattern and (b) particle
size distribution obtained from DLS measurements.
159
coherence was created by radio frequency field strength of
112,500 Hz. The zero quantum coherence was converted into sin-
gle quantum coherence with a third ‘‘soft” pulse of 15 ls duration.
The spinning frequency was set to 15 kHz and rotation-synchro-
nized acquisition was used. Shearing of the 27Al-3QMAS NMR spec-
tra was performed with the program XfShear, which align the
anisotropic axis of the 2D spectra parallel to the F2 dimension.
1500 scans per slice were recorded to obtain well resolved spectra.
All, 27Al-MAS and MQMAS NMR measurements were carried out at
room temperature with [Al(NO3)3
x(H2O)] as external standard
reference.
3. Results and discussions
3.1. Characteristics of the primary zeolite beta nanocrystals
Prior to be employed in pellets preparation, zeolite beta nano-
crystals were characterized by XRD. The powder XRD pattern of
the as-synthesized sample (Fig. 2a) presents peaks characteristic
of pure zeolite beta with a broad peak in the range 6.5–8.5° 2h. This
large peak is associated to the presence of two polymorphs of zeo-
lite beta (polymorph A and B) [30,31].
Zeolite nanocrystals mean particle size and particle size distri-
bution was determined in water suspension by DLS. As can be seen,
nanocrystals have a monomodal distribution. The particle size ran-
ged from 40 to 400 nm with an average value of 100 nm (Fig. 2b).
The good crystallinity of zeolite beta nanocrystals was also con-
firmed by nitrogen adsorption measurements where micropore
volume and micropore surface area were close to those reported
in literature for pure and well crystallized zeolite beta nanocrystals
(see Table 1).
3.2. Zeolite pellets characterization
Centimeter-sized (32  2 mm) zeolite pellets were prepared by
the procedure summarized in Fig. 1. After the secondary growth
treatment and calcination steps, the pellets retained the shape
and only a slight difference in the color was observed (Fig. 3).
The latter is a consequence of carbon residue remained in the
pellets. The TG analysis showed that this carbon content did not
exceed 0.2 wt%. It should be mentioned that the calcination proce-
dure included calcinations under nitrogen flow (for 4 h) then under
air flow (for 2 h). Without applying the calcination under nitrogen
very brittle and cracked pellets were obtained.
Zeolite beta–alumina binder pellets were subjected to many
treatments such as: calcination, mechanical pressing and second-
ary growth treatment. In this respect, XRD analysis of zeolite
Intensity (a.u.)
50 0.1 1 10 100 1000 10000
Particle size (nm)
160 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166

Table 1
Nitrogen adsorption/desorption data of calcined zeolite beta nanocrystals and zeolite beta–alumina binder pellets before and after one (sample A) and two (sample B) secondary
growth treatments.

Sample SBET a Micropore surface area a

External surface area a
Micropore volume b
Mesopore volume b

(m2 g 1
) (m2 g 1) (m2 g 1) (cm3 g 1) (cm3 g 1)
Zeolitec beta nanocrystals 630 390 240 0.23 0.49
Zeolitec beta–alumina binder pellet before 400 260 140 0.14 0.32
secondary growth
Samplec A 380 290 90 0.16 0.17
Samplec B 360 330 30 0.20 0.04
a
Surface areas are calculated using the BET equation.
b
Micropore and mesopore volumes are obtained by the t-plot method.
c
Samples are calcined before analyses.

Fig. 3. Optical images of calcined zeolite beta–alumina binder pellets (A) prior to and (B) after the secondary growth treatments.

beta–alumina binder pellets prior to and after the secondary
growth treatment was necessary to study the effect of these treat-
ments on the zeolite crystallinity.
The secondary growth treatment was carried out one (sample A)
or two times (sample B). As can be seen in Table 1 after one
treatment (sample A) inter-particle porosity was still detected
(0.17 cm3 g 1). In the following discussion only the pellets
obtained after two consecutive secondary growth steps will be
considered. The XRD patterns of zeolite beta–alumina binder
pellets before (Fig. 4a) and after (Fig. 4b) the secondary growth
treatment are quite similar and present all characteristic peaks of
zeolite beta with no co-crystalline phase. However, after the
secondary growth treatment the XRD peaks are more intense
Intensity (a.u.)
revealing a higher zeolite content. These results show that the sec-
ondary growth treatment results in the formation of zeolite beta
phase and that such a treatment did not alter the crystallinity of
zeolite materials. Finally, it should be mentioned that, in both cases
(prior to and after the secondary growth treatments), compared to
the XRD pattern of the as-synthesized nanocrystals (Fig. 2a), an
increase of peaks width is observed. This enlargement can be ex-
plained by a slight decrease of nanocrystals crystallinity due to
the thermal treatment performed on the pellets during calcination.
The zeolite beta–alumina binder pellets were also subjected to
SEM analysis (Fig. 5). It is shown that the pellets are formed of
nanocrystals aggregates with many inter-particle voids. However,
after the secondary growth treatment (Fig. 5C and D), the pellets
seem to be more compact with reduced inter-particle porosity.
That could be related to the secondary growth treatment which re-
sults in the formation of new zeolite beta nanocrystals in the inter-
particle voids at the surface and the volume of the pellets.
To confirm this assumption, nitrogen adsorption/desorption
analyses were performed. Nitrogen adsorption/desorption
isotherms of zeolite beta–alumina binder pellets prior to and after

two secondary growth treatments are presented in Fig. 6 and

textural properties are summarized in Table 1. For comparison, the
textural features of sample A (obtained after only one secondary
growth treatment) are also reported in this table.
The adsorption isotherm of the calcined zeolite beta–alumina
binder pellet prior to the secondary growth treatment (Fig. 6a) pre-
b sents a hysteresis loop at P/P0 of 0.8–1, which indicates the pres-
ence of textural mesopores related to the inter-particle voids
a resulting from assembling zeolite beta nanocrystals and alumina
binder particles. Mesopore volume is close to 0.4 cm3 g 1 which
10 20 30 40 50
constitutes 80% of the total pore volume. Concerning the micropo-
2 theta / CuKα (°)
rous properties, this pellet presents micropore volume and micro-
Fig. 4. XRD patterns of calcined zeolite beta–alumina binder pellets: (a) prior to and pore surface area of 0.14 and 260 m2 g 1, respectively (see Table 1).
(b) after two secondary growth treatments. These values are less important than zeolite beta nanocrystals
 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166
Fig. 5. SEM images of zeolite beta–alumina binder pellets before (A and B) and after (C and D) two secondary growth treatments. Images (A and C) and (B and D) present
respectively top and cross section views of the pellets.
350
adsorption
Adsorbed volume (cm g ) S.T.P.
300 desorption
250
3 -1
200
150
100
50
0 penetrated into the pellet is crystallized during the secondary
0 0.2 0.4 0.6
Relative pressure (P/P0)
Fig. 6. Nitrogen adsorption/desorption isotherms of calcined zeolite beta–alumina
binder pellet (a) prior to and (b) after two secondary growth treatments.
values. Such decrease in microporosity is due to the presence of the
binder (40 wt%). In fact, the alumina binder after the calcination of
the pellet does not possess any microporosity. So, having in mind
that prior to the secondary growth treatment the crystalline zeolite
beta content in the pellet is of 60 wt% only, one could expect a de-
crease of about 40% of the micropore volume and micropore sur-
face area of this pellet compared to the primary zeolite beta
nanocrystals. Experimental data shows thus a logical trend and
indicates that the alumina binder does not block the micropores
of the zeolite beta nanocrystals in the pellet and that the decrease
of the micropore volume is only due to a less amount of zeolitic
material in this pellet. After two secondary growth treatments
(sample B), the pellet presents an isotherm of type I typical for
microporous materials. No hysteresis loop was observed at high
relative pressures which indicates the absence of inter-particle
161
mesopores. Indeed, for sample B, almost no mesopore volume
and a very low external surface area are reported in Table 1. These
a results show clearly that, during the secondary hydrothermal
treatment, the precursor solution diffuses into the pellet and fill
in the inter-particle mesopores. After heating at 100 °C for two
days, the synthesis leads to the formation of secondary intergrown
zeolite beta nanocrystals in the inter-particle voids at the surface
b
and volume of the pellet which allows the elimination of the
inter-particle mesoporosity. On the other hand, micropore volume
and surface area substantially increase after two secondary growth
treatments and reach values very close to pure zeolite beta ones. In
fact, if we consider that the entire amount of the solution
0.8 1 growth treatment, and that, as will be shown below, only 10% of
amorphous binder remains in the pellet after the two secondary
growth treatments, the micropore surface area and the micropore
volume should be about 350 and 0.2 cm3 g 1, respectively which is
the case for sample B. That confirms the total crystallization of the
secondary growth solution and indicates that the secondary hydro-
thermal treatment does not affect the textural properties of the
nanocrystals in the primary pellet.
Nitrogen adsorption/desorption analyses allowed the study of
small mesopores evolution after the secondary growth treatment.
However, in order to evaluate changes in large mesopores and
macropores ranges, Hg porosimetry measurements were necessary.
The results from these measurements (presented in Fig. 7 and
Table 2) are in agreement with the nitrogen adsorption/desorption
ones. Indeed, the total cumulative volume, representing the large
mesopores and macropores contribution, decreased from 0.5 to
0.1 cm3 g 1 after two secondary growth treatments (see Table 2).
However, from Fig. 7 the persistence of certain porosity
(0.1 cm3 g 1) is clearly evidenced. Such a result is fairly surprising
since from nitrogen adsorption/desorption measurements the
mesopore volume was close to 0.04 cm3 g 1. Therefore, pores
162 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166

18

16
Relative pore volume (%)

14

Intensity (a.u.)
12

10 * *
b
8

4 a
2 20 40 60 80 100
2 theta / CuKα (°)
0
0.001 0.01 0.1
Fig. 8. XRD patterns of aluminum binder (a) before and (b) after calcination. Peaks
Pore dimension (µm) indicated with stars are X-ray diffraction peaks of c-Al2O3 phase.

Fig. 7. Results of the mercury porosimetry analyses: figure showing the variation of
the relative pore volume at different pore size ranges of the pellets before (d) and
after (H) two secondary growth treatments. Vertical lines were added in order to
facilitate comparison at different pore size.

Table 2
Textural properties of zeolite beta–alumina binder pellets before and after two * * e
secondary growth treatments, results from mercury porosimetry analyses.

Sample Total pore Specific

volume surface area
(cm3 g 1) (m2 g 1) * *
d
Zeolite beta–alumina binder pellet before the 0.50 125
secondary growth treatment
Zeolite beta–alumina binder pellet after two 0.10 30
secondary growth treatments (sample B)
* * c

detected by mercury porosimetry analyses could be attributed to
intrusive pores resulting from samples preparation before analyses
(pellets were broken in pieces).
3.3. Effect of the binder on zeolite properties
At first, we studied the crystallinity of the aluminum binder in
the calcined pellets prior to and after the secondary growth treat-
ment. The XRD pattern of the uncalcined aluminum binder (Fig. 8a)
shows characteristic peaks of boehmite (AlOOH) phase. After
calcination, these peaks disappear and peaks of c-Al2O3 phase
(indicated by stars) appear on the XRD pattern. The intensity of
these peaks is very low suggesting that, after calcination, the major
part of AlOOH is transformed into an amorphous alumina phase
with traces of c-Al2O3 phase. Thus, the crystallinity evolution of
the binder could be summarized as following: (i) starting from
Al(OH)3 solution, evaporation at 70 °C in order to obtain powder,
leads to the transformation of Al(OH)3 to AlOOH via a dehydration
process. (ii) The AlOOH phase, after calcination of the zeolite beta–
alumina binder pellets essential prior to and after the secondary
growth treatment to eliminate the organic structure directing
agent, is transformed to mainly amorphous alumina binder. Conse-
quently, no peaks emanating from the binder are observed on the
XRD patterns of calcined zeolite beta–alumina binder pellets prior
to and after the secondary growth treatment (Fig. 4a and b). There-
fore, these patterns show only characteristic peaks of zeolite beta
with no intrusive phase.
Further characterization was made by using solid-state NMR.
The 27Al-MAS NMR of zeolite beta nanocrystals (Fig. 9a) consists
* * b
a
200 150 100 50 0 -50 -100 -150 -200
δ (ppm)
Fig. 9. 27Al-MAS NMR spectra of the following series of samples: (a) calcined zeolite
beta nanocrystals; (b) uncalcined zeolite beta–alumina binder pellet prior to the
secondary growth treatment; (c) calcined zeolite beta–alumina binder pellet prior
to the secondary growth treatment; (d) calcined zeolite beta–alumina binder pellet
after two secondary growth treatments; (e) calcined alumina binder. The reso-
nances indicated by stars are spinning side bands.
of a single sharp resonance whose chemical shift is about
50 ppm, within the range generally assigned to tetrahedral
aluminum bound to Si atoms through oxygen [32]. The latter result
is typical for zeolite beta materials with no extra-framework
aluminum Al(VI) species (or co-amorphous phase). The 27Al-MAS
NMR spectrum of the calcined alumina binder (Fig. 9e) presents
large signals at 5 and 67 ppm, respectively assigned to Al(VI) and
Al(IV) of a c-Al2O3 type component [33]. The spectra of calcined
zeolite beta–alumina binder pellets prior to and after secondary
growth (Fig. 9c and d) consist both of a resonance at 5 ppm as-
signed to Al(VI) in the alumina binder and a signal at 57 ppm with
a shoulder at 68 ppm. The width and form of this signal and the
shoulder at 68 ppm indicate the presence of two different sites of
Al(IV), which could be assigned to zeolite beta framework and
binder tetracoordinated aluminum. The comparison between the
 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166 163

a
S1

S1

200 150 100 50 0 -50 -100

δ (ppm)

b
* S2

S2

S1
S1

200 150 100 50 0 -50 -100

δ (ppm)

S2
c

S2 S1
S1

S3
S3 S3

200 150 100 50 0 -50 -100

δ (ppm)

Fig. 10. 27Al-3QMAS NMR spectra of: (a) zeolite beta nanocrystals; (b) uncalcined zeolite beta–alumina binder pellet before secondary growth; (c) calcined zeolite beta–
alumina binder pellet before secondary growth; (d) calcined zeolite beta–alumina binder pellet after two secondary growth treatments; (e) calcined Al2O3 binder;. The
spectra at the right represent the slices corresponding to each 27Al-3QMAS NMR signal. Signals S1, S2 and S3 are attributed respectively to Al(IV) in the zeolite framework,
Al(VI) and Al(IV) initially present in the alumina binder. In spectrum (b) the resonances indicated with stars are spinning side bands.
164 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166
d
S2
S1
S3
S2
S3
Fig. 10 (continued)
27
Al-MAS NMR spectra of the zeolite beta–alumina binder pellets
prior to (Fig. 9b) and after calcination (Fig. 9c) shows different
amounts of Al(VI) and Al(IV), as the amount of the latter increases
after calcination. The same trend is observed after the secondary
growth treatment and followed calcination (Fig. 9d), i.e., the
relative portion of Al(IV) increases in the composite pellets while
the relative portion of Al(VI) decreases. Therefore, as suggested in
previous studies [18,19], an amount of the aluminum issued from
the binder probably incorporates into the zeolite framework. In
order to confirm this hypothesis, to distinguish the Al(IV) species
initially present in the binder and those possibly integrated into
the zeolite framework and to follow the variation of each alumi-
num site, 27Al-3QMAS NMR experiments were performed. This
technique was fundamental to obtain comprehensive information
about the aluminum behavior during the secondary growth and
calcination steps.
The 27Al-3QMAS NMR spectra presented in Fig. 10 show
unambiguously the presence of three different signals: S1 at about
50 ppm, S2 at 5 ppm and S3 at 65 ppm attributed respectively to
Al(IV) in zeolite beta framework, Al(VI) and Al(IV) initially present
in the alumina binder. 27Al-3QMAS NMR spectra were decomposed
into slices. The chemical shift and the width of each slice has been
used to deconvolute the corresponding 27Al-MAS NMR spectra
S1
S2
200 150 100 50 0 -50 -100 -150 -200
δ (ppm)
S2
S3
200 150 100 50 0 -50 -100
δ (ppm)
[34]. These experiments allowed us to determine the relative
percentage of each aluminum site in each sample. The results are
reported in Fig. 11.
Before calcination, all the aluminum in the binder is in hexaco-
ordinated form Al(VI). After calcination, the major part of Al is still
in the form of hexacoordinated aluminum species (75%) and only
25% is in the tetracoordinated form (Fig. 11E). That explains the
high content of Al(VI) in the calcined zeolite–alumina binder pel-
lets prior to (Fig. 11C) and after (Fig. 11D) the secondary growth
treatment (58% and 46%, respectively). On the other hand, before
calcination no signal assigned to Al(IV) from the binder (no S3 sig-
nal) is observed in the 27Al-3QMAS NMR spectrum of the uncal-
cined zeolite-binder pellet prior to the secondary growth
treatment (Fig. 10b). This result is expected since the binder ini-
tially in the form of AlOOH is consisting of only hexacoordinated
aluminum species. After calcination, it is transformed to c-Al2O3
with tetra- and octahedral aluminum components. Such assign-
ments were also confirmed by XRD analyses.
Compared to the calcined zeolite beta–alumina binder pellet
before secondary growth (Fig. 10c), the calcined one after second-
ary growth presents an important increase of the Al(IV) content
in the zeolite framework (from 24% to 54%). Simultaneously,
the Al(VI) components in the binder markedly decreases (from
 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166 165

100 Al(IV) from the binder Finally, it is worth noting that after the partial incorporation of
100 aluminum from the binder into the zeolite framework, almost 10%
Al(VI)
of the binder remains as amorphous alumina component in the
Al(IV) from zeolite framework
80
pellets.
Tetra- and hexacoordinated

80 75
aluminum content (%)

58
4. Conclusions
60 54

46 Centimeter-sized zeolite beta pellets of intergrown nanocrys-

tals with textural properties close to those of zeolite single crystals
40
were prepared by a multi-step procedure. The first step includes
25
20 18
24 mixing of zeolite nanocrystals and an aluminum hydroxide binder
20 and their shaping upon mechanical pressure. This step was fol-
lowed by one or two secondary growth treatments allowing the
0 0 0 0 0 formation of zeolite beta nanocrystals in the zeolite body
0
inter-particle voids. Thus, after two secondary growth treatments,
A B C D E
Sample centimeter-sized zeolite beta–alumina binder pellets with no
inter-particle mesoporosity were obtained. Finally the pellets were
Fig. 11. AlIV and AlVI content of zeolite beta–alumina binder pellets at different subjected to high temperature calcination.
preparation steps: (A) calcined zeolite beta nanocrystals; (B) uncalcined zeolite The evolution of the binder during different stages of pellet
beta–alumina binder pellet before secondary growth; (C) calcined zeolite beta–
preparation was studied. The set of experimental results provided
alumina binder pellet before secondary growth; (D) calcined zeolite beta–alumina
binder pellet after two secondary growth treatments; and (E) calcined alumina evidences for the insertion of aluminum from the alumina binder
binder. into zeolite beta framework which increases the aluminum content
in the crystals. The resultant zeolite beta pellets displayed rela-
tively low amount of binder (10%) and no inter-particle porosity.

Table 3
X-ray fluorescence analyses data for zeolite-binder composites at different stages of
the preparation process.
Sample Moles number for
100 g of product
Na Al(total)
Uncalcined zeolite beta 0.02 0.06
nanocrystals
Calcined zeolite beta–alumina 0.10 0.36
binder pellet after two
secondary growth treatments
(sample B)
a 27
Values calculated according to the percentage of Al(IV) determined from
NMR measurements (see Fig. 11).
58% to 46%) and a very weak S3 signal (indicated by an arrow on
Fig. 10d) persists. The latter results mean that, during the
secondary growth treatment, the aluminum present in the binder
reacts with the pellet and the secondary growth solution and
partially integrates the zeolite beta framework. To a less extend,
a similar behavior seems to be observed when the pellets are
calcined before the secondary growth, the Al(IV) content in the
zeolite framework increases from 20% to 24% (compare Fig. 11B
and C). However, this variation (4%) is quite weak and is in the
range of the experimental error.
From X-ray fluorescence analyses, the Si/Al molar ratio of the
zeolite material in the pellets prior to and after the secondary
growth treatment was determined, considering only the percent-
age of Al(IV) in the zeolite framework obtained from the NMR
experiments. The results (Table 3) are consistent with the NMR
investigation and show that the Si/Al molar ratio decreases from
20 to 6 after two secondary growth treatments followed by
calcination. At the same time, the sodium content substantially
increases to counter-balance the negative charges created by the
aluminum insertion in the framework. Nevertheless, the sodium
content is lower than the Al(IV) content in the zeolite. This result
can be due to the accuracy of FX analysis and/or to the presence
of extra framework aluminum species which compensate the neg-
atively charged zeolite framework.
Acknowledgement
We express our gratitude to the ‘‘Direction Générale de
Si/Al(zeolite) l’Armement” (DGA) for financial support under contract 2007
25 042.
Si Al(IV)
zeolite
a References
1.2 0.06 20
[1] Z.A.D. Lethbridge, R.I. Walton, A. Bosak, M. Krisch, Chem. Phys. Lett. 471 (2009)
286.
1.2 0.19 6 [2] J. Sun, G. Zhu, Y. Chen, J. Li, L. Wang, Y. Peng, H. Li, S. Qiu, Microp. Mesop. Mater.
102 (2007) 242.
[3] A. Saitoh, K. Tanaka, Solid State Commun. 149 (2009) 750.
[4] P. Simoncic, T. Armbruster, Microp. Mesop. Mater. 81 (2005) 87.
[5] X. Yang, D. Albrecht, J. Caro, Microp. Mesop. Mater. 90 (2006) 53.
Al [6] S. Hashimoto, K. Samata, T. Shoji, N. Taira, T. Tomita, S. Matsuo, Microp. Mesop.
Mater. 117 (2009) 220.
[7] O. Terasaki, K. Yamazaki, J.M. Thomas, T. Ohsuna, D. Watanabe, J.V. Sanders,
J.C. Barry, Nature 330 (1987) 58.
[8] Z.A.D. Lethbridge, J.J. Williams, R.I. Walton, K.E. Evans, C.W. Smith, Microp.
Mesop. Mater. 79 (2005) 339.
[9] S. Qiu, J. Yu, G. Zhu, O. Terasaki, Y. Nozue, W. Pang, R. Xu, Microp. Mesop.
Mater. 21 (1998) 245.
[10] D. Breck (Ed.), Zeolite Molecular Sieves, John and Son, New York, 1974, p. 725
(Chapter IX).
[11] V.R. Choudhary, P. Devadas, A.K. Kinage, M. Guisnet, Appl. Catal. A: General
162 (1997) 223.
[12] P. Canizares, A. Duran, F. Dorado, M. Carmona, Appl. Clay Sci. 16 (2000) 273.
[13] F. Dorado, R. Romero, P. Canizares, Ind. Eng. Chem. Res. 40 (2001) 3428.
[14] F. Dorado, R. Romero, P. Canizares, Appl. Catal. A: General 236 (2002) 235.
[15] V.R. Choudhary, A.K. Kinage, C. Sivadinarayana, P. Devadas, S.D. Sansare,
M. Guisnet, J. Catal. 158 (1996) 34.
[16] V.R. Choudhary, P. Devadas, A.K. Kinage, C. Sivadinarayana, M. Guisnet, J. Catal.
158 (1996) 537.
[17] J.M. Fougerit, N.S. Hugues, Zeolites and Related Microporous Materials: State
of the Art 1994, in: J. Weitkamp, H.G. Karge, H. Pfeifer, W. Hölderich (Eds.),
Proceedings of the 10th International Zeolite Conference, Germany, 1994,
Stud. Surf. Sci. Catal. 84 (1994) 1723.
[18] D.S. Shihabi, W.E. Garwood, P. Chu, J.M. Miale, R.M. Lago, C.T.W. Chu,
C.D. Chang, J. Catal. 93 (1985) 471.
[19] N. Kubicek, F. Vaudry, B.H. Hudec, F. Di Renzo, P. Schulz, F. Fajula, Appl. Catal.
A: General 175 (1998) 159.
[20] L. Toshiva, M. Holzl, T.H. Metzger, V. Valtchev, S. Mintova, T. Bein, Mater. Sci.
Eng. C 25 (2005) 570.
[21] Z. Huang, J.-F. Su, Y.-H. Guo, X.-Q. Su, L.-J. Teng, Chem. Eng. Commun. 196
(2009) 969.
[22] E.G. Derouane, I. Schmidt, H. Lachas, C.J.H. Christensen, Catal. Lett. 95 (2004) 13.
[23] G. Wine, J.P. Tessonier, S. Rigolet, C. Marichal, M.J. Ledoux, C. Pham-Huu, J. Mol.
Catal. A: Chem. 248 (2006) 113.
[24] A. Corma, L.T. Nemeth, M. Renz, S. Valencia, Nature 412 (2001) 423.
[25] Y. Bouizi, I. Diaz, L. Rouleau, V. Valtchev, Adv. Funct. Mater. 15 (2005) 1955.
166 L. Itani et al. / Microporous and Mesoporous Materials 138 (2011) 157–166

[26] S. Mintova, V. Valtchev, T. Onfroy, C. Marichal, H. Knözinger, T. Bein, Microp.
Mesop. Mater. 90 (2006) 237.
[27] D. Massiot, C. Bessada, J.P. Coutures, F. Taulelle, J. Magn. Reson. 90 (1990) 231.
[28] A. Samoson, E. Lippmaa, Phys. Rev. B 28 (1983) 6567.
[29] J.P. Amoureux, C. Fernandez, S. Steuernagel, J. Magn. Reson. A 123 (1996) 116.
[30] B.W. Lu, H. Jon, T. Kanai, Y. Oumi, K. Itabashi, T. Sano, J. Mater. Sci. 41 (2006)
1861.
[31] I. Schmidt, C. Madsen, C.J.H. Jacobsen, Inorg. Chem. 39 (2000) 2279.
[32] G. Engelhardt, D. Michel (Eds.), High-Resolution Solid-State NMR of Silicates
and Zeolites, John Wiley and Sons, 1987 (p. 106, Chapter IV).
[33] C.D. Chang, C.T.W. Chu, J.N. Miale, R.F. Bridger, R.B. Calvert, J. Am. Chem. Soc.
106 (1984) 8143.
[34] D. Massiot, F. Fayon, M. Capron, I. King, S. Le Calvé, B. Alonso, J.O. Durand, B.
Bujoli, Z. Gan, G. Hoatson, Magn. Reson. Chem. 40 (2002) 70.