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"Molecules in Confined Spaces: The Interplay between Spectroscopy and Theory to develop
Structure-Activity Relationships in the fields of Heterogeneous Catalysis, Sorption, Sensing and
Separation Technology"
Guest Editor: Bert Weckhuysen
Editorial Highlight
Editorial Highlight: Molecules in confined spaces
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DOI: 10.1039/b905015a
Perspectives
Nanoporous oxidic solids: the confluence of
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John Meurig Thomas, Juan Carlos Hernandez-Garrido,
Robert Raja and Robert G. Bell, Phys. Chem. Chem. Phys.,
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Supported vanadium oxide in heterogeneous catalysis:
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Correlating phase behaviour and diffusion in
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gradient NMR
Rustem Valiullin, Jörg Kärger and Roger Gläser, Phys.
Chem. Chem. Phys., 2009
DOI: 10.1039/b822939b
Communications
Viscosity sensing in heated alkaline zeolite synthesis
media
Lana R. A. Follens, Erwin K. Reichel, Christian Riesch, Jan
Vermant, Johan A. Martens, Christine E. A. Kirschhock and
Bernhard Jakoby, Phys. Chem. Chem. Phys., 2009
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A small molecule in metal cluster cages: H2@Mgn (n = 8 to
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Phys., 2009
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Papers
Confinement effects on excitation energies and
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Alex Borgoo, David J. Tozer, Paul Geerlings and Frank De
Proft, Phys. Chem. Chem. Phys., 2009
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Rotation dynamics of 2-methyl butane and n-pentane in
MCM-22 zeolite: a molecular dynamics simulation study
Shiping Huang, Vincent Finsy, Jeroen Persoons, Mark T.F.
Telling, Gino V. Baron and Joeri F.M. Denayer, Phys. Chem.
Chem. Phys., 2009
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Reactivity in the confined spaces of zeolites: the interplay
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Mercedes Boronat, Patricia Concepción, Avelino Corma, María
Teresa Navarro, Michael Renz and Susana Valencia, Phys.
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The influence of the chemical compression on the electric
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Anna Kaczmarek and Wojciech Bartkowiak, Phys. Chem.
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Multinuclear gallium-oxide cations in high-silica zeolites
Evgeny A. Pidko, Rutger A. van Santen and Emiel J. M.
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Metal–organic frameworks as high-potential adsorbents
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2009
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Tetramethyl ammonium as masking agent for molecular
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Kun Zhang, Belén Albela, Ming-Yuan He, Yimeng Wang and
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Photovoltaic activity of layered zirconium phosphates
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The characterisation and catalytic properties of
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Bart A. De Moor, Marie-Françoise Reyniers and Guy B. Marin,
Phys. Chem. Chem. Phys., 2009
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Accelerated generation of intracrystalline mesoporosity in
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Sònia Abelló and Javier Pérez-Ramírez, Phys. Chem. Chem.
Phys., 2009
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 PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics

Accelerated generation of intracrystalline mesoporosity in zeolites

by microwave-mediated desilication
Sònia Abellóa and Javier Pérez-Ramı́rez*ab
Published on 27 February 2009. Downloaded by McMaster University on 28/08/2015 14:17:29.

Received 5th November 2008, Accepted 4th February 2009

First published as an Advance Article on the web 27th February 2009
DOI: 10.1039/b819543a

Microwave-mediated desilication was successfully used to fabricate hierarchically structured

zeolites combining micro- and mesoporosity. The application of microwave radiation
during alkaline treatment of commercial ZSM-5 samples in aqueous NaOH solution at
338 K spectacularly accelerates the development of intracrystalline mesoporosity compared
to the standard treatment (conventional heating). This is attributed to the more efficient transfer
of thermal heating to the zeolite solution, thus enhancing the rate of silicon extraction. Very
short exposure times (3–5 min) resulted in hierarchical zeolites with mesopore surface areas
up to 230 m2 g 1 and pores centred around 10 nm, while preserving the crystallinity of the
parent sample. The benefits of this treatment can be extrapolated to other zeolite
structures.

Introduction selective extraction of silicon in an alkaline medium (typically

Zeolites are a unique class of crystalline aluminosilicates with
very high surface areas, being a consequence of ordered
micropores of molecular dimensions (typically 0.25–1 nm)
that enable shape-selective transformations.1 However, the
sole presence of micropores often imposes diffusion limita-
tions, which largely limit the activity, and occasionally also the
selectivity and lifetime, of the zeolite. In exceptional cases,
though, diffusion constraints can be used to the benefit of the
catalytic process, for example to enhance the selectivity of
p-xylene in toluene alkylation over ZSM-5.2 Intensive
synthetic efforts have resulted in an assorted variety of new
or modified zeolites with improved accessibility and molecular
transport.3 Two fundamentally different approaches can be
adopted: (i) increasing the effective diffusivity by enlarging the
width of the micropores4 or (ii) shortening the micropore
diffusion path length by the manufacture of hierarchically
structured zeolites in the form of nanocrystals,5 nanosheets,6
composites,7 and mesoporous crystals.8 Hierarchical zeolites
couple in a single material the unique catalytic features of
micropores with the facilitated transport consequence of a
complementary mesopore network of inter- or intracrystalline
nature.3
The main short-term need in industry is having suitable
methods that can be economically realised on a multi-ton
scale, with the potential of enhancing the performance of
commercial off-the-shelf zeolites. Our efforts in this topic have
focused on desilication, which can be categorised as a
top-down non-templating demetallation method.3,9 The
a
Institute of Chemical Research of Catalonia (ICIQ),
Avinguda Paı¨sos Catalans 16, Tarragona, 43007, Spain.
E-mail: jperez@iciq.es; Fax: +34 (0)977 920 224;
Tel: +34 (0)977 920 236
b
Catalan Institution for Research and Advanced Studies (ICREA),
Passeig Lluı´s Companys 23, Barcelona, 08010, Spain
NaOH) is an effective, versatile, and simple treatment to create
accessible mesoporosity in zeolites such as MFI,10 MTW,11
MOR,12 BEA,13 AST,14 and FER.15 The improved molecular
transport11,16,17 and catalytic performance12,18–24 of alkaline-
treated zeolites compared to the parent purely-microporous
counterparts have been demonstrated decidedly. Based on
manifold successful applications, we continue the exploration
of novel or modified desilication treatments towards mesoporous
zeolites.
The microwave-mediated synthesis of zeolites has extensively
been researched for more than 15 years. The reported benefits of
microwave heating compared to conventional heating are
(i) much shorter crystallisation times25,26 and (ii) better control
of particle size distribution and morphology.27 This is typically
related to the rapid and uniform heat-up time induced by the
microwave radiation and its selective interaction with certain
reagents or solvents.25–28 The application of microwaves in post-
synthesis treatments aiming at porosity development in crystal-
lised zeolites is scarce in comparison to its frequent use in
synthesis.29–32 Exceptionally, Pavel and Schmidt33 obtained a
hierarchical titanosilicate ETS-10 zeolite, possessing the native
micropores (0.7 nm), newly created supermicropores (0.85 nm),
and intracrystalline mesopores (10 nm) by microwave-assisted
detitanation in H2O2 solutions at 353 K for 15 min. The same
treatment without microwaves induced no mesoporosity.34
Herein we have studied for the first time the effect of
microwave heating on the alkaline treatment of zeolites for
mesoporosity generation. It was found that microwaves
greatly accelerate the development of intracrystalline meso-
porosity by selective silicon extraction in commercial ZSM-5
zeolites compared to the standard treatment. The amount and
size of the mesopores formed under optimal conditions were
very similar for both treatment variants. The benefit of
microwaves associated with faster mesopore formation applies
to other zeolite topologies.

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c the Owner Societies 2009 Phys. Chem. Chem. Phys., 2009, 11, 2959–2963 | 2959
 Experimental
Materials and treatments
The ZSM-5 zeolites used in this study were purchased from
Zeolyst International: CBV 8014 (NH4-form, Si/Al = 40) and
CBV 8020 (NH4-form, Si/Al = 37). Prior to any treatment, the
Published on 27 February 2009. Downloaded by McMaster University on 28/08/2015 14:17:29.
as-received powders were calcined in static air at 823 K for 5 h at
5 K min 1. These samples are hereafter denoted as parent (P).
Standard alkaline treatments were carried out in a 16-parallel
reactor system (MultiMax, Mettler Toledo) and microwave-
assisted alkaline treatments were performed in a CEM Explorer
single-mode microwave reactor with a maximum power output
of 300 W. In both cases, the reactor tubes were filled with 5 cm3
of 0.2 M NaOH aqueous solution, sealed, and introduced in the
reactor block at 338 K. In the microwave reactor, the solution
was heated by 150 W microwave power. Temperature was
monitored by a vertically-focused IR sensor located at the
bottom of the microwave cavity hosting the reactor, and
controlled by automated power adjustment based on tempera-
ture feedback and air cooling. Once the temperature was
stabilised, the zeolite sample (166 mg) was added to the reactors
and stirred during different times (3–30 min). After the alkaline
treatments, the zeolite suspensions were quenched in an
ice–water mixture and filtered. The resulting solids were washed
with distilled water until pH neutral, dried at 373 K for 12 h,
and finally calcined in static air at 823 K for 5 h at 5 K min 1.
The codes of the samples were AT-x (standard alkaline
treatment) and AT-MW-x (microwave-mediated alkaline
treatment), in which x denotes the treatment time in min.
Techniques
Si and Al concentrations in the solids were determined by
inductively coupled plasma–optical emission spectroscopy
(ICP–OES) (Perkin-Elmer Optima 3200RL). Powder X-ray
diffraction (XRD) patterns were measured in a Siemens D5000
diffractometer with Bragg–Brentano geometry and Ni-filtered
Cu-Ka radiation (l = 0.1541 nm). Data were typically recorded
in the range 5–551 2y with an angular step size of 0.051 and a
counting time of 8 s per step. Nitrogen isotherms at 77 K were
measured in a Quantachrome Quadrasorb-SI gas adsorption
analyser. Prior to the measurement, the samples were degassed
in vacuum at 623 K for 12 h. The BET method35 was applied to
calculate the total surface area, which is used for comparative
purposes. The t-plot method36 was used to discriminate between
micro- and mesoporosity. The mesopore size distribution was
obtained by the BJH model37 applied to the adsorption branch of
the isotherm. Scanning electron microscopy (SEM) was carried
out in a JEOL JSM-6400 microscope. Transmission electron
microscopy (TEM) was carried out in a JEOL JEM-1011
microscope operated at 100 kV and equipped with a SIS
Megaview III CCD camera. A few droplets of the sample
suspended in ethanol were placed on a carbon-coated copper
grid followed by evaporation at ambient conditions.
Results and discussion
The molar Si/Al ratios in the parent CBV 8014 (Z1) and CBV
8020 (Z2) were 42 and 37, respectively (Table 1). These values
2960 | Phys. Chem. Chem. Phys., 2009, 11, 2959–2963
fall in the optimal Si/Al range for mesoporosity development
by NaOH treatment.38 Both samples showed the typical X-ray
diffraction pattern of the MFI structure. The N2 isotherms of
the parent zeolites exhibited a high uptake at low relative
pressure that confirmed their microporous character (Fig. 1).
The micropore volume (Vmicro = 0.17 cm3 g 1) is charac-
teristic of ZSM-5. The mesopore surface area (Smeso = 58 m2 g 1
in Z1 and 40 m2 g 1 in Z2) results from the crystals’ external
surface, the surface roughness of the individual crystals, and the
intercrystalline porosity derived from the aggregated nano-
crystals o1 mm (determined by SEM, not shown).
The parent zeolites were subjected to the standard alkaline
treatment in 0.2 M NaOH at 338 K for 30 min (AT-30 in
Table 1). In agreement with previous results,9,10 the mesopore
surface areas increased from 58 m2 g 1 in Z1 and 40 m2 g 1 in
Z2 to 208 and 225 m2 g 1, respectively. Concomitantly, the
micropore volume of the alkaline-treated samples decreased
and the total pore volume increased. Due to the selective
extraction of silicon by the NaOH solution, the molar Si/Al
ratio in the zeolites decreased from 42 to 26 in Z1 and from 37
to 24 in Z2. However, as reported elsewhere,9,10 the original
crystallinity of the zeolites was not altered based on X-ray
diffraction.
The influence of using microwaves during desilication was
studied over the two zeolites keeping the same NaOH
concentration and temperature as in the standard treatment and
varying the treatment time between 3 and 30 min. As shown in
Table 1, the microwave-mediated alkaline treatments created
substantial mesoporosity. The N2 isotherms of the alkaline-
treated zeolites were characteristic of hierarchical porous
systems combining micro- and mesoporosity, irrespective of
the treatment time. Fig. 1 shows representative isotherms of
desilicated samples in the presence of microwaves. The corres-
ponding isotherms exhibited an enhanced uptake at intermediate
and high pressures and a distinct H3 hysteresis. The largely
parallel progressing of the adsorption and desorption
branches of the hysteresis loops, without a forced closure of
the desorption branch at p/p0 B 0.45, suggests the presence of
accessible mesopores connected to the outer surface.39 Very
similar isotherms were obtained upon standard alkaline treat-
ment of the samples during 30 min. The molar Si/Al ratio and
micropore volume in the microwave-treated zeolites decreased
to equivalent values as in the conventionally treated zeolites.
The major difference between the standard and the micro-
wave-mediated NaOH treatment is that the development of
mesoporosity is much faster in the latter case. This can be
visualised in Fig. 2, in which the Smeso versus time dependences
with and without microwave radiation are shown. We have
previously determined that the majority of the mesoporosity
development in ZSM-5 under conventional heating is developed
in the first 15 min of the treatment.40 In addition, it was shown
that the Smeso goes through an optimum at 30 min and finally
decreases upon increasing the treatment time. This volcano-type
dependence was related to the existence of an optimum degree
of silicon extraction toward distinct mesoporosity development;
a short treatment time induces a low degree of mesoporosity.
On the other hand, long treatment times lead to a decline in
mesopore surface area due to formation of larger pores caused
by the excessive silicon leaching.
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c the Owner Societies 2009
 Table 1 Chemical composition and textural properties of the parent and alkaline-treated (0.2 M NaOH, 338 K) zeolites

Si/Ala/ Vpore/ Vmicrob/ Smesob/ SBETc/

1
Series Sample mol mol cm3 g 1
cm3 g 1 m2 g 1 m2 g 1
Z1 P 42 0.28 0.17 58 449
AT-30 26 0.50 0.10 208 461
AT-MW-3 28 0.52 0.13 156 463
AT-MW-5 26 0.53 0.10 212 471
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AT-MW-15 26 0.63 0.10 224 452

AT-MW-30 26 0.55 0.12 141 427
Z2 P 37 0.26 0.17 40 430
AT-30 24 0.53 0.13 225 450
AT-MW-3 24 0.50 0.11 230 492
AT-MW-5 24 0.49 0.12 204 500
AT-MW-15 23 0.56 0.13 196 502
AT-MW-30 23 0.57 0.13 166 471
a b
ICP–OES. t-Plot method. c BET method.

created mesoporosity at the optimal times of the conventional

(30 min) and microwave-assisted (3 min) treatments practi-
cally coincides. Powder X-ray diffraction confirmed that the
fingerprint of the zeolite structure was maintained in all
samples irrespective of the treatment time during microwave-
assisted desilication (Fig. 3). The reflections of the microwave-
treated zeolites presented a slight shift to lower 2y values,
suggesting a somewhat larger unit cell. This is probably related
to the change in framework composition (lower Si/Al ratios)
due to the selective silicon extraction. As expected, the
mesoporosity in the desilicated zeolites is not regular, as no
reflections at 2y o 51 characteristic of ordered mesoporous
silica-based materials were identified.
Fig. 1 Nitrogen isotherms of the parent (open symbols) and alkaline-
The results in Table 1 and Fig. 2 unequivocally show that
treated (solid symbols) ZSM-5 samples.
the development of mesoporosity by selective silicon extrac-
tion is accelerated upon exposure to microwave radiation. In
conventional heating, reactions can be strongly influenced by
the rate of heat transfer through the walls of the containing
vessel and the resulting thermal gradients across the reaction
volume. These limitations are overcome when microwave
heating is applied.41 A variety of thermal effects, including
direct and uniform bulk superheating and differential heating
between the solid and the solution are present in microwave-
mediated alkaline treatments as compared to the convention-
ally heated treatment.25,26 The zeolite behaves as a microwave
absorber as it takes up the energy from the microwave field

Fig. 2 Mesopore surface area versus time upon alkaline treatment of

Z2 zeolite by microwaves (solid symbols) or conventional heating40
(open symbols). Conditions: 0.2 M NaOH and 338 K.

Both standard and microwave-assisted alkaline treatments

display an optimal time to maximise mesopore formation of
the ZSM-5 samples. However, the volcano curve in the
presence of microwaves is shifted to much shorter treatment
times as compared to that obtained by conventional heating.
The mesopore surface area of Z2 increases up to 230 m2 g 1
after a 3 min microwave treatment, with the concomitant
decrease in micropore volume to 0.13 cm3 g 1 (Table 1).
Longer treatments induce a general decrease in Smeso, reaching
165 m2 g 1 after a 30 min microwave treatment. The same Fig. 3 X-Ray diffraction patterns of the parent and alkaline-treated
pattern applies to Z1 (see Table 1). Interestingly, the newly ZSM-5 zeolites (Z1 series).

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c the Owner Societies 2009 Phys. Chem. Chem. Phys., 2009, 11, 2959–2963 | 2961
 and gets heated up very rapidly.27 As a consequence, the rate
of silicon extraction towards mesopore generation is greatly
enhanced. Besides, in reacting systems containing ionic species
like NaOH, the energy could also be dissipated through
ionic conduction,28 thus undergoing unforeseen increases in
temperature and pressure that might further contribute to a
more rapid desilication process.
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The differences in mesoporosity development observed in

Fig. 2 are confirmed by the BJH adsorption pore-size distribu-
tions (Fig. 4). Short microwave irradiation times (5 min in Z1
or 3 min in Z2) during alkaline treatment show the formation
of mesopores with a slightly broader pore-size distribution
centred at ca. 10 nm. Similar distributions were obtained in the
conventionally treated samples (AT-30). Although the
acceleration of mesoporosity formation by microwave heating
could be a priori expected, it is less evident to anticipate that
the dissolution can be controlled to obtain defined intra-
crystalline mesopores. In fact, the amount and characteristics
of the mesopores (in terms of size and accessibility) are not
significantly influenced by this treatment variant. The lower
degree of mesoporosity attained at longer microwave treat-
ment times agrees with the broadening of the BJH mesopore
size distribution, thus leading to the formation of larger pores
(420 nm). These pores contribute to the increased total pore
volume but to a lesser extent to the mesopore surface area.
The large amount of intracrystalline mesoporosity gener-
ated and the uniform size concluded by nitrogen adsorption
are substantiated by transmission electron microscopy (Fig. 5).
The alkaline-treated samples exhibit the presence of perforated
crystals due to Si extraction as compared to the solid dense
crystals of the purely microporous parent sample. The size of
the intracrystalline mesopores in the range of 8–12 nm in
AT-MW-5 is in excellent correspondence with the mesopore
size distribution. Larger pores (430 nm) can be visualised in
AT-MW-30.
Based on the results over MFI, it can be anticipated that the
microwave-mediated desilication can accelerate mesoporosity
development when applied to other zeolite topologies,
e.g. MTW, MOR, BEA, and FER. This strategy is particularly
advantageous for structures requiring severe conditions (long
Fig. 5 Transmission electron micrographs of the parent and selected
treatment times and high temperatures) such as ferrierite.15,42
alkaline-treated ZSM-5 zeolites (Z1 series). The scale bar applies to all
the samples.

For example, the Smeso of a commercial ferrierite (Zeolyst,

CP 914, Si/Al = 27.5) is 28 m2 g 1, and was increased to 90 m2 g 1
after alkaline treatment in 0.2 M NaOH at 353 K for 9 h. The
same degree of mesoporosity was obtained in only 2 h after
treatment in microwaves. Obviously, optimisation of the
treatment conditions in the microwave-assisted desilication
for each specific zeolite is required.

Fig. 4 BJH adsorption pore size distributions of the parent and
alkaline-treated ZSM-5 samples. The labels of the PSDs in Z1 and
Z2 are the same.
Conclusions
Microwave irradiation accelerates the generation of defined
intracrystalline mesopores in ZSM-5 zeolite by desilication in
NaOH solutions compared to the standard treatment by
conventional heating. Microwave treatments of 3–5 min at
338 K resulted in hierarchically structured zeolites with Smeso

2962 | Phys. Chem. Chem. Phys., 2009, 11, 2959–2963 This journal is

c the Owner Societies 2009
 up to 230 m2 g 1 and pores centred around 10 nm, while
preserving the crystallinity of the parent sample. The beneficial
effect of microwaves is attributed to the more efficient transfer
of thermal heating to the zeolite solution, thus enhancing the
rate of silicon extraction towards mesopore formation. The
type of mesopores generated under optimal conditions was
equivalent for both treatment variants. These results have
Published on 27 February 2009. Downloaded by McMaster University on 28/08/2015 14:17:29.
practical implications as the generation of hierarchical zeolites
can be greatly accelerated by microwave-assisted desilication
treatments. This treatment has prospective applications to
other zeolite families. Preliminary microwave treatments of
ferrierite also indicated substantial shortening of the required
time for mesoporosity development.
Acknowledgements
This research was supported by the Spanish MEC
(CTQ2006-01562/PPQ, PTQ05-01-00980, and Consolider-
Ingenio 2010 CSD2006-0003) and the ICIQ Foundation.
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