Applied Catalysis A: General 364 (2009) 191–198

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Applied Catalysis A: General

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

Mesoporous ZSM-5 zeolite catalysts prepared by desilication with organic

hydroxides and comparison with NaOH leaching
Sònia Abelló a, Adriana Bonilla a, Javier Pérez-Ramı́rez a,b,*
a
Institute of Chemical Research of Catalonia (ICIQ), Avinguda Paı̈sos Catalans 16, 43007, Tarragona, Spain
b
Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluı´s Companys 23, 08010, Barcelona, Spain

A R T I C L E I N F O A B S T R A C T

Article history: Hierarchical zeolites combining micro- and mesoporosity were prepared by desilication of ZSM-5 (Si/
Received 27 March 2009 Al = 42) in aqueous solutions of tetraalkylammonium hydroxides (TPAOH, TBAOH). Similarities between
Received in revised form 27 May 2009 the treatment mediated by organic hydroxides and the conventional NaOH leaching comprised (i) the
Accepted 27 May 2009
requirement to work with a starting zeolite in the optimal Si/Al window of 25–50 and (ii) the minor
Available online 6 June 2009
influence of the counter-cation (H+, NH4+, Na+) on the degree of mesoporosity developed. However, both
desilication media presented distinctive kinetic and mechanistic characteristics. The use of organic
Keywords:
hydroxides directly produced the protonic form of the mesoporous zeolite upon calcination, simplifying
Hierarchical zeolites
the final ion exchange with NH4NO3 characteristic of the NaOH treatment. Silicon dissolution in TPAOH
Mesoporous ZSM-5
Desilication (or TBAOH) was much slower than in NaOH, making the demetallation process highly controllable. The
Organic base treatment in the organic base was less selective for silicon extraction, i.e. a higher amount of aluminum
Tetraalkylammonium hydroxide was leached to the solution compared to the NaOH treatment. The differences in porosity development
NaOH and chemical composition of the final solid can be assigned to the effect of the bulky
Benzene alkylation tetraalkylammonium cation. The optimal hierarchical ZSM-5 zeolite (treated in 1 M TPAOH at 338 K
and 8 h) had a mesopore surface area of 160 m2 g 1 and the intrinsic zeolite properties were largely
preserved. This sample displayed improved catalytic performance in the liquid-phase benzene
alkylation with ethylene compared to the parent and NaOH-treated zeolites.
ß 2009 Elsevier B.V. All rights reserved.

1. Introduction typically assigned to the shortened micropore diffusion path

Catalytic cracking, alkylation, and isomerization are well-
established processes in industry making use of the unique
advantages of zeolites [1]. However, the microporous nature of
these solid acids imposes diffusion limitations in reactions
involving bulky hydrocarbons. Mass-transfer constraints limit
the catalytic activity and occasionally also the selectivity and
lifetime. A representative example is the liquid-phase alkylation of
benzene with ethylene over conventional ZSM-5 [2], which shows
poor activity, relatively low ethylbenzene selectivity, and fast
deactivation due to formation of polyethylbenzenes. In such cases,
it is convenient to increase the accessibility and molecular
transport to/from the active sites in zeolites to reach their full
catalytic potential. Hierarchical zeolites have emerged as an
important class of materials leading to improved catalytic
performance compared to their microporous parents [3]. This is
* Corresponding author at: Institute of Chemical Research of Catalonia (ICIQ),
Avinguda Paı̈sos Catalans 16, 43007, Tarragona, Spain. Tel.: +34 977 920 236;
fax: +34 977 920 224.
E-mail address: jperez@iciq.es (J. Pérez-Ramı́rez).
length as a result of a secondary mesopore network of inter- or
intracrystalline nature.
The selective extraction of framework silicon by treatment in
alkaline solutions, referred to as desilication or base leaching, is
now a widely used top-down method to prepare hierarchical
porous zeolites [4–8]. The controlled leaching of Si by OH forms
intracrystalline mesopores, which facilitate the access and
diffusion of molecules in the zeolite [9–11]. This modification
brings important benefits in catalysis associated with higher
activity, selectivity, and/or lifetime [3,11–19]. Strong inorganic
bases (namely NaOH but also KOH and LiOH) have been
successfully used to introduce extra mesoporosity in ZSM-5
[20]. The treatment yields a hierarchical zeolite in the alkaline
form due to ion exchange of NH4+ or H+ in the starting zeolite with
excess Na+, K+, or Li+ in the alkaline solution. Consequently, an
additional ion exchange with NH4NO3 followed by calcination is
required in order to have the mesoporous zeolite in the often
desired protonic form. In addition, using NaOH, most of the
mesoporosity is developed in the first 15 min of the treatment
[5,20]. The fast kinetics of silicon dissolution sometimes offers
limited opportunities to precisely control the process of
mesopore formation. A recent strategy to tailor the degree of

0926-860X/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.05.055
192 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198
mesoporosity comprises NaOH treatment of partially detem-
plated zeolites [21]. The template-containing regions in the
crystal are far less prone to desilication than template-free
regions. Accordingly, the template content basically determines
the volume of attackable zeolite by NaOH and therefore the
amount of extra-mesoporosity.
The use of strong organic bases as the desilicating agent, such
as quaternary ammonium hydroxides, can simplify the final ion-
exchange step intrinsic of the inorganic hydroxides. The organic
cation can be decomposed by calcination, rendering the zeolite
in its protonic form. This has been shown by Holm et al. [22],
who carried out the one-step desilication and ion exchange of
microporous Na-beta zeolite to mesoporous H-beta zeolite using
tetramethylammonium hydroxide (TMAOH). These authors
reported that mesopore formation in TMAOH requires longer
times and higher temperatures than in NaOH, and hypothesized
that TMA+ is able to stabilize the zeolite structure during
desilication. Surprisingly, no mesopores were formed when the
starting zeolite was in the protonic form. Besides, the catalytic
performance of the TMAOH-treated beta was not evaluated and
compared with the parent and NaOH-treated counterparts.
Deeper insights into the mechanism and kinetics of the
desilication process mediated by organic hydroxides are required.
Herein we have prepared mesoporous H-ZSM-5 by desilication in
aqueous solutions of tetrapropylammonium or tetrabutylammo-
nium hydroxides. The influence of temperature and time on the
chemical composition, porosity, morphology, and acidity of the
resulting zeolites has been investigated and complemented by
catalytic tests in the liquid-phase benzene alkylation. Zeolites with
different Si/Al ratio (17, 42, and 176) and form (H+, NH4+, Na+) were
used as starting materials. Analogies and differences between
desilication in tetraalkylammonium hydroxides and sodium
hydroxide have been drawn.
2. Experimental
2.1. Parent zeolites and treatments
A commercial ZSM-5 zeolite with Si/Al ratio of 42 (CBV 8014,
Zeolyst, NH4-form) was primarily used in this study, although
ZSM-5 samples with Si/Al ratios of 17 (CBV-3024E, Zeolyst, NH4-
form) and 176 (PZ 2/40, Chemie Uetikon, NH4-form) were also
employed. The as-received zeolites were typically calcined in static
air at 823 K for 5 h using a heating rate of 5 K min 1. These
conditions were identical in subsequent calcinations. Occasionally,
the as-received samples were brought into the sodium form via
three consecutive exchanges in 0.1 M NaNO3 followed by
calcination.
Alkaline treatments were carried out in a MultiMax parallel
reactor system from Mettler Toledo. The reactors were filled with
5 cm3 of 1 M aqueous solutions of tetrapropylammonium hydro-
xide (TPAOH) or tetrabutylammonium hydroxide (TBAOH),
sealed, and introduced in the reactor block at 338 or 358 K. The
zeolite powder (166 mg) was added to each reactor and stirred
magnetically at 500 rpm for periods ranging from 30 min to 8 h.
Afterwards, the zeolite suspension was quenched by immersion of
the reactor in an ice–water mixture and filtered. The resulting
solid was washed with distilled water until pH neutral, dried at
373 K for 12 h, and calcined as described above. For comparative
purposes, the parent zeolite was also treated in sodium hydroxide
using standard conditions (0.2 M NaOH, 338 K, and 30 min) [5],
brought into the ammonium form via three consecutive
exchanges in 0.1 M NH4NO3, and calcined. The notation used
along the manuscript was P for the parent zeolite, OT for the
zeolites treated in organic hydroxides, and AT for the reference
NaOH-treated zeolite.
2.2. Characterization methods
The content of silicon and aluminum in the solids and filtrates
was determined by inductively coupled plasma-optical emission
spectroscopy (ICP-OES) (PerkinElmer Optima 3200RL (radial)).
Powder X-ray diffraction (XRD) patterns were acquired in a
Bruker AXS D8 Advance diffractometer equipped with a Cu tube, a
Ge(1 1 1) incident beam monochromator (l = 0.1541 nm), and a
Vantec-1 PSD. Data were recorded in the range of 5–508 2u with an
angular step size of 0.0168 and a counting time of 6 s per step.
N2 isotherms at 77 K were measured in a Quantachrome
Quadrasorb-SI gas adsorption analyzer. Prior to the measurement,
the samples were degassed in vacuum at 573 K for 12 h. The t-plot
method was used to discriminate between micro- and mesopor-
osity [23]. The mesopore size distribution was obtained by the BJH
model applied to the adsorption branch of the isotherm [24].
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 drops of the sample suspended
in methanol were placed on a carbon-coated copper grid followed
by evaporation at ambient conditions.
Fourier transform infrared spectroscopy (FTIR) was carried out
at 723 K in a Nicolet Magna 550 spectrometer. Prior to the
measurements, the catalysts were pressed in self-supporting discs
(diameter: 1.6 cm, 7 mg cm 2) and pretreated in the IR cell
attached to a vacuum line at 723 K for 4 h up to 10 6 Torr. Spectra
were recorded in the range 1800–4000 cm 1 by co-addition of 64
scans and with a nominal resolution of 2 cm 1. All spectra were
normalized to 10 mg wafers.
The heat profiles upon contacting aqueous solutions of TPAOH
(1 M) and NaOH (0.2 M) with the parent zeolite were determined
in a SuperCRCTM microcalorimeter from Omnicaltech. The zeolite
(ca. 100 mg) was introduced in a glass vial sealed with a septum
and located inside a Teflon reactor. The reactor was heated to 338 K
and allowed to stabilize. Thereafter, a volume of the alkaline
solution (3 cm3) was dosed by means of a syringe. Simultaneously,
the same volume of distilled water was added to the reference vial
containing 100 mg of zeolite. Both vials were stirred magnetically
and the heat flow was recorded at intervals of 3 s during 30–
60 min. The enthalpy per gram of zeolite was determined by
integration of the heat flow versus time profiles.
2.3. Alkylation tests
The zeolites were tested in the liquid-phase alkylation of
benzene with ethylene in a 500 cm3 commercial titanium batch
autoclave (Premex). First, 200 cm3 of benzene were introduced in
the reactor with approximately 100 mg of powdered catalyst that
was previously pretreated at 573 K in He for 12 h to remove
moisture. After purging with N2, the reactor was heated to 438 K
under mechanical stirring (1000 rpm). Subsequently, ethylene was
introduced in the reactor until the molar benzene:ethylene ratio
was 4:1 and a total pressure of 23 bar was obtained. During the
reaction, liquid aliquots (0.2 cm3) were extracted from the reactor,
which were analyzed with a GC (Agilent 6890N) equipped with a
CPSil-8B column and an FID detector.
3. Results and discussion
3.1. Mesoporosity development: organic versus inorganic hydroxides
The results shown in Table 1 and in the illustrations below
correspond to the zeolite with Si/Al = 42 in the protonic form and
the products derived from alkaline treatment. The XRD pattern of
the parent zeolite (P) exhibits the MFI structure as the only
crystalline phase (Fig. 1). The N2 isotherm presents a high uptake at
 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198 193

Table 1
Chemical composition and textural properties of the parent and alkaline-treated zeolites.

Sample Base C (M) T (K) t (min) Molar Si/Al Sifiltratea (ppm) Alfiltratea Yieldb Vpore Vmicroc Vmesod Smesoc
ratioa (ppm) (%) (cm3 g 1
) (cm3 g 1
) (cm3 g 1
) (m2 g 1)

Solid Filtrate
e
P – – – – 42 – – – – 0.28 0.17 0.11 60
OT-1 TPAOH 1 338 30 40 – – – 95 0.29 0.17 0.12 80
OT-2 TPAOH 1 338 300 38 – – – 90 0.36 0.14 0.22 125
OT-3 TPAOH 1 338 480 38 90 1007 11 82 0.37 0.13 0.24 160
OT-4 TPAOH 1 358 300 32 79 5598 68 61 0.59 0.13 0.46 180
OT-5 TBAOH 1 338 480 – – – – 77 0.38 0.15 0.23 150
AT NaOH 0.2 338 30 26 902 4967 5 62 0.57 0.09 0.48 277
a
ICP-OES.
b
Grams of solid after workup per gram of sample treated.
c
t-plot method.
d
Vmeso = Vpore Vmicro.
e
The parent zeolite from which the various OT and AT samples were derived was CBV 8014 in the protonic form.

low relative pressures, confirming the microporous character
(Fig. 2, left). The micropore volume of 0.17 cm3 g 1 is characteristic
of MFI. The contribution of mesoporosity (Smeso = 60 m2 g 1) is a
consequence of the crystal’s external surface and the surface
roughness. The zeolite was subjected to standard sodium
hydroxide treatment (AT). The resulting N2 isotherm shows
enhanced uptake at intermediate pressures (Fig. 2, left), which
is indicative of the formation of a hierarchical porous system
combining micro- and mesoporosity. As shown in Table 1, the
mesopore surface area and mesopore volume increased from 60 to
277 m2 g 1 and from 0.11 to 0.48 cm3 g 1, respectively. Conco-
mitantly, the micropore volume decreased from 0.17 to
0.09 cm3 g 1. Mesopore formation is due to the OH -assisted
selective extraction of framework silicon [7]. Accordingly, the Si/Al
ratio in the resulting solid decreased from 42 in P to 26 in AT
(Table 1). The molar Si/Al ratio in the filtrate amounts to ca. 1000,
evidencing the high selectivity of NaOH towards silicon leaching.
The yield of the AT treatment, defined as grams of solid after
workup per gram of sample treated was 62%, meaning that ca. 40%
of the silicon leached to the solution. However, the hierarchical
zeolite preserves the long-range crystallinity according to X-ray
diffraction (Fig. 1).
In contrast to NaOH, treatment of H-ZSM-5 in 1 M TPAOH at
338 K for 30 min caused minor alteration of the porosity and
chemical composition (sample OT-1 in Table 1). The micropore
Fig. 1. Powder XRD patterns of the parent and alkaline-treated samples.
volume was unchanged with respect to the parent sample and the
mesopore surface area slightly increased to 80 m2 g 1. This is likely
due to the limited attack by OH to Si–OH defects thereby
increasing the roughness of the crystal’s external surface. The yield
of this treatment was ca. 95%, indicating the very low silicon
dissolution compared with NaOH. This control experiment enables
to conclude the relatively low reactivity of the organic hydroxide
compared to sodium hydroxide, in spite of the equivalent alkalinity
of both basic solutions (pH of 1 M TPAOH is 14 and 0.2 M NaOH is
13.2). Microcalorimetry substantiates the much lower degree of
silicon extraction by the organic hydroxide. Fig. 3 shows the heat
flow profiles upon interaction of the zeolite with 0.2 M NaOH or
1 M TPAOH aqueous solutions at 338 K. The total heat released,
determined by integration of the profiles, was ca. 12 times higher
with NaOH (81 J g 1) than with TPAOH (7 J g 1). In agreement with
the limited mesoporosity development concluded from N2
adsorption, the TPAOH profile is mostly associated with adsorption
of the TPA+ cations on the zeolite surface with a minor contribution
of the OH -assisted silicon hydrolysis. The NaOH profile is
consistent with the extensive silicon dissolution generated during
the first 30 min of the treatment.
The slow desilication kinetics of ZSM-5 by tetraalkylammonium
hydroxides can be advantageous, as it enables a precise control of
the mesopore formation. With this in mind, we screened
conditions with the organic hydroxide leading to enhanced silicon
leaching and thereby to substantial mesopore formation. Treat-
ments in 1 M TPAOH were conducted at 338 or 358 K during 300 or
480 min. These relatively long treatments at 338 K effectively
increased the mesopore surface area of the zeolites, reaching 125
and 160 m2 g 1 in OT-2 and OT-3, respectively (Table 1). The N2
isotherms of these samples, e.g. OT-3 in Fig. 2, left, display
enhanced uptake at intermediate pressures, i.e. a typical finger-
print of hierarchical porous zeolites. The values of Smeso and Vmeso
of OT-2 and OT-3 were significantly lower compared to AT.
However, the TPAOH-treated samples offer two benefits: (i) the
better preservation of the micropore volume (25% of Vmicro is lost in
the organic hydroxide in contrast with the 50% loss in NaOH) and
(ii) the higher solid yield (>80%). The above effects are a direct
consequence of the lower proneness of the organic hydroxide to
dissolve framework silicon. It should be stressed that only one
reference NaOH treatment (0.2 M, 338 K, 30 min) was considered
in this work for comparison with the organic hydroxides. Of course,
the use of NaOH at lower concentration (<0.1 M), lower
temperature (<338 K), and shorter time (<15 min) would imply
a higher solid yield, better preserved micropore volume, and a
lower mesopore surface area [5].
The limited Si leaching with the organic hydroxide also brings
differences in the size of the mesopores. As shown by the BJH pore
194 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198
Fig. 2. N2 isotherms at 77 K of the parent and alkaline-treated zeolites (left) and the corresponding adsorption BJH pore size distributions (right).
size distribution (Fig. 2, right), the zeolite treated in TPAOH at
338 K shows the formation of smaller mesopores (OT-3, 6–7 nm)
compared to the NaOH treatment (AT, 10 nm). Holm et al. [22]
reported the formation of larger pores in H-beta zeolite (covering
the broad range of 2–50 nm) by treatment in TMAOH (0.1 M, 323–
373 K, 2 h), while smaller pores (3–4 nm) were attained by
conventional NaOH treatment. However, the type of zeolite
framework and starting form, organic base, and experimental
conditions differed from those investigated by us.
In addition to H-ZSM-5, we conducted desilication experiments
using OT-3 conditions over ZSM-5 in the sodium and ammonium
forms. In analogy with NaOH [20], the counter-cation in the
starting zeolite (H+, Na+, NH4+) had a minor influence on the
mesoporous surface area by silicon extraction with organic
hydroxides. This result contrasts with the limited mesoporosity
obtained by Holm et al. [22] with TMAOH when the starting beta
zeolite was in the protonic form, while extensive mesoporosity
was developed with the sodium form.
Fig. 3. Microcalorimetric profiles upon contacting the parent zeolite with (*) 1 M
TPAOH and (*) 0.2 M NaOH aqueous solutions at 338 K.
Another common feature of the treatments in TPAOH and NaOH
is the dependence of the mesopore surface area on the Si/Al ratio of
the parent zeolite. It is well known that a key condition to fabricate
mesoporous ZSM-5 zeolites by desilication with sodium hydroxide
is to start with samples with a molar Si/Al ratio in the range 25–50
[7]. Treatment of H-ZSM-5 with Si/Al ratios of 17 and 176 using OT-
3 conditions did not significantly alter the mesopore surface area of
the parent samples (from 30–40 m2 g 1 to 60–70 m2 g 1).
The advantages of the organic base represented by OT-3 vanish
if the treatment conditions become too harsh. For instance,
increasing the temperature of the TPAOH treatment to 358 K for
300 min (sample OT-4) induces a somewhat higher N2 uptake at
high p/p0 compared to OT-3 (Fig. 2, left). As a matter of fact, OT-4
resembles the NaOH-treated zeolite judging from the similar
increase in Vmeso. Besides, the solid yields in OT-4 and AT are
practically identical (Table 1). Accordingly, under certain condi-
tions, an equivalent amount of silicon can be leached using organic
or inorganic hydroxides. Due to the excessive dissolution of silicon
with temperature, the PSD of OT-4 broadens and is shifted to larger
pore sizes (centered at 20 nm, Fig. 2, right). The creation of larger
pores in OT-4 compared to AT explains the lower mesopore surface
area of the former sample. Surprisingly the micropore volume of
OT-4 was decreased to a lesser extent compared to AT (0.13 versus
0.09 cm3 g 1).
The mesoporous zeolites obtained by desilication in organic
hydroxides preserved the long-range crystallographic order, as
shown by X-ray diffraction (Fig. 1). Transmission electron
microscopy confirmed the generation of intracrystalline meso-
porosity in the TPAOH-treated samples (Fig. 4). In good agreement
with the pore size distribution derived from nitrogen adsorption,
OT-3 presents mesopores in the range of 6–10 nm. The extent of
mesopore formation is enhanced in OT-4. The zeolite aggregates
are perforated by the base, resulting in the formation of larger
pores (>20 nm) and wide entrances to the center of the crystal due
to a more pronounced dissolution. The micrographs of the AT and
OT-4 zeolites were rather similar.
Noteworthily, the treatments in NaOH and TPAOH do not only
provoke porosity differences in the resulting materials due to the
distinct Si dissolution kinetics, but also changes in the chemical
composition. The Si/Al ratios of OT-3 and OT-4 are significantly
higher than in AT (Table 1). This is due to the more selective
character of the inorganic base towards silicon extraction
compared to the organic base. Accordingly, the Si/Al ratio in the
 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198 195

Fig. 4. Transmission electron micrographs of the parent and alkaline-treated zeolites.

filtrate was around 10 times higher in NaOH than in TPAOH, i.e. a mesoporous zeolite is directly obtained by decomposition of the
higher degree of aluminum leaching occurs with the organic organic cation. In contrast, the infrared spectrum of NaOH-treated
hydroxide. zeolite after calcination shows no band at 3610 cm 1 due to Na+
The desilication treatment has been exemplified above for cations occupying ion exchange positions [7]. The Brønsted feature
TPAOH. However, the attainment of substantial mesoporosity
coupled with the preservation of microporosity also applies to
other alkylammonium hydroxides. To check this, treatment in
tetrabutylammonium hydroxide (TBAOH) under the same condi-
tions as OT-3 was carried out (sample OT-5 in Table 1). The
textural parameters of the zeolite (Smeso = 151 m2 g 1 and
Vmicro = 0.15 cm3 g 1) and solid yield largely resemble OT-3. Other
characterization (N2 isotherm and pore size distribution, XRD, TEM)
was equivalent too and is not shown for conciseness. This result
suggests that the nature of the organic cation in the hydroxide (at
least TPA+ and TBA+) does not significantly affect the amount and
type of mesopores. We also conducted treatments with typical Lewis
organic bases, such as triethylamine or triethanolamine. As
expected, the latter did not create mesoporosity in the zeolite. This
is due to the weaker basicity associated with the presence of the lone
pair of electrons on the nitrogen atom, which makes these bases
acting as proton acceptors rather than hydroxide donors.
Fig. 5 shows the FTIR spectra in the OH-stretching region of the
parent and hierarchical zeolites. The contribution at 3610 cm 1
stems from the Si–OH–Al stretching vibration associated with
Brønsted acid sites [25]. This contribution gradually decreases in
OT-3 and OT-4 due to the concomitant loss of micropore volume.
The alkaline treatment simultaneously induces the progressive
development of isolated silanol groups at 3740 cm 1, due to the
enhanced external surface area associated with the formation of
intracrystalline mesoporosity. It should be recalled that the OT-3
and OT-4 samples were obtained by calcination of the TPAOH- Fig. 5. Infrared spectra in the OH stretching region of the parent and alkaline-
treated zeolites, confirming that the protonic form of the treated zeolites.
196 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198
was regained after three successive ion exchanges with NH4NO3
followed by calcination (AT in Fig. 5). The spectrum of AT shows a
weak but detectable band at 3660 cm 1, which can be attributed to
hydroxyl groups connected to extra-framework Al species [26]. In
agreement, several authors have shown that upon desilication of
ZSM-5 by NaOH, the relative amount of Lewis sites in the
mesoporous zeolite increases [27,28], pointing to the transforma-
tion of some of the Brønsted sites into Lewis sites. The 3660 cm 1
band cannot be discerned in any of the TPAOH-treated samples.
This is probably connected with a different desilication mechanism
running with NaOH and the organic hydroxide, which is put
forward in the next section.
3.2. Desilication mechanism
Our results evidence the slower desilication kinetics in ZSM-5
by tetraalkylammonium hydroxides compared to NaOH. With the
organic base, longer treatment times and/or higher temperatures
are required to induce substantial intracystalline mesoporosity.
This feature enables a good control of the pore formation process
compared to NaOH, as the amount of silicon extracted is
importantly reduced. As a consequence, the micropore volume
is preserved to a larger extent, the newly created intracrystalline
mesopores are smaller, and a higher solid yield is attained. The
latter parameter can be easily obtained and provides a primary
measure of the treatment effectiveness based on the weight loss.
Besides, higher Si/Al ratios were obtained, i.e. a higher amount of
aluminum was leached to the solution in TPAOH compared to
NaOH. This is additionally supported by the lower Al content in the
resulting OT-3 sample (389 mmol g 1) with respect to AT
(533 mmol g 1). These observations reveal the less selective
character of the organic hydroxide towards silicon extraction
compared to the inorganic base. Fig. 6 summarizes the differences
observed between both organic and inorganic base treatments.
A different demetallation mechanism, mostly induced by the
nature of the organic cation, should be responsible for the above
differences. Bearing in mind the equivalent basicity of both
TPAOH and NaOH solutions, one should consider additional
effects related to solvation, stability, and steric hindrance of the
species involved during the desilication process. In a highly polar
solvent like water, strong bases like hydroxides are completely
Fig. 6. Pictorial comparison of zeolite desilication by tetraalkylammonium hydroxides and sodium hydroxide.
dissociated into the cation and the hydroxyl anion. In our case,
whether the cation is Na+, TPA+, or TBA+, the formation of hydrated
ion dipoles or solvent-separated ion pairs can be foreseen.
However, tetraalkylammonium cations are not strongly solvated
in aqueous solution compared to Na+, due to their larger effective
cationic diameter [29] (e.g. TPA+ ca. 0.9 nm [30] versus Na+
0.19 nm [31]), and the hydrophobicity of their alkyl groups [32],
causing the attraction of less water molecules. This is confirmed
by the lower hydration enthalpy of tetraalkylammonium cations
(ca. 135 kJ mol 1) with respect to Na+ (406 kJ mol 1), tending to
make the former cation less soluble [33]. Besides, TPA+ exhibits a
high structure stabilizing ability, taking into consideration that it
is the standard structure-directing agent in the synthesis of ZSM-
5. The hydrophobicity of the long hydrocarbon chains on TPA+
motivates propyl groups to interact with the hydrophobic silicate
species rather than with the polar water molecules [34]. Both
arguments likely make the relatively bulky TPA+ cation being
more stable on the zeolite surface. Consequently, in the presence
of tetraalkylammonium cations, the zeolite surface is better
shielded from the attack by OH with respect to sodium cations
(Fig. 6), i.e. the higher affinity of TPA+ for the zeolite combined
with its intrinsic steric hindrance, slows down the kinetics of the
desilication process.
In support of this behavior, the presence of TPA+ cations is also
responsible for the formation of smaller mesopores as compared to
the treatment in NaOH. This can be explained by the fact that
protected regions inhibit extensive silicon extraction. Harsher
experimental conditions are able to generate the formation of
larger pores in the organic base-free regions (sample OT-4). By the
same reasoning, a higher amount of aluminum was found in the
filtrates as TPA+ deposited on the zeolite surface appears to limit
the realumination of the zeolite, contrarily to what it occurs in
NaOH [7,35]. This is in agreement with infrared results, which
suggest the absence of extra-framework Al species in the TPAOH-
treated samples. The concept of pore growth inhibition with
hydroxides of tetralkylammonium cations is somewhat related to
the partial detemplation-desilication treatment recently demon-
strated over large beta crystals [21]. In the latter case, the
quaternary ammonium cation (TEA+) was occluded in the zeolite
pores and effectively limited the silicon hydrolysis and derived
mesopore formation.
 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198
3.3. Alkylation performance
Hierarchical zeolites aim at an improved catalytic performance
by combination in a single material of the catalytic power of
micropores and the improved transport consequence of a
complementary mesopore network. The assessment of function-
ality of the samples investigated in this work has been procured in
the liquid-phase alkylation of benzene with ethylene. This reaction
suffers from diffusion limitations and the poor transport of
benzene in the microporous crystals enables ethylene molecules
to react with the aromatic ring, leading to oligomerization.
The production of ethylbenzene (EB) after 400 min of reaction
over the parent and alkaline-treated samples is shown in Table 2.
The ethylbenzene productivity over the parent zeolite was
2 mmol gcat 1. The productivity over the mesoporous AT sample
is 4 times higher with respect to the parent sample. The improved
performance over the mesoporous AT sample is attributed to the
enhanced molecular transport to/from the active sites as a
consequence of the extensive introduction of mesopores. Zhao
et al. [11] have recently reported a doubled conversion in cumene
cracking over the mesopore structured ZSM-5 catalyst compared
to the purely microporous counterpart, which was attributed to
the 2–3 order of magnitude increased diffusion coefficient. As
previously reported for mesoporous mordenite [13], the enhanced
selectivity of AT (97%) compared to the parent sample (90%) is also
consequence of the improved transport of reactants and products
in the shortened micropores of the former sample, which minimize
successive alkylation steps (i.e. polyalkylbenzenes formation).
As described in Section 3.2, the use of alkylammonium
hydroxides as desilicating agents enables to control the extent
of mesopore formation while keeping a higher degree of
microporosity than in NaOH. Accordingly, the intrinsic properties
of the derived samples might induce interesting differences in the
catalytic performance. In fact, the EB productivity of the OT-3
sample is 5 times higher than over the parent zeolite, and exceeds
the value of the conventional alkaline-treated sample. The EB
productivity corrected by the aluminum content in each catalyst
provides the same trend, but the differences are even more
pronounced. For example, OT-3 is around 4 and 2 times more
active per Al atom compared to the parent and AT samples,
respectively, indicating the more efficient site utilization. Such
reactivity in the organic base-treated samples was not necessarily
expected. In fact, considering the above results, the facilitated
transport through mesopore formation in OT-3 appears not to be
the governing factor for explaining the activity differences, as the
Smeso of this sample is much lower than that of AT. In contrast, the
micropore volume in OT-3 is preserved to a larger extent
(0.13 cm3 g 1).
In this particular reaction, the intracrystalline small meso-
pores observed in the OT-3 sample facilitate the access to the
active sites, leading to a more efficient utilization of the crystal
volume. In parallel, the higher degree of microporosity plays a
more significant role, thus increasing the functionality of the
active sites. Accordingly, it is underlined that the improved
catalytic performance of the organic base-treated samples derives
from an elegant and precise interplay between the preserved
Table 2
Catalytic performance of the zeolites in the liquid-phase benzene alkylation with
ethylene. Conditions: Ratio C6H6:C2H4 = 4:1, T = 438 K, P = 23 bar, t = 400 min.
Sample Ethylbenzene productivity S(EB) (%)
1 1
mmol EB gcat mmol EB mmol Al
P 2 7 90
OT-3 10 26 98
AT 8 15 97
197
microporosity and the newly created mesoporosity. The protect-
ing capability of alkylammonium cations enables not only to
control the extent of mesopore formation but also to design
hierarchical zeolites with flexible properties.
The possibly different type of aluminum species in the OT-3 and
AT samples should not be neglected in the comparison of the
ethylbenzene productivity per mol of Al. The realumination
phenomenon during NaOH leads to additional Lewis sites whereas
these will be mostly absent in the TPAOH-treated zeolites. A
systematic study assessing the strength, nature, and location of
acid sites in the NaOH and TPAOH-treated zeolites is required to
better understand the effect of the distribution of aluminum
species on the catalytic performance. This will be tackled in future
work.
4. Conclusions
Hierarchical zeolites combining micro- and mesoporosity were
successfully prepared by desilication of ZSM-5 (Si/Al = 42) in
aqueous solutions of tetraalkylammonium hydroxides (TPAOH or
TBAOH). Common features of the treatment with organic hydro-
xides and the conventional NaOH leaching are the requirement to
work with a starting zeolite in the optimal Si/Al window of 25–50
and the minor influence of the counter-cation (H+, NH4+, Na+) on
the degree of mesoporosity developed. However, both desilication
media present distinctive kinetic and mechanistic characteristics.
Organic bases are intrinsically less reactive towards silicon
dissolution than inorganic hydroxides. This makes the demetalla-
tion process highly controllable in comparison with the fast silicon
dissolution kinetics in NaOH. Besides, the use of organic
hydroxides directly produced the protonic form of the mesoporous
zeolite upon calcination, simplifying the final ion exchange with
NH4NO3 characteristic of the NaOH treatment. The organic
hydroxide is less selective for silicon extraction, i.e. higher Al
leaching compared to NaOH is observed and therefore higher Si/Al
ratios in the mesoporous zeolites are attained. The above
differences in porosity and composition are determined by the
nature of the cation in the organic base. In particular, the steric
hindrance induced by the relatively bulky organic cation is
responsible for this distinct demetallation mechanism. The
TPAOH-treated mesoporous ZSM-5 is an efficient catalyst for the
liquid-phase alkylation of benzene with ethylene. For this
particular reaction, our results highlight the importance of tuning
mesoporosity formation to facilitate transport and microporosity
preservation in hierarchical porous zeolites. The different type of
aluminum species in the TPAOH and NaOH-treated zeolites can
also influence the catalytic performance. Therefore, a more
systematic characterization of the acidic properties of the samples
is required in order to properly quantify the eventual effect. Of
course, in terms of practical implementation, a major inconve-
nience of using tetraalkylammonium hydroxides as desilication
agent is the high cost compared to NaOH, even though an extra ion-
exchange step is avoided.
Acknowledgments
The Spanish MICINN (CTQ2006-01562/PPQ, PTQ05-01-00980,
and Consolider-Ingenio 2010, grant CSD2006-0003) and the ICIQ
Foundation. Dr. Pablo Ballester (ICREA-ICIQ) is acknowledged for
helpful discussions.
References
[1] H.F. Rase, Handbook of Commercial Catalysts, first edition, CRC Press, Boca Raton,
2000.
[2] A. Corma, V. Martı́nez-Soria, E. Schnoeveld, J. Catal. 192 (2000) 163.
198 S. Abelló et al. / Applied Catalysis A: General 364 (2009) 191–198

[3] J. Pérez-Ramı́rez, C.H. Christensen, K. Egeblad, C.H. Christensen, J.C. Groen, Chem. [19] Y. Li, S. Liu, Z. Zhang, S. Xie, X. Zhu, L. Zhu, Appl. Catal. A 338 (2008) 100.
Soc. Rev. 37 (2008) 2530. [20] J.C. Groen, J.A. Moulijn, J. Pérez-Ramı́rez, Ind. Eng. Chem. Res. 46 (2007) 4193.
[4] M. Ogura, S. Shinomiya, J. Tateno, Y. Nara, M. Nomura, E. Kikuchi, M. Matsukata, [21] J. Pérez-Ramı́rez, S. Abelló, A. Bonilla, J.C. Groen, Adv. Funct. Mater. 19 (2009) 164.
Appl. Catal. A 219 (2001) 33. [22] M.S. Holm, M.K. Hansen, C.H. Christensen, Eur. J. Inorg. Chem. (2009) 1194.
[5] J.C. Groen, L.A.A. Peffer, J.A. Moulijn, J. Pérez-Ramı́rez, Colloids Surf. A 241 (2004) [23] B.C. Lippens, J.H. de Boer, J. Catal. 4 (1965) 319.
53. [24] E.P. Barret, L.G. Joyner, P.H. Halenda, J. Am. Chem. Soc. 73 (1951) 373.
[6] J.C. Groen, L.A.A. Peffer, J.A. Moulijn, J. Pérez-Ramı́rez, Microporous Mesoporous [25] A. Zecchina, S. Bordiga, G. Spoto, D. Scarano, G. Petrini, G. Leofanti, M. Padovan,
Mater. 69 (2004) 29. J. Chem. Soc. Faraday Trans. 88 (1992) 2959.
[7] J.C. Groen, L.A.A. Peffer, J.A. Moulijn, J. Pérez-Ramı́rez, Chem. Eur. J. 11 (2005) [26] I. Kiricsi, C. Flego, G. Pazzuconi, W. O: Parker, R. Millini, C. Perego, G. Bellussi,
4983. J. Phys. Chem. 98 (1994) 4627.
[8] J.C. Groen, J.A. Moulijn, J. Pérez-Ramı́rez, J. Mater. Chem. 16 (2006) 2121. [27] M.S. Holm, S. Svelle, F. Joensen, P. Beato, C.H. Christensen, S. Bordiga, M. Bjørgen,
[9] X. Wei, P.G. Smirniotis, Microporous Mesoporous Mater. 97 (2006) 97. Appl. Catal. A 356 (2009) 23.
[10] J.C. Groen, W. Zhu, S. Brouwer, S.J. Huynink, F. Kapteijn, J.A. Moulijn, J. Pérez- [28] F. Thibault-Starzyk, I. Stan, S. Abelló, A. Bonilla, C. Fernandez, J.-P. Gilson, J. Pérez-
Ramı́rez, J. Am. Chem. Soc. 129 (2007) 355. Ramı́rez, J. Catal. 264 (2009) 11.
[11] L. Zhao, B. Shen, J. Gao, C. Xu, J. Catal. 258 (2008) 228. [29] R.J. Fessenden, J.S. Fessenden, Organic Chemistry, second edition, PWS Publish-
[12] Y. Song, X. Zhu, Y. Song, Q. Wang, Appl. Catal. A 288 (2006) 69. ers, Boston, 1982.
[13] J.C. Groen, T. Sano, J.A. Moulijn, J. Pérez-Ramı́rez, J. Catal. 251 (2007) 21. [30] W.J. Roth, Pol. J. Chem. 80 (2006) 703.
[14] M. Bjørgen, F. Joesen, M.S. Holm, U. Olsbye, K.-P. Lillerud, S. Svelle, Appl. Catal. A [31] F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, fourth edition, John
345 (2008) 43. Wiley & Sons, New York, 1996.
[15] C. Mei, P. Wen, Z. Liu, H. Liu, Y. Wang, W. Yang, Z. Xie, W. Hua, Z. Gao, J. Catal. 258 [32] D.D. Ensor, H.L. Anderson, T.G. Conally, J. Phys. Chem. 78 (1974) 77.
(2008) 243. [33] M.B. McBride, M.M. Mortland, Clays Clay Miner. 21 (1973) 323.
[16] S. Gopalakrishnan, A. Zampieri, W. Schwieger, J. Catal. 260 (2008) 193. [34] M.M. Helmkamp, M.E. Davis, Annu. Rev. Mater. Sci. 25 (1995) 161.
[17] L. Jin, X. Zhou, H. Hu, B. Ma, Catal. Commun. 10 (2008) 336. [35] G. Lietz, K.H. Schnabel, Ch. Peuker, Th. Gross, W. Storek, J. Völter, J. Catal. 148
[18] F. Jin, Y. Cui, Y. Li, Appl. Catal. A 350 (2008) 71. (1994) 562.