Microporous and Mesoporous Materials 69 (2004) 29–34

www.elsevier.com/locate/micromeso

On the introduction of intracrystalline mesoporosity

in zeolites upon desilication in alkaline medium
a,*
J.C. Groen , L.A.A. Peffer a, J.A. Moulijn b, J. P
erez-Ram
ırez c

a
Applied Catalyst Characterization, DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
b
Reactor and Catalysis Engineering, DelftChemTech, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
c
Norsk Hydro, Agri Research Centre, Nitric Acid Technology, P.O. Box 2560, N-3907 Porsgrunn, Norway
Received 10 October 2003; received in revised form 12 January 2004; accepted 12 January 2004

Abstract

The development of considerable mesoporosity without destruction of the intrinsic zeolite properties has been attained in various
commercial zeolites by treatment in alkaline medium. Zeolites MFI, BEA, MOR and FER appear to be susceptible to extensive
mesopore formation by extraction of framework Si in the parent material (desilication). Each structure requires particular treatment
conditions. Variation of treatment time and temperature enables tailoring of the mesopore size and volume leading to hierarchical
porous materials. The versatility of this alkaline treatment opens new avenues to improve diffusion characteristics in zeolite-cata-
lyzed applications.

2004 Elsevier Inc. All rights reserved.

Keywords: Alkaline treatment; Desilication; Hierarchical porosity; Mesopore formation; Zeolites

1. Introduction lead to dealumination [8]. Desilication was firstly ap-

Zeolites are used in many catalytic and separation
processes due to unique properties such as uniform
pores of molecular dimensions, intrinsic acidity, and the
ability to confine active metal species [1,2]. However, the
microporous character of these materials often leads to
intracrystalline diffusion limitations, which adversely
affect catalytic performance. A breakthrough was the
synthesis of mesostructured aluminosilicates [3]. Emerg-
ing mesoporous materials however generally do not
comply with most practical requirements as a result of
limited thermal stability and poor acidic properties.
Consequently, new synthesis procedures for preparation
of small zeolitic crystals [4] or post-treatment procedures
to create extra-porosity [5] are increasingly investigated.
Conventional steaming and acid leaching methods or
the less-known treatments in alkaline media have been
applied to alter various properties of zeolites. The last
method removes preferentially Si from the zeolite
framework (desilication) [6,7], while the former ones
*
Corresponding author. Tel.: +31-15-278-4371; fax: +31-15-278-
4452.
E-mail address: j.c.groen@tnw.tudelft.nl (J.C. Groen).
plied to study chemical changes of MFI crystals upon
contact with NaOH solutions [6,7], but only recently this
treatment has shown to induce a significant mesopo-
rosity in MFI-type zeolites [9–12]. Creation of such ex-
tra-porosity in other zeolitic materials by controlled
desilication would be of significant practical impact. In
the present contribution, we show by means of adsorp-
tion studies and electron microscopic investigations that
via alkaline treatment in NaOH significant mesoporos-
ity is created in a variety of commercial zeolitic struc-
tures, including not only MFI, but also BEA, MOR,
and FER. Important characteristics of the parent
material, i.e., the long-range crystallinity and acidity are
preserved under suitable treatment conditions.
2. Experimental
The commercial zeolites used in this study were ob-
tained from Zeolyst: BEA (CP 811C, nominal Si/
Al ¼ 150, H-form), FER (CP 914, nominal Si/Al ¼ 27,
NH4 -form), MFI (CBV 8020, nominal Si/Al ¼ 37,
NH4 -form), and MOR (CBV 90A, nominal Si/Al ¼ 45,
H-form). For alkaline treatment ca. 330 mg of calcined

1387-1811/$ - see front matter
2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2004.01.002
30 J.C. Groen et al. / Microporous and Mesoporous Materials 69 (2004) 29–34

zeolite was vigorously stirred in 10 ml NaOH (0.1–1 M) SEM) was carried out in a JEOL JSM-6700F micro-
solution at a certain temperature (298–358 K) for a scope. High-resolution TEM (HR-TEM) micrographs
certain period of time (0.25–10 h). The zeolite suspen- were acquired with a Philips CM30UT electron micro-
sion was then cooled down immediately using an ice scope. Si and Al concentrations in the solid materials
bath. The remaining product was filtered, carefully and in the filtrate obtained upon alkaline treatment were
washed until neutral pH and finally dried at 373 K. The determined by ICP-OES on a Perkin–Elmer Optima
alkaline-treated samples were converted into the H-form 3000DV. NH3 -TPD experiments were carried out on a
by three consecutive exchanges in 0.1 M NH4 NO3 Micromeritics TPR/TPD 2900 in the temperature range
solution followed by air-calcination at 823 K for 5 h. 473–823 K, after three consecutive saturation steps with
The as-received materials were calcined under identical pure NH3 at 473 K.
conditions prior to the characterization and hereafter
denoted as non-treated.
N2 adsorption and desorption isotherms and low- 3. Results and discussion
pressure argon adsorption isotherms were recorded on a
Quantachrome Autosorb-6B and a Micromeritics ASAP In an exploratory program a broad range of alkaline
2010, respectively. X-ray diffraction patterns were mea- treatment conditions (time, temperature, and alkaline
sured in a Bruker-AXS D5005 diffractometer with concentration) was investigated to assess appropriate
Bragg–Brentano geometry. Field-emission SEM (FE- conditions for mesoporosity development in various

400 500

dV/dlogd (cm3/g)
dV/dlogd (cm3/g)

400
300
Vads (cm3 STP/g)

Vads (cm3 STP/g)

300

200
1 10 100
1 10 1 00
dp (nm) dp (nm)
200

100
100

MFI BEA
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1. 0
p/p0 (-) p/p0 (-)

600 400
dV/dlogd (cm3/g)

dV/dlogd (cm3/g)

300
Vads (cm3 STP/g)
Vads (cm3 STP/g)

400

1 10 1 00
200
1 10 1 00
dp (nm) dp (nm)

200
100

MOR FER
0 0
0.0 0.2 0.4 0.6 0.8 1. 0 0.0 0.2 0.4 0.6 0.8 1.0
p/p0 (-) p/p0 (-)

Fig. 1. N2 adsorption and desorption isotherms at 77 K and BJH adsorption pore size distribution (inset) of (h, j) non-treated and (M; N) alkaline-
treated zeolites. Conditions of alkaline treatment for each structure as defined in Table 1.
 J.C. Groen et al. / Microporous and Mesoporous Materials 69 (2004) 29–34
zeolite structures. The conditions used in this manu-
script aim at formation of substantial mesoporosity
while preserving the intrinsic properties of the zeolite
(high surface area, shape selectivity, and acidity). We
have previously reported on the optimization of the
alkaline treatment of MFI zeolites [13]. For sake of
clarity, only the treatment conditions to obtain a well
developed combined micro- and mesoporosity are
discussed in this manuscript. Fig. 1 shows the N2
adsorption and desorption isotherms at 77 K for the
non-treated and alkaline-treated zeolites. The non-trea-
ted materials generally exhibit a type I isotherm with a
plateau at higher relative pressures as a result of the
microporous nature of the material with limited meso-
porosity. Upon alkaline treatment in NaOH all the
zeolitic structures show an enhanced uptake of N2 at
higher relative pressures accompanied by a hysteresis
loop, being indicative of extra mesoporosity [14]. The
BJH [15] pore size distribution derived from the
adsorption branch of the isotherm confirms the in-
creased mesoporosity in the alkaline-treated zeolites
(inset Fig. 1), and shows in particular a well-defined
distribution of mesopores in MFI and BEA. The con-
ditions typically applied for suitable porosity develop-
ment by desilication are structure dependent: BEA
zeolite shows the easiest Si extraction, probably a result
of both the less stable framework and the relatively large
Fig. 2. FE-SEM of MFI (a–c) and FER (d–e) zeolites. (a) non-treated, (b) 0.2 M NaOH 338 K 30 min, (c) 0.2 M NaOH 353 K 300 min, (d) non-
treated and (e) 0.5 M NaOH 348 K 600 min.
31
interconnected channels, leading to an adequate trans-
port of hydroxyl ions through the channels for hydro-
lysis of Si–O–Si bonds. The latter feature is also
applicable to the MFI framework but differs from the 1-
dimensional character of MOR and the relatively small
pores in FER. Accordingly, MOR and FER require
more severe treatment conditions for creation of meso-
porosity. This leads to a partial dissolution of the outer
surface of the crystals and creation of larger pores than
in MFI and BEA, as is shown in Fig. 2. FER crystals
show distinct dissolution effects (Fig. 2(e)), whereas the
outer surface of the MFI crystals apparently remains
intact upon suitable treatment conditions (Fig. 2(b)).
More severe conditions ultimately lead to a substantial
dissolution of the MFI crystals (Fig. 2(c)), indicating the
importance of treatment optimization. The preserved
characteristics of the outer crystal surface in MFI sug-
gest an intracrystalline character of the mesoporosity
(measured by N2 adsorption), in contrast with the
explanation of pore formation by Ogura et al. [16], who
suggested intercrystalline porosity by removal of amor-
phous SiO2 between twinning crystals. Reports on Si
leaching in as-synthesized and calcined MFI samples by
 zmek et al. [7] support our conclusion. These authors
Ci
reported a much higher rate of Si dissolution in the
calcined MFI crystals, due to the absence of the organic
template molecules. Consequently, an accessible internal
32 J.C. Groen et al. / Microporous and Mesoporous Materials 69 (2004) 29–34
Fig. 3. HR-TEM of MFI (a) non-treated and (b) alkaline-treated (0.2
M NaOH 338 K 30 min).
microporous network and thus a largely increased sur-
face area is available for Si extraction. The presence of
intracrystalline mesoporosity in our alkaline-treated
materials is further supported by HR-TEM investiga-
tions, evidencing the mesopore formation, while crystal-
linity is preserved (Fig. 3). The mesopore size estimated
from Fig. 3(b) is in excellent agreement with the pore size
distribution derived from N2 adsorption (10 nm).
Upon alkaline treatment the various structures show
a different average mesopore size (inset Fig. 1), which
can be controlled to a certain extent by varying treat-
ment time and temperature. Fig. 4 shows an example of
the treatment temperature dependency of the mesopore
formation in the MFI zeolite in the range of 308–358 K.
No substantial mesopore formation is observed at
temperatures up to 318 K. At 328 K some extra-porosity
in the pore size range 2–10 nm starts to develop, which
becomes substantial at 338 K, showing a relatively
narrow distribution of pores centered around 10 nm.
Above 338 K the pore size distribution broadens con-
siderably, leading to a higher mesopore volume and fi-
nally to a lower mesopore surface area. The treatment
temperature of 338 K is considered as optimal, com-
bining an extensive mesopore formation and a largely
preserved microporosity. Severe conditions, i.e., high
Fig. 4. Influence of alkaline treatment temperature on mesopore size
development in MFI zeolite. Pore size distribution derived from the
adsorption branch by application of the BJH model. Conditions of
alkaline treatment: 0.2 M NaOH for 30 min at temperatures in the
range of 308–358 K.
temperatures, long treatment times, and high concen-
tration of alkaline in the aqueous solution, in general
lead to broadening of the mesopore size distribution
with an increased pore volume, but obviously negatively
affect the properties associated with the crystalline
microporous structure. Ultimately the framework col-
lapses, leading to an amorphous aluminosilicate and a
high degree of dissolved species.
The BET [17] surface areas derived from the isotherms
in Fig. 1 are listed in Table 1 and evidence that the
alkaline-treated zeolites can be used more effectively in
terms of porosity than the non-treated zeolite in view of
the generally higher surface areas of the former. Al-
though validity of the BET model for surface area cal-
culations on microporous materials is questionable [18],
these values can reasonably be used for comparative
purposes. Most spectacular is the increased mesoporos-
ity. Application of the t-plot [19] indicates that a signifi-
cantly increased mesoporosity (>90 m2 /g) is developed in
the alkaline-treated zeolites compared to the non-treated
zeolites, while only a limited decrease in microporosity
<30% is observed. Low-pressure argon adsorption mea-
surements support the decrease in micropore volume and
simultaneously reveal that the micropore size in the
alkaline-treated zeolites remains unaltered compared to
the non-treated materials. X-ray diffraction analysis
 J.C. Groen et al. / Microporous and Mesoporous Materials 69 (2004) 29–34 33

Table 1
Characterization results of selected zeolites
Zeolite Channel dimensions Molar SBET b Smeso c Vmicro c NH3 uptaked
(nm) Si/Ala (m2 /g) (m2 /g) (cm3 /g) (mmol/g)
MFI non-treated 0.51 · 0.55 37 430 40 0.17 0.27
0.53 · 0.56
MFI 0.2 M 338 K 30 min 24 550 225 0.13 0.34

BEA non-treated 0.66 · 0.67 122 590 45 0.24 0.07

0.56 · 0.56
BEA 0.1 M 298 K 30 min 89 700 325 0.15 0.09
MOR non-treated 0.65 · 0.70 45 550 50 0.20 0.13
0.26 · 0.57
MOR 0.2 M 358 K 60 min 24 610 140 0.18 0.28
FER non-treated 0.42 · 0.54 28 340 20 0.13 0.46
0.35 · 0.48
FER 0.5 M 348 K 600 min 8 310 130 0.08 0.54
a
ICP-OES.
b
BET method.
c
t-Plot method.
d
NH3 -TPD.

confirms the preservation of the long-range crystal

Fig. 5. X-ray diffraction patterns of ( ) non-treated and ( ) alkaline-
treated zeolites. Conditions of post-treatment as defined in Table 1.
ordering in the samples, with a certain decrease of the
characteristic reflections (Fig. 5).
ICP-OES measurements in both the filtrate and the
solid material confirm the preferential leaching of Si,
leading to a lower Si/Al ratio in the alkaline-treated
materials (Table 1). Treatment in alkaline medium for a
longer time and at higher concentration results in a
higher degree of Si removal, according to FER >
MOR > MFI > BEA. These physico-chemical changes
upon desilication are also reflected in the acidity of the
post-treated zeolites, as measured by NH3 -TPD. The
number of strong acid sites in the alkaline-treated zeo-
lites is generally increased due the lower Si/Al ratio
(Table 1), while the acid strength hardly changes (Fig.
6). The preservation of the strong acidic properties was
also confirmed by 27 Al MAS-NMR, where most of the
Al in the alkaline-treated zeolites remains tetrahedrally
coordinated.
Although the use of commercial zeolites presented in
this study involves a more complicated characteriza-
tion, due to small crystal size and less controlled sample

Fig. 6. NH3 -TPD of ( ) non-treated and ( ) alkaline-treated zeolites. Conditions of post-treatment as defined in Table 1.
34 J.C. Groen et al. / Microporous and Mesoporous Materials 69 (2004) 29–34
genesis, their high practical relevance in catalytic appli-
cations justifies the research on these materials. Investi-
gations on model zeolite systems consisting of well-defined
larger crystals, to derive more detailed mechanistic and
kinetic information on the desilication process are in
progress. In addition, the application of alternative post-
treatment media for fine-tuning the porous properties of
the modified zeolites is currently being researched.
4. Conclusions
We have shown that intracrystalline mesopore for-
mation by desilication in alkaline medium results in
hierarchical porous zeolites. The mesopore size and
volume can be controlled to a certain extent by varying
treatment time and temperature and under suitable
conditions the original zeolitic properties, including
acidity, micropore size, and long-range ordering are
preserved. Since intracrystalline porosity is developed,
desilication of zeolites by the alkaline treatment opens
novel avenues for catalyst design by improved diffusion
characteristics, and thus a better utilization of the zeolite
crystal for catalytic applications.
Acknowledgements
Acknowledgement is made to Dr. P.J. Kooyman and
Ing. N. van der Pers for HR-TEM and XRD investi-
gations, respectively. M. van den Hooven, Z. Sagir, and
T. Blok are thanked for performing alkaline treatment
experiments.
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