Microporous and Mesoporous Materials 89 (2006) 39–46

www.elsevier.com/locate/micromeso

Amorphous microporous molecular sieves with different

pore dimensions and topologies: Synthesis, characterization
and catalytic activity
Avelino Corma *, Marı́a J. Dı́az-Cabañas
Instituto de Tecnologı́a Quı́mica, UPV-CSIC, Universidad Politécnica de Valencia, Avenida de los Naranjos s/n, E-46022 Valencia, Spain

Received 15 June 2005; received in revised form 27 September 2005; accepted 29 September 2005
Available online 22 November 2005

Abstract

A new family of silica based amorphous microporous molecular sieve materials with different pore topologies has been synthesized by
self-assembling of organic structure directing agents (OSDA) and silica. The regular pore dimensions and micropore volume of these
materials can be fine tuned by means of the OSDA, and they are thermally and hydrothermally stable upon calcination. While being
amorphous to XRD, IR spectroscopy and electron diffraction, they present pore dimensions and topologies very close to zeolites,
and behave as shape selective catalysts. These materials can be considered as zeolite precursors (ZP) during the synthesis of zeolites.

2005 Elsevier Inc. All rights reserved.

Keywords: Amorphous; Microporous; Zeolites; Synthesis

1. Introduction reaction steps: multidentate binding of the silicate oligo-

Nanoporous solids are scientifically and technologically
relevant materials that, by themselves or acting as a host,
are finding numerous applications in electronics, sensors,
magnetism, light emitting devices and catalysis, among
others [1,2]. Their pore dimensions range from 0.35 to
more than 10 nm in diameter and from crystalline to amor-
phous mesoporous materials [3,4]. The development and
application of porous solids has strongly increased with
the introduction of mesoporous materials of uniform pore
dimensions. This has been achieved by a synthesis proce-
dure involving self-assembling of inorganic species with
organic structure directing agents (OSDA), and the best
example is the formation of molecular sieves mesoporous
materials using surfactants as OSDA [3]. In the original
preparation, the synthesis process can be divided into three
*
Corresponding author. Tel.: +34 96 3877800; fax: +34 96 3877809.
E-mail address: acorma@itq.upv.es (A. Corma).
mers to the cationic surfactant, preferential silicate
polymerization in the interface region, and charge density
matching between the surfactant and the silicate [5]. This
model would predict that the properties and structure of
a particular system are not determined by the organic
arrays, with long-range pre-organized order, but by the
dynamic interplay among ion-pairs in organic and inor-
ganic species. Thus, different phases can be readily
obtained through small variation of controllable synthesis
parameters.
In the case of crystalline microporous molecular sieves,
such as zeolites, they are also synthesized using organic
structure directing agents [6,7]. Following the general
organic–inorganic interaction mechanism outlined above,
we should expect an interaction between the silicate species
and the OSDA in the first step of the synthesis. This is due
to preferential silicate polymerization and charge density
matching between the charged OSDA and the silicate
[8–11]. Therefore, in the first step of the synthesis, an
assembled organic–inorganic amorphous material may be
formed. In this material, the size and shape of the organic

1387-1811/$ - see front matter
2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.09.028
40 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46
may preclude the potential pore dimensions and topolo-
gies. This will evolve into ordered (crystalline) nucleus, that
will grow to give the final zeolite crystals. Following the
above, we have drawn an energetic diagram for the differ-
ent steps occurring during the synthesis of zeolites (see
Fig. 1). From this diagram, it appeared to us that, in an
analogous way as it occurs with the mesoporous molecular
sieves, it should be possible to synthesize stable amorphous
microporous molecular sieves with pore dimensions
pre-defined by the size and shape of the organic structure
directing agent. These materials could open new applica-
tions for nanoporous materials, on the bases of their flexi-
bility, and possibilities to introduce metals or organic
molecules [12].
Here we will show that, by controlling the synthesis con-
ditions, a type of thermally and hydrothermally stable
amorphous microporous molecular sieves, with pore
dimensions and micropore volume determined by the size
and shape of the OSDA, have been obtained. These mate-
rials present some advantages over zeolites, since they can
always be obtained in high yields, with shorter synthesis
times and in larger compositional ranges. We will also
show that this work also bring some light into the mecha-
nism of zeolite formation, since we have found that these
amorphous materials can be transformed into zeolites that
maintain very closely the same pore dimensions. This
agrees with the proposed synthesis mechanism [8–11].
Therefore, one can also consider them as amorphous
zeolite precursors (ZP), and we report here a detailed char-
acterization study of these materials by combining X-ray
diffraction (XRD), infrared spectroscopy (IR), thermo-
gravimetric analysis (TG), multinuclear solid state nuclear
magnetic resonance spectroscopy (NMR) and N2 and Ar
adsorption measurements.
Fig. 1. Scheme for the crystallization mechanism.
2. Experimental
2.1. Synthesis of the materials
The syntheses were carried out under hydrothermal con-
ditions in Teflon-lined stainless steel autoclaves and contin-
uous stirring from gels of composition:
xGeO2:ð1
xÞSiO2 : yAl2 O3 : zOSDAOH : zHF : wH2 O
In these syntheses, germanium oxide (from Aldrich),
when introduced, was firstly dissolved in the SDA hydrox-
ide solution. Then, tetraethylorthosilicate and (when
required) aluminium isopropoxide (both from Aldrich),
used as silica and alumina sources, respectively, were added
and stirred at room temperature until the Si and Al precur-
sors were completely hydrolysed and the gel concentration
was reached. Finally, the appropriate amount of HF was
added, the mixture was homogenized by stirring and auto-
claved at the desired temperature under continuous rota-
tion (30 rpm). The final solid was recovered by filtration,
washed with distilled water and dried at 373 K. The sam-
ples were calcined at 823 K in air for 3 h with a heating rate
of 3 C/min.
2.2. Characterization
The products were identified by powder X-ray diffrac-
tion patterns recorded in a Philips XÕPert MPD diffractom-
eter equipped with a PW3050 goniometer provided with a
graphite secondary monochromator using CuKa12 radia-
tion (k = 1.5406, 1.5441 Å), variable divergence and anti-
scatter slits and working in the fixed irradiated area mode.
The IR spectra in the region of framework vibrations
(400–1800 cm
1) were recorded in a Nicolet 710 FTIR
spectrometer using the KBr pellet technique. The N2
adsorption isotherms were measured at 77 K using an
ASAP 2000 Micromeritics instrument. N2 adsorption data
are used extensively to determine surface area and micro-
pore volume of microporous and mesoporous materials.
The micropore volume of the products was calculated by
the t-plot method. The Ar adsorption isotherms were
measured at 85 K using an ASAP 2000 Micromeritics
instrument. These data are used to determine pore size dis-
tributions in porous materials, and were calculated using
the Howarth–Kawazoe formalism. 29Si and 19F solid state
NMR spectra were recorded under magic angle spinning
(MAS) at ambient temperature with a Varian VXR-S 400
WB spectrometer at 79.5 and 376.3 MHz, respectively.
The 29Si and 19F chemical shifts were referred to TMS
and CFCl3 respectively. An RT CP/MAS Varian probe
with zirconia rotors (7 mm in diameter) was used for 29Si,
while 19F experiments were carried out with a Doty XC4
probe using silicon nitride and zirconia rotors, respectively,
of 4 mm outer diameter. The 29Si Bloch decay (BD) spectra
were acquired using pulses of 4 ls to flip the magnetization
an angle of 34p radians, and a recycle delay of 60 s. The 19F
 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46 41

p/2 pulse length was 5 ls, and the contact time 5 ms. A
recycle delay of 80 s was used to ensure the complete recov-
ery of the 19F magnetization to record the 19F spectra, with
pulses of 5 ls corresponding to a magnetization flip angle
of p/2, and spinning rates of 16–17 kHz.
3. Results and discussion
Although several theories have been developed, nucle-
ation and growth of zeolitic materials are still an experi-
mental subject. However, it is mostly accepted that
several steps, sometimes overlapping, are involved in zeo-
lite synthesis. These steps are (a) an induction period, (b)
nucleation, in which viable nuclei are formed and (c)
growth of the nuclei to form zeolite crystals. Following
the reaction steps given in Fig. 1, it should be possible to
synthesize and isolate, before nucleation occurs, stable
amorphous microporous materials. These new micropo-
rous stable materials can then be considered as amorphous
zeolite precursors (ZP), since they show no crystallinity by
different spectroscopic techniques, as will be presented
later.
Several microporous ZP materials were prepared here
under hydrothermal conditions, by working with relatively
concentrated gels, using fluoride anions as mineralizer and
OSDA with different sizes and shapes (Fig. 2). Moreover,
different microporous materials can be obtained with the
same OSDA by changing the synthesis conditions (Table
1) in the same way that different zeolitic materials could
be prepared with the same OSDA. Besides, it is possible
to obtain ZP materials, with the desired properties of
microporosity, with compositions for which it has not been
possible to obtain the final zeolite, enlarging in this way the
range of composition in which a microporous molecular
sieve material, though amorphous, can be obtained, as it
is the case of germanium free ITQ-21.
Table 1 gives the gel compositions used to form different
stable ZP, as well as the zeolitic phases that can be obtained
from those. Nitrogen and argon adsorption measurements
were carried out in the calcined samples to determine

Fig. 2. Organic cations used in this work as structure directing agents (OSDA).

Table 1
Synthesis conditions employed for protozeolites
SDAa Gel composition Temperature (K) Time (days) Phase
MSPT 0.96SiO2:0.04GeO2:0.02Al2O3:0.5MSPT(OH):0.5HF:3H2O 448 0.25 ZPITQ-21
2 ITQ-21
MSPT SiO2:0.02Al2O3:0.5MSPT(OH):0.5HF:3H2O 448 0.50 ZPITQ-21
2 ITQ-30
M6BTM 0.96SiO2:0.04GeO2:0.28M10BTM(OH)2:0.56HF:7H2O 408 6 ZPITQ-13
10 ITQ-13
M6BQ SiO2:0.25M6BQ(OH)2:0.5HF:15H2O 423 1 ZPZSM-12
5 ZSM-12
M8BQ SiO2:0.01Al2O3:0.25M8BQ(OH)2:0.5HF:15H2O 448 7 ZPNU-87
15 NU-87
M8BQ SiO2:0.25M8BQ(OH)2:0.5HF:7.5H2O 408 7 ZPBeta
12 Beta
TEA SiO2:0.54TEA(OH):0.54HF:7.25H2O 448 0.25 ZPBeta
1 Beta
E4ABO SiO2:0.5E4ABO(OH):0.5HF:3H2O 423 4 ZPITQ-7
7 ITQ-7
a
SDAs structures are shown in Fig. 2.
42 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46

Table 2 sional 12-R channel), NU-87 (bi-dimensional 10-R pore)

Pore size (PD) and micropore volume (MV) of the different ZP materials and ITQ-21 (three-dimensional 12-R channels) (entries 4,
compared with the corresponding zeolites
5 and 7 of Table 1, respectively). A detailed characteriza-
SDA ZP material Zeolite Phase tion study of the ZPs and the corresponding zeolites was
MV (cm3 g
1) PD (Å) MV (cm3 g
1) PD (Å) performed, by combining X-ray diffraction (XRD), IR
MSPT 0.26 7.5 0.25 7.8 ITQ-21 spectroscopy, thermogravimetric analysis (TG) and multi-
M6BQ 0.13 6.3 0.12 6.1 ZSM-12 nuclear solid-state nuclear magnetic resonance spectros-
M6BTM 0.14 5.5 0.16 5.6 ITQ-13 copy (MAS-NMR).
M8BQ 0.16 6.0 0.17 5.8 NU-87
M8BQ 0.20 6.7 0.21 6.8 BETA
TG analysis of samples obtained at different crystalliza-
TEA 0.20 6.7 0.22 6.8 BETA tion times are given in Table 3. The weight loss observed
E4ABO 0.22 6.9 0.22 6.9 ITQ-7 during the calcination at 823 K to eliminate the organic
agent occluded inside the pores of the ZP isolated materials
was similar to that of the corresponding zeolites, as well as
micropore volume, pore diameter and pore size distribu- to that of the mixtures ZP-zeolite, obtained when prolong-
tion of the ZP materials, and the results are presented in ing the synthesis times. Three steps are included: from
Table 2 and Fig. 3 together with the values for the corre- room temperature to 473 K. The main difference without
sponding crystalline materials obtained. Micropore volume amorphous and crystalline materials is at the low tempera-
data are usually used as a direct measure of crystallinity in ture range. Weight loss is higher in amorphous samples,
synthesis of zeolites to evaluate the percentage of crystal- probably due to its less hydrophobic nature. At tempera-
line and amorphous material during the crystallization ture higher than 473 K, the behaviour is very similar.
process [13]. However, it can be seen than the zeolite pre- Therefore, TG analysis can be used as a preliminary char-
cursors, not only are stable upon calcination, but give pore acterization technique of ZP materials, since, as will be
size distribution and micropore volume in the same range shown, XRD cannot distinguish between ZPs and other
as for the zeolites, so they can be considered as micropo- potential amorphous materials.
rous molecular sieves. Nevertheless, as we will show later, The organic content, measured by chemical analysis, in
these microporous molecular sieves are amorphous and, amorphous and crystalline materials is very close and the
consequently, they cannot be considered as zeolites. difference is lower than 1% in weight. The C/N ratio corre-
Since the method presented here appears to be quite sponds in all cases with that of the SDA employed. There-
general for obtaining amorphous microporous materials fore, we can conclude that the SDA is occluded intact
with controlled pore diameter, some ZP materials, corre- inside the pores.
sponding to zeolites with different channels systems, have XRD patterns of the as-made solids obtained at differ-
been selected to be fully characterized, in order to establish ent crystallization times show clearly that ZP materials
whether they are amorphous or crystalline. The selected are amorphous and have no order at short or long range
materials were the precursors of ZSM-12 (mono-dimen- (Fig. 4). Diffractograms of the calcined materials (not

0.05 0.14 0.14

0.12 0.12
d(pore vol.)/d(pore diam.) (cm3/g/A)

0.04

0.10 0.10

0.03
0.08 0.08
ZSM-12 NU-87 ITQ-21

0.06 0.06
0.02

0.04 0.04

0.01
0.02 0.02

0.00 0.00 0.00

4 8 12 16 20 4 8 12 16 20 4 8 12 16 20

Pore diameter (A)

Fig. 3. Pore size distribution of some ZP materials (black squares) compared with the corresponding zeolites (blue triangles): ZSM-12, NU-87 and ITQ-
21. (For interpretation of reference to colour in this figure, the reader is referred to the web version of this article.)
 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46 43

Table 3
Thermogravimetric analysis (TG) of samples obtained at different crystallization times, under the synthesis conditions as listed in Table 1, and of the
different ZP materials compared with the corresponding zeolites
Phase Crystallization time (days) Weight loss (%)
Total 273–473 K 473–873 K 873–1073 K
Amorphous 0.25 4.2 2.1 1.6 0.5
ZP 1.50 12.4 2.4 8.9 1.1
ZP + ZSM-12 3 12.1 1.3 9.5 1.3
ZSM-12 5 12.3 0.8 10.0 1.5
Amorphous 2 5.3 3.2 0.6 1.5
ZP 7 15.8 2.2 11.8 2.0
ZP + NU-87 8 16.0 1.8 12.0 2.2
NU-87 14 15.6 1.2 12.1 2.3
Amorphous 0.05 4.3 2.8 0.7 0.8
ZP 0.50 26.5 2.3 21.8 2.4
ZP + ITQ-21 1 26.4 2.0 22.3 2.1
ITQ-21 3 26.2 1.9 22.0 2.3

ZSM-12 NU-87 ITQ-21

Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
0 10 20 30 40 0 10 20 30 40 0 10 20 30 40
2θ (degrees) 2θ (degrees) 2θ (degrees)

Fig. 4. Powder X-ray diffraction patterns of the samples obtained at different crystallization times. From top to bottom: fully crystalline zeolite, mixture of
zeolite and ZP, ZP and non-porous amorphous material. Crystallization times are listed in Table 3.

shown) are similar. Nevertheless, one may claim that these is a suitable technique to detect the presence of crystalline
materials may only be apparently amorphous since they zeolite nucleus in the synthesis products. Taking this into
could be composed of zeolitic nucleus which are too small account, and in order to confirm or reject the amorphous
to give X-ray diffraction [14]. Indeed, previous work [15] nature of our zeolite precursors, we have obtained the IR
has shown that while Y and ZSM-5 zeolites with crystal spectra of the samples in the skeleton vibration region,
size below 8 nm appear amorphous to XRD, IR spectros- and the results are compared with the spectra of the solids
copy was able to show the vibrations of the skeleton for obtained at different crystallization times, including the
samples with even a few unit cells [14,16]. Therefore, IR final zeolites ZSM-12, NU-87 and ITQ-21 (Fig. 5). Large

ZSM-12 NU-87 ITQ-21

Absorbance

Absorbance

Absorbance

1800 1600 1400 1200 1000 800 600 400 1800 1600 1400 1200 1000 800 600 400 1800 1600 1400 1200 1000 800 600 400
Wavenumber (cm-1) Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 5. Infrared spectra of as-made samples obtained at different crystallization times. From top to bottom: fully crystalline zeolite, mixture of zeolite and
ZP, ZP and non-porous amorphous material. Crystallization times are listed in Table 3.
44 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46

[17]. Clear bands are observed for the crystalline zeolites,

but there is only a broad band at 460 cm
1 in the Si–O
bending region in the amorphous ZPs, as it occurs in Aero-
sil 200 and MCM-41 materials (Fig. 6). Therefore, the IR
spectra of ZP are rather similar to those of amorphous sil-
icas and no bands associated to crystalline structure can be
appreciated. Electron diffraction experiments also showed
MCM-41
no crystallinity in agreement with the IR results.
It should be noticed that these amorphous micropo-
rous molecular sieves present a N2 adsorption isotherm
Absorbance

(see Fig. 7) of type Ia, according to the IUPAC nomen-

clature, which is characteristic of microporous materials.
Aerosil Thus, N2 and Ar adsorption measurements clearly indi-
cate that the pore diameter and micropore volume of
the different ZP materials re-assemble those of the final
zeolites (Table 2). 29Si MAS NMR spectra (Fig. 8) of
the calcined ZP materials show the presence of Q4, Q3
and Q2 species (ratios are listed in Table 4). The distribu-
PZ ITQ-21 tion of Q2, Q3 and Q4 species in the Si NMR spectra of
calcined materials present some differences with the as-
made materials. Q2 species are of the same order, Q3
1500 1000 500
are lower and Q4 are higher in calcined materials, showing
Wavenumber (cm-1)
that there is silanol condensation when calcining. High sil-
Fig. 6. Infrared spectra of as-made ZP materials, amorphous silica ica zeolites synthesized in fluoride media have very few
(Aerosil 200) and MCM-41. defects [18], and since we are carrying out the synthesis
in fluoride media, the presence of a relatively large pro-
differences can be seen in 400–650 cm
1 region, where the portion of Q3 and Q2 species in ZP materials proba-
bands associated to rings in zeolitic structures appear bly arises from an incompletely formed framework. This

800 600
1000
ZSM-12 NU-87 ITQ-21
Volume (cm3 g-1)

Volume (cm3 g-1)

600 800
Volume (cm3 g-1)

400
600
400

200 400
200
200

0 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 0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure Relative pressure Relative pressure

Fig. 7. Adsorption isotherms of nitrogen of the zeolite precursors (black) compared with the corresponding zeolites (blue). (For interpretation of reference
to colour in this figure, the reader is referred to the web version of this article.)

ZSM-12 NU-87 ITQ-21

-80 -90 -100 -110 -120 -130 -140 -80 -90 -100 -110 -120 -130 -140 -80 -90 -100 -110 -120 -130 -140
δ (ppm) δ (ppm) δ (ppm)

Fig. 8. 29Si MAS NMR spectra of the calcined ZP materials and the corresponding zeolites. From top to bottom: spectrum of the calcined zeolite,
spectrum of calcined ZP, simulation with deconvoluted components and individual deconvoluted components.
 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46 45

Table 4 porous amorphous molecular sieve synthesized with MSPT

Relative areas of Q2, Q3 and Q4 species in the
29
calcined ZP materials
Material Q2 Q3
ZPZSM-12 4.3 12.6
ZPNU-87 3.3 23.7
ZPITQ-21 3.1 11.7
(PyH)+
1700 1600 1500
-1
Wavenumber (cm )
Fig. 9. Infrared spectra of the ZP material synthesized with MSPT. The
C@C and C@N stretching region of the adsorbed pyridine after
desorption at 423 K.
agrees with XRD and IR results that show no short or
long range order.
19
F MAS NMR spectroscopy is a powerful technique to
characterize the presence of crystalline nucleus in zeolites
synthesized in fluoride media. Indeed, F tends to locate
into and stabilize small cages, for instance D4R in zeolites
[19], giving very characteristic specific 19F MAS NMR
bands [20–25], which can be used to detect the presence
of very small zeolitic nucleus, not detectable by XRD. It
is remarkable that the ZP samples synthesized with MSPT,
M6BTM and E4ABO (see Table 1) give none of such bands,
while they are clearly visible in the corresponding ITQ-21,
ITQ-13 and ITQ-7, confirming therefore the amorphous
nature of the former microporous molecular sieves.
27
Al MAS NMR shows that in Al containing calcined
zeolite precursors, it is in tetrahedral coordination and
gives raise to Brönsted acidity, as we have observed by
pyridine-adsorption/desorption measurements (Fig. 9).
These acid sites are active and selective for catalyzing car-
boniogenic reactions. In order to investigate that, cracking
and alkylation reactions of hydrocarbons were catalyzed
with aluminosilicate ZP materials (Table 5).
The catalytic results presented in Table 5 were carried
out in a continuous fixed reactor, and show that the micro-
Si
NMR spectra of
(ZPITQ-21) gives the same catalytic activity than the corre-
sponding large pore zeolite (12-R) ITQ-21 for cracking
Q4 1,3-diisopropylbenzene (DIPB), which can easily diffuse
83.1 into 12-ring pore zeolites. However, for cracking the bulk-
73.0 ier 1,3,5-triisopropylbenzene (TIPB), ZPITQ-21 is more
85.2
active than ITQ-21, showing the presence of slightly larger
pores, probably due to incompletely formed cages and cav-
ities in the former material.
(Py : Lewis) The above observation fits very well with the distribu-
tion of the trimethylpentane isomers (TMP) obtained dur-
ing alkylation of 2-butene with isobutane (Table 5). Indeed,
ZPITQ-21 is more selective towards the bulkier 2,2,4-TMP
423 K and 2,2,3-TMP (which have the highest octane numbers)
than the corresponding ITQ-21. It has to be remarked that
the molar ratio R (R = (2,2,4-TMP + 2,2,3-TMP)/(2,3,4-
1400
TMP + 2,3,3-TMP)) has been associated with shape selec-
tivity effects in zeolites, being this ratio higher for zeolites
with larger pores [26,27].
It is interesting to notice that Nicolle et al. [28] found
that TEA-permutite with a irregular local organization
can be formed during the synthesis of Beta. The authors
believe that the TEA-permutite can either enhance zeolite
formation by providing heterogeneous nucleation sites, or
hinder the crystallization by competing with zeolites for
common growth units. They observed a much smaller
micropore volume for TEA-permutite than for Beta zeo-
lite. However, in the case of the amorphous zeolite precur-
sors presented here, the micropore volume is always
practically the same as for the final zeolite, indicating that
they are probably a partially arranged amorphous version
of the zeolite with already a large amount of Si–O–Si bonds
formed, but with still an important fraction of internal
defects, as was evidenced by 29Si MAS NMR.
4. Conclusions
In conclusion, we have found that it is possible to pre-
pare materials which can be seen as stable amorphous
microporous molecular sieves, which appear to be zeolite
precursors. They can be synthesized with different pore
diameters and micropore volumes that can be controlled
by the size and shape of the OSDA. Despite their impor-
tant amount of defects, they are stable for steam calcina-
tion at least up to 923 K.

Table 5
Catalytic activity of a ZP material synthesized with MSPT (ZPITQ-21)
Catalyst Cracking (·102)a Alkylation selectivities in the trimethylpentane (TMP) fractionb
KDIPB KTIPB KDIPB/KDIPB Conversion (%) 2,2,4 + 2,2,3-TMP 2,3,4 + 2,3,3-TMP Rc
ZPITQ-21 5.9 7.1 0.82 92.8 61 39 1.6
ITQ-21 6.0 6.1 0.99 92.5 33 67 0.5
a
Cracking: T = 773 K; time on stream = 60 s; amount of catalyst = 0.200 g; K units = g hydrocarbon g catalyst
1 s
1.
b
Alkylation of 2-butene with isobutane: T = 323 K; P = 25 bar; WHSV (h
1) = 0.8; molar ratio isobutane/2-butene = 15.
c
R = selectivity(2,2,4 + 2,2,3-TMP)/selectivity(2,3,4 + 2,3,3-TMP).
46 A. Corma, M.J. Dı́az-Cabañas / Microporous and Mesoporous Materials 89 (2006) 39–46

Acknowledgments [13] V.P. Valtchev, K.N. Bozhilov, J. Phys. Chem. B 108 (2004) 15587.
[14] D.D. Kragten, J.M. Fedeyko, K.R. Sawant, J.D. Rimer, D.G.
Vlachos, R.F. Lobo, M. Tsapatsis, J. Phys. Chem. B 107 (2003)
The authors thank CICYT (MAT 2003-07945-C02-01) 10006.
for financial support and Dr. J. Martı́nez and Dr. C. Martı́- [15] (a) B. Fahlke, P. Starke, V. Seefeld, W. Wieker, K.P. Wendlandt,
nez for performing the catalytic tests. Zeolites 7 (1987) 209–213;
(b) P.A. Jacobs, E.G. Derouane, J. Weitkamp, J. Chem. Soc. Chem.
References Commun. (1981) 591.
[16] G. Coudurier, C. Naccache, J.C. Vedrine, J. Chem. Soc. Chem.
Commun. (1982) 1413.
[1] M.E. Davis, Nature 417 (2002) 813.
[17] E.M. Flanigen, H. Khatami, H.A. Szymanski, Adv. Chem. Ser. 101
[2] A. Corma, J. Catal. 216 (2003) 298.
(1971) 201.
[3] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge,
[18] E.M. Flanigen, R.L. Patton, US Patent 4,073,865, 1978.
K.D. Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, J. Am.
[19] J.L. Guth, H. Kessler, J.M. Higel, J.M. Lamblin, J. Patarin, A. Seive,
Chem. Soc. 114 (1992) 10834.
J.M. Chezeau, R. Wey, ACS Symp. Ser. 398 (1989) 176.
[4] C.S. Cundy, P.A. Cox, Chem. Rev. 103 (2003) 663.
[20] H. Koller, A. Woelker, L.A. Villaescusa, M.J. Diaz-Cabanas, S.
[5] (a) G.D. Stucky, Q. Huo, A. Firouzi, B.F. Chmelka, S. Schacht, I.G.
Valencia, M.A. Camblor, J. Am. Chem. Soc. 121 (1999) 3368.
Voigt-Martin, F. Schuth, in: H. Chou, S.-K. Ihm, Y.S. Uh (Eds.),
[21] A. Corma, M.J. Diaz-Cabanas, J. Martinez-Triguero, F. Rey, J. Rius,
Progress in Zeolite and Microporous Materials, Stud. Surf. Sci.
Nature 418 (2002) 514.
Catal., vol. 105, Elsevier, Amsterdam, 1996, p. 3;
[22] A. Corma, M. Puche, F. Rey, G. Sankar, S.J. Teat, Angew. Chem.
(b) C.J. Glinka, J.M. Nicol, G.D. Stucky, E. Ramli, D.I. Margolese,
Int. Ed. 42 (2003) 1156.
Q. Huo, Mater. Res. Soc. Symp. Proc. 371 (1995) 47.
[23] A. Corma, F. Rey, S. Valencia, J.L. Jorda, J. Rius, Nature Mater. 7
[6] R.F. Lobo, S.I. Zones, M.E. Davis, J. Inclusion Phenom. Mol.
(2003) 493.
Recog. Chem. 21 (1995) 47.
[24] G. Sastre, J.A. Vidal-Moya, T. Blasco, J. Rius, J.L. Jorda, M.T.
[7] A. Corma, M.E. Davis, Chem. Phys. Chem. 5 (3) (2004) 304.
Navarro, F. Rey, A. Corma, Angew. Chem. Int. Ed. 41 (2002) 4722.
[8] (a) S.L. Burkett, M.E. Davis, Chem. Mater. 7 (1995) 920–928;
[25] Y.X. Wang, J.Q. Song, H. Gies, Solid State Sci. 5 (2003) 1421.
(b) M.E. Davis, R.E. Lobo, Chem. Mater. 4 (1992) 756–768;
[26] A. Corma, V.I. Costa-Vaya, M.J. Diaz-Cabanas, F.J. Llopis, J. Catal.
(c) H. Gies, B. Marler, Zeolites 12 (1992) 42.
207 (2002) 46.
[9] C.D. Chang, A.T. Bell, Catal. Lett. 8 (1991) 305.
[27] J. Weitkamp, in: B. Imelik, C. Naccache, Y. Ben Taarit, J.C. Vedrine,
[10] (a) S.L. Burkett, M.E. Davis, J. Phys. Chem. 98 (1994) 4647–4653;
G. Coudurier, H. Praliaud (Eds.), Catalysis by Zeolites, Stud. Surf.
(b) S.L. Burkett, M.E. Davis, Chem. Mater. 7 (1995) 1453.
Sci. Catal., vol. 5, Elsevier, Amsterdam, 1980, p. 65.
[11] W.H. Dokter, T.P.M. Beelen, H.F. van Gardener, R.A. van Santen,
[28] M.A. Nicolle, F. Di Renzo, F. Fajula, P. Espiau, T. Des Courieres, in:
W. Bras, G.E. Derbyshire, G.R.J. Mant. Appl. Cryst. 27 (1994) 901.
R. von Ballmoos, J.B. Higgins, M.M.J. Treacy, Proc. Int. Zeolite
[12] (a) A. Corma, H. Garcia, Chem. Rev. 103 (2003) 4307–4365;
Conf. 9th, 1993, p. 313.
(b) A. Corma, H. Garcia, Chem. Commun. (2004) 1443–1444;
(c) A. Corma, H. Garcia, Eur. J. Inorg. Chem. (2004) 1143.