View Article Online / Journal Homepage / Table of Contents for this issue

PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics

In situ monitoring of desilication of MFI-type zeolites in alkaline

medium
Johan C. Groen,a Gerben M. Hamminga,a Jacob A. Moulijna and
Javier Perez-Ramrezbc
Received 10th April 2007, Accepted 18th June 2007
First published as an Advance Article on the web 5th July 2007
DOI: 10.1039/b705418a
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.

In situ pH and Attenuated Total Reection (ATR) infrared techniques have been successfully
applied in order to gain insights into the dissolution process connected to mesopore formation
occurring upon alkaline treatment of ZSM-5 zeolites. Online pH measurements reveal a similar
consumption of OH ions in the initial stage of the reaction independent of the Si/Al ratio of the
zeolite. In view of the greatly dierent mesoporosity development, the extraction of polymeric
silica entities is anticipated, its structure depending on the framework Si/Al ratio. In agreement,
ATR-IR experiments have conrmed dissolution of polymeric silicon-containing species that in
the course of the alkaline treatment disintegrate into smaller entities. A direct relation between
the type of porosity developed and the process of silicon extraction as measured in the liquid
phase cannot be drawn.

1. Introduction ers4,5 have previously reported on the dissolution of high-silica

Framework silicon extraction in alkaline medium is an e-
cient approach to create intracrystalline mesoporosity in MFI
type zeolites1 in order to obtain improved molecular transport
in the micropore network.2 In recent work, several descriptors
such as time and temperature of the treatment, concentration
and type of base, stirring speed, etc. were identied and
optimized.3 We have concluded that the Si/Al ratio of the
MFI zeolite mainly determines the eciency of the alkaline
treatment in terms of mesoporosity development. An optimal
range of Si/Al ratios of 2550 was established, where sub-
stantial mesoporosity was achieved leading to mesopore sur-
face areas up to 250 m2 g 1, which represents an increase of
more than 400%. At lower Si/Al ratios, a very limited
mesoporosity development was attained as a result of a low
degree of framework silicon extraction, whereas at higher
Si/Al ratios excessive extraction led to the formation of large
pores.1
Limited information is available on the kinetics of the
desilication process and particularly on the nature of the
extracted silicon species. Understanding the mechanism and
kinetics of desilication can be essential in order to tailor the
porous properties of zeolites according to practical require-
ments. A hurdle to gain insights into this process is that studies
are typically practiced ex situ, i.e. arresting the reaction at a
certain time, exposing to dierent conditions, handling, and
analyzing the product thereby obtained. Cizmek and co-work-
a
Department DelftChemTech, Delft University of Technology,
Julianalaan 136, 2628 BL Delft, The Netherlands. E-mail:
J.C.Groen@tudelft.nl; Fax: +31 15 278 44 52; Tel: +31 15 278 43
71
b
Institute of Chemical Research of Catalonia (ICIQ), Av. Pasos
Catalans 16, 43007 Tarragona, Spain
c
Catalan Institution for Research and Advanced Studies (ICREA),
Pg Llus Company 23, 08010 Barcelona, Spain ICIQ
MFI zeolites in concentrated sodium hydroxide solutions.
Changes in silicon and aluminium concentration in the treat-
ment solution were investigated ex situ, via the withdrawal of
samples at various reaction times, ltration, and subsequent
analysis by ICP-OES. Their results showed a lower rate of
silicon dissolution with increased framework aluminium con-
centration. Despite the fact that these investigations were per-
formed at much higher concentrations of NaOH (5 mol l 1) as
compared to our previous experiments (0.10.8 mol l 1),3
their conclusion appears to be in good agreement with
our observations over commercial zeolites with varying Si/Al
ratio.6 A higher Si/Al ratio of the treated zeolite similarly
led to a higher concentration of silicon in the ltrate and
vice versa.
The main drawback of the ex situ approach is that the
various steps to be taken possibly impact on the original
properties of the extracted species. This has recently been
conrmed by in situ and ex situ Raman studies concerning
the structure of water-soluble silicates, in which sample with-
drawal distinctly altered the surface properties of the silicate
species.7 Moreover, the withdrawal of samples can also induce
an alteration the reaction medium. Accordingly, in situ meth-
odologies are highly preferred, since they guarantee that the
sample being analyzed is truly representative of the reaction
matrix. Besides, the continuous monitoring provides a more
accurate description of the dynamics of the process.
In situ investigations aiming at information on silicon
compounds mostly make use of 29Si MAS-NMR.8 Despite
the high specicity of NMR allowing dierentiation among
silicon atoms attached to dierent ligands,9 the relatively low
sensitivity makes this technique a less suitable in situ tool to
study these desilication reactions. To achieve more insight
into the extracted silicon species in solution and avoid
labor-intensive batch-wise sampling and subsequent

4822 | Phys. Chem. Chem. Phys., 2007, 9, 48224830 This journal is

c the Owner Societies 2007
 View Article Online

characterization, the relatively novel ATR-IR technique was

selected. This approach enables to acquire real time FTIR
spectra in liquid-phase applications under operating condi-
tions with reasonable sensitivity,1013 even in aqueous solu-
tions.14 So far, the ATR methodology has mostly been applied
to study kinetics of catalyzed reactions. Some examples of
successful application of this technique comprise the liquid-
phase hydrogenation of butyrolactone over CuZnO cata-
lysts11 and the photo-assisted decomposition of malonic acid
over TiO2.12 Due to its relative novelty, the full capability of
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.

ATR has not been exploited and limited information is avail-

able on the application of this technique to acquire mechan-
istic and kinetic information for optimization of materials
treatments.15
In this manuscript, we have integrated in situ pH measure-
ments and ATR-IR spectroscopy in order to (i) gain mechan-
istic and kinetic insights into the desilication process in
relation to the process of silicon extraction, dissolution, and
mesopore formation, and (ii) investigate the opportunities of
online monitoring. To this end, MFI zeolites with a Si/Al ratio
below (15), in (25) and above (200) the optimal range for
mesopore formation have been investigated. Whereas the
ATR-IR technique enables identication of the types of silicon
species that are being (trans)formed in the course of the
alkaline treatment over the various zeolites, pH analyses
provide direct kinetic information on the OH consumption.
2. Experimental
2.1 Materials and treatment
Zeolites. The commercial MFI zeolites used in this study are
listed in Table 1. To prevent ion exchange with Na ions during
the desilication treatment in NaOH solutions, all samples were
rstly converted into the Na-form by three successive ion-
exchange steps in 0.1 mol l 1 sodium acetate. After the ion
exchange procedure, the zeolites were calcined in static air at
823 K for 5 h.
Fig. 1 The experimental set-up used for the combined pH and
ATR-IR experiments.
2.2 Characterization
N2 adsorption at 77 K was performed in a Quantachrome
Autosorb-6B gas adsorption analyzer to derive information on
the porous characteristics of the non-treated and treated
samples. The samples were treated in vacuum at 573 K for
12 h prior to the adsorption measurement. The BET method16
was applied in the adapted relative pressure range of 0.010.1
to calculate the apparent total surface area, while the t-plot
method17 was used to discriminate between micro- and meso-
porosity. In case of the t-plot, the reported mesopore surface
area (Smeso) consists of contributions from the outer surface of
the particles as well as mesopores and macropores. The BJH
model applied to the adsorption branch of the isotherm
provides information on the mesopore size distribution.18 Si
and Al concentrations in the zeolites and in the ltrates
obtained upon alkaline treatment were determined by
ICP-OES in a Perkin-Elmer Optima 3000DV.

2.3 In situ monitoring of desilication treatment

Alkaline treatment. Alkaline treatment of the zeolites was
performed in an aqueous 0.2 mol l 1 NaOH solution at 338 K.
To this end, 660 mg of sample were vigorously stirred in
20 cm3 of NaOH solution in a wide-neck polypropylene ask
(40 cm3) in order to simultaneously accommodate the ATR-IR
probe and the pH glass electrode. To prevent CO2 from
entering the NaOH solution, which could subsequently alter
the pH, the ask was covered with paralm and a purge ow
of N2 gas was applied. Along the manuscript, the alkaline-
treated samples are denoted with the sux -at.
The experimental set-up used in this study is shown in Fig. 1.
In order to attain data on the physical and chemical changes
during the alkaline treatment of the various zeolites, both the
ATR and pH probes were incorporated in the same reaction
vessel. FTIR spectra were collected using the ReactIRt 1000
spectrophotometer, equipped with a six reections Dicomp
(diamond composite) Attenuated Total Reectance (ATR)
insertion probe (ASI Applied Systems, Millersville). Spectra
were automatically collected every 30 s in the range of
4000650 cm 1, with the most important absorption bands

Table 1 Chemical composition and textural properties of the commercial MFI zeolites

Sample namea Commercial code and supplier Si/Alb SBETc/m2 g 1

Smesod/m2 g 1
Vmicrod/cm3 g 1

Z-15 CBV 3024E, Zeolyst 17 415 40 0.15

Z-25 PZ 2/40, Chemie Uetikon 26 410 35 0.16
Z-200 PZ 2/400, Chemie Uetikon 176 405 30 0.17
a b
The number in the sample name denotes the nominal molar Si/Al ratio; measured by ICP-OES; c BET method; d
t-plot method.

This journal is

c the Owner Societies 2007 Phys. Chem. Chem. Phys., 2007, 9, 48224830 | 4823

related to silicon in the range of 1300800 cm 1. The data
points of the collected spectra were the average of 32 scans at a
nominal resolution of 4 cm 1. The spectrum obtained in the
NaOH solution at 338 K without zeolite was subtracted as a
background from the reaction spectra. Results were post-
processed using the ConcIRTt Opus I software, which ana-
lyzes intensity changes in the acquired spectra as a function of
time. This makes it possible to extract absorption bands
belonging to the same component and to build its individual
spectrum and corresponding prole.
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.
pH measurements were performed using a Metrohm 620
pH-meter and a 6.0259.100 combined glass electrode, suitable
for operating at high pH and temperatures up to 353 K. The
recorded analogue mV signal was transferred to a computer
for data collection. Calibration of the pH equipment required
special eort due to the so-called alkali error.19 Despite the
extremely high sensitivity of the glass electrode of H+ over
Na+, at low concentration of H+, i.e. high pH, and a high
concentration of alkali metal ions, the pH reading is de-
creased. This in turn would lead to erroneous OH concentra-
tions. Since the obtained pH nally needed to be converted to
a consumption of hydroxyl ions, the calibration was con-
ducted using NaOH solutions of dierent OH concentration,
but with xed Na+ concentration. In this way, the desilication
Fig. 2 N2 adsorption (open symbols) and desorption (lled symbols) isotherms (left) and corresponding adsorption BJH pore size distributions
(right) of the non-treated (D) and alkaline-treated (B) zeolites.
4824 | Phys. Chem. Chem. Phys., 2007, 9, 48224830
View Article Online
treatment can be adequately mimicked, as hydroxyl ions are
consumed for the hydrolysis of silica species, whereas the
sodium concentration remains relatively constant. The Na+
concentration was xed at 0.2 mol l 1, while the OH con-
centration ranged from 0.001 to 0.2 mol l 1. Moreover, as the
desilication experiments were conducted at 338 K, the calibra-
tion was also performed at this temperature, so as to avoid
inconsistencies regarding the impact of temperature on e.g.,
the water dissociation constant pKw.20
A typical experiment was conducted as follows: the ATR
probe and the pH electrode were submersed in the alkaline
solution, which was subsequently heated to 338 K under
magnetic stirring (800 rpm). After reaching a stable tempera-
ture and electrode signal, the FTIR background was recorded,
which was subtracted from the reaction spectra. Then the
zeolite powder was poured into the solution, which was the
starting point of the reaction and the collection of the pH
reading and FTIR spectra.
3. Results and discussion
3.1 Physico-chemical properties of the zeolites
The N2 adsorption isotherms and the thereof derived Pore Size
Distributions (PSDs) depicted in Fig. 2 provide information
This journal is
c the Owner Societies 2007
 View Article Online

Table 2 Chemical composition and textural properties of the alkaline-treated MFI zeolites

Sample name Si/Ala SBETb/m2 g 1

Smesoc/m2 g 1
Vmicroc/cm3 g 1
[Si]ltratea/g l 1
[Al]ltratea/g l 1

Z-15-at 15 390 50 0.14 0.57 0.008

Z-25-at 18 505 195 0.13 3.60 0.003
Z-200-at 133 425 105 0.16 5.30 0.002
a b
measured by ICP-OES; BET method; c t-plot method.

on the porosity development upon alkaline treatment of the sumption, in accordance with the high concentration of silicon
dierent ZSM-5 zeolites in 0.2 mol l 1 NaOH solution. The measured in the ltrate (Table 2). The consumption of OH
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.

adsorption isotherms of the parent zeolites conrm the pre- after 30 min treatment is ca. 75%, while 495% is consumed
dominantly microporous character. A relatively high uptake at after 60 min. It should be noted that at this nal concentration
low pressure related to the micropore lling and a minor of ca. 0.01 mol l 1 NaOH, the pH still amounts to B12.
increase in adsorption capacity at higher relative pressure Interestingly, the dierence in consumption between Z-15 and
due to the absence of signicant mesoporosity. Upon alkaline Z-25 after 30 min treatment is not that pronounced. This is in
treatment, the isotherm of Z-15 experiences a minor alteration contrast to what one would expect based on the dierent
of the adsorption properties, due to the restricted framework porous properties developed in these materials after 30 min of
silicon extraction (Table 2) and connected mesopore forma- alkaline treatment (Fig. 2) and the signicantly higher degree
tion. This should be attributed to the relatively high concen- of silicon extraction in Z-25 (Table 2). The similar conversion
tration of framework aluminium that suppresses framework of OH during the rst 10 min could tentatively be ascribed to
silicon extraction, as explained in detail in previous work.1 the dissolution of the outer surface of the zeolite crystals, as
Contrarily, the isotherm of the alkaline-treated Z-200 shows a this parameter is quite similar in all three samples (values of
distinct uptake at high relative pressure, indicative of the Smeso in Table 1). However, we have observed recently that in
formation of relatively large pores, which is conrmed by the rst 510 min of the alkaline treatment, the majority of the
the BJH adsorption pore size distribution. Due to the forma-
tion of relatively large pores in the range of 3050 nm, the
mesopore surface area increases moderately from 30 m2 g 1 in
the starting material to 105 m2 g 1 in the alkaline-treated
zeolite. In agreement, a high degree of silicon extraction has
been measured in the resulting ltrate. In the case of sample
Z-25, having a framework composition within the previously
identied optimal range of Si/Al ratios,6 the controlled silicon
extraction leads to formation of mesopores centered around
10 nm and a largely increased mesopore surface area of
195 m2 g 1. The distinct dierences in silicon extraction and
mesopore formation have been further assessed by means of in
situ pH and ATR-IR measurements.

3.2 pH measurements
Calibration of the glass electrode was initially performed at
room temperature and subsequently at the operating tempera-
ture of 338 K (Fig. 3). The excellent t of the data obtained at
298 K by means of the Nernst equation21 coupled to the
derived pKw value of 14 conrms both the good correlation
among the various prepared NaOH solutions and the high
quality of the pH measurements during desilication. The
results acquired upon calibration at 338 K also present a good
agreement between the experimental data and the theoretical
description of the electrodes response, which can be used to
convert the measured pH values during the desilication experi-
ments to OH concentrations.
The experimental curves obtained upon alkaline treatment
of the various zeolites in 0.2 mol l 1 NaOH at 338 K are
depicted in Fig. 4. The OH consumption in the rst 10 min of
the desilication treatment is very similar. Only after ca. 10 min
the various curves start to diverge: the OH conversion after
longer reaction times decreases in the order Z-200 4 Z-25 4 Fig. 3 pH calibration curves of the glass electrode at 298 K and
Z-15. Particularly sample Z-200 shows a relatively high con- 338 K.

This journal is

c the Owner Societies 2007 Phys. Chem. Chem. Phys., 2007, 9, 48224830 | 4825
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.
Fig. 4 OH concentration proles derived from pH measurements during desilication of the dierent zeolites in 0.2 mol l
porosity is already established.3 This makes the similar OH
consumption at rst sight remarkable. However, the pore
directing role of framework aluminium could induce the
extraction of dissimilar silicon containing species of dierent
size in the various zeolites. This is schematically presented in
Scheme 1, where the fragment X represents a hydroxyl group
in case of monomeric species or a siloxane chain for polymeric
entities. This would also indicate that the recorded OH
consumption does not enable a quantitative assessment of
the desilication treatment, as the stoichiometry of silicon
extraction by OH ions diers from 1 and ultimately depends
on the zeolite in question. This observation is further ad-
dressed in the next section. The structure-sensitive character-
istics of infrared absorption spectroscopy should allow gaining
mechanistic information on the extraction of various silica
entities, which would be particularly meaningful over the
zeolites Z-15 and Z-25 that develop a very dierent porosity,
whereas the OH consumption is very similar in the initial
stage of the treatment.
3.3 ATR-IR
Contribution of solid particles. In principle, only liquid-phase
species are analyzed by the ATR-IR technique.22 However,
controversial statements have been reported in the literature
on the contribution of suspended solid particles to the re-
corded ATR proles.8,23,24 This is obviously a crucial aspect in
order to discriminate between contributions from liquid and
Scheme 1 Tentative schematic representation of the extraction of silicon-containing species from the zeolite framework upon treatment in NaOH
solution.
4826 | Phys. Chem. Chem. Phys., 2007, 9, 48224830
View Article Online
1
NaOH at 338 K.
solid phases. Pintar et al.23 did not observe any catalyst
contribution in the ATR-IR spectra during enantioselective
hydrogenation reactions catalyzed over Pd/C. Contrarily,
Hamminga et al.10,24 concluded a pronounced contribution
of the interaction of the reactant with the silica catalyst
particles when executing esterication and etherication reac-
tions of 1-octanol and hexanoic acid. This interaction resulted
in a pronounced additional band centred at 1100 cm 1, which
has been assigned to the siliceous catalyst particles despite the
fact that silica was not expected to dissolve in the non-polar
solvent.
The potential contribution of solid zeolite particles to the
ATR spectra in our experiments was preliminary investigated
by recording (i) the ATR proles of the zeolite particles
dispersed in demineralized water and (ii) the impact of stirring
on the intensity of the bands during the dissolution experi-
ments in NaOH solution. When recording the ATR spectra of
the dierent zeolites after dispersion of the samples in water,
no signicant bands could be observed. This suggests that the
original zeolite particles do not signicantly contribute to the
spectra. If the zeolite powder suspended in the NaOH solution
would participate, stopping the stirring procedure should
aect the intensity of the several bands, due to settling of the
particles. However, the intensity of the various bands was not
altered after precipitation. Both observations support the
hypothesis that in our experiments the original zeolite particles
do not signicantly inuence the ATR spectrum and thus the
This journal is
c the Owner Societies 2007
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.
Fig. 5 Waterfall ATR-IR plots upon treatment of Z-15 and Z-25 in
0.2 mol l 1 NaOH at 338 K.
recorded proles can be exclusively attributed to dissolved
silicon-containing species.
Desilication experiments. Representative waterfall plots
upon desilication of Z-15 and Z-25 in 0.2 mol l 1 NaOH at
338 K are depicted in Fig. 5. Various absorption bands can be
perceived that change in intensity in the course of the treat-
ment. At the onset of the treatment, an intense broad band
appears around 1100 cm 1, which has generally been assigned
to asymmetric SiOSi stretching in siloxane chains.25,26 At
higher wavenumbers, an additional band at 1220 cm 1 is
present. This band is characteristic of SiOSi vibrations of
ve-membered rings (5 MR) present in the MFI framework,
not being observed for amorphous silica.2729 The presence of
this band suggests that silica entities with partially zeolitic
properties are extracted during the desilication treatment of
the zeolites. In a relatively short-time scale, these two bands
reach maximum intensity and new bands appear at 1020 cm 1
and 880 cm 1. The band centered around 1020 cm 1 is
attributed to the presence of SiOSi in innite siloxane chains
and/or SiOH deformation vibrations in condensed state. In
the case of SiOSi stretching, generally the bands observed at
1100 and 1020 cm 1 have similar intensity.25 In our spectrum,
the intensities are clearly dissimilar and accordingly the band
at 1020 cm 1 should be assigned to SiOH deformation.
Finally, the band observed around 910830 cm 1 must be
attributed to SiO stretching vibrations in SiOH groups.26
From the evolution of the various bands, it can be concluded
that initially mostly polymeric silica species with 5 MR
characteristics that are extracted during the treatment disin-
This journal is
c the Owner Societies 2007
View Article Online
Fig. 6 Evolution of the 1100 cm 1 (top) and 880 cm 1 (bottom)
bands over Z-15 and Z-25 upon alkaline treatment in 0.2 mol l 1
NaOH at 338 K.
tegrate into smaller entities likely of monomeric nature and a
relatively high concentration of silanol groups. This is in
agreement with previously reported dissolution studies over
quartz and amorphous silica at temperatures of 298 K and
363 K.30 In that work, it was proposed that polymeric species
are present to a large extent at pH 4 11, while at lower pH
values these polymeric species are less stable and formation of
smaller species is favored. Throughout the alkaline treatment,
consumption of OH will induce a decrease in pH (Fig. 4) and
thus the polymeric silica species will become less stable. This
can explain the decline in the characteristic band at 1100 cm 1
in favor of the bands centered around 1020 and 880 cm 1,
being characteristic of smaller sized silica species with
increased SiOH features.25
Plotting the evolution of the 1100 cm 1 band with time
reveals that, in the initial stage of the treatment, the intensity
over Z-25 is ca. two times higher than in Z-15 (Fig. 6, top).
This indicates that the degree of silicon extraction is indeed
more extensive in Z-25, in agreement with ICP-OES analyses
of the ltrates obtained upon alkaline treatment. During the
next 30 min of the treatment, a decrease in this characteristic
band can be observed. The observation that in the early stage
of the treatment a maximum intensity is observed should likely
be attributed to the crucial role of framework aluminium on
the silicon extraction process and related mesoporosity devel-
opment.1 Relatively easily hydrolyzable silicon species are
extracted in the initial stage of the treatment and these species
subsequently disintegrate into smaller entities. As a
Phys. Chem. Chem. Phys., 2007, 9, 48224830 | 4827

Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.
Fig. 7 Correlation between the Si4+ concentration measured in the
ltrate and the consumption of OH determined from pH measure-
ments after 30 min alkaline treatment of the dierent zeolites in
0.2 mol l 1 NaOH at 338 K.
consequence, the SiOSi vibration-related contributions
weaken. This disintegration of extracted species is more
pronounced in Z-25 than in Z-15, as can be concluded from
the larger intensity decline in the former. The higher alumi-
nium concentration in Z-15 not only suppresses silicon extrac-
tion from the parent zeolite particles, but also controls the
further dissolution of extracted aluminosilicate lumps. More-
over, the relatively low consumption of OH by Z-15 pre-
serves the relatively high pH, which enables the co-existence of
polymeric silica species.30 The further dissolution of extracted
silicate species leads to an enhanced concentration of SiOH
groups and as a result, the associated bands at 1020 cm 1 and
880 cm 1 gain intensity. This appears to proceed faster in Z-25
than in Z-15 (Fig. 6, bottom), which is also related to frame-
work aluminium in the extracted fragments. The potential
contribution of these aluminium-related vibrations could not
be discerned in the spectra since (i) the concentration of these
species is very low and (ii) the wavenumbers at which AlO
stretching vibrations and AlOH bending vibrations contri-
bute are very similar to those of silicon-related entities.3133 In
the course of the treatment, additional small portions of the
parent zeolite particles can be extracted, due to the stabilizing
role of framework aluminium. That induces a moderate
alteration of the mesoporosity after longer treatment times,
as has been observed previously.1 Based on the above discus-
sion, it can be anticipated that the majority of the mesopor-
osity is already established after 610 min treatment. This is in
fairly good agreement with previous observations during
scale-up studies of the alkaline treatment, which revealed that
7590% of the ultimate mesopore surface area increase was
achieved within 15 min.3
The role of framework aluminium in the subsequent dis-
solution of extracted silica fragments is substantiated by the
pH experiments. In Fig. 7, the concentration of silicon in the
ltrate as measured by ICP-OES (Table 2) versus the OH
consumption as derived from pH measurements is plotted. As
concluded above, the Si : OH stoichiometry for treatment of
the various zeolites diers from 1. In case of the more siliceous
Z-25 and Z-200, the molar ratio is 1.6 and 1.3, respectively.
4828 | Phys. Chem. Chem. Phys., 2007, 9, 48224830
View Article Online
This conrms indeed that even after 30 min treatment poly-
meric entities should be present in the NaOH solution and that
a higher degree of monomeric-type silicon species is obtained
in Z-200 than in Z-25. The latter can be explained by the very
low aluminium content in the more siliceous Z-200 sample that
hardly impacts on the further disintegration of the larger silica
entities to monomeric species. Surprisingly, the relatively low
silicon extraction in sample Z-15 leads to a molar ratio Si : OH
that is much smaller than 1. This can tentatively be attributed
to the somewhat higher degree of aluminium leaching to the
ltrate coupled with an overall low degree of silicon extraction
(Table 2) and related interaction of these (non-framework)
aluminium species with extracted silicon thereby forming a
non-soluble aluminosilicate.
Scheme 2 recapitulates the development of the materials
properties addressed in this contribution. In the initial stage of
the alkaline treatment, dierently sized silica entities are
extracted, whose size depends on the Si/Al ratio of the zeolite.
In the case of relatively low framework aluminium content (i.e.
a high Si/Al ratio), a signicant amount of larger polymeric
entities are extracted that, in the course of the treatment,
further disintegrate into smaller entities. This leads to a
maximum in the intensity of the band associated with SiOSi
vibrations and a subsequent decrease upon disintegration of
these species (Scheme 2, top). Materials with a relatively high
framework aluminium concentration exhibit a limited extrac-
tion of silica species, thus leading to a lower intensity of the
SiOSi related band (Scheme 2, bottom). The higher alumi-
nium content also suppresses further dissociation of the
extracted entities, resulting in a smaller decline of this band
in the course of the treatment. This also implies that the
extraction of siloxane chains, as given in Scheme 1, can be
succeeded by a further disintegration into smaller entities also
requiring the consumption of OH .
In summary, the applied in situ techniques provide comple-
mentary information on the desilication process upon alkaline
treatment through kinetic and mechanistic information on the
extracted silicon-containing species. The extraction of dier-
ently sized entities has been identied. Accordingly, a direct
relation between liquid-phase properties and solid-phase char-
acteristics in terms of porosity developed cannot be drawn. As
a result, the application of o-line techniques that provide
direct information on the porous properties of the solid
product, such as N2 adsorption, is additionally required. In
view of on-line process monitoring, particularly ATR-IR has
proven to be a suitable technique due to its relatively high
specicity. Similar to the application of UV/Vis microspectro-
scopy in the preparation of supported metal oxide catalysts34
and the combination of UV/Vis and Raman spectroscopy to
obtain information on catalyst regeneration during the dehy-
drogenation of propane,35 this approach can be eectively
used for monitoring catalyst preparation.
4. Conclusions
The successful application of in situ techniques for monitoring
the desilication process has been addressed. ATR-IR spectro-
scopy combined with pH measurements have provided valu-
able mechanistic insights into the extraction and evolution of
This journal is
c the Owner Societies 2007
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17. View Article Online

Scheme 2 Schematic representation of the evolution of extracted silicate species and the 1100 cm 1 band in MFI zeolites with an optimal (top)
and sub-optimal (bottom) framework Si/Al ratio. The species given in black are liquid-phase entities that contribute to the ATR-IR spectrum,
whereas the grey species are in the solid and thus considered to be non-visible for the technique.

silica species during alkaline treatment of MFI zeolites with
varying Si/Al ratio. Quantitative analysis of the OH conver-
sion via pH measurements points to the extraction of dierently
sized silica entities. ATR-IR provides conrmative results that
the silicon extraction correlates with the framework Si/Al ratio
of the zeolites: a low degree of extraction at low Si/Al ratios and
vice versa. ATR-IR experiments have furthermore concluded
that the initially extracted polymeric silica species disintegrate
into smaller entities, which is controlled by framework Al. Due
to the resulting variable Si : OH stoichiometry, the extracted
species as measured in the liquid phase do not provide full
insight into the nal porosity obtained.

This journal is

c the Owner Societies 2007 Phys. Chem. Chem. Phys., 2007, 9, 48224830 | 4829

Acknowledgements
The authors thank S. J. Huynink (TU Delft) for his valuable
contribution to the pH investigations. Dr S. Abello (ICIQ,
Tarragona, Spain) is acknowledged for fruitful discussions on
the ATR data.
References
1 J. C. Groen, L. A. A. Peer, J. A. Moulijn and J. Perez-Ramrez,
Chem.Eur. J., 2005, 11, 4983.
Published on 05 July 2007. Downloaded by University of Waikato on 09/07/2014 13:50:17.
2 J. C. Groen, W. Zhu, S. Brouwer, S. J. Huynink, F. Kapteijn, J. A.
Moulijn and J. Perez-Ramrez, J. Am. Chem. Soc., 2007, 129, 355.
3 J. C. Groen, J. A. Moulijn and J. Perez-Ramrez, Ind. Eng. Chem.
Res., 2007, 46, 4193.
4 A. Cizmek, B. Subotic, R. Aiello, F. Crea, A. Nastro and C. Tuoto,
Microporous Mater., 1995, 4, 159.
5 A. Cizmek, B. Subotic, I. Smit, A. Tonejc, A. Rosario, F. Crea and
A. Nastro, Microporous Mater., 1997, 8, 159.
6 J. C. Groen, J. C. Jansen, J. A. Moulijn and J. Perez-Ramrez,
J. Phys. Chem. B, 2005, 108, 13062.
7 I. Halasz, M. Agarwal, R. Li, N. Miller, Catal. Today, 2007, DOI:
10.1016/j.cattod.2006.09.032.
8 G. E. Maciel and I. S. Chuang, Surf. Sci. Ser., 2006, 131, 425.
9 T. N. M. Bernards, M. J. van Bommel and A. H. Boonstra, J. Non-
Cryst. Solids, 1991, 134, 1.
10 G. Mul, G. Hamminga and J. A. Moulijn, Vib. Spectrosc., 2004,
34, 109.
11 G. Hamminga, G. Mul and J. A. Moulijn, Chem. Eng. Sci., 2004,
59, 5479.
12 I. Dolamic and T. Burgi, J. Phys. Chem. B, 2006, 110, 14898.
13 T. Burgi and A. Baiker, Adv. Catal., 2006, 50, 227.
14 M. R. Dadd, D. C. A. Sharp, A. J. Pettman and C. J. Knowles,
J. Microbiol. Methods, 2000, 41, 69.
15 M. I. Tejedor-Tejedor, L. Paredes and M. A. Anderson, Chem.
Mater., 1998, 10, 3410.
4830 | Phys. Chem. Chem. Phys., 2007, 9, 48224830
View Article Online
16 S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938,
60, 309.
17 B. C. Lippens and J. H. de Boer, J. Catal., 1965, 4, 319.
18 E. P. Barret, L. G. Joyner and P. H. Hallenda, J. Am. Chem. Soc.,
1951, 73, 373.
19 H. Galster, pH Measurement, Fundamentals, Methods, Applications
Instrumentation, VCH, Weinheim, 1991, pp. 138141.
20 M. Whiteld, in Chemical Oceanography, ed. J. P. Rily and G.
Skirrow, Academic Press, London, 1975, vol. 1, 2nd edn.,
pp. 44171.
21 H. Galster, pH Measurement, Fundamentals, Methods, Applications
Instrumentation, VCH, Weinheim, 1991, pp. 2122.
22 N. J. Harrick, Internal Reection Spectroscopy, Interscience
Publishers, New York, 1967.
23 A. Pinar, R. Malacea, C. Pinel, G. Fogassy and M. Besson, Appl.
Catal., A, 2004, 264, 1.
24 G. M. Hamminga, G. Mul and J. A. Moulijn, Catal. Lett., 2006,
109, 199.
25 N. B. Clothup, L. H. Daly and S. E. Wiberly, Introduction to
Infrared and Raman Spectroscopy, Academic Press, London, 1990,
2nd edn, pp. 358362.
26 G. Socrates, Infrared and Raman Characteristic Group Frequencies:
Tables and Charts, Wiley, Chichester, 2001, 3rd edn, pp. 243246.
27 C. P. Bezouhanova and L. Zarev, Catal. Lett., 1994, 25, 169.
28 J. Park, S. B. Kim, J. M. Ha, H. S. Park and H. S. Hahm, Catal.
Lett., 2001, 75, 125.
29 R. Szostak, Molecular SievePrinciples of Synthesis and Identi-
cation, Blackie, London, 1989, pp. 310312.
30 J. Eikenberg, On the Problem of Silica Solubility at High pH, Paul
Scherrer Institut, Wurenlingen und Villigen, Switzerland, 1990.
31 L. M. Kustov, Top. Catal., 1997, 4, 131.
32 A. C. Geiculescu and T. F. Strange, Thin Solid Films, 2003, 426, 160.
33 A. Gritco, M. Moldovan, R. Grecu and V. Simon, J. Optoelectron.
Adv. Mater., 2005, 7, 2845.
34 L. G. A. van de Water, J. A. Bergwer, T. A. Nijhuis, K. P. de
Jong and B. M. Weckhuysen, J. Am. Chem. Soc., 2005, 127, 5024.
35 T. A. Nijhuis, S. J. Tinnemans, T. Visser and B. M. Weckhuysen,
Chem. Eng. Sci., 2004, 59, 5487.
This journal is
c the Owner Societies 2007