Microporous and Mesoporous Materials 33 (1999) 173185

www.elsevier.nl/locate/micmat

Characterization of the acidity of ultrastable Y, mordenite,

and ZSM-12 via NH -stepwise temperature programmed
3
desorption and Fourier transform infrared spectroscopy
Wenmin Zhang, Eric C. Burckle, Panagiotis G. Smirniotis *
Department of Chemical Engineering, University of Cincinnati, Cincinnati, OH 45221-0171, USA
Received 25 January 1999; received in revised form 15 May 1999; accepted for publication 8 June 1999

Abstract
The acidity of ultrastable Y ( USY ), mordenite, and ZSM-12 of variable Si/Al ratios has been characterized by
coupling NH -stepwise temperature programmed desorption (STPD) and FT-IR. The former technique allows us to
3
quantify accurately the ammonia chemisorbed on acid sites of different strengths. In contrast to other acidic oxide
catalysts, it was found that protonated zeolites possess distinct limits of acid strength and that chemisorbed ammonia
desorbs from each type of site only within particular temperature ranges. It was observed that for zeolites with Si/Al
ratios smaller than about 20 the number of ammonia molecules chemisorbed on both Lewis and Brnsted sites is
smaller than the total number of Al atoms present in the zeolite. However, an increase in the Si/Al ratio above this
threshold results in a 1:1 relation between the total number of acid sites and the amount of ammonia adsorbed. It
was found that for mordenite and ZSM-12 an increase of the dealumination severity results in a decrease of the acid
site strength. For USY the acid strength decreased with steam treatment, but then increased with acid leaching. The
FT-IR studies revealed that for the protonated USY, Lewis-bound ammonia is evolved within each temperature stage.
For mordenite, the Lewis sites are associated with desorption up to 250C. The non-dealuminated ZSM-12 (Si/Al=
35) sample possesses a relatively small number of Lewis sites, whereas the ZSM-12 samples with higher Si/Al ratios
had only Brnsted acid sites. A peak deconvolution procedure was performed in order to decompose accurately the
complex hydroxyl region of USY and mordenite and was used to separate the Lewis peak from structural vibrations
for ZSM-12. As a result, important information concerning the nature of the aluminum species present in these
zeolites (extraframework species, framework species present within the side pockets of mordenite, framework species
present within the b cages of USY, etc.) was obtained. 1999 Elsevier Science B.V. All rights reserved.
Keywords: FT-IR; Mordenite; NH -stepwise temperature programmed desorption (STPD); USY; ZSM-12
3

1. Introduction
Knowledge of the acidic properties of zeolites
has been shown to be very valuable in explaining
* Corresponding author. Tel.: +1-513-556-1474;
fax: + 1-513-556-3473.
E-mail address: panagiotis.smirniotis@uc.edu
(P.G. Smirniotis)

or predicting their behavior as catalysts for several

reactions. The dealumination of zeolites, which
commonly aims at achieving better time stability,
often may result in unexpected trends in the acid
strength and in the Brnsted to Lewis site ratio.
These properties are of great importance to their
catalytic performance. It has been observed that
the dealuminating agent, as well as the dealumination severity, plays a very important role in the

1387-1811/99/$ - see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S1 3 8 7 -1 8 1 1 ( 9 9 ) 0 0 13 6 - 5

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W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

final properties of the zeolite(s). For example, the

earlier work of Dumesic and co-workers [1]
showed that the increase of the steam severity
during the dealumination of ultrastable Y ( USY )
faujasite resulted in a decrease of Brnsted acid
site strength and a significant decrease of the
Brnsted to Lewis ratio. Others [2] observed that
acid leaching of USY samples results in uniform
removal of Al, whereas steaming results in zeolite
particles with significantly higher surface Al
concentration.
In the present paper, we investigate the acidity
of three zeolites in conjunction with their Si/Al
ratio. The zeolites studied, namely USY,
mordenite, and ZSM-12, are representative of
three-, two-, and one-dimensional pore structures
respectively, and are used quite extensively for
numerous processes. NH -stepwise temperature
3
programmed desorption (STPD) coupled with
FT-IR was used for the characterization of acidity.
The STPD procedure, introduced by us in Ref. [3],
permits the quantitative determination of ammonia
desorbing from acid sites of different strengths.
Combining this information with that obtained
from the FT-IR experiments allows us to characterize fully the acid sites; both type and strength
can be determined.

2. Experimental
2.1. Preparation of the protonated zeolites
The USY samples studied in this work were
obtained from the PQ Corporation and belong to
the CBV-family. The USY-500-2.6 sample (industrial name CBV-500 with a bulk Si/Al ratio of
2.6) was generated by the PQ Corporation via
steam dealumination of the parent USY
(CBV-100). In this paper, the first number after
the name USY will indicate the commercial name
of the CBV-XXX sample and the second number
in the name of each sample will refer to the bulk
Si/Al ratio. The samples having higher Si/Al were
obtained by acid leaching [2] of the USY-500-2.6
sample ( Table 1). The aforementioned dealuminations of USY were performed by the PQ
Corporation. Post-synthesis modification pro-

cedures performed by our group involved only

cation exchange with a 2 N NH+ solution followed
4
by heating to 450C for 1 h to remove NH , thus
3
resulting in the protonated form of the zeolite.
The parent mordenite was obtained from UOP
and was further dealuminated in our laboratory
with (NH ) SiF . The dealumination of mordenite
42 6
was carried out at 90C for 24 h under reflux with
the appropriate amount of (NH ) SiF added
42 6
dropwise. ZSM-12 was synthesized hydrothermally
[4] in our laboratory from an aluminosilicate
gel with composition 88SiO :Al O :6.6Na O:
2 2 3
2
13TEABr:900H O (where TEABr stands for tetra2
ethyl-ammonium bromide). Samples of higher
Si/Al ratios were prepared by acid leaching using
different concentrations of HCl. It is worth noting
that ZSM-12 preserves its crystallinity even under
highly acidic environments. The protonated zeolites were obtained by a cation exchange of 2 g of
each zeolite sample with 2.0 N NH Cl solution in
4
a 1 l flask at 90C for 4 h followed by calcination
in air at 450C for 1 h.
2.2. Acidity characterization experiments
NH -STPD coupled with FT-IR was used to
3
quantify the ammonia desorbing from different
types of site. In contrast to the traditional temperature desorption techniques, where the bed is
heated at a constant heating rate, we employ an
optimized stepwise heating profile that allows the
desorption of chemisorbed ammonia from sites of
different strengths. The temperature profile consisted of a series of isothermal periods separated
by steps of constant heating. The isothermal holding periods were at 180, 250, 350, 440, and 540C,
as described in Ref. [3]. It should be noted that
the addition of more isothermal periods does not
result in any change in the ammonia desorption
profile; five peaks are present. However, a decrease
in the number of isothermal periods or a variation
in the heating steps results in the overlapping of
the peaks. This work elucidates the optimum temperature profile for desorption of NH from the
3
zeolite catalysts.
For each experiment, 50 mg of the protonated
zeolite was loaded into the middle of a 6 mm I.D.
horizontal tube. In order to clean the sample, high

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W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Table 1
Properties of the zeolite samples studied
Zeolite

Sample

Source or dealumination method

Si/Ala

Crystallinity (%)

USY
USY
USY
USY
USY
Mordenite
Mordenite
Mordenite
ZSM-12
ZSM-12
ZSM-12

USY-100-2.6
USY-500-2.6
USY-712-5.8
USY-740-21
USY-760-28
MOR-9.5
MOR-18
MOR-36
ZSM-12-35
ZSM-12-54
ZSM-12-69

PQ Corporation
PQ Corporation
PQ Corporation
PQ Corporation
PQ Corporation
UOP
2 g (NH ) SiF
42 6
25 g (NH ) SiF
42 6
Synthesized in lab
3 N HCl
5 N HCl

2.6
2.6
5.8
21
28
9.5
18
36
35
54
69

100
83
81
79
72
100
83
71
100
#100
#100

a Bulk ratio determined from ICP analysis.

purity helium was passed through the bed for 1 h

at a temperature of 550C. The sample was then
cooled to 150C and anhydrous ammonia (4% in
helium) was admitted to the bed for 1 h to ensure
the complete saturation of all acid sites. The
temperature of 150C was selected in order to
exclude any physisorbed ammonia [57]. After
this step, high purity helium (30 cm3/min) was
supplied to the sample at 150C for 1 h to remove
excess NH . After this point, the STPD experiment
3
was started, and the ammonia desorption peaks
were recorded. Several replicates were performed
for each sample. The parameters introduced by
Gorte [8] were used to test for transport limitations
that may occur during the STPD experiments.
Indeed, we calculated a value greater than one for
the readsorption parameter, thus indicating that
readsorption is possible (very common for traditional TPD experiments). However, we have limited the effects of readsorption on our STPD
results by having a high flow rate and allowing
sufficient time for desorption between each heating
step. This is indicated by the fact that the results
were highly reproducible. To verify whether saturation of ammonia molecules on the zeolites is
complete, additional experiments were performed
using pure ammonia during the adsorption step.
All other experimental procedures were the same.
The results when using pure ammonia were the
same (within experimental error) as those obtained
with 4% ammonia in helium and, therefore,
demonstrate that complete saturation is occurring

and that the partial pressure of ammonia is not a

factor in our STPD experiments.
FT-IR spectroscopy was used to identify the
NH peaks obtained from the STPD as either a
3
Lewis or Brnsted acid site. Thin wafers (thickness
of about 50 mm) of the protonated form of each
zeolite sample were prepared by pressing about
5 mg of dry powder. The wafer was placed in a
bakeable IR cell with CaF windows. The cell,
2
equipped for the continuous flow of gases through
it, was placed in the compartment of a Bio-Rad
FTS-40 spectrophotometer. Prior to each experiment, the sample was heated at 550C for 1 h in
high purity helium for cleaning. During the cooling
step to 150C, anhydrous ammonia (4% in helium)
was admitted to the sample. The flow of ammonia
was continued after reaching 150C for 1 h to
ensure that complete saturation was achieved. The
sample was then purged with helium for several
hours to ensure the removal of any physisorbed
ammonia and to achieve equilibrium. Then the
wafer was heated to the required temperature to
simulate the exact conditions for desorption during
the NH -STPD experiments, and the IR spectra
3
were recorded. The spectra were obtained by averaging 16 scans taken with an open aperture and a
resolution of 8 cm1. From the spectra, it was
observed that there is a particular desorption temperature above which all Lewis-bound ammonia
has been driven off. After the desorption step from
350C to 440C, only Brnsted-bound ammonia is
present. Since the amount of ammonia driven off

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W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Table 2
Ammonia chemisorbed on the zeolite samples studied
Sample

NH /grama
3

NH /Al
3

Brnsted sites
(mmol/g catalyst)

Lewis sites
(mmol/g catalyst)

USY-100-2.6
USY-500-2.6
USY-712-5.8
USY-740-21
USY-760-28
MOR-9.5
MOR-18
MOR-36
ZSM-12-35
ZSM-12-54
ZSM-12-69

25.6
22.6
12.0
5.5
5.2
29.3
17.1
9.3
10.4
6.8
5.7

0.24
0.38
0.47
0.53
0.87
0.81
0.88
0.91
0.98
0.99
1.06

0.647
0.351
0.141
n.d.b
0.106
0.609
0.213
0.112
0.389
0.300
0.250

0.417
0.589
0.359
n.d.b
0.110
0.611
0.499
0.275
0.071
0.000
0.000

a Milliliters of ammonia under STP conditions.

b n.d. not determined.

during the last desorption step (from 440 to 540C )

is measurable and is due to only Brnsted sites,
the extinction coefficients for Brnsted-bound
ammonia can be calculated. This extinction
coefficient can then be used to determine the
amount of ammonia adsorbed on Brnsted sites
prior to desorption. The amount of Lewis-bound
ammonia is then obtained by assuming ammonia
adsorbs only on Brnsted and Lewis sites
( Table 2). A deconvolution procedure was performed by first subtracting the baseline from the
region of interest. The Curvefit subroutine in the
Win-IR software package was then used to specify initial values for the peak positions and heights.
A Gaussian shape was used for every peak. The
software then performed an iterative process
during which these values were allowed to vary
slightly in order to obtain individual, deconvoluted
peaks. R2-correlation coefficients were used to
indicate accuracy and were always greater than
99%.

ature profile one can obtain as many as five distinct

ammonia desorption peaks in the range from 150
to 540C that correspond to acid sites of different
strengths.
3.1. USY faujasites
Since it is used for numerous important industrial processes, the acidity of USY has been
studied very extensively in the past. The results of
the NH -STPD experiments of USY zeolites sub3
jected to dealumination of different extents are
presented in Fig. 1. The heating patterns for all
the USY samples started at 150C in order to
exclude desorption of physisorbed ammonia occur-

3. Results and discussion

The NH -STPD used earlier in our studies
3
involving b zeolite [3] provided an effective way
to identify quantitatively Brnsted and Lewis acid
sites of different strengths. The main advantage of
this technique is that by optimizing the temper-

Fig. 1. NH -STPD profiles from the USY samples.

3

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

ring at temperatures below about 130C [57]. It

should be noted that starting the heating of the
sample at 100C resulted in an additional desorption peak due to physisorbed ammonia. All the
USY faujasite samples gave five individual desorption peaks when heated up to 550C with the
optimized temperature profile. Heating the sample
to higher temperatures was avoided in order to
prevent the dehydration of Brnsted sites to form
Lewis acid sites. As mentioned earlier, it was
impossible to obtain additional peaks in this temperature range. Post and van Hooff [6 ] were able
to obtain five ammonia desorption peaks by deconvoluting the two major peaks of the traditional
NH -TPD experiments performed on HZSM-5 by
3
using a constant heating rate. One can observe
that the second and third STPD peaks, which
correspond to desorption temperatures of about
250C and 350C respectively, are the most dominant ones. Of course, the total area of the peaks
decreases with the increase of Si/Al ratio.
For the USY sample with the highest Si/Al ratio
( USY-760-28), one can observe that there is an
almost 1:1 relation ( Table 2) between the number
of ammonia molecules chemisorbed during the
experiment and the number of Al atoms present.
A similar conclusion was derived from our earlier
work [3] involving dealuminated b zeolites with
Si/Al ratios in the range of 15 to 130, indicating
that every Al site is occupied by one ammonia
molecule. In contrast, for the USY samples with
lower Si/Al ratios (<#6) the amount of ammonia
chemisorbed on the acid sites was significantly
lower than the amount one would expect if ammonia could occupy all the Al sites (e.g. for
USY-100-2.6 the ratio is 0.24). The case of incomplete saturation of the samples with ammonia
should be excluded because the ammonia fed to
the bed was far more than the amount required to
saturate the sample completely. Attempts to saturate the sample with ammonia for longer periods
gave exactly the same results. It should be noted
that a very similar behavior was observed for nondealuminated L zeolite with Si/Al=3.8 [9]. This
observation was reproduced repeatedly, and leads
us to conclude that this behavior is directly related
to the high density of aluminum sites. We propose
that, for zeolites that inherently possess high alumi-

177

num content, the chemisorption of even small

probe molecules such as NH (kinetic diameter
) on a portion of the Al3 atoms within the
2.6 A
zeolite can prevent the adsorption on adjacent Al
atoms due to steric limitations. Similar results were
observed by Pope [10] for adsorption of amines
of different lengths on ZSM-5.
The IR absorbance spectra of the USY samples
show a large peak at 1445 cm1. This peak is due
to ammonia adsorbed on Brnsted acid sites
(asymmetric NH+ bending) and decreases with
4
increasing desorption temperature for all samples.
For the USY-100-2.6 and the USY-500-2.6 samples
this peak remains large even after desorption at
440C (Figs. 2 and 3 respectively). For samples
subjected to more extensive dealumination
( USY-712-5.8), however, this peak disappears at
this desorption temperature. This indicates that
the strength of the Brnsted acid sites decreases
with increasing dealumination. In particular, this
decrease in acid strength occurs when the zeolite
has undergone acid leaching (sample USY-712-5.8
underwent steaming followed by mild acid leaching, whereas samples USY-740-21 and USY760-28 both underwent strong acid leaching
following steaming). After desorption at 540C,
the peak at 1445 cm1 completely disappears for
all USY samples, indicating complete desorption
of ammonia from the Brnsted acid sites.
A similar behavior is observed for the peak at
1630 cm1. This peak is associated with Lewis
acidity and is also seen to decrease with temperature for all USY samples. This peak disappears
after heating to 440C, indicating complete desorption of ammonia from Lewis sites. Using this
information in conjunction with the STPD data,
we may assign the first four peaks from the STPD
chromatogram to desorption from both Brnsted
and Lewis acid sites, whereas the last peak is due
exclusively to the Brnsted sites. The peak at
1685 cm1 is due to NH+ deformation [11,12].
4
This peak is present for all samples and changes
appreciably only at high temperatures. For the
acid-leached samples ( USY-712-5.8, -740-21, and
-760-28), a peak at 1540 cm1 appears and remains
constant for all temperatures. This peak is most
likely due to defects in the crystal structure that
are a result of the acid leaching. The fact that this

178

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Fig. 2. FT-IR data for USY-100-2.6 taken after desorption at (a) 150C, (b) 180C, (c) 250C, (d) 350C, (e) 440C, and (f ) 540C.

Fig. 3. FT-IR data for USY-500-2.6 taken after desorption at (a) 150C, (b) 180C, (c) 250C, (d) 350C, (e) 440C, and (f ) 540C.
The spectrum (region from 3450 to 3750 cm1) obtained after desorption at 150C contains six peaks located at (1) 3674 cm1, (2)
3645 cm1, (3) 3614 cm1, (4) 3593 cm1, (5) 3560 cm1, and (6) 3530 cm1. The measured peak and the summation of the calculated
peaks overlap.

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

peak does not change with increasing desorption

temperature indicates that it is not associated with
ammonia.
The band at 3743 cm1 ( Fig. 2), which is not
clearly resolved for the USY-100-2.6 sample due
to overlapping with the neighboring bands at lower
wavenumbers, belongs to the terminal silanol
groups. As expected, this IR band becomes more
pronounced at higher temperatures due to the
desorption of ammonia from the hydroxyl groups
( lower wavenumbers). Of course, the relative
height of this band increases significantly with the
extent of dealumination. The IR bands in the
range of 3700 to 3400 cm1 correspond to
hydroxyl stretching vibrations. One can observe a
broad peak in this region that results from several
bands and loses its area with an increase in temperature. For samples with higher Si/Al, such as
USY-500-2.6, USY-712-5.8, this band becomes
better resolved and a deconvolution procedure
may be performed. The deconvolution of this peak
was attempted (Fig. 3) based on information for
the bands in this region found in the literature.
Makarova et al. [13] attributed the peak located
at about 3540 cm1 to hydroxyl groups of the b
cages of the HY faujasite. Others [14] found for
Hb zeolite a peak at 3605 cm1 and another peak
at 3660 cm1, which correspond to binding OH
and non-framework AlMOH respectively.
The FT-IR results were found to be strongly
dependent on the type and extent of dealumination
performed on the USY samples. The deconvolution procedure applied to the steam-dealuminated
sample, USY-500-2.6, resulted in six individual
peaks (see Fig. 3). The peak located at
3674 cm1 corresponds to internal silanol groups
(or silanol defects) within the zeolite framework.
This arrangement is a result of the removal of
aluminum atoms from the zeolite structure. The
peak at 3614 cm1 is a result of the interaction of
extraframework hydroxyl groups with the high
frequency (HF ) framework AlMOH (hydroxyl
groups in the supercages) located at 3645 cm1 as
described by Corma et al. [15]. The peak at
3593 cm1 indicates the presence of hydroxyl
groups inaccessible to NH . The interaction of
3
extraframework hydroxyl groups with framework
AlMOH appears again at 3530 cm1. This peak is

179

due to the interaction with the low frequency (LF )

framework AlMOH (hydroxyl groups within the
b cages) located at 3560 cm1.
The sample USY-712-5.8 underwent steaming
followed by mild acid leaching. The result of the
deconvolution for the 37003500 cm1 range is
presented in Fig. 4. Again, six peaks were found
at 3673, 3639, 3614, 3596, 3555, and 3530 cm1.
The assignments of these peaks are as described
above. It should be noted that although most
peaks are similar for both USY-500-2.6 and
USY-712-5.8, a marked difference can be seen for
the internal silanol defects (peak 3673 cm1). In
the latter sample this peak has become significantly
smaller. This implies that acid leaching is capable
of repairing the silanol defects via a condensation
mechanism to form SiMOMSi bonds. This condensation of the SiMOH groups was also observed by
others [16 ] for mordenite samples that were
steamed, acid leached, and calcined. Following the
calcination, the samples showed a decrease in the
silanol defects [16 ]. Furthermore, we observed that
an increase in the acid-leaching severity (samples
USY-740-21 and USY-760-28) resulted in the complete disappearance of the silanol defect peak at
3674 cm1. Thus the severity of the acid leaching
plays a role in the extent of recrystallization of the
zeolite samples. For mild acid-leached samples
( USY-712-5.8) the repair of the silanol defects is
slight, whereas that of the samples that underwent
strong acid attack is complete.
Previous studies have shown that steam dealumination results in the formation of extraframework
aluminum hydroxyl groups, whereas acid leaching
removes them [2]. This was observed for the
samples that underwent strong acid leaching.
The hydroxyl region of the USY-740-21 and
USY-760-28 samples (both underwent steam dealumination followed by strong acid leaching)
possessed well-resolved peaks in this region. At
low desorption temperatures, one peak was
observed (figure not shown) in this region for the
USY-740-21 sample at 3613 cm1. This peak corresponds to the framework aluminum hydroxyl
groups. Upon further heating to 350C this peak
splits into two components: HF framework
AlMOH at 3622 cm1 and LF framework AlMOH
at 3560 cm1. It should be noted that the HF

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W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Fig. 4. FT-IR data for USY-712-5.8 taken after desorption at (a) 150C, (b) 180C, (c) 250C, (d) 350C, (e) 440C, and (f ) 540C.
The spectrum (region from 3450 to 3750 cm1) obtained after desorption at 150C contains six peaks located at (1) 3673 cm1, (2)
3639 cm1, (3) 3614 cm1, (4) 3596 cm1 (5) 3555 cm1, and (6) 3530 cm1. The measured peak and the summation of the calculated
peaks overlap.

hydroxyl, though completely resolved from its LF

component, has shifted to a lower wavenumber
when
compared
with
the
USY-500-2.6
(3645 cm1) and USY-712-5.8 (3639 cm1)
samples. Thus, the position of this HF hydroxyl
peak depends on the extent of dealumination. The
FT-IR spectra show an increase in the HF and
LF peaks due to the uncovering of the hydroxyl
sites after desorbing ammonia at 440C. This
height increase is accompanied by a shift of the
HF and LF peak positions to lower wavenumbers
(3620 cm1 and 3555 cm1 respectively). This phenomenon is again encountered after desorption at
540C. In this case the HF and LF peak positions
have shifted to 3617 cm1 and 3553 cm1 respectively. This shift is due to the presence of ammonia.
As ammonia desorbs, the perturbation of the OH
stretching frequency decreases and the peaks return
to the unperturbed positions. Similar results were

obtained for USY-760-28. However, at low temperatures (and high concentration of adsorbed
ammonia) the hydroxyl peaks are absent altogether. After desorption at 350C the HF peak
appeared at 3622 cm1, whereas the LF was at
3558 cm1. Again, these peaks shifted to lower
frequencies after desorption at 440C and 540C;
the HF peak shifted to 3618 and then to
3616 cm1, whereas the LF was at 3555 and
3552 cm1.
3.2. Mordenite
Mordenite possesses a two-dimensional network
of channels consisting of straight 12-membered
7.0 A
) connected by twisted
ring pores (6.5 A
5.7 A
side pockeight-membered pores (of 2.6 A
ets) [17]. The NH -STPD patterns obtained for
3
protonated mordenite samples of different Si/Al

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Fig. 5. NH -STPD profiles from the mordenite samples.

3

are presented in Fig. 5. As in the case of USY, we

observed five individual desorption peaks for each
sample. It is worth noting that, in contrast to the
USY samples, where the largest desorption peaks
occurred at relatively low temperatures, desorption
of NH from the acid sites of the mordenite
3
samples occurred mainly at high temperatures.
This indicates that mordenite possesses stronger
acid sites. A comparison of the results obtained in
our earlier study [3] involving b zeolites (the
majority of the peaks were located at intermediate
temperatures) with the present samples, indicates
that mordenite possesses, on average, stronger
sites. However, from the IR data, we conclude
that the majority of acid sites in mordenite are
Lewis acid sites ( Table 2). This might explain the
high activity but fast deactivation of mordenite in
acid-catalyzed reactions.
Karge and Dondur [18] studied the acidity of
dealuminated mordenites of comparable Si/Al
ratios to those of our study. By using pyridine as
the probe molecule for temperature desorption
experiments, they obtained four peaks that were
assigned to weak Lewis sites, Brnsted sites of
lower strength, Brnsted sites of higher strength,
and Lewis sites of higher strength. It should be
noted that the last type of Lewis site was formed
by the dehydroxylation of Brnsted acid sites that
occurs at high temperature (the TPD experiments
of Karge and Dondur [18] involved a pretreatment
at 800C ). As our STPD experiments did not
approach this temperature, and thus did not
include these Lewis sites of higher strength, only

181

the first three peaks obtained by Karge and

Dondur may be compared with those obtained in
our study. It is worth noting that the use of
pyridine instead of ammonia as the probe molecule
[18] gave one less desorption peak for Brnsted
sites. This was probably the case because the use
of pyridine did not enable the above researchers
to probe the acid sites located in the eight-membered ring pores of mordenite due to space constraints. Finally, in the above study [18] it was
concluded that the increase of the extent of dealumination results in a decrease of the strength
of the Brnsted sites. The heating profile used in
our study is capable of resolving these desorption
peaks even further, so that we obtain five individual peaks. Evidently, the stepwise heating of the
sample followed in our study provides unique
flexibility in distinguishing very accurately the
strength of acid sites.
The coupling of the STPD experiments with
FT-IR studies performed at the same temperatures
can assist us in correlating the ammonia desorption
peaks of the former experiments with the type of
acid site. More specifically, by comparing the
1630 cm1 peaks of MOR-9.5 for increasing temperature (Fig. 6), we observe that desorption from
the Lewis acid sites occurs only during the first
two desorption steps (180 and 250C ). This indicates that the remaining three STPD peaks are
due to desorption only from Brnsted acid sites.
When examining the Brnsted peak at 1440 cm1
we see a decrease in peak height with every scan,
thus indicating desorption of ammonia from
Brnsted acid sites during every desorption step.
This is seen not only for the MOR-9.5 sample, but
also for the dealuminated samples, and indicates
that the first two peaks from the STPD experiments
are associated with ammonia desorbing from Lewis
and Brnsted sites. From the NH -STPD experi3
ments that we performed on mordenite, we found
that the relative area of the high desorption temperature STPD peaks decreases with increasing
Si/Al. Concurrently, the third peak becomes more
dominant ( Fig. 5). Hence, one can conclude that
the strong Brnsted sites are preferentially lost
with an increase in the dealumination severity.
The FT-IR spectra of the mordenite samples
show a number of overlapping peaks within the

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W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Fig. 6. FT-IR data for MOR-9.5 taken after desorption at (a) 150C, (b) 180C, (c) 250C, (d ) 350C, (e) 440C, and (f ) 540C. The
spectrum (region from 3450 to 3750 cm1) obtained after desorption at 150C contains three peaks located at (1) 3649 cm1, (2)
3610 cm1, and (3) 3568 cm1. The measured peak and the summation of the calculated peaks overlap.

hydroxyl region. This region may be deconvoluted

to obtain information on the individual hydroxyl
peaks. Other research groups [1921] attributed
the band located at 3612 cm1 to the vibration of
hydroxyl groups located in the main channels of
mordenite (12-membered ring pores) and the peak
at about 3585 cm1 to the hydroxyl groups located
in the side pockets of mordenite. The deconvolution performed on the MOR-9.5 sample resulted
in three peaks (see Fig. 6). The most intense peak,
located at 3649 cm1, is due to extraframework
AlMOH. The peak located at 3610 cm1 corresponds to HF framework AlMOH located within
the 12-membered ring channels. The framework
bridging hydroxyl groups located within the small
channels ( low frequency AlMOH ) resulted in the
peak at 3568 cm1. We obtained similar results for
the mordenite samples dealuminated with ammonium hexafluorosilicate. However, upon dealumination, a fourth peak appeared at 3693 cm1 that

was assigned to internal silanol groups [19]. As

expected, this peak increased in height with the
amount of dealumination. For higher wavenumbers one can observe a sharp peak at
3748 cm1 that is due to terminal silanol groups.
3.3. ZSM-12
In contrast to the majority of the other zeolites,
the acidity characteristics of ZSM-12 have not
been extensively studied. ZSM-12 is a high silica,
large-pore zeolite that possesses one-dimensional,
6.2 A
) [17].
non-interpenetrating channels (5.7 A
Even though it is a unidirectional zeolite (it is well
known that one-dimensional zeolites can be more
susceptible to deactivation due to coking), ZSM-12
samples with relatively high Si/Al ratios demonstrated superior performance for acid-catalyzed
reactions [9,22,23]. Gorte and co-workers [24,25]
studied the acidity of ZSM-12 by means of calorim-

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Fig. 7. NH -STPD profiles from the ZSM-12 samples.

3

etry and TPD and concluded that the probe molecules adsorb on the catalyst surface in a 1:1 ratio
with the Brnsted acid sites for all the zeolites
tested ( ZSM-12, ZSM-5, and mordenite). In recent
work [25], it was shown that there is a distribution
of acid strength of ZSM-12, since the desorption
of the probe molecule took place gradually as a
function of temperature. It was also concluded
that both ZSM-12 and ZSM-5 possess very similar
acid sites, even though their crystallographic structures are different. Moreover, in that study, it was
concluded that other zeolites, such as mordenite,
which have substantially stronger acid sites, possess only comparable catalytic activity.
Our NH -STPD experiments ( Fig. 7) on the
3
ZSM-12 samples containing different Si/Al ratios
gave similar results: two almost equal size peaks
at 180C and 250C, followed by a large peak at
about 350C and two smaller desorption peaks at
440C and 540C. The profiles obtained from the
STPD experiments were not sensitive to slight
variations of the temperature profile used, thus
indicating that both the Lewis and Brnsted sites
of all the zeolite samples had distinct strength
limits.
From the IR spectra, we observe that the peak
at 1460 cm1 due to NH+ bending (ammonia
4
adsorbed on Brnsted acid sites) decreases in
height at each desorption step and is completely
gone at 440C. This trend holds for all the ZSM-12
samples regardless of Si/Al ratio. Curve deconvolution for the broad peak in the range from 1560 to
1740 cm1 (Fig. 8) indicated that for the ZSM-12

183

sample with an Si/Al ratio equal to 35 there is a

small Lewis band present at temperatures below
250C. This peak disappears upon heating at
higher temperatures. It should be noted that the
maximum of the IR band in this range is at about
1640 cm1, due to the coexistence of the Lewis
peak (1625 cm1) and structural vibrations at 1640
and 1680 cm1. The Lewis peak was absent for all
other ZSM-12 samples studied. These results agree
well with our MAS-NMR studies [26 ] that showed
octahedral Al species (Lewis sites) only for the
as-synthesized sample (ZSM-12-35). Thus the first
two STPD peaks for the sample ZSM-12-35 are
due to desorption from Brnsted and Lewis sites,
whereas the last three peaks are due only to
desorption from Brnsted sites. The STPD peaks
for the dealuminated ZSM-12 samples, on the
other hand, are due to desorption of ammonia
only from Brnsted sites. The shapes of the desorption profiles of ZSM-12 are similar to that of
zeolite b [3], where a major part of the ammonia
desorption occurred at intermediate temperatures,
indicating that both zeolites possess sites of intermediate strength. In contrast, it was shown earlier
in this paper that the mordenite samples possess
acid sites of the highest strength in comparison
with the other zeolites studied.
The STPD desorption experiments performed
on these zeolites ( USY, mordenite, and ZSM-12)
all resulted in five distinct peaks due to desorption
from Lewis and Brnsted acid sites. Fewer desorption peaks may be obtained by a rapid increase in
temperature due to the overlapping of the original
five peaks. In contrast to this, decreasing the rate
of temperature increase or addition of more isothermal periods will not result in more peaks. This
was not the case for acidic TiO -based DeNOx
2
catalysts [27,28], where the desorption pattern was
a very strong function of the temperature profile
followed. More specifically, it was observed that
for each ramping step, regardless of the temperature range, a new ammonia desorption peak was
generated, indicating that the desorption process
was very sensitive to temperature. Those experiments were coupled with FT-IR investigations and
it was concluded that the desorbed ammonia was
removed from both Lewis and Brnsted sites at
all temperatures, indicating that for those oxidebased catalysts both the Lewis and Brnsted sites

184

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

Fig. 8. FT-IR data for ZSM12-35 taken after desorption at (a) 150C, (b) 180C, (c) 250C, (d ) 350C, (e) 440C, and (f ) 540C.
The spectrum (region from 1540 to 1750 cm1) obtained after desorption at 150C contains three peaks located at (1) 1680 cm1,
(2) 1640 cm1, and (3) 1625 cm1. The measured peak and the summation of the calculated peaks overlap.

have comparable strengths; this is not the case for

the zeolite acid sites. As shown above, the STPD
experiments, when applied to acidic zeolites, can
effectively reveal their specific acid site characteristics related to the strength and type of acid site.

4. Conclusions
It was found that the STPD of ammonia can
be an effective method for the characterization of
acid sites of different strengths. In contrast to the
traditional TPD experiments, the STPD offers an
improved quantitative determination of the
amount of the base chemisorbed on the acid sites
of zeolites. A one-to-one relationship between
ammonia molecules and aluminum sites in the
adsorption process was not found for high alumi-

num content zeolites. This is attributed to steric

hindrances that occur between ammonia molecules
when distances between adjacent aluminum sites
are sufficiently small so as to prevent free access.
Based on the average desorption temperature
from the NH -STPD data, we conclude that,
3
among the zeolites tested, mordenite has the
strongest acid sites. However, from the IR data,
we have found that the majority of acid sites in
mordenite are Lewis acid sites. Also, it was found
that dealuminated ZSM-12 possesses only
Brnsted acid sites. The acid strength distribution
of each zeolite is a function of the Si/Al ratio and
of the specific dealumination procedure employed.
Moreover, the specific zeolite structure plays an
important role in the acidic properties of the zeolite
even when the same dealumination procedure is
followed.

W. Zhang et al. / Microporous and Mesoporous Materials 33 (1999) 173185

From the IR experiments performed, it was

discovered that the silanol defects formed during
steam dealumination of Y can be repaired by acid
leaching. This is an interesting phenomenon, as it
results in a more stable crystal structure.
Deconvolution of the complex hydroxyl region is
an effective tool in obtaining detailed information
on the position and type of aluminum site.

Acknowledgements
The authors wish to acknowledge the
support of the National Science Foundation
through the CAREER Award (CTS-9702081).
Acknowledgment is made to the donors of The
Petroleum Research Fund, administered by the
ACS, for support of this research through the
grant ACS-PRF 31606-G5. The authors wish to
thank Mr G. Robb for setting and calibrating the
thermal conductivity detector and performing
some of the preliminary STPD runs.

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