16th Saudi Arabia-Japan Joint Symposium

Dhahran, Saudi Arabia, November 5-6, 2006

Brnsted Acidity in HY and USY

Studied by IRMS-TPD of Ammonia

Miki NIWA, Katsuki SUZUKI, and Naonobu KATADA

Department of Materials Science, Faculty of Engineering
Tottori University,
Koyama-cho, Tottori 680-8552, Japan
e-mail : mikiniwa@chem.tottori-u.ac.jp

ABSTRUCT
Brnsted acidity in HY and USY was studied by IRMS-TPD of ammonia which was
recently developed by us. With the improved property of the method, the Brnsted acidity was
characterized in detail, and the active site created in the USY was found. Relationship between the
Brnsted acidity and the catalytic cracking activity was mentioned. Alkali-cation exchanged Y
zeolite was also studied additionally.

INTRODUCTION

Y-zeolite is an industrially important catalytic material, and has been studied from various
view-points. However, due to its complex property, the Brnsted acidity is not totally characterized.
Dealumination by steaming at higher temperature is necessary to make the Y-zeolite active for
petroleum refinery process. The so-called USY (Ultra-stable Y) zeolite has the property different
from an inherent Y zeolite, because only the former has the catalytic activity. The generation of
active phase in the USY is therefore so interesting, but it has not been clearly understood yet.
Ammonia TPD (temperature programmed desorption) has been often used for the
characterization of acidity. Number and strength of the acid sites has been measured using this
method. However, the nature of acid site, Brnsted or Lewis acidity, could not be identified.
Therefore, another technique such as IR observation of pyridine adsorption has to be taken
additionally. In order to improve the drawback, recently, we proposed an IRMS-TPD of ammonia,
in which infrared and mass spectroscopies are working together to follow up thermal behavior of not
only adsorbed ammonia species but also desorbed ammonia in gas phase, and by comparison
between them, Brnsted and Lewis acid sites are measured individually. Such a precise and direct
measurement has never been performed to study the acid sites in zeolites.
Our previous studies revealed another advantage of this method; i.e., the distribution of

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16th Saudi Arabia-Japan Joint Symposium
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Brnsted acidity could be studied in detail [1]. Therefore, our purpose of the present study is directed
to understanding the Brnsted acidity in Y zeolites, inherently prepared and activated in the forms of
USY and alkali cation exchanged. Catalytic cracking of octane will be measured on these zeolites,
and the characterization data will be correlated with the catalytic activity of cracking.

Determination of number and strength of acid site from ammonia TPD [2, 3]

Prior to explaining the present topics, fundamentals of a method of TPD of ammonia should be
elucidated. This technique has been utilized often to characterize the acidity of samples, however,
mistakes in the measurements are often observed. To measure the acid site, first, identification of
desorption peaks are required. Mordenite, a typical zeolite with the strong solid acidity, has two
desorption peaks at low and high temperatures called l- and h-peaks. However, the l-peak is not
ascribable to ammonia adsorbed directly on the acid sites; it is assigned to ammonia which had been
adsorbed on NH4+. Therefore, counting the l-peak as the acid site leads to the over-estimation.
Intensity of the l-peak depends on the experimental conditions, and at the very small W/F, the
intensity becomes negligibly small.
On the other hand, the h-peak is ascribed to NH3 directly adsorbed on the acid sites; therefore
from the h-peak number of the acid site can be quantitatively measured. Thus measured number of
the acid site in zeolites is equal to Al in the framework of zeolite. The fundamental observation is
supported by the structure model of Brnsted acid site, which is created by isomorphous replacement
of aluminum with silicon in the tetrahedral position.
Strength of the acid site is used to be a parameter difficult to obtain correctly. Ammonia TPD
was used, at the early stage of investigation, as a simple method to evaluate the acid strength, and
people depended on the desorption temperature. It had been recognized that, the higher the
temperature of ammonia desorption, the stronger the acid site. However, this concept could not be
applied to the method. Under the usual conditions of TPD, ammonia is freely re-adsorbed during the
TPD experiment. Equilibrium between ammonia molecules adsorbed on the surface and in the gas
phase is fulfilled instantly, and therefore the experiment is not controlled kinetically but
thermodynamically. Temperature of the desorption shifts high with increasing number of acid sites,
though the acid sites have the equal strength. Strength of the acid site, thereby, is obtained as a
parameter H heat of ammonia desorption based on the following theoretical equation.
A0W d P0 H S
Cg = = exp exp eq. (1)
F dT 1 RT RT R
where Cg is the concentration of ammonia in the carrier, and the change of Cg with temperature
shows the TPD profile: , A0, W, F, , P0, and R denote ramp rate of temperature, concentration of
acid sites, weight of sample, flow rate of carrier gas, coverage by ammonia, standard pressure (1.013 x

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16th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 5-6, 2006

105 Pa), and gas constant (8.31 J K-1 mol-1), respectively. H and S are changes of enthalpy and
entropy upon desorption of ammonia, respectively. By assuming the value of S, H is calculated
as a parameter to show the strength of acid sites by fitting the theoretical profile to the experimentally
observed TPD of ammonia (curve-fitting method).
On the other hand, because dCg/dT = 0 at the peak maximum, eq (2) is derived by
differentiation of eq. (1) with respect to T,

A0W H (1 m ) (H RTm )
2
ln Tm ln = + ln eq. (2)
F RTm P 0 exp(S / R )

Because the second term of the right hand side is practically a constant, plots of the value in left
hand side against 1/Tm gives a straight line of slope H/R, from which H is measured (one-point
method). H could be measured by these two methods.

In situ prepared Y zeolite [4]

Y zeolite is believed to have the simple structure,

because there is only one T (Si or Al) site. Four
oxygens are bonded to the T site in the tetrahedral
configuration. Four oxygens, O(1) to O(4), exist, as
named in Figure 1, therefore, four kinds of Brnsted
acid site are possible. Among them, two OH, O(1)H
and O(4)H, are located in the super cage, O(2)H in the
sodalite cage, and O(3)H in the hexagonal prism. First
of all, interaction of ammonia with these OH will be
studied, from which number and strength of the OH
will be measured.
Fig. 1. Four kinds of oxygen numbered 1
It has to be mentioned that Y-zeolite is so fragile,
to 4 in the structure of Y-zeolite.
particularly, when the proton type Y-zeolite is formed
and exposed to humidity in the atmosphere [5].
Therefore, measurements are carefully carried out on the sample prepared in situ in the IR cell from
NH4Y, which is not exposed to atmosphere. When ex situ prepared, structure of Y-zeolite is altered
and therefore clear and correct information is not obtained.

information is not obtained.

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Dhahran, Saudi Arabia, November 5-6, 2006

1.5

1430
1496
1369
373K
1

1665

1320
Absorbance
473K
Back ground
573K
0.5

4000 3000 2000

Wavenumber/cm-1

Fig. 2. Difference spectra after ammonia adsorption measured at 373 to 773 K during the TPD
experiment on in situ prepared NH4Y.

A self-compressed wafer of NH4Y (96 % NH4+ and 4 % Na+) was put into the IR cell, to which
helium carrier gas was fed. Inside was pumped from the exit to keep 25 Torr, and MS monitored the
concentration of ammonia in the gas phase. After evacuation at 773 K, temperature was lowered
to373 K at which ammonia was adsorbed and then evacuated. TPD experiment was then studied,
and not only adsorbed species but also ammonia in gas phase was followed by IR and MS during the
TPD experiment, respectively. Difference spectra were calculated from IR intensities measured
before and after the adsorption of ammonia (Figure 2). Ammonia stretching and bending vibrations
were observed in the regions of 3400 to 2000, and 1700 to 1400 cm-1. Simultaneously, the
decreased intensity of OH was observed. From the change of intensity, these OH was identified as
the Brnsted acid sites.
NH4+ bending vibration was analyzed by deconvolution into three portions at 1496, 1430 and
1369 cm-1, but these assignments were difficult. Enlarged difference spectra of OH stretching
vibration in Fig. 3 show interesting profiles, because two OH bands (HF; high frequency and LF; low
frequency) were further divided into each two components; i.e., totally four kinds of OH were
detected. Based on previous studies, two OH in LF were assigned as O(2)H and O(3)H at higher
and lower frequency, respectively. Because the assignment of OH in HF band was incomplete,
these were assigned as O(1)H and O(1' or 4)H positioned at higher and lower wave numbers,
respectively. Assignments of these OH were summarized in Table 1.

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16th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 5-6, 2006

20 [10 ]
-4
0.6 MS 4

{-d(A(N)-N(A))/dT}/K-1
0.4 10 1430
Absorbance

Cg/mol m-3
1665 1496 1369
0.2
3648
3625

3571

3526
0 0
0
3571
3625
3648
473K -2
-0.2 -10
373K
3526
3700 3600 3500 300 400 500 600 700
-1
Wavenumber/cm Temperature/K

Fig. 3. Enlarged difference spectra of Fig. 4. Comparison between MS- and IR-TPD for
OH stretching vibration in Fig. 2. A back NH4+ and OH.
ground obtained at 373 K (dotted line) is
shown as a comparison.

In this method, a differential change of IR intensity is calculated at the selected wave number,
and plotted against the temperature. This is corresponding to the rate of decrease of the adsorbed
species, and called IR-TPD, which could be compared with MS-measured TPD. IR-TPD of NH4+
(3 portions) and OH (4 kinds of OH) are shown in Fig. 4; MS-measured TPD is added to for a
comparison.

Table 1. Assignment and quantitative data for Brnsted OH in Y zeolite

Band
A0 H
Position Assignment Position cm
-1 mol kg-1 kJ mol-1
/cm mol-1

3648 O(1)H 0.58 108 1.4

Super cage
3625 O(1' or 4)H 0.57 110 1.3

3571 O(2)H Sodalite cage 1.1 119 0.52

3526 O(3)H Hexagonal prism 0.80 105 1.3

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16th Saudi Arabia-Japan Joint Symposium
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It was found from Fig. 4 that

NH4+ species were desorbed at the high 40 [10-4]
MS corrected IR-TPD (NH 3)
temperature, consistent with desorption 3.3I1 4 6 9 + 3.3I1 3 6 9 + 1 I1 4 3 0
4

-1
at the high temperature. The NH4+ 30

{-d(A(T)-N(T))/dT}/K
3

Cg/mol m -3
band at 1430 cm-1 was removed at the 20 19I1 6 6 5

1 I1 4 3 0 2
highest temperature, and those of 1496 3.3I1 3 6 9
3.3I1 4 9 6

and 1369 cm-1 were desorbed at the

10 1

lower temperature. OH groups at 3571, 0 0

300 400 500 600 700
-1
3625, and 3648 cm changed the Temperature/K
40
intensity at the same temperature region. -1.44 IO(1 )H -1.5 IO(1 ' o r 4 )-6 IO(2 )H
3.3I1 4 6 9+3.3 I1 3 6 9+1I1 4 3 0
This means that NH4+ species is
-1

30
{-d(A(T)-N(T))/dT}/K

-6IO(2 )H

adsorbed on these OH, i.e., O(2)H, O(1' 19I1 6 6 5

20 -1.44 IO(1 )H

or 4)H, and O(1)H. Further precise -1.6 IO(3 )H

-1.5 IO(1 ' o r 4 )

analysis being made, it was found that 10

the O(3)H accommodated NH3 species 0

300 400 500 600 700
observed at 1665 cm-1, which would be Temperature/K

identified as NH4+ or NH3. The O(3)H

is located in the hexagonal prism, and an Fig. 5. Curve fitting of IR-TPD to MS-TPD.
interaction of ammonia with the OH is Three bands of NH4+ were fitted to high temperature
hindered due to the small space. A desorption, while the band at the O(3)H was fitted to
different cation species or different the low temperature desorption.
mode of ammonia adsorption is
therefore postulated on the O(3)H.
A curve fitting method was made to measure number and strength of the Brnsted OH.
Parameters to cancel the extinction coefficient, i.e., reciprocal of extinction coefficient is required to do
the curve-fitting, shown in Fig. 5. Thus measured parameters of the Brnsted acid site are
summarized in Table 1. Measurements were made on other HNaY samples with different cation
exchange degree, and distribution of acid sites was found to depend on the degree of Na cation
exchange. Band positions of four OH did not change, and only the concentration varied with
changing with Na cation.
Summary for the Y zeolite is following,
(1) Four kinds of Brnsted acid site are observed. Maybe, these have different structures.
(2) The strongest acid site is located in the sodalite cage.
(3) A previously reported strength of Y zeolite, 110 kJ mol-1, is an averaged value.

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USY zeolite [6]

0.4
Y zeolite has so poor catalytic
activity only, as long as the clear
0.2

Absorbance
structure is retained and the amount of 3595
extra framework Al is small. In the
0
study shown above on the in situ
prepared HY, no information of the 473K
catalytic activity is provided, because the -0.2 373K
in situ Y zeolite is almost free from the 3700 3600 3500
Wavenumber/cm-1
extra framework Al (EFAl). Therefore,
we study the USY to know the
enhancement of the catalytic activity by
Fig. 6. Enlarged portion of difference spectra of
the EFAl.
OH in USY during ammonia TPD.
In our previous study, a procedure
to prepare the excellent catalyst was studied [7]. A steaming should be performed at ca. 823 K to
remove about half of framework Al.
Dislodged Al remains in the USY [10-4]

zeolite. Next, a treatment with 0.5 1

-1
{-d(A(N)-N(A))/dT}/K

Na2H2-EDTA must be carried out; after

-3
Cg/mol m
the treating, the strong Brnsted acid 0 0

sites are created to enhance the catalytic :NH4+

:NH3
-0.5 :Super-cage -1
activity. In the EDTA-USY, the :Sodalite-cage
:strong
Brnsted acidity is prevailing. :MS
300 400 500 600 700
A technique of IRMS-TPD was Temperature/K

applied to the EDTA-USY. As

mentioned above, difference spectra Fig. 7. IR-TPD for NH4+ and OH , compared with
showed NH4+ bending vibration and MS-TPD.
decreased intensity of OH stretching
vibration. During the recovery behavior upon desorption ammonia, an interesting observation was
found, as shown in Fig. 6. Typical two kinds of OH, HF and LF, were observed in the Figure, but
one more OH band, which was not found in usual HY, was clearly detected at 3595 cm-1.
IR-TPD in Fig. 7 shows that the OH band at 3595 cm-1 changed the intensity at temperatures
higher than those of usual OH in HF and LF. This means that the additional OH has the stronger
acidity than two OH inherently existed in Y zeolite.

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The H measured on the OH at 3595 140

cm was 137 kJ mol-1, which was similar to that

-1 USY

Acid strength H/kJ mol-1

of HZSM-5. A high catalytic activity of the 130

OH is thereby estimated, and this is the active USY

CaHY in situ HY
120
site for catalytic cracking. ex situ HY
LaHY ex situ HY
USY
We speculate that EFAl in the vicinity of
110
Brnsted acid site acts as an electron withdrawer LaHY

in situ HY in situ HY
to activate the site. The structure is not actually 100
3650 3600 3550 3500
known from the present study, and another OH/cm-1
investigation is needed, for example NMR
measurement. Quantitative information about Fig. 8. Relationship between band position
the catalytic active site in USY is provided in and H of the Brnsted acid site. Closed
this study. and open circle shows the OH bands at super
(12 MR) and sodalite cages (6 MR),
respectively.

Relationship between the strength of acid site

and IR band position [10 ] 3
-2
USY

In this study, IR band position of the

2
Brnsted acid site is measured. The IR
-1
TOF/s

position of OH is, so often, measured in ex situ HY

characterization studies. However, only in this 1

CaHY
study, the strength is also measured in addition LaHY

to the band position. This technique was 0

in situ HY
100 110 120 130 140
applied to alkali cation exchanged zeolites, i.e., Acid strength H/kJ mol-1
Ca and La exchanged HY. It is interesting to
study the relationship between these parameters. Fig. 9. Dependence of the TOF of octane
As shown in Fig. 8, a straight relationship was cracking on the H of the Brnsted acid site.
observed between H and band position for the
OH in the super cage, but no relation was found
on the OH in the sodalite cage. The relationship observed in the super cage is, as a matter of fact, a
portion of the relationship found in various kinds of zeolite species. As long as the OH is located in
8, 10, and 12 member rings, there is a relation between the H and the band position; i.e., the stronger
the OH, the lower the wave number of IR band position.

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Dhahran, Saudi Arabia, November 5-6, 2006

Quantitative study on the relationship between the catalytic activity and the Brnsted acidity

As mentioned above, we can precisely measure number and strength of the Brnsted acid sites
in zeolites. This method allows us to measure these values directly and quantitatively. Such a
precise information has never been provided yet. Therefore, these measurements provide us a very
fundamental basis to study the catalysis on the Brnsted acid sites.
Haag and Dessau proposed that the cracking of hydrocarbons proceeded according to two
kinds of reaction mechanism which depended on the conditions [8]. Mono molecular reaction
proceeds under the conditions of high temperature and low partial pressure of reactant. At the
conditions, such a paraffin as octane is activated on the Brnsted acid site to become a
penta-coordinate carbonium ion as the reaction intermediate as shown below. Therefore, the
monomolecular reactions conditions were selected, because it would become easier to study the
cracking reaction. We found that 773 K and 14 Torr of octane are enough to regard the reaction to
proceed through the monomolecular reaction mechanism [9]. Brnsted acid sites located in the super
cage are postulated to play the active site. Turn over frequency (TOF) is therefore provided based on
number of the Brnsted acid site in the super cage. Thus measured TOF should be related with the
strength of the acid site, and we found the relationship between H and TOF, as shown in Fig. 9.

Monomolecular reaction mechanism

Scheme. Monomolecular mechanism of cracking of octane through

penta-coordinate carbonium ion.
Brnsted acid sites are therefore active sites for catalytic cracking.

CONCLUSION

Using the IRMS-TPD, the Brnsted acid sites in HY pure or modified were measured
quantitatively. Following conclusions are obtained.
1. HY zeolite has four kinds of structure-different OH. Two OH are located in the super cage,

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16th Saudi Arabia-Japan Joint Symposium
Dhahran, Saudi Arabia, November 5-6, 2006

one in the sodalite cage, and one in the hexagonal prism.

2. In USY, one more OH was detected additionally at 3595 cm-1.
3. Number and strength of OH were measured quantitatively. Strength of acid site H was
correlated with the IR band position only in large pores.
4. Catalytic cracking activity depended on the H, thus implying the Brnsted acid sites
being active site.

REFERENCES
1. M. Niwa, K. Suzuki, N. Katada, T. Kanougi, T. Atoguchi, J. Phys. Chem., B, 109, 18749
(2005)
2. M. Niwa, M. Sawa, N. Katada, Y. Murakami, J. Phys. Chem., 99, 8812 (1995).
3. N. Katada, H. Igi, J. H. Kim, M.. Niwa, J. Phys. Chem., B, 101, 5969 (1997).
4. K. Suzuki, N. Katada, M. Niwa, J. Phys. Chem., B, submit
5. N. Katada, Y. Kageyama, M. Niwa, J. Phys. Chem. B, 104, 7561 (2000).
6. M. Niwa, K. Suzuki, K. Isamoto, N. Katada, J. Phys. Chem., B, 110, 264 (2006).
7. N. Katada, Y. Kageyama, K. Takahara, T. Kanai, H. A. Begum, M. Niwa, J. Mol. Catal., A:
Chemical, 211, 119 (2004).
8. W. O. Haag, R. M. Dessau, "8th International Congress on Catalysis, Proceedings", Verlag
Chemie, Weinheim, 1984, Vol. II, p.305.
9. T. Hashiba, D. Hayashi, N. Katada, M. Niwa, Catal. Today, 97, 35 (2004).

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